D2AM, upgrade, highlights and perspectives of the French ... · D2AM, upgrade, highlights and...

D2AM, upgrade, highlights and perspectives

of the French anomalous CRG beamline at ESRF.

presented by Nils Blanc and Nathalie Boudet

April 3, 2014

Contents.

1 Introduction 2

2 D2AM: a French CRG 3

2.1 Description . . . . . . . . . . 3

2.2 Associated laboratories . . . . 3

2.3 User access . . . . . . . . . . 4

2.4 Upgraded beamline overview 5

3 Scientific results 10

3.1 Applied Materials . . . . . . . 10

3.2 chemistry - soft or amorphousmaterials . . . . . . . . . . . 13

3.3 Surface and nanostructurecharacterization . . . . . . . . 18

3.4 Hard condensed matter . . . 233.5 Methods and instrumentation 28

4 Conclusion-perspectives 294.1 in-situ studies . . . . . . . . . 294.2 2D data treatment . . . . . . 314.3 Kirkpatrick-Baez optics for a

microbeam experiment . . . . 314.4 Upgrade phase II of the ESRF 32

5 Scientific production 2009-2013 335.1 Theses . . . . . . . . . . . . . 335.2 Articles . . . . . . . . . . . . 345.3 Conferences . . . . . . . . . . 465.4 Books and chapters . . . . . . 485.5 Softwares . . . . . . . . . . . 48

This document is the collective work of all those participating in the beamline. They are to bethanked for their written contributions and for their help and comments in preparing this booklet.

1

1 INTRODUCTION

1 Introduction

The BM2-D2AM Beamline is a French CRG dedicated to Materials Science, which wasone of the first lines to operate at start-up of the ESRF in 1994. It is dedicated to studies of themicroscopic structure of materials using two principle techniques: (i) wide angle X-ray scattering,which provides information on long-range ordering at the atomic scale and (ii) small angle X-rayscattering, which provides information on the shapes of objects at the mesoscopic scale (typically 0.1to 1 micron). Both of these methods can be coupled with ”anomalous” X-Ray scattering, which yieldsadditional chemical information by providing contrast between different kinds of atoms.

The upgrade and perspectivesSince the last review, in 2009, the beamline has been completely refurbished with the aim of pro-

viding state-of-the-art optics on a bending magnet beamline and versatile instruments where usersin-situ apparatuses can be inserted. Recent developments in materials science require the ability toperform X-ray characterization on heterogeneous, multi-scale samples under specific conditions, suchas:

• In operando and time-resolved studies of advanced materials used for energy production andstorage (batteries, membranes)

• In situ mechanical stress applied to biopolymers

• In situ and time-resolved annealing of thin films, nanostructures, ... under controlled atmosphereto obtain new structural properties

During the review period, 2009-2013, 212 experiments were performed, still covering a broad rangeof materials science studies, 252 reviewed articles were published and 46 PhD were defended thatincluded work done at the beamline. The table below lists the publications with the highest impactfactors (left column) and the most common journals (right column) :

High IF Journal total 2009-2013 Journal total 2009-2013

Chem. Soc. Rev. 1 J. Phys. Chem. C 4Surf. Sci. Rep. 2 soft Matter 8

ACS Nano 1 Macromolecules 15Adv. Functional Materials 2 Biomacromolecules 9

J. Am. Chem. Soc. 1 Acta Materialia 13Phys. Rev. Let. 1 J. Phys. Chem. B 6

Nanoscale 1 Langmuir 12J. of Biomedical Nanotechnology 1 Appl. Phys. Lett. 5

J. Mater. Chem. 2 Nanotechnology 5Chemistry of Materials 2 Phys. Rev. B 10

After the description of the beamline and its upgrade, selected experiments that are repre-sentative of the activity at D2AM in recent years are presented to the 2014 ESRF review panel. Aselection of significant papers are reprinted in the appendix. They are representative of the variousscientific topics in which the beamline is involved : from soft condensed matter to semi-conductornano materials.

April 3, 2014@ 9:30 D2AM report to the ESRF BLRP 2 of 49

2 D2AM: A FRENCH CRG

2 D2AM : a French CRG beamline

2.1 Description

The D2AM (Diffraction et Diffusion Anomale Multilongueurs d’onde) beamline is dedicated to struc-tural studies using wide angle X-ray scattering, which provides information on long-range orderingat the atomic scale and small angle X-ray scattering, which provides information on shape at themesoscale. Both can be coupled with anomalous scattering, which yields additional chemical informa-tion by providing contrast between different kinds of atoms. It is also the beamline on which DiffractionAnomalous Fine Structure (DAFS) spectroscopy was developed [Proietti1999, Renevier2003]. A majorrecent improvement is the possibility of performing Multiwavelength Anomalous Diffraction and DAFSspectroscopy in grazing incidence geometry, so as to reduce the substrate scattering contribution andto focus on the structural properties of nanoobjects. In the past few years MAD and DAFS have beenapplied to systems of great technological interest, e.g. to determine independently strain and compo-sition within semiconductor nanostructures [Grenier2002, Letoublon2004, Coraux2007, Proietti2008,Katcho2011]. The beamline has been used in a very wide range of Materials Science, characterizingshort-range and long-range order from gels and amorphous materials to quasi-crystals [Takakura2007]and nanostructures. It allows both bulk and/or surface characterization. Its main scientific fields arenanomaterials, microelectronics, catalysts and soft condensed matter. It is the most advanced Frenchbeamline in the field of anomalous scattering, with the most developed user community. Recent stud-ies cover glassy materials [Hosokawa2009], alloys [Marlaud2010] and Anomalous SAXS [Simon2009].D2AM was at the heart of the organization of the REXS2011 conference dedicated to Resonant X-RayScattering (Aussois, June 2011: a book is published in European Physical Journal Special Topics).D2AM is also well recognized for its versatile SAXS experiment where it is easy to adapt various sampleenvironments (temperature [Saiani2004], mechanical tests [Humbert2010], pressure [Nishiyama 2010])for in situ/ in operando studies. In 2008-2009, a GISAXS chamber was adapted on the SAXS benchto allow in vacuo transfer of users samples [Babonneau2009]. And now it is even possible to performa GISAXS experiment with the sample aligned on the KAPPA goniometer.

2.2 Staff and associated laboratories

The 4 French CRG beamlines at ESRF are administrated as a common national instrumentby the CNRS and the CEA which delegates to a local structure the day to day organization. Theoperation and developments of each beamline are made by teams involving researchers, engineers andtechnicians from CEA-INAC, Neel Institute and the Structural Biology Institute : D2AM for materialsscience, IF for surface studies, FAME for environmental studies and FIP for bio-crystallography. Thebeamlines are financially supported by the CNRS and the CEA for staff as well as part of runningcosts and small investments. Only very specific tasks are supported by the ESRF through the CRG-coordination staff. These instruments are open to the French and European communities throughnational and international peer-reviewed committees.

The day-to-day activity of D2AM is supported by 4 permanent CNRS employees of the Neel Insti-tute:

S. Arnaud N. Blanc N. Boudet B. Caillottechnician scientist responsible engineer

The former beamline responsible J.F. Berar retired in 2013 and the computing engineer B. Caillotwill retire in June 2015.

In addition, research workers from laboratories in Grenoble are involved through their own on-going activities in development, support of external users and in-house research. About 10 scientistsparticipate in these activities on a part-time basis, that is about 1-2 full-time equivalent staff members.The participation of these laboratories enables the staff to cover various scientific topics, some examplesof which are given in the following table.


2.3 User access 2 D2AM: A FRENCH CRG

NEEL Institut Neel, CNRS-UJF J.-L. Hodeau, T. Nguyen,P. Martinetto

crystallography,functional materials

SIMaP Science et Ingenierie desMateriaux et Procedes,Grenoble INP

M. de Boissieu, M. Maret,J.-P. Simon (retired since2012), F. De Geuser

physics of metal andengineering

LMGP Laboratoire des Materiaux etdu Genie Physique, GrenobleINP

H. Renevier nano materials

CERMAV Centre de Recherche sur lesMacromolecules Vegetales,CNRS

C. Rochas soft condensedmatter

LIPhy Laboratoire Interdisciplinairede Physique, UJF

E. Geissler, I. Morfin soft condensedmatter

INAC Institut Nanosciences etCryogenie, CEA/INAC

V. Favre-Nicolin nano materials

2.3 User access to the D2AM beamline and training activities

Users can gain access to the D2AM beamtime through the French CRG committee and the interna-tional ESRF committee. Each of them allocates beamtime within the ESRF ratio rule, respectively 2/3and 1/3. The ”pressure” ratio between requested and allocated beamtime is on the CRG committeeabout 2 to 3 and for the ESRF one about 2 to 5.

In 2010, our French CRG committees were combined with those of SOLEIL. This was an oppor-tunity to enlarge the number of our referees to cover the many different subjects submitted.

The table below displays the distributed shifts over the review period:

Total† BLC IHR Users∗ ESRF users CRG usersyear shifts shifts shifts shifts shifts proposals shifts proposals

2009 699 45 144 525 147 12 378 272010 687 45 96 528 159 15 369 292011 432 27 93 309 84 6 225 182012 399 84 54 255 87 6 168 152013 507 114 69 321 126 9 195 17

Beamtime distribution over all the reviewed years : total (†including teaching andindustrial shifts), commissioning (BLC), in-house (IHR) and delivered to users byESRF and CRG review committees , the Users total (∗) includes shifts deliveredto users on ”reserve” lists.

We note a decrease of the total shifts in 2011 and 2012. During the last 3 years, the beamtime wasimpacted by building work on the ESRF side and for the upgrade of the beamline. First, in the year2011, the experimental hutch was extended, which caused an interruption of service for 3 months.Then, in 2012, the upgrade phase I of the ESRF with the construction of a new experimental hall gaverise to a 5 month stop. Finally, at the beginning of this last year we changed all the optical elements(2 mirrors and the monochromator), causing a 3 month shut-down and to a large number of beamlinecommissioning shifts. We are now back to normal activity.

During these years, very few experiments where stopped by beamline failure (furnace , specialsfeatures of the new goniometer) and we managed to postpone any lost time in the following monthsusing our maintenance shifts.

As attested by the graph on figure 1, the number of experiments performed on the beamline andthe number of publications are in the same range. Note that our role also involves education : thefigure below shows the number of PhDs defended that included work performed at the beamline. We


2.4 Upgraded beamline overview 2 D2AM: A FRENCH CRG

also contribute through practicals to the HERCULES and ESONN courses. Finally the beamline staffwas strongly involved in the organization of the REXS2011 conference, devoted to resonant scatteringin condensed matter, the proceedings of which gave rise to an issue of the European Physical JournalSpecial Topics, gathering reviews and regular articles on fundamentals and applications of ResonantElastic X-Ray Scattering in Condensed Matter.

Figure 1: Evolution of scientific production, number of experiments and PhDs

As shown on the left hand graph of figure 2, the share between the 2 instruments is nearly constant: roughly 50% saxs, including the GISAXS part and 50 % diffraction (7 cercle goniometer until 2011and kappa geometry goniometer since 2012) including the DAFS experiment. In the right hand figure,we outline the main scientific topics : the hard condensed matter increased slightly, while appliedmaterials and chemistry, soft condensed matter remained almost constant. Cultural heritage occupiedonly 1 or 2 experiments and is therefore very sensitive to fluctuation in accepted proposals. Methodand instrumentation corresponds to our in-house XPAD developments.

Figure 2: Left: beamtime share between the 2 instruments. Right: evolution of the main scientifictopics

2.4 Upgraded beamline overview

The beam line is located on the BM02 bending magnet and uses the 0.85 Tesla source with a criticalenergy of 20.6 keV. For better energy resolution combined with focussing capability, the D2AM opticsis symmetrical, with a double monochromator situated between two mirrors. The optics employs twoinstruments located in a common experimental hutch.

Between 2010 and 2012, the whole beamline was refurbished with new instruments and state-of-the-art X-ray optics. To finance this large project, the scientific goal that was presented to the



previous review panel was split into several smaller projects to address different calls.

The successful ones were :

• the NAIDA project at Grenoble Nanosciences Foundation

• the QMAX ANR-09-NANO-031 project at the French National Research Agency

• the CRG/F EQUIPEX project

• a collaboration contract with CEA/LETI who agreed to contribute in part to the upgrade inexchange for the share of a post-doc position on the beamline to work on their research program.

In the last 3 years, part of our annual budget, given by the CNRS (60%) and the CEA (40%) foroperational costs and small investments, was naturally dedicated to this upgrade. The total cost ofthis project is about 1.8 Meuros.

2.4.1 Optics

The X-Ray optics is symmetrical: the 2 crystal monochromator, with a relative energy selection of10−4, lies between 2 cylindrically curved Platinum/Ruthenium-coated mirrors that focus the X-Raybeam into a 100x200 µm2 spot on the sample.

• The new mirrors are Si coated with Pt and Rh stripes. The Rh strip, despite its lower reflectivity,is dedicated to anomalous studies closed to the Pt L2−3 edges (Ge, Ga, Au...). The new polishedsilicon mirrors have slope errors smaller than 0.3 microradians (a gain of a factor of 16 over theprevious mirrors), at all radii of curvature : the Irelec benders are compensated so as not todeteriorate the slope errors. During commissioning, the improvement was immediately visible :we can now focus the 1 meter long mirror into a spot of 80 to 100 microns FWHM. With theprevious mirrors we had hardly 200 microns and were often obliged to use only half the mirrorlength.

Figure 3: View of the 2 strip 1st mirror, water cooled on both sides



• The new monochromator, already designed for spectroscopy by Alain Prat (Institut Neel “instru-mentation pole”) for the BM30B-FAME beamline was adapted to our geometry. It yields veryprecise and reproducible positioning in energy. It is equipped with a 1st crystal, water cooledand designed by J.S. Micha (CEA-INAC and BM32 beamline) to avoid the thermal bump1. The2nd crystal ensures the sagittal focussing. Since the ribs at the rear of the crystal degrade thefocal point, we designed a new type of crystal without ribs on the 5 mm central part. Thisproduces a perfect 150 microns focal point on the sample.

Figure 4: Left : Inside the monochromator, 2nd crystal on its sagittal bender. Right : perspectiveview of the 1st and 2nd Si crystal.

2.4.2 Instruments

A ”kappa geometry” diffractometer is now available. It allows easy switching from surface tovolume diffraction and, compared to Euler geometry, offers a much larger free space to install varioussample environments. We purchased a Newport diffractometer, run by XPS controllers and, afterseveral exchanges with G. Swislow (http://www.certif.com/), it is now well integrated in the SPECprogram with PSIC geometry (FOURC is also used for fixed phi experiments, not yet supported inPSIC).

The SAXS bench is now 4 meters long to access smaller scattering angles, and thus smaller valuesof scattering momentum Q.

With the coupling of the 2 instruments, users can now also perform GISAXS experiments with thesample aligned on the goniometer and with an in-vacuo distance to the detector between 50 cm and5.5 m.

1J-S Micha, O. Geaymond, F. Rieutord, Thermal bump removal of a crystal monochromator by designing an optimalshape , NIM A, Volume 710, 155-160 (2013).



Figure 5: Overall view of the Experimental Hutch with the diffractometer and SAXS bench at therear

2.4.3 Detectors

Both instruments share detectors : scintillators/photomultipliers , a 1D gas detector (Vantec) and 2Dcameras.

The most commonly used 2D-detector until now was a fibre optic coupled CCD (60 × 50 mm2):Roper Scientific FOC CCD 1340 × 1300. Since 2011, the beamline is also equipped with 2 Xpadprotoptype detectors (15x7 cm2, 540000 pixels) and, in 2014, we started to use an IMXPAD S70(1.5x7 cm2).

The Imxpad start-up produces and sells the Xpad detector with the XPAD3.2 chip developed inour collaboration with CPPM lab in Marseille and the SOLEIL detector group. More details are givenin the following highlight.

The beamline is also involved in 2 high-energy pixel detector development projects (HiZPAD,ChipSPeCT).


parametric amplification is an extremely useful scheme applied in optics, electronics and also mechanics. in mechanics it occurs when a mechanical parameter of the oscillator (such as its spring constant) is modulated at twice the resonance frequency of the oscillator mode studied. We have recently achieved this type of amplification with an extremely small device, a silicon nano-electro-mechanical system (a nemS).

Efficient parametric amplification in a nano-electro-mechanical device

Our structure resonates around 7 MHz. It consists of two “feet” (length l’ ≈ 3 µm) linked by a “paddle” (l ≈ 7 µm), see top image in Fig. 1. It moves in the out-of-plane first flexural mode. The width and thickness of the three beams are about 200 nm.

We use the magnetomotive scheme to actuate and detect the motion of the paddle. An AC current is fed through the device thanks to a conducting metallic coating, which along with a static magnetic field generates a Laplace force, at frequency f

0=7 MHz. The 7 MHz motion in turn

creates a voltage (Lenz’s law), which is detected with a lock-in amplifier (referenced at f

0). The spring constant

is modulated at 2f0 by a voltage applied on a strongly

capacitively-coupled gate electrode (gap between electrode and NEMS g ≈ 100 nm). The electric field adds a strongly nonlinear restoring force which we use here to implement the parametric amplification scheme.

We use the Laplace force as our test force to be amplified by the parametric scheme. Depending on the relative phase between this force (i.e. the drive current at f

0) and the

modulation of the spring constant (i.e. the gate voltage at 2f

0), one can either amplify or “de-amplify” (squeeze) the

vibration, see Fig. 2. (“Squeezing” means that a particular phase-component of the vibration is attenuated while the other component is unaffected).

8

Of course, the actual gain obtained at the limit h=1 is never infinite, but limited by unavoidable experimental imperfections. With our device, amplification of the driving force with gains up to a 100 has been achieved, see Fig. 3. This is exceptional for an oscillator that is moving about 5 nm, a substantial fraction of its thickness, under these optimal conditions.

We have developed a theoretical model to describe the limiting parameters of this parametric amplification scheme. Our model has been applied to study the fine structure of the friction mechanisms occurring in the metallic coating films deposited on the nano-mechanical device. An unprecedented resolution of 0.5 % in the damping coefficient has been achieved in our measurements.

Figure 1: Sample and experimen-tal setup. The device (see text for description) resonates at 7 MHz. A dual channel generator drives the mechanical vibrations at f

0= 7 MHz

and the gate voltage at 2f0= 14 MHz;

a lock-in detector measures the vibra-tion amplitude.

néel institute / Highlights 6

9

XPADs (X-ray Pixel chips with Adaptive Dynamics) have many advantages over earlier detectors. They are hybrid pixel detectors : silicon sensors are “bump-bonded” directly, pixel by pixel, to an underlying, dedicated electronics chip. They measure the position and the number of incident photons with specific new characteristics compared to the CCD (Charge Coupled Device) detectors used previously. In CCD cameras, X-ray photons are converted to visible light which is accumulated over a given period. In these new detectors, the X-Ray photon counts are processed individually and only the events above a certain energy threshold are counted, reducing spurious noise sources. In addition, with XPADs one can accumulate many more photons without reaching saturation, therefore gaining in dynamic range, and one can record more than 1000 frames per second. Further, the 3rd generation detector “XPAD3” has an electronic shutter which can be triggered by an external signal, allowing nanosecond resolution in time-resolved experiments. The performances achieved by XPADs allow us to envisage new synchrotron experiments that would have been impossible with conventional detectors. Moreover, these detectors will also find their place in laboratory experiments and in medical X-Ray applications.

The initial role of Néel Institute staff in the XPAD project was to start up the collaboration and define the key

Hybrid pixel detectors will mark the end of the era of ccd cameras in numerous experiments using x-rays. the ”xpad” technology, born of a collaboration involving the néel institute, is one example of such a detector. this development has produced three generations of xpad detectors and has led to the birth in 2010 of imxpad, a startup company dedi-cated to production and commercialization of these detectors. initially, hybrid pixel detectors were designed for particle physics. in the 1990’s, experiments done on the new synchrotrons, such as the european Synchrotron radiation facility (eSrf) in Grenoble, suffered from the lack of x-ray detectors with fast enough dynamics to exploit the new potentiali-ties offered by synchrotron x-ray beams. Since then, néel institute staff in charge of the french collaborative research Group beamline ”d2am” at the eSrf have worked with people at the centre de physique des particules in marseille (cppm) and the Soleil synchrotron (paris) to develop three generations of the ”xpad” hybrid pixel detector technology.

XPAD detectors: from the laboratory to industrialization

furtHer readinG xpad3-S : a faSt HYbrid pixel rea-dout cHip for x-raY SYncHro-tron facilitieSP. Pangaud, S. Basolo, N. Boudet, J-F. Bérar et al.Nucl.Instr.andMeth.A591,159(2008).

performance and applicationS of tHe cdte- and Si-xpad3 pHo-ton countinG 2d detectorK. Medjoubi, S. Hustache, F. Picca, J.-F. Bérar, N. Boudet et al.J.Instrumentation6,C01080(2011).

contactS

Nathalie [email protected]@esrf.fr

Jean-François [email protected]@esrf.fr

features of the electronics chips: dynamics, counting rate, energy resolution, pixel size, etc. Subsequently, our main role has been the testing and calibration of XPAD detectors using synchrotron radiation. To illustrate the performance of XPADs, we present (Fig. 2) some X-Ray diffraction results obtained on the D2AM beamline. These concern the structural and compositional properties of Indium Gallium Nitride (InGaN) alloy “core-shell” nanowires, properties important for optimizing the nanowires’ emission wavelength. The extended DAFS (Diffraction Anomalous Fine Structure) spectra give information on the In content and the local atomic environment of the resonant atoms (Ga), i.e. they show how the strains resulting from the unequal sizes of Ga and In atoms are accommodated locally.

Figure 1 : Inside a prototype Silicon XPAD3 detector : 8 modules are tiled as close as possible to each other to offer a 7x12 cm² detection surface with almost 540000 pixels of size 0.13x0.13 mm².

Here, the main interest of the 2D pixel detector XPAD is the high counting dynamics per pixel, which allows us to benefit from the high counting rate for diffracted X-Ray photons when measuring DAFS oscillations. Moreover the detector allows measurement of several DAFS spectra and the fluorescence background simultaneously.

At present, XPAD detectors use well-tested silicon sensors, but detection efficiency is quickly lost for X-Rays from 15-20 keV onwards. In parallel, we have also worked on using more efficient sensors. We have obtained very good results with prototype Cadmium Telluride (CdTe) sensors. These are available only in limited sizes so far and it is intended to continue our collaboration with CPPM-Marseille and SOLEIL to create CdTe detectors with larger surfaces.

Figure 2: From an X-Ray diffraction study of InGaN core-shell nanowires grown on GaN : The red trace is a Diffraction Ano-malous Fine Structure (DAFS) spectrum extracted from reciprocal space maps at several energies from 10.1 keV to 10.9 keV. One such map is put, color-co-ded, as the background 2D image. Around the intense GaN (101) reflection (red, brown) coming from the substrate, the map shows a surrounding signal (yellow, green) due to the scattering of the InGaN core-shell nanowires. The measurement was performed at the Gallium K-edge without attenuators using a XPAD3 pixel detector on beamline D2AM at the ESRF. The quality of the DAFS spectrum acqui-red in only 15 seconds is remarkable.

Figure 2: Phase dependence of mechanical gain. One can amplify (point ”Maximum”), or squeeze (point ”Minimum”) the mechanical vibrations depending on the relative phase between the 7 MHz test force and the 14 MHz spring-constant modulation. The line is a theoretical fit, with parametric pumping factor h=0.87.

The modulation of the spring constant is expressed in normalized units as a pumping factor h. At the amplification working point (“Maximum” in Fig. 2), the gain increases continuously as h approaches 1, its theoretical upper bound (above h=1, the system starts to self-oscillate). At the “squeezing” working point (point “Minimum” in Fig. 2), the gain tends towards ½. These are characteristic features of the parametric amplification scheme.

Figure 3 : Mechanical gain measured at the phase setting ”Maximum” of Fig. 2 as a function of pumping factor h. The line is a theoretical fit, and h=1 is the limit of the amplifying scheme.

ph.d Studentmartial de foort

furtHer readinGnonlinear parametric amplifi-cation in a tri-port nanoelec-tromecHanical deViceE. Collin, T. Moutonet, J.-S. Heron, O. Bourgeois, Yu. M. Bunkov, H. GodfrinPhys.Rev.B84,054108(2011).

contactS

Eddy [email protected]

Olivier [email protected]



3 SCIENTIFIC RESULTS

3 A materials science beamline : scientific results

In the following, to describe the wide ”materials science” research activity on the beamline, we selectedseveral relevant experiments and grouped them by topics.

3.1 Applied Materials

3.1.1 Precipitation mechanisms in an aluminium alloy during ramp heating

Structural strengthening aluminium alloys undergo modifications of their mechanical properties whenaged at temperature in the range 100-300˚C. Solute atoms form precipitates that hinder the motion ofdislocations. For kinetic reasons, several metastable phases may form, which are not equally effectiveas strengthening objects. It is therefore essential to study the transitions between the phases and inwhich conditions the desired phase forms. Ramp heating experiments give a synthetic view of a possibleprecipitation sequence (the sequence can be different depending on the experimental conditions, andof course, on the alloy). Figure 6 shows a differential scanning calorimetry trace obtained during rampheating (50K.min−1) in an industrial AA2198 Al-Li-Cu alloy where plate-shaped precipitates of the T1

(Al2CuLi) phase form in the Al matrix. In such results, peaks are typically interpreted as formation(when exothermic) or dissolution (when endothermic) of the successive phases.

Figure 6: Top : DSC thermogram (50K.min−1) obtained on the Al-Li-Cu alloy. The red markscorrespond to the SAXS images of the bottom figure. Bottom : Selected SAXS patterns obtained onthe same Al-Li-Cu alloy. The streaks are characteristic of plate-shaped precipitates (T1, θ’).

We have measured the variation of the SAXS pattern obtained on the same alloy by performing thesame ramp heating in situ in a dedicated furnace on the D2AM SAXS camera. The experiment resultedin a continuous monitoring of the SAXS pattern, which can be analysed in terms of precipitate size,morphology and volume fraction by applying an appropriate interpretation protocol to the scatteringstreaks due to the presence of the precipitates2. Selected snapshots are shown in figure 6 bottom,corresponding to the red marks of figure 6. They clearly reveal that the largest event on the DSCcurve (B) corresponds to the formation of the T1 precipitates, but at this stage they form withconstant thickness corresponding to a single unit cell. Only during event C do they show evidenceof thickening (shortening of the streaks on the SAXS pattern). This unambiguously shows that thedesired T1 precipitates have a two-step formation mechanism (corresponding to 2 events in the DSC

2F. De Geuser, F. Bley, and A. Deschamps, A new method for evaluating the size of plate-like precipitates by small-angle scattering, J. Appl. Crystallogr., 45-6 (2012).


3.1 Applied Materials 3 SCIENTIFIC RESULTS

thermogram). This example demonstrates how unique and powerful in situ SAXS can be in the studyof solid state phase transformation kinetics.

Principal authors and publication :T. Dorin, A. Deschamps, F. De Geuser, W. Lefebvre, and C. Sigli, Quantitative description of theT1 formation kinetics in an Al–Cu–Li alloy using differential scanning calorimetry, small-angle X-rayscattering and transmission electron microscopy, Philos. Mag., in press 2014.

3.1.2 microelectronics applications

Following the recent collaboration with the ”X-ray lab” in LETI, the D2AM beamline has been exten-sively used for microelectronics applications in the past year. Many subjects of interest are accessibleby the capability of the beamline either in SAXS/GISAXS or WAXS configuration. Furthermore, thebeam size is compatible with e-beam lithography on small areas (a few hundred µm2). Among thelastest subjects studied on the beamline, the following are notable:

• Texture/stress/phase measurements of ultrathin Ni-based mono-germanosilicide at the bottomof trenches

• Self-assembly of grapho-epitaxied block copolymers studied by GISAXS (see below)

• GISAXS experiments on Conductive Bridging Random Access Memory

• Anomalous SAXS/WAXS study of bimetallic Cu/Ru nanoparticles

Figure 7: GISAXS patterns for BCP films self-assembled jointly on the line grating (a) and on a neigh-bour unpatterned area(b); the dashed semi-circle represents the intersection of the Ewald sphere withthe reciprocal lattice of the grating. Corresponding horizontal line-cuts calculated at qz=0.35nm−1(c-d): experimental data (crosses) and best fits of the 10 rod (red curves).

We would also emphasize that following the successful previous experiments on germanosilicidationand some very recent published papers3, we would now like to develop in-situ, full 3D Reciprocal SpaceMapping (RSM). This method allows fast and efficient measurement of volumes in reciprocal spaceby X-ray diffraction using area detectors. The goal of this technique is to obtain a complete overviewof reciprocal space to detect and characterize the nature and orientation of all the phases present inthe material. Data reduction and then conversion into 3D RSM, which is a generic demand for manymaterials studies, is a project in progress performed by a postdoc co-directed by the D2AM team andthe X-ray lab in LETI. Many subjects will benefit from these developments:

3S. Gaudet et al, J. of Vacuum Science and Technology A 31, 021505 (2013) and C. Mocuta et al, Appl. Cryst. 46,1842–1853 (2013)


3.1 Applied Materials 3 SCIENTIFIC RESULTS

• In-situ study of the Solid State Reaction between an ultrathin metallic film and an InGaAssubstrate

• Toward the origin in Ni-based germano-silicides thermal degradations

• Microstructural variation of PZT thin films under applied electric field

GISAXS study of directed self-assembly of block copolymersSelf-assembling of diblock copolymers (BCP) is a powerful and low-cost route to generate templatesfor the fabrication of nanoscopic elements for the CMOS industry as well as for ultrahigh densitymagnetic storage media. Tuning the composition and molecular weight of BCP, microdomain arrayswith cylindrical, lamellar or spherical morphology are spontaneously formed after baking, but withrandom orientation, reducing considerably their potential applications. Nowadays, a huge researcheffort is thus devoted to improving long-range ordering of self-assembly. At the LETI, thin films of apolystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymer (BCP) are self-assembled on ahydrogen silsesquioxane (HSQ) e-beam line grating which guides the orientation of the hexagonal arrayconsisting of perpendicular PMMA cylinders in a PS matrix. Such an approach, called graphoepitaxy,couples directed self-assembly with a first lithography level, and allows multiplication of the patterndensity with a possible resolution down to 10 nm. Optimization of the grating parameters (line andtrench widths) with respect to the intrinsic period of the self-assembled polymer was previously studiedby SEM4. Nevertheless, such an approach has a limited resolution, restricted to areas of a few squaremicrometers, and involves only the film surface.

Figure 8: GISAXS patterns recorded during annealing of a 60nm-thick BCP film at a) 170˚C (sampleposition: y+1) and b) 187˚C (position:y+2), marked by stars on the temperature profile (countingtime= 10 s and αi=0.14˚). (c,d) Variations of the horizontal profiles as a function of annealing tem-perature, calculated around the Yoneda peaks of BCP and Si, respectively (corresponding integrationareas are indicated by the dotted red and blue rectangles in patterns (a) and (b)). L0: polymer periodsclose to the BCP surface (c) and Si substrate (d).

GISAXS experiments were thus done on self-assembled BCP using a photon energy of 9.8 keV,under an incidence angle close to the critical angle of the BCP film. Due to the weak electronic densitycontrast between PS and PMMA, PMMA was removed from the cylinders prior to the measurements.From the patterned area (10x1 mm2) written at the center of the Si wafers (10x10 mm2) a comparisoncould be made of the ordering of BCP films self-assembled on the line grating and the unpatternedneighbouring area. The effect of the line grating is illustrated in Figure 7 when the line direction isaligned with the incident beam. Whereas for the film self-assembled on the unpatterned area, thesuccessive rods characteristic of a 2D hexagonal array with a period of 36 nm are observed to comefrom randomly oriented domains, only the l,0 (l=1,2..) Bragg rods are measured for the graftedfilm, revealing the formation of a single extended domain over a large area. To gain an accurate

4R. Tiron et al, J. Vac. Sci. Technol., B 29-6, 06F206 (2011).


3.2 chemistry - soft or amorphous materials 3 SCIENTIFIC RESULTS

description of the change in cylinder shape and polymer period with film thickness, thermal balanceand PMMA removal process, GISAXS measurements were also done in several series of self-assembledBCP films. In particular, the line grating guides not only self-assembly of BCP such that the denserows of cylinders are parallel to the lines, but also enhances the ordering kinetics. Furthermore, in-situ GISAXS measurements performed under nitrogen have revealed that self-assembly starts around140˚C and close to the film surface with a period smaller than at the end of the ordering process.They also revealed that annealing up to 240˚C is required to form homogeneous self-assembled films(Figure 8). Finally, these GISAXS measurements provide accurate and valuable information aboutthe structural changes in self-assembled BCP films with multiple fabrication parameters, which will behelpful in their application as template materials for density multiplication in nanolithography (figure9).

Figure 9: GISAXS patterns recorded for PS-b-PMMA films after acetic acid surface reconstruction(a), O2 plasma etching (b), acid acetic + plasma etching (c) (counting time=1200 s). From (d) to (f)the corresponding simulated 2D ‖F(q)‖2 form factors of cylindrical holes to explain the extinction ofpeculiar hl rods observed in the GISAXS patterns. From (g) to (i) the corresponding SEM images.

Principal authors and publication:M. Maret, R. Tiron, X. Chevalier, P. Gergaud, A. Garbi, C. Lapeyre, J. Pradelles, V. Jousseaume,G. Fleury, G. Hadziioannou, N. Boudet and C. Navarro, Probing Directed Self-Assembly of Cylin-drical Morphology Diblock Copolymer using Grazing Incidence Small-Angle X-Ray Scattering, Macro-molecules 2014.

3.2 chemistry - soft or amorphous materials

3.2.1 amorphous materials for rewritable optical devices

Rewritable optical devices, like digital DVD-RAM or blu-ray have meanwhile become common mediafor data storage. The writing/erasing process on these devices is attained by a reversible laser-inducedcrystalline-amorphous transition of so-called phase-change materials, such as Ge2Sb2Te5 (GST). Thetransition occurs on a timescale of a few nanoseconds and is accompanied by a significant change ofthe optical and electrical properties. On the other hand, both of the phases are stable for more thanten years at ambient conditions. To understand the mechanism in the phase transition, we performedanomalous X-ray scattering (AXS) experiments at incident X-ray energies close to the Ge, Sb, and TeK edges, and the data obtained were analyzed using reverse Monte Carlo (RMC) modeling. Circlesin Fig. 10 (a) show differential structure factors, ∆kS(Q), together with the total structure factor,S(Q), and the solid lines indicate results of the best RMC results, which are in good agreement withthe experimental data. Figure 10(b) shows the partial pair-distribution functions, gij(r).From the RMC analysis of the AXS data, we obtained several interesting structural features: 1) Ge ismostly fourfold coordinated with 0.7 Ge-Ge wrong bond; 2) Ge-Ge wrong bond chains are frequentlyobserved; 3) The bond angles around Ge have ∼50% tetrahedral and ∼50% octahedral contributions;



4) Sb is mostly threefold coordinated, and the bond angles are ∼90˚, similar to the crystal phase; 5)Puckered four-membered rings are observed, and more than half of the Ge atoms belong to them. Fig.10(c) shows the comparison between the typical structures of (A) crystalline and (B-D) amorphousphases based on the present AXS + RMC results. (B) Fragments of octahedral crystal structures withdistorted rocksalt structure would be the reason of the fast phase change process. The movementsof the Ge atoms induce the tetrahedral Ge sites with (C) puckered four membered rings or (D) theGe-Ge wrong bond chains, which may cause the long lifetime of the optical storage devices.

Figure 10: (a) ∆kS(Q) with S(Q) (circles), and the best RMC results (solid curves). (b) gij(r) obtainedfrom AXS + RMC. (c) The structural features of crystalline and amorphous phases. The figures aretaken from Ref. cited below.

Principal authors and publication :S. Hosokawa, W.-C. Pilgrim, A. Hohle, D. Szubrin, N. Boudet, J.-F. Berar, and K. Maruyama, Keyexperimental information on intermediate-range atomic structures in amorphous Ge2Sb2Te5 phasechange material, J. Appl. Phys. 111, 083517 (2012)

3.2.2 Water management in Fuel cells

Proton Exchange Membrane Fuel Cells (PEMFCs) are considered as the most promising power sourcefor automotive, stationary and portable applications. A PEMFC is a stack of elementary cells com-posed of a membrane electrode assembly (MEA) sandwiched between two gas diffusion layers (carbontissues) and two bipolar plates for gas distribution, current collection and thermal control. The controlof water management is a key issue for the optimization of the fuel cells performance. Water moleculesare produced at the cathode and transported from the anode to the cathode by electro-osmosis. Thisgenerates a water concentration profile across the membrane and thereby a back-diffusion. Differenttechniques have been developed for the study of the water management in operating fuel cells (Small-Angle Neutron Scattering, neutronography, magnetic resonance imaging, Raman confocal microscopy,...)5.

The small-angle scattering technique appears up to now as the most powerful technique in termsof spatial and time resolution in addition to the possibility of applying relevant operating conditionsas demonstrated in previous studies using SANS6.

5S.Deabate, P.Huguet, A. Morin G. Gebel, G.Pourcelly, In situ and operando determination of water distribution inproton conducting membranes for fuel cells, a critical review, Energy and Environmental Science 5, 8827-8847 (2012)

6F. Xu, O. Diat, G. Gebel, A. Morin, Determination of transverse water concentration profile through MEA in a fuel



Ionic conduction in fuel cell membranes depends strongly on water content. In the cell, water isgenerated at the cathode and the proton transport attracts water to the anode (electro-osmosis), thusgenerating a concentration profile across the membrane. The control of the water must therefore beunderstood and optimized so that the useful lifespan can be increased and to enable the system tobe simplified. Since very few methods are available to detect in situ the water in membranes insidea working cell, we have developed a technique based on small angle neutron scattering. We havetransposed this method to small angle X-ray scattering on the BM02 beamline at the ESRF, wherethe high flux and small beam cross-section yield good spatial resolution, and in particular allow kineticinvestigations during current discharge.

Figure 11: In-operando Fuel cell transparent to x-rays with 6 positions of analysis (inlet, middle, outletand in front of the channels and of the ribs) and the SAXS spectra recorded at 80˚C and steady statein these different positions for various current densities from 0 to 720 mA/cm2.

Our experiments have demonstrated the feasibility of such measurements, and in particular thedifferences in swelling under the ribs and in the channels, as well as the possibility of monitoringmembrane swelling during current flow. The results confirm the heterogeneous water content in themembrane and especially the difference between areas in front of the gas distribution channel and infront of the rib. Further experiments are planned to study water management at elevated temperaturesin order to analyze the effect of ageing on water management.

Principal authors and publication :G. Gebel and C. RochasHeterogeneous water management in operating fuel cells using the small-angle X-ray scattering tech-nique and modelling approach, A. Morin, G. Gebel, P. Schott, S. Lyonnard, H. Mendil-Jakani, J. PowerSources, In preparation.

cell, using Neutron Scattering, J. of the Electrochemical Society 154, B1389 (2007)A. Morin, F. Xu, G. Gebel, O. Diat, Influence of PEMFC gas flow configuration on performance and water distributionstudied by SANS: Evidence of the effect of gravity, Int. Journal of Hydrogen Energy 36 (4) 3096-3109,(2011)A. Morin, F. Xu, G. Gebel, O. Diat, Evolution of water distribution in PEMFC during On/Off Cycling, Fuel cells 12,156-161 (2012)Water management in proton exchange membrane fuel cell at sub-zero temperatures: a SANS-EIS coupled study SolidState Ionics (2013) in press



3.2.3 Evidence of double-walled Al-Ge imogolite-like nanotubes. A cryo-TEM, AFMand SAXS investigation

Imogolites (OH)3Al2O3Si(OH) are natural minerals discovered in 1962 in Japanese volcanic soils. Theyare made of a curved gibbsite sheet Al(OH)3 forming a nanotube 2 nm in diameter. Tetrahedral siliconatoms inside the nanotube are linked to three Al-O-Si bonds. The mismatch between the size of thesilicon tetrahedra and the vacant site of the gibbsite sheet leads to the curvature of the tube. The firstsynthetic imogolite was obtained as early as 1977. Imogolite nanotubes are extremely monodisperse indiameter with lengths up to the micrometre scale. However, early synthesis routes were effective onlyin very dilute conditions. The difficulty of synthesizing large quantities of this mineral has probablyhindered the development of industrial applications. Nevertheless, imogolites have been used as ananti-static agent in the formulation of photographic films.

Recently, a new synthetic process with increased synthesis yield was made possible by replacingsilicon with germanium. Indeed, we were able to synthesise large quantities of an Al-Ge imogoliteanalogue. The structure of these analogues has been analyzed in detail by small angle X-ray scatteringat beamline BM02, by AFM and cryo-TEM microscopy.

The SAXS analysis unravelled the controversial nature of the so-called proto-imogolite (imogoliteprecursor) that was poorly known. We demonstrated that the proto-imogolite consists of roof tileshaped 5 nm imogolite nanotube pieces. The curvature of these pieces is less than that of the finaltubes7. We have also shown that these imogolite analogues have the local structure of imogolitenanotubes, but with two different shapes depending on the synthesis conditions. It is possible toproduce single-walled tubes of 3.5 nm in diameter, similar to their natural counterpart, and alsodouble-walled tubes of 4 nm in diameter. Indeed, the SAXS results give distinctly different signals inthe large-q range (Figure 12 left).

Figure 12: Left: SAXS curves of 0.5 and 0.25 M Al-Ge imogolite-like nanotubes. Experimental dataare plotted as dots, and the lines are the theoretical scattering curves of the represented structures.Right: Computer-assisted Cryo-TEM composite image obtained by alignment and superposition ofmany nanotubes. The double-walled structure of the 0.25 M Al-Ge imogolite-like nanotubes is clearlyobserved.

In the case of single-wall nanotubes, regular oscillations were measured whereas the double-walledstructure gave irregular oscillations due to the contribution of the inter wall scattering term. Thedifferences between single and double-wall structures were confirmed by cryo-TEM observations of thesamples (Figure 12 right). Such double-walled imogolite-like nanotubes were reported for the first timeand opened a new research field. Finally, using time resolved SAXS measurements, we have studiedin detail the growth kinetics of the Al-Ge imogolite analogues. We showed that the growth is mainlycontrolled by a reaction limited edge-edge assembly of the nanotubes. The complete simulation of the

7C. Levard, J. Rose, A. Thill, A. Masion, E. Doelsch, P. Maillet, O. Spalla, L. Olivi, A. Cognigni, F. Ziarelli and J.Y.Bottero, Chemistry of Materials 22, 2466-2473 (2010).



growth kinetics showed that it could be possible to accelerate considerably the growth kinetics of theimogolite nanotubes8.

Principal autors and publication :P. Maillet, C. Levard, E. Larquet, C. Mariet, O. Spalla, N. Menguy, A. Masion, E. Doelsch, J. Roseand A. Thill, J. Am. Chem. Soc. 132, 1208–1209 (2010).

3.2.4 Nanoscale organized copolymer thin films

Nanoscale periodic patterning in self-organized block copolymer thin films has attracted considerableattention as one of a next generation of lithographic materials in the semiconductor industry. Thegroup in CERMAV has prepared a variety of poly or oligosaccharide-based block copolymer systemsand studied morphologies of their self-assembled thin films. Strong repulsions between oligosaccha-ridic blocks and synthetic blocks, expressed by a large Flory-Huggins parameter χ, force micro-phaseseparation. Using a thermal annealing the inter-domain size of nano-organized morphologies is forceddown to less than 20 nm.9

Also the first nano-organized glyco thin film of the oligosaccharide-based block copolymer (polystyrene-block-maltoheptaose) was obtained by solvent annealing in co-solvent (THF/H2O) vapor atmosphere.10 nm feature sizes, with hexagonally packed cylinder morphology was detected and 2D scatteringpatterns of the thin film samples obtained by GISAXS clearly indicated horizontal and perpendicularorientation of the cylinder morphology.

Figure 13: Left: AFM thin film phase images with their 2D Fourier-transformed images (upper) andbulk SAXS profiles (middle) of poly(ε-caprolactone)-block -maltoheptaose annealed for 30 min at (a)150˚C, (b) 190˚C, and (c) 240˚C. Right: 2D GISAXS patterns of polystyrene-block-maltoheptaosethin films annealed with (left) THF/H2O = 1/1 (w/w) and (right) THF/H2O = 4/1 (w/w).

Principal author and references :I. Otsuka, S. Tallegas, Y. Sakai, C. Rochas, S. Halila, S. Fort, A. Bsiesy, T. Baron, R. Borsali, Controlof 10 nm Scale Cylinder Orientation in Self-Organized Sugar-Based Block Copolymer Thin Films,Nanoscale 2013, 5, 2637 - 2641.

8 P. Maillet, C. Levard, O. Spalla, A. Masion, J. Rose and A. Thill, Growth kinetic of single and double-walledaluminogermanate imogolite-like nanotubes : an experimental and modeling approach, Physical Chemistry ChemicalPhysics 13(7), 2682-2689 (2011).

9K. Aissou, I. Otsuka, C. Rochas, S. Fort, S. Halila, R. Borsali, Nano-Organization of Amylose-b-Polystyrene BlockCopolymer Films Doped with Bipyridine, Langmuir 27, 4098-4103 (2011).I. Otsuka, T. Isono, C. Rochas, S. Halila, S. Fort, T. Satoh, T. Kakuchi, R. Borsali, 10 nm Scale Cylinder-Cubic PhaseTransition Induced by Caramelization in Sugar-Based Block Copolymers, ACS Macro Lett. 2012, 1, 1379-1382.T. Isono, I. Otsuka, D. Suemasa, C. Rochas, T. Satoh, R. Borsali, T. Kakuchi, Synthesis, Self-Assembly, and Ther-mal Caramelization of Maltoheptaose-Conjugated Polycaprolactones Leading to Spherical, Cylindrical, and LamellarMorphologies, Macromolecules 2013, 46, 8932-8940.


3.3 Surface and nanostructure characterization 3 SCIENTIFIC RESULTS

3.3 Surface and nanostructure characterization

The knowledge of strain, chemical composition, atomic short range order, polarity, structure at inter-faces, ... are of great importance to understand the growth mechanism as well as the electronic andoptical properties of hetero- and nanostructures. In the past few years anomalous diffraction (Multi-wavelength Anomalous Diffraction) and spectroscopy in diffraction condition (Diffraction AnomalousFine Structure) have been applied at beamline BM2-D2AM to many systems of great technologicalinterest as for instances GeSi/Si Quantum dots, GaN/AlN Quantum dots, GaN or AlGaN nanowires,InGAN core shell nanowires, ... In the case of QDs, grazing incidence geometry was used 10, 11. It hasbeen shown that the combination of Reciprocal Space Mapping, Multiwavelength Anomalous Diffrac-tion, Diffraction Anomalous Fine Structure and ab initio calculations is a very powerful approach inthe study of the structural properties of hetero- and nanostructures. Thanks to the new diffractometerand monochromator and the use of pixel detectors, anomalous diffraction will stay a leading activityand will be applied to a broader class of materials and to in situ, operando studies.

3.3.1 Combining spectroscopy and simulations to probe the structural properties ofGe/Si(001) nano-islands

Both long and short range scales are of interest in studying structural properties of matter such ashetero nanostructures. This is particularly true for the study of growth mechanism of materials as wellas for their electronic and optical properties, strain, chemical composition, interface quality, and atomicordering12. To address such a general issue, we have combined grazing-incidence multiwavelengthanomalous diffraction spectroscopy (MAD) and grazing-incidence diffraction anomalous fine structure(DAFS) spectroscopy at beamline BM02. This unique combination, together with recent atomisticsimulations based on molecular dynamics (MD), is a powerful approach to disentangle strain andcomposition and to detect atomic ordering inside SiGe nano-islands.

We present here some recent results on dome-shaped Ge nano-islands grown on nominally flatSi(001) at 650˚C by molecular beam epitaxy (MBE). Their average size and height were about 80 nmand 19 nm, respectively. MAD was performed at the Ge K-edge (11103 eV), close to the in-plane Si400 Bragg reflection at incident angle αi = 0.1˚(the Si critical angle αc = 0.163˚at 11 keV). Figure14 top a) shows the square root of the scattered intensity at 11053 eV (Iexp), the modulus of the Geand Si structure factors, as well as the Ge content (xGe), as a function of the reciprocal lattice indexh and height (z) above the Si surface (h can be associated with different heights z in the nano-islands,according to the iso-strain method). MAD results clearly show a strong Si/Ge intermixing, the Gecontent is about 0.6, together with a slight linear increase of xGe starting above z = 4 nm. Figure 14up b) shows background-subtracted extended DAFS spectra together with the best-fit curves. Thethree experimental EDAFS spectra were recorded in grazing incidence geometry, close to the in-planeSi 440 Bragg reflection, at h = 3.939, 3.959, and 3.979, corresponding to z = 3 nm, 6 nm and 9 nm,respectively. The fits show that the Ge content increases slightly from the base to top of the dome(xGe = 0.54 and 0.6 at h = 3.959 and 3.939, respectively). The EDAFS results are in very goodagreement with MAD results, except near the Si Bragg peak corresponding to the substrate-islandinterface region (h = 3.979). Interestingly, in this region, the Ge content obtained from MAD (xGe

∼ 0.2) is lower than that obtained from EDAFS (xGe = 0.55). MD simulations clearly show (Figure14 bottom) that in the case of an island-substrate interface with a sharp change in GeSi composition,information is lost, and an artificially smooth gradient is found by MAD owing to the scatteringcontribution of the strained Si substrate region beneath the islands (Figure14 bottom a)). In contrastEDAFS oscillations are much less sensitive to the presence of the interface (Figure 14 bottom c)),

10V. Favre-Nicolin, M. G. Proietti, C. Leclere, N. A. Katcho, M. -I. Richard, H. Renevier, Multiwavelength anomalousdiffraction and diffraction anomalous fine structure to study composition and strain of semiconductor nanostructures,Eur. Phys. J. Special Topics 208, 189 (2012).

11H. Renevier and M.G. Proietti, Grazing Incidence Diffraction Anomalous Fine Structure in the study of structuralproperties of nanostructures , in Characterization of Semiconductor Heterostructures and Nanostructures II, G. Agostini,C.E. Lamberti (Eds.), Elsevier, Amsterdam, The Netherlands, (2013). Chapter 8.

12J. Stangl, V. Holy and G. Bauer, Rev. Mod. Phys. 76, 725 (2004).



Figure 14: up : a) MAD results : quare root of the diffracted intensity measured at 11.053 keV (50eV below Ge K edge) and at an incidence angle αi = 0.1˚, |FGe|, |FSi| and the Ge composition xGe.They are plotted as a function of reciprocal index h, close to the in plane Si 400 reflection and asa function of height z in the island. b) From top to bottom: raw EDAFS spectra (triangles) andbest-fit curves (solid lines) recorded at 3 different h values: 3.939, 3.959 and 3.979, corresponding toheights of z = 3 nm, 6 nm and 9 nm, respectively. Curves are shifted for clarity. Bottom : Moleculardynamics simulations. MAD and extended DAFS of SiGe/Si(100) islands (aspect ratio equal to 0.16,about 20x106 atoms). Ge concentration (—) corresponding to a sharp (a, model C1) and smooth (b,model C2) composition gradient and Ge concentration (...) extracted back from the simulated MAD.An artificial composition gradient is found in the case of model C1 (c)-(d) Extended DAFS χ(k) formodels C1 and C2. The EDAFS oscillations are barely sensitive to the interface in the case of modelC1.

since EDAFS spectroscopy probes only the Ge local environment. Therefore, there was no evidencefor the presence of a Si-rich core below 4-5 nm in the nano-islands that we have studied, as suggestedby others.

In summary, this study demonstrates the power of combining MAD and EDAFS and shows thatatomistic simulations at a realistic scale (20x106 atoms in the present case) are of fundamental im-portance in providing a deeper and more reliable data interpretation.

Principal author and publication :N.A. Katcho, M.-I. Richard, M.G. Proietti, H. Renevier, C. Leclere, V. Favre-Nicolin, J.J. Zhang andG. Bauer, Eur. Phys. Lett. 93, 66004 (2011).

3.3.2 Polarity of GaN Nanowires Grown by Plasma-Assisted Molecular Beam Epitaxyon Si(111)

Polarity is an intrinsic property of non-centrosymmetrical crystalline structures such as GaN wurtzite.The lack of center of symmetry induces a spontaneous polarization within the cell along the [0001]direction, leading to the presence of an internal electrical field in the same direction.



Furthermore, if biaxial strain exists, an additional piezoelectric polarization contributes to the totalelectric field, which gives rise to a carrier separation responsible for a red-shift in the luminescence(Quantum Confined Stark Effect). In the case of 2D layers, it has been found that polarity influencesthe morphology of the surface, the crystal quality, and, most importantly, incorporation of impuritiesand vacancies during the growth, which itself critically affects the optical properties. Last, but notleast, in the case of GaN NWs the polarity is determined at the early stage of growth. Therefore,knowledge of the NWs polarity for different growth parameters, substrate and surface preparationsgives, in turn, much information on the NW growth mechanism.

Polarity refers to the direction along which GaN grows by considering the Ga-N bond that iscolinear with the c-axis of the wurtzite cell. The vector going from Ga and pointing towards Nconventionally defines [0001]. A structure is said to be Ga-polar or Ga-terminated when its growthdirection is [0001]. Reciprocally, a structure is said to be N-polar when its growth direction is [000-1].

The well-known breakdown of Friedel’s law states that a disparity in the diffracted intensity ofBijvoet pairs of reflections must occur for non-centrosymmetrical systems when the imaginary termof the scattering amplitude is no longer negligible. Friedel pairs refer to reflections with Miller indiceshkl and hkl while Bijvoet pairs refer to reflections symmetrically equivalent to hkl and hkl reflections.In the case of GaN wurtzite structure, the space group is P63mc, the Laue group is 6/mmm and thepoint group is 6mm. The latter gives the equivalent reflection when Friedel’s law is no longer valid.Resonant XRD at the Ga K-edge (10367 eV) was used to vary the Ga scattering amplitude and todetermine GaN NWs polarity unambiguously at a macroscopic scale.

Two samples were studied. One was GaN NWs grown by PAMBE directly on Si. Another withupended NWs (u-NWs) was obtained from the reference sample. X-ray diffraction experiments withmonochromatic synchrotron radiation were carried out at BM02/D2AM. Beam size at the focal pointwas about 0.3 × 0.15 mm2 (resp. horizontally and vertically), thus illuminating a large assembly ofNWs. The background intensity was additionally monitored to correct data for fluorescence. Experi-mental data obtained from the as-grown and upended GaN NWs samples as well as the best fits (solidlines) are shown in Figure 15 right. The a-NWs as N-polar and the u-NWs are clearly identifiable asGa-polar.

The N-polarity character is believed to be a consequence of the formation of a thin SixN1−x layeron the Si surface prior to or at the beginning of GaN growth due to the strong Si - N affinity.

Figure 15: Left: bird’s eye view SEM images of (a) as-grown GaN NWs and (b) upended NWs. Right:variation of the intensity of the 11-22 and 11-2-2 pair of reflections with energy around the Ga K-edge.Red and blue full circles stand for fluorescence-corrected experimental data obtained from a-NWs (asgrown) and u-NWs (upended), respectively. Upper and bottom grey lines correspond to simulated fitsobtained for 11-2-2 and 11-22 reflections, respectively.

Principal author and references :

• K. Hestroffer, C. Leclere, C. Bougerol, H. Renevier, Bruno Daudin., Polarity of GaN NanowiresGrown by Plasma-Assisted Molecular Beam Epitaxy on Si(111), Phys. Rev. B 84, 245302 (2011).



• PhD Thesis : K. Hestroffer, Croissance et caracterisation de nanofils de GaN et d’heterostructuresfilaires de GaN/AIN. Defended on Oct. 2012. Universite de Grenoble

• PhD Thesis : Cedric Leclere, Spectroscopies X et diffraction anomale de boıtes quantiques GaNet d’hetero-structure III-N : inter-diffusion et ordre a courte distance. Defended on June 2013.Universite de Grenoble.

This work is supported by French National Agency (ANR) through Nanoscience and NanotechnologyProgram (Project BONAFO n˚ANR-08-NANO-031-01)

3.3.3 Hydrogen Electro-Insertion into Pd Nanofilms: in situ Surface X-ray DiffractionStudies

Thin palladium films can be very interesting as protective barriers against oxidation and/or as hy-drogen insertion promoters for hydrogen inserting complex hydrides from light elements, like Mg2Ni,LaNi5, NaAlH4, LiAlH4. Hydrogen electrochemical insertion into low-dimensional and well definedpalladium films can exhibit unusual properties. Indeed, the nanometer size of these protecting filmsraise some questions that are specific to the size reduction, like the influence of thickness on thecatalytic properties, as well as the effect of the film’s support on the hydrogen insertion/desorptionprocesses. In order to get a thorough comprehension of the mechanisms governing hydrogen insertioninto nanometric metallic films, we studied ultra-thin Pd layers (2-20 ML) electro-deposited onto singlecrystals, Pt(111), Au(111) and Pt(100). These systems are characterized by an original behaviour ofthe different thermodynamic parameters, like the maximum hydrogen insertion rate. We developedan electrochemical cell well suited for in situ Surface X-Ray Diffraction experiments, allowing themeasurement of the signal diffracted by the single crystal through about 100 microns of solution whilea potential is applied (see figure 16). Measurements have been made at different potentials, beforeand after hydrogen insertion and after hydrogen desorption. The effects of the substrate and of itsorientation have been revealed. By using the powerful approach of coupling electrochemistry with insitu Surface X-ray diffraction, we have been able to obtain deep insight into the strong relationshipbetween the detailed description at the atomic level of the film structure and the isotherm behaviour.

Figure 16: Experimental set-up for in situ SXRD in an electrochemical environment on the D2AMdiffractometer.



Principal author and references:

• C. Lebouin, Y. Soldo-Olivier, E. Sibert, M. De Santis, F. Maillard, R. Faure, Langmuir 25(8)(2009) 4251.

• Y. Soldo-Olivier, M. C. Lafouresse, M. De Santis, C. Lebouin, M. de Boissieu, E. Sibert, J. Phys.Chem. C. 115(24) (2011) 12041.

• Y. Soldo-Olivier, B. Previdello, M. De Santis, M. C. Lafouresse and E. Sibert, Electrochim. Acta112 (2013) 905.

• E. Sibert, L. Wang, M. De Santis, Y. Soldo-Olivier, submitted to Electrochim. Acta

• PhD thesis: L. Wang, 2012 (Grenoble-INP).

• PhD thesis: B. Previdello 2013 (Grenoble-INP).

3.3.4 Self-ordering on vicinal surfaces studied by 3D GISAXS measurements

Nanostructured systems made of islands deposited on oxide surfaces have both fundamental and tech-nological interest and are used in the field of electronics, linear or non-linear optics, and optoelectronics.The final properties of these systems depend on the shape and the size of nanoparticles and also ontheir organization. In this general framework, we aim at producing self-organized nanostructures usingvicinal surfaces13. Vicinal surfaces are obtained by cutting a single crystal with a small deviation ofthe surface normal with respect to a crystallographic plane, leading to a surface with terraces sepa-rated by steps. Suitable templates for the growth of self-organized nanostructures are created throughre-arrangement of the steps during thermal treatment (step bunching).

Figure 17: 3D GISAXS measurements

13R.Bachelet, S. Cottrino, G. Nahelou, V. Coudert, A.Boulle, B.Soulestin, F.Rossignol, R.Guinebretiere, A.Dauger,Nanotechnology, 2007, 18, 015301E.Thune, A.Boulle, D.Babonneau, F.Pailloux, W.Hamd, R.Guinebretiere, Applied Surface Science, 2009, 256, 924-928


3.4 Hard condensed matter 3 SCIENTIFIC RESULTS

Different types of nanostructured surfaces can be prepared and used as templates since the sub-strates exhibit one-dimensional (1D) or two-dimensional (2D) periodic patterns (fig. 17 a)). Thesurface morphology and the periodicity can be tuned with the thermal treatment parameters (i.e.annealing time, temperature and atmosphere) and also with the sample parameters (i.e. miscut andazimuthal angles). Ordered stepped oxide surfaces are characterized ex-situ after each treatment ona laboratory scale by Atomic Force Microscopy (AFM), which provides a direct image of the surfacemorphology (step height, step curvature, terrace width...) over a small probed area (a few µm2).

Quantitative analysis of the surface morphology has been studied by grazing incidence small anglescattering using a specific set-up implemented recently on the BM02 beamline at ESRF (Grenoble,France). Prior to the SAXS measurements, the samples were strictly oriented according to the primarybeam direction using a 3-axis sample holder. 3D reciprocal space maps around the (000) node werethen recorded on a 2D pixel detector through 360˚rotation of the samples around the azimuthal angle.Modelling of 2D sections of the (000) reciprocal space node was done with the FitGISAXS software14.Typical experimental and calculated maps are displayed in fig.17 b) and c). We demonstrate that the2D ordered surface is consistent with a rectangular centred periodic lattice decorated by truncatedtetrahedrons (see fig. 17 d)).

Principal authors :D. Babonneau and R. Guinebretiere; ANR founding : Qmax project 2010-2014.

3.4 Hard condensed matter

3.4.1 Diffuse scattering and phase transition in the Zn6Sc periodic approximant of anicosahedral quasicrystal

Quasicrystals are long range ordered materials, without lattice periodicity. Whereas their atomicstructure is now better understood, in particular in the CdYb Tsai type quasicrystal, the mecha-nisms that lead to the formation and the stabilisation of the long range quasi-periodic order is still achallenging and open question.

Periodic approximants to quasicrystals offer a unique opportunity to improve understanding of thisproblem. Both the icosahedral quasicrystal i-MgZnSc and its cubic approximant Zn6Sc are built upof the same atomic clusters, the so-called Tsai type cluster. It is constructed as a series of icosahedralshells, except for the first shell, which is a tetrahedron. In the periodic approximant and at roomtemperature, this cluster is packed on a bcc lattice with a lattice parameter equal to 1.3 nm. Whereasthe central tetrahedron appears as spatially disordered at room temperature, randomly occupying sixequivalent positions, an ordering occurs below 160K. This phase transition has been studied in detailon the D2AM beamline.

The phase transition occurs at Tc=159K and corresponds to symmetry breaking from the hightemperature cubic symmetry to a phase with monoclinic symmetry and doubling of the cell along the(110) direction, leading to so-called superstructure reflections. We have carefully studied the variationof these superstructure reflections above Tc : broad maxima of diffuse scattering are observed aboveTc. As shown in the figure 18 , the diffuse scattering sharpens rapidly as T approaches Tc, showingthat short range order sets in. In fact, on extracting the correlation length as a function of thetemperature, the correlation length evolves from 20 nm at 200K to 120 nm just above Tc. Althoughthe correlation length does not strictly speaking diverge, it behaves as in a second order type transitionwith a power low as shown on the figure 18 , so that the transition can be classified as weakly firstorder and almost second order like.

Quasielastic neutron scattering, together with atomic scale simulations, has demonstrated thatabove Tc the tetrahedron behaves as a ‘single molecule’ and reorients dynamically on a time scale ofthe order of 1ps.

In conclusion, the diffuse scattering study demonstrates unambiguously the tetrahedron-tetrahedronshort range order on a quite large length scale. This brings important information about the energetics

14 D. Babonneau, Journal of Applied Crystallography, 2010, 43, 929-936



behind the ‘tetrahedron-tetrahedron’ interaction and on the mechanisms stabilizing the approximantand the quasicrystal.

Figure 18: Top : illustration of the successive atomic shells in the Zn6Sc periodic approximant. Thegrey and red atoms stand for Zn and Sc respectively. The last right panel displays the cubic unit celland the neighbouring tetrahedra. Bottom : Left panel : temperature dependence of one superstructurereflection. Right panel : variation of the correlation length as a function of T. It almost diverges atTc.

Principal authors and reference:

• T. Yamada, H. Euchner, C. P. Gomez, H. Takakura, R. Tamura and M. de Boissieu: Short- andlong-range ordering during the phase transition of the Zn6Sc 1/1 cubic approximant J. Phys.:Condens. Matter, 25, 205405, (2013).

• H. Euchner, T. Yamada, H. Schober, S. Rols, M. Mihalkovic, R. Tamura, T. Ishimasa andM. de Boissieu: Ordering and dynamics of the central tetrahedron in the 1/1 Zn6Sc periodicapproximant to quasicrystal J. Phys.: Condens. Matter, 24, 415403, (2012).

3.4.2 Combined structural analysis of ancient ill-ordered carbon-based cosmetics andinks

Carbon black materials are easy to obtain by combustion of organic matter and were thus often usedsince prehistory, as pigments or drawing, writing, dyeing materials or even as cosmetics components15.Black carbon-based powders from the Roman site of Pompeii were analyzed. The six analyzed samplescome from ink and cosmetic containers made of bronze or glass. Ancient recipes as well as preliminarystudies in laboratory revealed the complexity of these precious materials containing both ill-orderedphases (mostly carbonaceous) and well-crystallized phases (metals and volcanic minerals). Diffractionpatterns thus show diffuse scattering signatures (broad oscillations16 from non-graphitic carbon) withBragg reflections superimposed (Figure 19 left).

Therefore the following two step strategy involving non destructive techniques and analysis ofreference carbon based materials was chosen and set up on D2AM:

15A. Varichon, Couleurs: Pigments et teintures dans les mains des peuples, Seuil, 2005 , H.G.M. Edwards, et al.,Journal of Molecular Structure, 2000.

16R.E Franklin, Acta Crystallographica, 1950.



1. Selective extraction of the total scattering signal of each phase present using x-ray DiffractionScattering- Computed tomography (DSCT)17

2. Structural characterization of amorphous phases by PDF analysis using x-ray scattering datacollected on a wide 2θ range with good statistics18.

DSCT experiments requiring displacement of the sample with a precise translation - rotationsystem, and involving data acquisitions of a few hours per sample, enabled us to localize and extractthe signal of the various phases present, as can be seen on Figure 19 right (e.g. cosmetic c39p). Thesefirst promising results are being completed by µ-beam data collected on Diffabs at SOLEIL, as someheterogeneities within the sample seem to be several tens of microns in size.

The treatment of data acquired at thirty increasing 2θ positions to reach a high Q-range has beenperformed. Assessment of the weight fraction of each crystallized phase in the archaeological samplesusing Rietveld refinements was first achieved. PDF calculations were compared with structural modelstaking into account the presence and proportion of each crystallized phase obtained in the previousstep. For the amorphous part, differences with graphite structure could be visualized and proved to berelevant for short range order arrangements. Other models mentioned in the literature (turbostraticpiles19 and/or curved-graphitic-sheets20) are still under test. Moreover quantitative comparison of thePDF of reference samples and archaeological samples, combined with Raman spectroscopy analysis21

performed in the laboratory, enabled us to discriminate carbon blacks according to their startingmaterial (e.g. soot, peach black, ...). Additionally the size of the coherent graphitic domains of thecarbon black structures may be estimated by both techniques between 5 to 15 A according to thesamples.

Figure 19: Left: (a) Photograph of ink and cosmetics Pompeian containers and (b) optical micro-scope image of an archaeological sample. (c) Diffraction patterns of archaeological samples. Right:Localization of the phases and extraction of the corresponding diffraction scattering patterns for anarchaeological cosmetic sample.

Principal authors and reference :S. Cersoy, P. Martinetto, P. Bordet, J.-L. Hodeau, E. Van Elslande, P. Walter, 10th Colloque RayonsX et Matieres, Nantes, France, 2013.

3.4.3 multiphase materials

From the experiment described hereafter on C60 transformation and on other samples, it was demon-strated that X-ray diffraction computed/scattering tomography (DSCT) provides nondestructive three-

17 P. Bleuet P., et al., Nature Materials, 2008.18T. Egami, et al., Underneath the Bragg peaks, Pergamon, Oxford, England, 2003.19B.E Warren, Journal of Physical Chemistry, 1934.20L. Hawelek, et al., Philosophical Magasine, 200721 A.C. Ferrari, et al.Physical Review B, 2000.



dimensional structural images of crystalline or amorphous multi-phased heterogeneous materials. Di-luted phases can be discriminated with very high spatial and local resolution. The method is suitedfor numerous practical applications, in static, dynamic or multi-modal variants, as demonstrated byan increasing number of publications in this field.

Diffraction/scattering computed tomography for three-dimensional characterizationof multi-phase crystalline and amorphous materials: Application for microstructuralmapping of C60 phase transformation into disordered graphite at high pressure

Figure 20: The 2D data set is azimuthally integrated to produce 1D patterns. The data representation(y,ω) required for the reconstruction is the global sinogram. Sinograms have been represented beforedirect beam intensity normalization. Different regions of interest (ROI) corresponding to differentBragg peaks are selected: a) C60 polymer b) disordered graphite c) capillary. The final reconstructionprovides the intensity distribution as a 2D image (x,y) for each ROI a) C60 polymer b) disorderedgraphite c) capillary. Volume analysis: the stack of 2D reconstructions versus 2θ is rotated by 90˚torecover a stack of 2D images versus x or y, then a selective 1D intensity profile versus 2θ can beextracted from a ROI as small as a voxel. The intensity can be visualized as a function of x, y or 2θ.

The 3D characterization method developed herein is based on diffraction and scattering techniquescombined with tomography and uses the variation of these signals to reconstruct a 2D/3D structuralimage. Principles and steps of this combined method are illustrated in figure 20. To emphasizethe capability of the method in discriminating different poorly-ordered phases, it is named Diffrac-tion/Scattering Computed Tomography (DSCT). This combination not only allows structural imaging,but also yields an enhancement of the weak signals coming from minor phases, thereby increasing thesensitivity of structural probes.

We have used this combined method to study simultaneously the phase distribution and microstruc-ture in phase transformation processes. This 3D non-invasive imaging approach has been applied tounderstand the phase transformation of C60 rhombohedral polymer (C60R) into disordered graphite(DG) at high pressure and high temperature (HP-HT). The heterogeneous sample was synthesized(5GPa, 1100K) using a Paris-Edinburgh cell and selective image reconstructions were achieved for alldifferent phases present in this sample. The DSCT analysis evidences DG elongated domains with afiber texture where nested (002)DG planes show ±70˚ preferential orientation relative to the compres-



sion axis. In contrast C60R domains are found to be small and spotty, preferentially in the middle ofthe sample. Parent and product phases are mutually interpenetrative and present a crystallographicrelationship (figure 21). This study evidences that formation of (002)DG planes occurs parallel to111C60C pseudo-cubic planes. Among these four possible alignments, uniaxial pressure favors one[111]C60C direction.

Figure 21: Reconstructed selective images and diffraction patterns: (A) X-ray scattering diagram ofthe whole sample derived from the sum of all measured y positions and ω orientations, the imageon the right corresponds to the full sample reconstruction. (B-E) selected X-ray diffraction/diffusesignal extracted from a given transformed sample area. (B) Amorphous glass capillary and support,(C) hexagonal Boron Nitride h-BN with parameters a= 2.508(1) A and c= 6.666(2) A, (D) disor-dered graphite DG phase with d (002)DG = 3.48(3) A, (E) 2D rhombohedral C60 polymer R-3/mwith parameters a= 9.189(4) A b= 24.262(6) A. Inserted images on the right part correspond to thereconstruction of each single phase using all reflections of the corresponding phase. The upper in-serted images are virtual slices calculated with only 2θ data corresponding to (003)C60R, (101)C60R,(102)C60R, (104)C60R ,(110)C60R and (015)C60R individual C60R reflections. The arrow on the topindicates the compression axis during synthesis.

As reconstruction artefacts can degrade the quality of the rendered images and limit their inter-pretation, the sources of error and limits of this method has been evaluated and compared with otherdiffraction-based techniques. As example to illustrate the importance of the scanning translation stepsize, DSCT experiments have been carried out with different probe sizes and δy step sizes (figure 22).Of course, the best reconstruction is based on the highest resolution data, namely the one that includesa total of 11041 2D-diffraction patterns. However, the medium resolution one, based on “only” 18132D-diffraction patterns with a 35µm step size – much smaller than the 150 x 150 µm beam size –,already gives well-resolved information and evidences the general sample shape. For the less-resolvedimage, built with 150 µm step size which nearly equals the beam size, it is difficult to distinguishsample shape or any other features.

Principal authors and reference:

• Alvarez-Murga M., Bleuet P. and Hodeau J.L, J. Appl. Cryst. 45, 1109-1124 (2012).

• Alvarez-Murga M., Bleuet P., Marques L., Lepoittevin C., Boudet N., Gabarino G., Mezouar


3.5 Methods and instrumentation 3 SCIENTIFIC RESULTS

Figure 22: Reconstructed slice of a carbon sample with different resolution and step sizes (see text).

M. and Hodeau J.L, J. Appl. Cryst. 44, 163-171 (2011).

• Alvarez-Murga M., Bleuet P., Garbarino G. , Salamat A. , Mezouar M. and Hodeau J.L, PhysicalReview Letters 109, 025502 (2012).

• Religieux, L. (2011) Master report, Development of a Local Structural Probe: Diffraction-Tomography for Extraction and Analysis of Pigments in Cultural Heritage Materials, GrenobleUniv. Joseph Fourier

3.5 Methods and instrumentation

The D2AM team continues its collaboration with the CPPM team and the SOLEIL detector groupwithin the CHiPSpeCT consortium whose aim is to build a large multi-module CdTe based photoncounting detector for hard X-ray applications. The development proposed in this project is creditedwith the highest priority for synchrotron radiation science since CdTe sensors can improve the detectionefficiency and thus the quality of the collected data.

X-ray detectors are usually based on CCD or CMOS pixels associated with a scintillation converter,directly coupled or coupled through optical fibre bundles. In certain cases, use of a light amplifierimproves performance. Detection is obtained by photon conversion charge integration. Owing totheir integration, signal charges cannot be differentiated from electronic background. Moreover, in thecase of CCDs, charges are transmitted from pixel to pixel and are read out at the end of the chain.This makes readout rather slow and introduces smearing from one pixel to the other. With hybridpixel detectors, photons are directly converted in the sensor substrate (made of Silicon or CadmiumTelluride) and the resulting charge is analyzed by integrated circuits bump bonded to the sensors.These devices are similar to CCDs, flat panel detectors using amorphous silicon pixels covered with ascintillation material, or CMOS pixels also named Active Pixel Sensors (APS), but they represent anew generation of digital X-ray detectors for which photon counting replaces charge integration. Thisnovel approach involves several advantages, among which the absence of dark noise and the abilityto set an energy threshold for the detected photons are of utmost importance for the development ofnew X-ray imaging approaches that will exploit spectral information on the detected X-rays.

In this on-going project, we tested nine XPAD3.2 single chip hybrids in various configurations(Ohmic and Schottky contacts with electron or hole collection mode) in order to select the mostefficient and best suited configuration for our experimental requirements. As shown on figure 23,chips were placed on test boards and calibrations were performed on our beamline as well as themetrology beamline at SOLEIL. The first results enabled us to select the best configuration, and morechips are under construction to assemble a large detector. Further tests with beam will be performedin July.

Principal authors and reference :C. Buton, A. Dawiec, J. Graber-Bolis, K. Arnaud, J. F. Berar, N. Blanc, N. Boudet, J. C. Clemens, F.Debarbieux, P. Delpierre, B. Dinkespiler, T. Gastaldi, S. Hustache, C. Morel, P. Pangaud, H. Perez-Ponce, E. Vigeolas, Comparison of three types of XPAD3.2 / CdTe single chip hybrids for hard X-rayapplications in material science and biomedical imaging, accepted in NIMA 2014.


4 CONCLUSION-PERSPECTIVES

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Figure 23: Top: XPAD3.2 detector and the same mounted on its acquisition card. Bottom: Thresholdmap (left) and count map at threshold (right) for the Schottky h+ configuration at 16 keV. The highvoltage wire as well as the pixels edge effects are easily noticeable on the count map.

4 Conclusion-perspectives

We still have some on-going projects to continue our efforts on the upgrade of the beamline. In2014-2015, we will finish installing and commissioning an ”O-shaped” detector on the D2AM SAXSinstrument and a KB focussing system, motivations are explained below. We also have an on-goingproject to develop a high temperature furnace : heating to 1700˚C in vacuum or in controlled atmo-sphere. We are also seeking financial support to buy a cryostat.

On a longer time scale, when we receive more precise information from the upgrade phase II ofESRF, we will start to see what can be done on bending magnet beamlines ...

4.1 in-situ studies

4.1.1 simultaneous saxs-waxs measurements

The Equipex CRG/F project aims to provide a more reliable structural characterization of disorderedmaterials, such as polymers, through simultaneous observation of diffuse scattering on very differentQ ranges. This is particularly important for materials whose structural properties may vary from onesample to another (or within a sample), leading to possible misinterpretation if the two measurementsare performed separately. This is the principal motivation for implementing a ”O-shaped” detectoron the D2AM SAXS instrument.

One first motivation for measuring WAXS and SAXS simultaneously is to optimize the practicaluse of the properties of polymers as structural materials that require an understanding of their mech-anisms of deformation or structuring. Semi-crystalline polymers are a very important part of suchmaterials for the reason that they offer the greatest diversity of behaviour from elastomers to verystiff thermoplastics. The nanoscale structuring of lamellar crystallites is particularly well suited tosmall angle X-ray scattering studies, in combination with crystallographic studies by X-ray diffraction.Traditionally, diffuse scattering is used for initial dimensional characterization of the semi-crystalline


4.1 in-situ studies 4 CONCLUSION-PERSPECTIVES

structure in relation to the implementation of the materials. The high brilliance of synchrotron radi-ation and the use of 2D detectors then allow in situ access to the texture distribution of crystallitesduring deformation and damage resulting in cavitation. Meanwhile, in situ diffraction gives access tothe crystalline texture, which is not necessarily that of the strips in their entirety as a result of thephenomenon of crystalline shear. Diffraction also provides access to the very important phenomena ofphase transformation. Combining data obtained separately in the case of polyethylene [Hubert2004,Humbert2010] and polyamide6 [Ibanez2004] shows that there are correlations between the variousphenomena occurring at very different levels of scale but these correlations could not be clearly estab-lished so far due to lack of strict time correlation between the structural events captured in both typesof experiment, and macroscopic mechanical measurements. The prospect of coupling both techniquesallows the simultaneous investigation of various phenomena in situ during the deformation in order toreveal their correlations. Of particular interest are the links between changes of crystalline phase, tex-ture and damage. In addition, it gives the opportunity to determine more accurately the occurrenceof these various processes related to the initial orientation of crystalline lamellae in the spheruliticstructure and the instantaneous local stress state evaluated by diffraction via the crystal lattice elasticdeformations. Another advantage of a combined diffraction / small-angle scattering experiment isfor the in situ analysis of systems for which it is not possible to synchronize / compare experimentsperformed separately. This is particularly the case when two successive tests do not concern exactlycomparable samples because the experiment cannot be repeated in exactly the same way or at thesame spot. For example, during an in situ mechanical deformation, the characterization of the changesin semicrystalline morphology of polymer systems (in the case of semi-crystalline polymers) and / orcharged systems (in the case of nanocomposites) raises this kind of problem because the materialsbecome very quickly heterogeneous due to localization of the plastic deformation phenomena.

Two successive experiments are never exactly identical because of the initial fluctuations of cohesion/ morphology in the sample, which determine the development of necking zones or shear bands acrossthe sample. However, a coupled analysis allows characterization of the state of stress at the level ofinorganic or polymer crystals with a characterization of the deformation processes on a larger scale(lamellar clusters). Such an analysis was partially carried out by Ibanez et al., in the case of nylonfibers filled with organic and inorganic nanoparticles. The analysis allows one to trace back to thedeformation processes at various scales, which is a key to the important field of physics of condensedmatter and will greatly benefit from simultaneous WAXS and SAXS measurements.

4.1.2 Low temperature studies

Temperature is one of the main physical parameters, with pressure or external electro-magnetic fieldsfor instance, that can control a long range structural, electronic (charge or orbital) or magnetic or-dering. The temperature behaviour of the long-range coherent scattering of X-rays or neutrons bysuch structures allow determining the nature of the electronic and magnetic interactions. The natureof the structural transformations are measured by the temperature dependence of the scattering nearthe phase transitions and the phase transition temperature is a well-defined property of a material.As temperature usually destroys order, many phase transitions occur at low temperature, and mostof them below room temperature. A cryostat is therefore a mandatory instrument on a diffractometerto detect and determine the nature of a magnetic, structural or electronic phases.

Among our users, researchers in the SIN group of the Institut Neel grow by epitaxy thin films andmultilayers of metallic and strongly correlated materials of transition metal oxides with the prospectof technological use and fundamental science. Correlated materials are one of the main topics in con-densed matter for the coherent electronic and magnetic orderings that are stabilized by the electroniccorrelations. As the ordering is very temperature dependent, we require the ability to control thetemperature toward either low or high temperatures to evidence and study the electronic correlationsinvolved, and the usefulness of a device based on a particular transition metal oxide. A typical exam-ple is a magnetite sample a few monolayer thick coupled to a CoO antiferromagnetic layer. In thiscase, we would study the temperature dependence of the charge ordering in magnetite, and the mag-


4.2 2D data treatment 4 CONCLUSION-PERSPECTIVES

netic couplings together with a fine study of structural changes with the temperature with a precisediffractometer and a high flux photon beam.

4.1.3 High temperature studies

X-ray scattering at high or low angles under high temperature is a well-established method for followingthe solid state structural phase transitions and microstructural evolution of materials. The thin filmcase is of course more complicated. Indeed, the samples must be oriented with respect to the incidentbeam with an accuracy of a few thousandths of a degree and the irradiated volume is correspondinglyvery small. Many commercially available furnaces devoted to high temperature X-ray diffractionmeasurements on polycrystalline samples are made of a foil strip acting as a heating element and asa support of the powdered samples. The sample displacement on heating apparatus is incompatiblewith the alignment requirements of epitaxial thin films. A stable high temperature sample holdermust be used.

The main claim of our project is to deliver a data acquisition/analysis toolbox, which capturesand processes data near Q=0 (GISAXS) and at high Q (HR-XRD) in a combinatory way and as afunction of the temperature (between 20 and 1500˚C). The following microstructural characteristicsneed to be determined:

• Nano-island shape and dimensions and the associated statistical distributions

• Lateral pattern shape and size, and the associated statistical distributions and correlation length

• State of strain and strain relaxation

• Phenomenological disorder parameters: heterogeneous strain, strain confinement, strain gradi-ents, mosaıcity. . .

• Microscopic disorder parameters: nature and density of the defects (e.g. dislocation type anddensity, spatial correlation of dislocations, stacking fault type and density ...)

• Interfacial diffusion.

The design of the furnace is now well advanced. The key point is to find reliable heating elements. Thissummer, a prototype will be built with an already available heating element to heat up to 900˚C, whilewaiting for a higher temperature one. This protoptype will also help us to validate the simulationsand cooling system to keep the Berilyum dome at a temperature bellow 200˚C.

4.2 2D data treatment

Since the beginning of the beamline, we provided a C code to treat the 2D saxs data taken on theCCD and make radial distribution (bm2img tool, written by JF Berar, now retired). Great efforts arenow being made on the beamline with our post-doc, T. Nguyen, to build up reliable and consistentPython tools to put in shape the diffraction data collected either with the 1D or 2D detectors. Thekey is to take into account the distortions induced by a small rotational misorientation of the detectorwhen mounted on the 2θ goniometer arm.

4.3 Kirkpatrick-Baez optics for a microbeam experiment

We plan to reduce the beam size to a few tens of microns in order to reduce the footprint of the beamon the sample in grazing incidence geometry. This reduced size will also allow us to access smaller partsof heterogeneous or patterned samples, as the microelectronic ones. For grazing incidence MAD andDAFS experiments, we hope that the KB system will help us to stabilize the position and geometryof the beam versus energy. This will noticeably avoid the DAFS spectra distortions induced by thebeam geometrical changes as a function of energy.


4.4 Upgrade phase II of the ESRF 4 CONCLUSION-PERSPECTIVES

additional KB mirrors

source - primary mirror : 26 msource - monochromator : 28 msource - second mirror : 29.8 msource - last D2AM slits : 35.295 msource - SAXS slits : 40.745 m

beam width 200µm

D2AM optical hutchto add in D2AM experimental hutch

updated D2AM optics

15 m

slits

1 m

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E (~ 15-25 KeV)

monochromator - goniometer : 9.5 m

Figure 24: Sketch of the KB to be installed in the experimental hutch.

4.4 Upgrade phase II of the ESRF

The upgrade of the machine is an opportunity for ESRF ID beamlines but also BM beamlines (mainlyCRGs!) to remain competitive with other national and international beamlines.

The opportunity, already discussed with the machine division, to have now wiggler on our beamlinewould allow us at least to have the same number of photons in 2 mrad instead of the 6 mrad thatwe have now and that we never use, because we are not able to focus them properly neither for thegrazing incidence nor for the SAXS experiments. Since the beginning of the beamline, we only veryseldom used more than 5 mm of the beam (versus the 50 mm available). That is why we purchasedthe 2nd crystal with a 5 mm area without ribs (we tried 20 mm but we had a vertical anticlasticbroadening). As soon as the final geometry of our new source is determined, we will start the designof a new bending system and optimize the crystal shape.


5 SCIENTIFIC PRODUCTION 2009-2013

5 Scientific production 2009-2013

5.1 Theses

Theses, PhD 2009

1. Serrero , Developpement d un adhesif biologique a base de polysaccharides pour des applications biomedicales,2009-12-08, Universite Lyon

2. Rivas Roccio Noemi , Fibres creuses multimembranaires pour la regeneration tissulaire: Elaboration etcaracterisation microstructurale, 2009-12-00, Lyon-Gvmt Mexicain

3. Dejoie Catherine, Nano composites organo-mineraux : du pigment bleu maya aux nouveaux hybridescolorants., 2009-10-21, Univ. J. Fourier, Grenoble

4. Fribourg Guillaume, Precipitation and plasticity couplings in a 7xxx aluminium alloy: application tothermomechanical treatments for distortion control of aerospace components, 2009-05-09, Grenoble-INP

5. Clemenson Sandra, Nanostructuration de systemes polymeres/metal hybrides pour applications fonction-nelles, 2009-05-00, Lyon

6. Collet Jean-Louis, Les mecanismes de deformation d’un acier TWIP FeMnC : une etude par diffractiondes rayons X, 2009-03-09, Grenoble-INP

7. Imbert Bruno, Etude de la formation du Siliciure de Nickel-Platine integre dans la fabrication de tran-sistors CMOS pour les technologies 65 et 45 nm., 2009-02-26, Universite Paul Cezanne - Aix-MarseilleIII

8. Herrera Quintero L.K., Physico-Chemical Research of Cultural Heritage Materials Using Microanalyticalmethods, 2009-02-01, Universidad de Sevilla

9. Liscio Fabiola, Self assembled magnetic nanostructures prepared by molecular beam epitaxy on low energysurfaces.Fabiola Liscio, 2009-01-30, Grenoble-INP et Universite Roma Tre

10. Frederix Caroline, M-lange et soudage de poly-thyl-nes , 0000-00-00, Universit- Lille11. Stoclet G., Caracterisation des proprietes thermomecaniques et structurales d’un polymere issu de ressources

renouvelables : l’acide polylactique 6Directeurs : Jean-Marc Lefebvre, Roland Seguela, , Universite Lille12. Frederix Caroline, Melange et soudage de polyethylenes , , Universite Lille

French DHDR ... 2009

1. Dooryhee Eric, Etude par diffraction de super reseaux d’oxydes perovskites, 2009-03-25, UJF, Grenoble

Theses, PhD 2010

1. Gamys Ce Quinto, Macroprecurseurs de materiaux hybrides organiques-inorganiques : Synthese, auto-assemblage et hydrolyse-condensation, 2010-11-16, Universite Lyon

2. Kamar Zaccharias, Gainage de fibrilles de polymere covalent par des nanotubules auto-assembles, 2010-09-22, Universite de Strasbourg-Universite d’Oujda (Maroc)

3. Pichon Pascal, Fatigue thermomecanique des elastomeres polyurethane : caracterisation experimentale del’evolution des microstructures et modelisation des echanges thermiques , 2010-09-17, INSA-Lyon

4. Decreus Benjamin, Etude de la precipitation dans les alliages Al-Li-Cu de troisieme generation. Relationsentre microstructures et proprietes mecaniques., 2010-05-22, Grenoble-INP

5. Attia Judith, Auto-assemblages de linoleate et d‘argent pour la synthese par radiolyse de nano-objetsorganique-metalliques, 2010-02-09, Universite Pierre et Marie Curie

6. Baudot S., MOSFETs contraints sur SOI : analyse des deformations par diffraction des rayons X et etudedes proprietes electriques, 2010-00-00, Universite J. Fourier, Grenoble

7. Landre O., Etude de la nucleation et de la croissance de structures filaires GaN et AlN, 2010-00-00,Universite de Grenoble

Theses, PhD 2011

1. Bach Campa Cristina, Evaluation de la migration des constituants de l’emballage en poly(ethylene terephtalate)(PET) vers l’eau, des facteurs d’influence et du potentiel toxique des migrats, 2011-12-14, Institut nationalPolytechnique de Loraine

2. Chalal M., Structure Multi-echelle et Proprietes Physico-chimiques des Gels de Polymeres Thermosensi-bles, 2011-10-06, co-tutelle UJF-UNIVERSITE DES SCIENCES ET DE LA TECHNOLOGIE HOUARIBOUMEDIENE-ALGER

3. Desormes Mylene, Filage du chitosane pour l’elaboration de textiles biomedicaux innovants, 2011-06-20,Universite Claude Bernard Lyon 1


5.2 Articles 5 SCIENTIFIC PRODUCTION 2009-2013

4. Dupasquier Florence, Hydrogels physiques de chitosane pour la regeneration in vivo du tissu cutane apresbrulure du troisieme degre, 2011-05-13, Universite Claude Bernard Lyon 1

5. Bouty Salima, Etude du vieillissement thermique a long terme du PET: Application a l’isolation electriquedans des disjoncteurs haute tension, 2011-03-29, Institut National Polytechnique de Lorraine

6. Brombacher C., Rapid thermal annealing of FePt and FePt/Cu thin films , 2011-01-10, Department ofNatural Sciences, Chemnitz University of Technology (Germany)

7. Paineau E., Transitions de phases dans des suspensions d’argiles. Influence de la mineralogie et de lamorphologie. Comportement sous ecoulement et sous champs, 2011-00-00, Universite de Lorraine

8. Dal Bo A.G., Preparation et caracterisation de nouveaux amphiphiles fonctionnalises par des oligo-etpolysaccharides, 2011-00-00, Univ. de Grenoble

9. Tardif S., Nanocolonnes de GeMn: proprietes magnetiques et structurales a la lumiere du synchrotron,2011-00-00, Universite de Grenoble

10. Porret C., Effet du manganese sur l’epitaxie par jets moleculaires de nanofils de silicium et de germa-nium et fonctionnalisation de nanofils de germanium en vue d’applications en spintronique, 2011-00-00,(Universite de Grenoble)

11. Jain A., Injection de spin dans le germanium: de l’injecteur ferromagnetique metallique a l’injecteursemiconducteur (Ge,Mn), 2011-00-00, Universite de Grenoble

12. Dawiec A., Developpement d’une camera a rayons X ultra-rapide utilisant des detecteurs a pixels hybrides,2011-00-00, Universite de la Mediterranee-Aix Marseille II

Theses, PhD 2012

1. Wang L., Electrodeposition et la caracterisation de nanofilms palladium sur Au (111) pour le stockaged’hydrogene Electro-deposition and characterization of palladium nanofilms on Au (111) for hydrogenstorage , 2012-12-12, Laboratoire d’Electrochimie et de Physico-chimie des Materiaux et des Interfaces

2. Puydt Quentin, comportement mecanique de soudures en alliage d’aluminium de la serie 7000 :de lamicrostructure a la modelisation de la rupture, 2012-12-05, Universite de Grenoble

3. Laquievre A., Mecanismes elementaires de plasticite des systemes polymeres amorphes: influence de lamodification de la structure macromoleculaire par click chemistry, 2012-12-01, Universite Lille 1 Scienceset Technologies

4. Fiorentino B., Orientation cristalline de la matrice resultant de la deformation et des charges lamellairesdans des nanocomposites thermoplastiques, 2012-11-29, Univ. Claude Bernard Lyon 1

5. Hestroffer K., Croissance et caracterisation de nanofils de GaN et d’heterostructures filaire de GaN/AlN,2012-10-25, Univ. Grenoble

6. Becerra jose, Films mixtes Chitosane/Proteines : Interactions, morphologie et proprietes macroscopiques,2012-09-06, Universite Claude Bernard Lyon 1

7. Silioc Christelle, Synthese et etude des proprietes d’autoassociation de molecules amphiphiles derivees deD-glucose, 2012-06-14, Universite Claude Bernard Lyon 1

8. Thevenon A., Relations structure/proprietes thermomecaniques elongationelles de films polymeres ther-moplastiques , 2012-02-14, Universite Claude Bernard Lyon 1

9. Felmann Vincent, Croissance et caracterisations structurales et optiques d’heterostructures de nitruresd’elements III emettant dans l’UV, 2012-01-13, Univ. de Grenoble

10. Yamada T., Stability and phase transition of Tsai-type quasicrystals and their approximants, 2012-01-00,Tokyo University of Science

Theses, PhD 2013

1. Thomas M., Liquid Crystal Induced Ordering of Gold Nanorods,, 2013-12-09, Manchester2. Dorin T., Mecanismes de durcissement structural par des precipites anisotropes dans un alliage Al-Li-Cu

de troisieme generation, 2013-11-26, Grenoble3. Dupre L., Croissance confinee de nanofils de silicium a application solaire photovoltaıque, 2013-10-24,4. Leclere C., Spectroscopies X et diffraction anomale de boıtes quantiques GaN et d’hetero-structures III-N

: inter-diffusion et ordre a courte distance, 2013-06-06, Grenoble INP5. Previdello p., Effet de l’orientation sur les nanofilms de Pd/Pt(hkl) : electrodepot, caracterisation et

isothermes electrochimiques de Pd-H Orientation effect on Pd/Pt(hkl) nanofilms, 2012-04-08, UJF

5.2 Articles

Articles 2009



1. Auffret Y., Roux D. C. D., El Kissi N., Caton F., Pignot-paintrand I., Dunstan D.E., Rochas C., Agingyielding in a sheared AOT/iso-octane/water lyotropic lamellar phase, Eur. Phys. J. E (2009) 29, 51-60

2. Auffret Y., Roux D. C. D., El Kissi N., Caton F., Dunstan D.E., Pignot-paintrand I., Nishiyama N.,Rochas C., Ecoulement et non ecoulement d’une phase lamellaire chargee, Rheologie (2009), 1-10

3. Babonneau D., Camelio S., Lantiat D., Simonot L., Michel A., Waveguiding and correlated roughnesseffects in layered nanocomposite thin films studied by grazing-incidence small-angle x-ray scattering, Phys.Rev. B (2009) 80, 155446-1-155446-12

4. Baudot S., Andrieu F., Rieutord F., Eymery J., Elastic relaxation in patterned and implanted strainedsilicon on insulator, J. Appl. Phys. (2009) 105, 114302-1-114302-10

5. Bloch E., Llewellyn P.L., Phan T., Bertin D., Hornebecq V., On defining a simple empirical relationshipto predict the pore size of mesoporous silicas prepared from PEO-b-PS diblock copolymers, Chemistry ofMaterials (2009) 21, 48-55

6. Boulle A., Conchon F., Guinebretiere R., Strain profiles in thin films: influence of a coherently diffractingsubstrate and thickness fluctuations, J. Appl. Cryst. (2009) 42, 85-92

7. Boulle A., Rochas C., Synthesis of tin oxide nanosized crystals embedded in silica matrix through sol-gelprocess using alkoxide precursors, J. Non-Crystal. Solids (2009) 355, 951-959

8. Brunel F., Veron L., Ladaviere C., David L., Domard A., Delair T., Synthesis and structural characteri-zation of chitosan nanogels, Langmuir (2009) 25, 8935-8943

9. Camelio S., Babonneau D., Lantiat D., Simonot L., Pailloux F., Anisotropic optical properties of silvernanoparticle arrays on rippled dielectric surfaces produced by low-energy ion erosion, Phys. Rev. B (2009)80, 155434

10. Cassol Brunner F., Clemens J.C., Hemmer C., Morel C., Imaging performance of the hybrid pixel detectorsXPAD3-S, Phys. Med. Biol. (2009) 54, 1773-1789

11. Constantin D., Membrane-mediated repulsion between gramicidin pores, Biochimica et Biophysica Acta(2009) 1788, 1782-1789

12. Cotts , Compton J., Kranbuehl D. E., Espuche E., David M.L., Boiteux G., 286, Macromolecular Sym-posia (2009), 164-171

13. Czakkel O., Geissler E., Moussaıd A., Laszlo K., Copper-containing resorcinol-formaldehyde networks ,Micropor. Mesopor. Mat. (2009) 126, 213-221

14. Czakkel O., Geissler E., Szilagyi I., Szekely E., Laszlo K., Cu-doped resorcinol-formaldehyde (RF) polymerand carbon aerogelsJournal of Colloid and Interface Science 337, 513-522 (2009) , J. Colloid InterfaceSci. (2009) 337, 513-522

15. Dasgupta D., Srinivasan S., Rochas C., Ajayaghosh A., Guenet J.-M, Hybrid Thermoreversible Gels fromCovalent Polymers and Organogels, Langmuir (2009) 25 (15), 8593-8598

16. Dawn A., Rochas C., Guenet J.-M, Molecular compounds from ternary systems of syndiotactic polystyrene, Macromolecules (2009) 42, 6633-6639

17. Deschamps A., Ringeval S., Texier G., Delfaut-durut L., Quantitative characterization of the microstruc-ture of an electron-beamwelded medium strength Al-Zn-Mg alloy, Mat. Sci. Eng. A (2009) 517, 361-368

18. Dumont M., Bley F., Regula G., Characterisation of nanocavities in He+-implanted silicon by transmis-sion electron microscopy and small-angle X-ray scattering, Mat. Sci. Eng. B (2009) 162, 135-142

19. Etienne S., Hiver J.M., Billy M., Jonquieres A., Clement R., Stevenson I., Nikaj E., David L., Morphologyand dynamical behaviour of grafted copolymers, Mat. Sci. Eng. A (2009) 521-522, 259-262

20. Eymery J., Favre-Nicolin V., Froberg , Samuelson , X-ray measurements of the strain and shape ofdielectric/metallic wrap-gated InAs nanowires, Appl. Phys. Lett. (2009) 94, 131911-1-131911-11

21. Gonzales G., Gomes M.E., Vitale G., Castro G.R., Effect of Al content on phase transitions of zeoliteMEL, Micropor. Mesopor. Mat. (2009) 121, 26-33

22. Hosokawa S., Sato T.J., Ichitsubo T., Nakatake M., Happo N., Berar J.F., Boudet N., Usuki T., PilgrimW.-C., Matsubara E., Nishiyama N., Inhomogeneity and excellent glass-forming ability in Pd42.5Ni7.5Cu30P20bulk metallic glass., Phys. Rev. B (2009) 80, 174204

23. Jousseaume V., Rolland G, Babonneau D., Simon J.P., Influence of the polymeric porogen on porosityand on mechanical properties of spin coated Ultra Low K dielectrics, Thin Solid Films (2009) 517-15,4413-4418

24. Jousseaume V., Gourhant O., Zenasni A., Maret M., Simon J.P., Grazing incidence small angle x-rayscattering study of the structure of nanoporous ultralow-k dielectrics prepared by plasma enhancedchemicalvapor deposition, Appl. Phys. Lett. (2009) 95, 022901

25. Landre O., Bougerol C., Renevier H., Daudin B., Nucleation mechanism of GaN nanowires grown on(111) Si by molecular beam epitaxy, Nanotechnology (2009) 20, 415602

26. Lebouin C., Soldo-Olivier Y., Sibert E., De Santis M., Maillard F., Faure R., Evidence of the substrate ef-fect in hydrogen electroinsertion into palladium atomic layers by means of in situ surface X-ray diffraction,



Langmuir (2009) 25, 4251-425527. Makarov D., Krone P., Lantiat D., Schulze C., Liebig A., Brombacher C., Hietschold M., Hermann S.,

Laberty C., Grosso D., Albrecht M., Magnetization Reversal in Arrays of Magnetic Nanoperforations,IEEE T Magn. (2009) 45,10, 3515-3518

28. Marlaud T., et al , Influence of alloy composition and heat treatment on precipitate composition in Al-Zn-Mg-Cu alloys, Acta Materialia (2009)

29. Meneghini C., Boscherini F., Pasquini L., Renevier H., Diffraction anomalous fine structure study ofiron/iron oxide nanoparticles., J. Appl. Cryst. (2009) 42, 642-648

30. Paineau E., Antonova K., Baravian C., Bihannic I., Davidson P., Imperor-Clerc M., Dozov I., Liquid-crystalline nematic phase in aqueous suspensions of a disk-shaped natural beidellite clay, J. Phys. Chem.B (2009) 113, 15858-15869

31. Paineau E., Antonova K., Baravian C., Bihannic I., Davidson I., Dozov I., Imperor-Clerc M., Levitz P.,Madsen A., Meneau F., Michaud L.J., Liquid-Crystalline Nematic Phase in Aqueous Suspensions of aDisk-Shaped Natural Beidellite Clay., J. Phys. Chem. B (2009) 113, 15858-15869

32. Palancher H., Wieschalla N., Martin G., Tucoulou R., sabatier C., Petry W., Berar J.F., Valot C., DuboisS., Uranium-molybdenum nuclear fuel plates behaviour under heavy ion irradiation: An X-ray diffractionanalysis, J. Nucl. Mat. (2009) 385, 449-455

33. Popa-Nita S., Rochas C., David L., Domard A., Structure of Natural Polyelectrolyte Solutions: Role ofthe Hydrophilic/Hydrophobic Interaction Balance, Langmuir (2009) 25, 6460-6468

34. Reguer S., Mirambet f., Dooryhee E., Hodeau J.-L., Dillmann P., Lagarde P., Structural evidence forthe desalination of akaganeite in the preservation of iron archaeological objects, using synchrotron XRaypowder diffraction and absorption spectroscopy, Corrosion Science (2009) 51, 2795-2802

35. Renaud G., Probing surface and interface morphology with grazing incidence small angle X-ray scattering,Surf. Sci. Rep. (2009) 64, 255-380

36. Richard M.I., Favre-Nicolin V., Renaud G., Schulli T., Priester C., Zhong Z. , Metzger T.H., Multiplescattering effects in strain and composition analysis of nanoislands by grazing incidence X-rays, Appl.Phys. Lett. (2009) 94, 013112-1-013112-3

37. Richard M.I., Katcho N.A., Proietti M.G., Renevier H., Favre-Nicolin V., Zhong Z. , Chen G., StoffelM., Schmidt O., Renaud G., Schulli T., Bauer G., Structural properties of Ge/Si(001) nano-islands bydiffraction anomalous fine structure and multiwavelength anomalous diffraction, Eur. Phys. J-Spec. Top.(2009) 167, 3-10

38. Simon J.P., Babonneau D., Drouet M., Lyon O., Anomalous grazing incidence small-angle X-ray scatteringof carbon-encapsulated Au and Cu clusters., J. Appl. Cryst. (2009) 42, 312-322

39. Sushko R., Sarazin D., Rochas C., Kutsevol N., Guenet J.-M, Anomalous behaviour of comb-like dextran-polyacrylamide copolymers in mixed solvents, Eur. Polym. J. (2009) 45, 1698-1705

40. Thune E., Boulle A., Babonneau D., Pailloux F., Hamd W., Guinebretiere R., Nanostructured sapphirevicinal surfaces as templates for the growth of self-organized oxide nanostructures, Appl. Surf. Sci. (2009)256, 924-928

41. Wu Y.C., Hamd W., Thune E., Boulle A., Rochas C., Guinebretiere R., Synthesis of tin oxide nanosizedcrystals embedded in silica matrix through sol-gel process using alkoxide precursors, J. Non-Crystal. Solids(2009) 355, 951-959

Proceedings 2009 not cited in Conferences lists

1. Katcho N.A., Richard M.I., Landre O., Tourbot G., Proietti M.G., Renevier H., Favre-Nicolin V., DaudinB., Chen G., Zhang J.J., Bauer G., Structural properties of Ge/Si(001) nano-islands and AlGaN nanowiresby Diffraction Anomalous Fine Structure and Multiwavelength Anomalous Diffraction, J. Phys : Conf.Ser. (2009) 190, 012129-1-012129-12

Other publications 2009

1. Katcho N.A., Richard M.I., Landre O., Tourbot G., Proietti M.G., Renevier H., Favre-Nicolin V., DaudinB., Chen G., Zhang J.J., Bauer G., Combining spectroscopy and simulations to probe the structuralproperties of Ge/Si(001) nano-islands., ESRF Highlights (2009) Structure of materials, 32-34

Articles 2010

1. Bahloul W, Bounor-Legare V., David L., Cassagnau P., Morphology and Viscoelasticity of PP/TiO2Nanocomposites Prepared by In Situ Sol-Gel Method, J. Polymer Sc. B: Polymer Phys. (2010) 48(11),1213-1222



2. Baudot S., Andrieu F., Faynot O., Eymery J., Electrical diffraction characterization of short narrowMOSFETs on fully depleted strained silicon-on-insulator (sSOI) , Solid State Electronics (2010) 54 (9),861-869

3. Billy M., Ranzani Da Costa A., Lochon P., Clement R., Dresch M., Etienne S., Hiver J.M., DavidL., Jonquieres A., Cellulose acetate graft copolymers with nano-structured architectures: Synthesis andcharacterization , Eur. Polym. J. (2010) 46, 944-957

4. Brunel F., Veron L., David L., Domard A., Verrier B., Delair T., Self-assemblies on Chitosan Nanohy-drogels, Macromol. Bioscience (2010) 10(4) , 424-432

5. Cassol Brunner F., Benoit D, Berar J.F., Clemens J.C., Morel C., Study of the charge sharing effect inthe photon-counting pixel detector XPAD3-S , Nucl. Instr. and Meth. A (2010), in press

6. Chalal M., Ehrburger-Dolle F., Morfin I., Bley F., Aguilar M.R., Lopez M.L., San roman J., Bolgen N.,Piskin E., Ziane O., Casalegno R., SAXS Investigation of the Effect of Temperature on the MultiscaleStructure of a Macroporous Poly(N-isopropylacrylamide) Gel, Macromolecules (2010) 43, 2009-2017

7. Constantin D., The interaction of hybrid nanoparticles inserted within surfactant bilayers, J. Chem. Phys.(2010) 133, 144901

8. Dasgupta D., Kamar Z., Rochas C., Dahmani M., Mesini P., Guenet J.-M, Design of hybrid networks bysheathing polymer fibrils with self-assembled nanotubules, Soft Matter (2010) 6, 3573-358

9. Debelle A., Thome L., Dompoint D., Boulle A., Garrido F., Jagielski J., Chaussende D., Characterizationand modelling of the ion-irradiation induced disorder in 6H-SiC and 3C-SiC single crystals, J. Phys. D.(2010) 43, 455408-1

10. Dejoie C., Martinetto P., Dooryhee E., Strobel P., Blanc S., Bordat P., Brown R., Porcher F., Sanchez DelRio M., Anne M. , Indigo@Silicalite: A new organic-inorganic hybrid pigment, Appl. Mater. Interfaces(2010) 2, 2308-2316

11. Donnadieu P., Shao Y., De Geuser F., Botton G.A., Lazar S., Cheynet M., De Boissieu M., DeschampsA., Atomic structure of T1 precipitates in Al-Li-Cu alloys revisitedwith HAADF-STEM imaging andsmall-angle X-ray scattering, Acta Materialia (2010)

12. Dubourdieu C., Gelard I., Salicio O., Saint-girons G., Vilquin B., Hollinger G., Oxides heterostructuresfor nanoelectronics, Int. J. Nanotechnol. (2010) 7, 320-347

13. Ferragut R., Moia F., Fiori F., Lussana D., Riontino G., Small-angle X-ray scattering study of the earlystages of precipitation in a Mg-Nd-Gd (EV31) alloy, J. Alloys and Compounds (2010) 495, 408-411

14. Frederix C., Lefebvre J.M., Rochas C., Seguela R., Stoclet G., Binary blends of linear ethylene copolymersover a wide crystallinity range: Rheology, crystallization, melting and structure properties, Polymer (2010)51, 2903-2917

15. Geandier G., Renault P.O., Le Bourhis E., Goudeau P., Faurie D., Le bourlot C., Djemia P., CastelnauO., Cherif S. M., Elastic-strain distribution in metallic film-polymer substrate composites, Appl. Phys.Lett. (2010) 96 , 041905

16. Geissler E., Hecht A.-M., Horkay F., Scaling behavior of hyaluronic acid in solution with mono- anddivalent ions, Macromolecular Symposia (2010) 291-292, 362-370

17. Grelet E., Dardel s., Bock H., Goldmann M., Lacaze E., Nallet f., Morphology of open films of discotichexagonal columnar liquidcrystals as probed by grazing incidence X-ray diffraction, Eur. Phys. J. E (2010)31, 343-349

18. Haggerty R., Sarin P., Berar J.F., Apostolov Z.D., Kriven W.M., Powder diffraction by fixed incidentangle reflection using a curved position-sensitive detector, J. Appl. Cryst. (2010) 43, 560-569

19. Hestroffer K., Mata R., Camacho D., Leclere C., Tourbot G., Niquet Y.M., Cros A., Bougerol C., RenevierH., Daudin B., The structural properties of GaN/AlN core-shell nanocolumn heterostructures, Nanotech-nology (2010) 21, 415702-1

20. Humbert S., Lame O., Chenal J.M., Rochas C., Vigier G., Small strain behavior of polyethylene: In situSAXS measurements, J. Polymer Sc. B: Polymer Phys. (2010) 48, 1535-1542

21. Humbert S., Lame O., Chenal J.M., Rochas C., Vigier G., New insight on initiation of cavitation insemicrystalline polymers: In-situ SAXS measurements, Macromolecules (2010) 43 (17), 7212-7221

22. Lantiat D., Vivier V., Laberty-Robert C., Grosso D., Sanchez C., Gold nanoelectrode arrays and theirevaluation by impedance spectroscopy and cyclic voltammetry, ChemPhysChem (2010) 11, 1971-1977

23. Laszlo K., Guillermo A., Fluerasu A., Moussaıd A., Geissler E., Microphase structure of poly(N-isopropylacrylamide) hydrogels asseen by small and wide angle X-ray scattering and pulsed fieldgradient NMR ,Langmuir (2010) 26, 4415-4420

24. Laszlo K., Czakkel O., Dobos G., Lodewyckx P., Rochas C., Geissler E., Water vapour adsorption inhighly porous carbons as seen by small and wide angle X-ray scattering, Carbon (2010) 48, 1038-1048

25. Liscio F., Makarov D., Maret M., Doisneau-Cottignies B., Roussel H., Albrecht M., Growth, structureand magnetic properties of FePt nanostructures onNaCl(001) and MgO(001), Nanotechnology (2010) 21,



06560226. Maillet P., Levard C., Larquet E., Mariet C., Spalla O., Menguy N., Masion A., Doelsch E., Rose J., Thill

A., Evidence of Double-Walled Al-Ge Imogolite-Like Nanotubes. A Cryo-TEM andSAXS Investigation,J. Am. Chem. Soc. (2010) 132, in press

27. Marlaud T., Deschamps A., Bley F., Lefebvre W., Baroux B., Evolution of precipitate microstructuresduring the retrogression and re-ageing heat treatment of an Al-Zn-Mg-Cu alloy, Acta Materialia (2010)58 , 4814-4826

28. Marlaud T., Deschamps A., Bley F., Lefebvre W., Baroux B., Influence of alloy composition and heattreatmenton precipitate composition in Al-Zn-Mg-Cu alloys, Acta Materialia (2010) 58 , 248-260

29. Medjoubi K., Bucaille T., Hustache S., Berar J.F., Boudet N., Clemens J.C., Delpierre P., DinkespilerB., Detective quantum efficiency, modulation transfer function and energy resolution comparison betweenCdTe and silicon sensors bump-bonded to XPAD3S, J. Sync. Rad. (2010) 17, 486-495

30. Nikaj E., Stevenson-Royaud I., Seytre G., David L., Espuche E., Dielectric properties of polyamide 6-montmorillonite nanocomposites , J. Non-Crystal. Solids (2010) 356, Issues 11-17, 589-596

31. Nishiyama N., Putaux J.L., Montesanti N., Hazemann J.-L., Rochas C., B–¿A Allomorphic transition innative starch and amylose spherocrystals monitored by in situ synchrotron X-ray diffraction, Biomacro-molecules (2010) 11, 76-87

32. Osorio-madrazo A., Trombotto S., Lucas J.M., Peniche-covas C., David L., Domard A., Kinetics Study ofthe Solid-State Acid Hydrolysis of Chitosan: Evolution of the Crystallinity and Macromolecular Structure,Biomacromolecules (2010) 11(5), 1376-86

33. Pichon P. G., David L., Mechin F., Sautereau H., Morphologies of Cross-Linked Segmented Polyurethanes.Evolution during Maturation and Consequences on Elastic Properties and Thermal Compressive Fatigue,Macromolecules (2010) 43, 1888-1900

34. Popa-Nita S., Alcouffe P., Rochas C., David L., Domard A., Continuum of Structural Organization fromChitosan Solutions to Derived Physical Forms, Biomacromolecules (2010) 11, 6-12

35. Rivas-araiza R., Alcouffe P., Rochas C., Montembault A., David L., Micron Range Morphology of PhysicalChitosan Hydrogels, Langmuir (2010) 26(2), 17495-17504

36. Sel O., Soules A., Ameduri B., Boutevin B., Laberty-Robert C., Gebel G., Sanchez C., Original Fuel-CellMembranes from Crosslinked Terpolymers via a Sol-gel Strategy, Adv. Functional Materials (2010) 20,1090-1098

37. Stoclet G., Lefebvre J.M., Seguela R., Rochas C., New Insights on the strain-induced mesophase ofpoly(D,L-lactide): in situ WAXS and DSC study of the thermo-mechanical stability., Macromolecules(2010) 43, 7228-7237

38. Stoclet G., Seguela R., Lefebvre J.M., Li S., Vert M., Thermal and strain-induced ordering of polylactides:Influence of the stereo-isomer content, Macromolecules (2010) 43, 1488-1498

39. Tardif S., Favre-Nicolin V., Lancon F., Arras E., Jamet M., Barski A., Porret C., Bayle-GuillemaudP., Pochet P., Devillers T., Rovezzi M., Strain and correlation of self-organized Ge1-xMnx nanocolumnsembedded in Ge (001), Phys. Rev. B (2010) 82, 104101-1

40. Vazquez-santos M. B., Martinez-alonso A., Tascon J.M.D., Rouzaud J. N., Geissler E., Laszlo K., The keyrole of microtexture in the graphitisation of PBO fibre chars as seen by X-ray scattering and transmissionelectron microscopy, Carbon (2010) 48, 3968-3970

41. Wattiez B., Gourgues A.F., Deschamps A., Roemer A., Zermout Z., Experimental investigation of mi-crostructure and ageing behaviour of bulk Zn(1-18) Al(0-0.06) Mg alloys, Mat. Sci. Eng. A (2010) 527,7901-7911

42. Weber C., Drogoz A., David L., Domard A., Charles M.H., Verrier B., Delair T., Polysaccharide-basedvaccine delivery systems: Macromolecular assembly, interactions with antigen presenting cells, and invivo immunomonitoring , Journal of Biomedical Materials Research A (2010) 93, 1322-1334

Articles 2011

1. Abidi W., Pansu B., Krishnaswamy R., Beaunier P., Remita H., Imperor-Clerc M., Gold nanoparticlesconfined in lamellar mesophases, RSC Advances (2011) 1, 434-439

2. Aissou K., Otsuka I., Rochas C., Fort S., Halila S., Borsali R., Nano-organization of amylose-b-polystyreneblock copolymer films doped with bipyridine, Langmuir (2011) 27, 4098-4103

3. Alvarez-Murga M., Bleuet P., Marques L., Lepoittevin C., Boudet N., Gabarino G., Mezouar M., HodeauJ.-L., Microstructural mapping of C60 phase transformation into disordered graphite at high pressure,using X-ray diffraction microtomography, J. Appl. Cryst. (2011) 44, 163-171

4. Ayoub G., Zairi F., Frederix C., Gloaguen , Naıt-Abdelaziz M., Seguela R., Lefebvre J.M., Effects of crys-tal content on the mechanical behaviour of polyethylene under finite strains: Experiments and constitutivemodelling, Int. J of Plasticity (2011) 27, 492-511



5. Bach Campa C., Dauchy X., David L., Etienne S., Etude physico-chimique des bouteilles d’eau condi-tionnees en poly(ethylene terephtalate), Materiaux et Techniques (2011) 99, 391-408

6. Bardotti L., Tournus F., Melinon P., Pelarin M., Broyer M., Mass-selected clusters deposited on graphite:Spontaneous organization controlled by cluster surface reaction, Phys. Rev. B (2011) 83, 035425-1-8

7. Barrau S., Vanmansart C., Moreau M., Addad A., Stoclet G., Lefebvre J.M., Seguela R., CrystallizationBehavior of Carbon Nanotube-Polylactide Nanocomposites, Macromolecules (2011) 44, 6496-6502

8. Barucca G., Ferragut R., Fiori F., Lussana D., Mengucci P., Moia F., Riontino G., Formation andevolution of the hardening precipitates in a Mg-Y-Nd alloy, Acta Materialia (2011) 59, 4151-4158

9. Brunet T., Thiebaut O., Charlet E., Block H., Grelet E., Anchoring transition in confined discotic colum-nar liquid crystal films, , Europhys. Lett. (2011) 93, 16004

10. Buttard D., Gentile P., Renevier H., Grazing incidence X-ray diffraction investigation of strains in siliconnanowires obtained by gold catalytic growth, Surf. sci. (2011) 605 , 570-576

11. Cassol Brunner F., Benoit D, Berar J.F., Clemens J.C., Morel C., Study of the charge sharing effect inthe photon-counting pixel detector XPAD3-S, Nucl. Instr. and Meth. A (2011) 633, S111-S113

12. Chassagneux F., Bois L., Simon J.P., Desroches c., Brioude A., Elaboration and characterization ofbimetallic gold-silver nanoparticles supported on mesostructured silica films, J. Mater. Chem. (2011)DOI:, 10.1039/c1jm11331c

13. Chassagneux F., Bois L., Simon J.P., Desroches c., Brioude A., Reorganization induced by silver saltreduction inside a mesostructured block copolymer silica filmJournal of Physical Chemistry C 115, (2011),J. Phys. Chem. C (2011) 115, 25201-25208

14. Choisnard L., Geze A., Vanhaverbeke C., Yameogo J.B.G., Brasme B., Jullien L., Boullanger S., ElfakirC., Wouessidjewe D., Physicochemical characterization of α, β, and γ-cyclodextrins bioesterified withdecanoate chains used as building blocks of colloidal nanoparticles, Biomacromolecules (2011) 12, 3031-3038

15. Combet J., Rawiso M., Rochas C., Hoffman S., Boue F., Structure of polyelectrolytes with mixed mono-valent and divalent counterions: SAXS measurements and Poisson-Boltzmann analysis, Macromolecules(2011) 44, 3039-3052

16. Dal Bo A.G., Soldi V., Giacomelli F.C., Jean B., Pignot-paintrand I., Borsali R., Fort S., Self-assembledcarbohydrate-based micelles for lectin targeting, Soft Matter (2011) 7, 3453-3461

17. Dasgupta D., Srinivasan S., Rochas C., Thierry A., Schroder A., Ajayaghosh A., Guenet J.-M, Insightinto the gelation habit of oligo(para-phenylene vinylene) derivatives: effect of end-groups, Soft Matter(2011) 7, 2797

18. Dasgupta D., Srinivasan S., Rochas C., Ajayaghosh A., Guenet J.-M, Solvent-mediated fiber growth inorganogels, Soft Matter (2011) 7, 9311

19. Decreus B., De Geuser F., Deschamps A., Donnadieu P., Sigli C., Precipitation Sequences in Two Al-Li-CuAlloys, Solid State Phenomena (2011) 172, 267-272

20. Deschamps A., De Geuser F., On the validity of simple precipitate size measurements by small-anglescattering in metallic systems, J. Appl. Cryst. (2011) 44, 343-352

21. Deschamps A., Bastow T.J., De Geuser F., Hill A.J., Hutchinson C.R., In situ evaluation of the mi-crostructure evolution during rapid hardening of an Al-2.5Cu-1.5Mg (wt.%) alloy, Acta Materialia (2011)59(8), 2918-2927

22. Donnadieu P., Shao Y., De Geuser F., Botton G.A., Lazar S., De Boissieu M., Deschamps A., Atomicstructure of T1 precipitates in Al-Li-Cu alloys revisited with HAADF-STEM imaging and small-angleX-ray scattering. , Acta Materialia (2011) 59(2), 462-472

23. Faurie D., Renault P.O., Geandier G., Le Bourhis E., Time resolved synchrotron X-ray strain measure-ments of gold thin film on flexible substrate, Thin Solid Films (2011) 520, 1603-1607

24. Fribourg G., Brechet Y., Deschamps A., Simar A., Microstructure-based modelling of isotropic and kine-matic strain hardening in a precipitation-hardened aluminium alloy, Acta Materialia (2011) 59, 3621-3635

25. Fribourg G., Deschamps A., Brechet Y., Mylonas G., Labeas G., Heckenberger U., Perez M., Microstruc-ture modifications induced by a laser surface treatment in an AA7449 aluminium alloy, Mat. Sci. Eng.A (2011) 528, 2736-2747

26. Galimberti P., Lay S., Antoni-Zdziobek A., Coindeau S., Veron L., Bley F., De Boissieu M., Precipitationand hardening behaviour of the Fe20Co18W alloy aged at 800 ˚C, Intermetallics (2011) 19, 556-562

27. Gamys , Beyou E., Bourgeat-Lami E., David L., Nanostructured Organic-Inorganic Hybrid Films Pre-pared by the Sol-Gel Method from Self-Assemblies of PS-b-PAPTES-b-PS Triblock Copolymers, J. Appl.Polymer Science (2011) 49, 4193

28. Girault B., Eyidi D., Chauveau T., Babonneau D., Renault P.O., Le Bourhis E., Goudeau P., Coppercoverage effect on tungsten crystallites texture development in W/Cu nanocomposite thin films, J. Appl.Phys. (2011) 109, 014305-1-12



29. Gun’ko V. M., Meikle S. T., Kozynchenko O. P., Tennison S. R., Ehrburger-Dolle F., Morfin I., MikhalovskyS., Comparative Characterization of Carbon Adsorbents and Polymer Precursors by Small-Angle X-rayScattering and Nitrogen Adsorption Methods, J. Phys. Chem. C (2011) 115, 10727-10735

30. Gun’ko V. M., Turov V. V., Kozynchenko O. P., Nikolaev V.G., Tennison S. R., Meikle S. T., SnezhkovaE. A., Sidorenko A. S., Ehrburger-Dolle F., Morfin I., Klymchuk D. O., Mikhalovsky S., Activation andstructural and adsorption features of activatedcarbons with highly developed micro-, meso- and macrop-orosity, Adsorption (2011) 17, 453-460

31. Hennet L., Pozdnyakova I., Bytchkov A., Drewitt J.W.E., Kozaily J., Leydier M., Brassamin S., ZanghiD., Fisher H., Greaves G.N., Price D.L., Application of time resolved x-ray diffraction to study the solid-ification of glass-forming melts, High Temperatures - High Pressures (2011) 40, 263-270

32. Hestroffer K., Leclere C., Bougerol C., Renevier H., Daudin B., Polarity of GaN nanowires grown byplasma-assisted molecular beam epitaxy on Si(111), Phys. Rev. B (2011) 84, 245302

33. Hosokawa S., Oh I., Sakurai M., Pilgrim W.-C., Boudet N., Berar J.F., Kohara S., Anomalous x-rayscattering study of GexSe1-x glassy alloys across the stiffness transition composition, Phys. Rev. B(2011) 84, 014201-1-13

34. Hosokawa S., Pilgrim W.-C., Berar J.F., Kohara S., Recent developments of anomalous X-ray scatteringfor non-crystalline materials with help of reverse Monte Carlo modeling: The example of GeSe2 glass ,Physica Status Solidi (2011) A 208, 2544-2551

35. Jacques V., Ravy S., Lebolloc’h D., Pinsolle E., Sauvage M., Livet F., Bulk dislocation core dissociationprobed by coherent X rays in silicon, Phys. Rev. Let. (2011) 106, 065502-1-4

36. Jain A., Jamet M., Barski A., Devillers T., Yu I.S., Porret C., Bayle-Guillemaud P., Favre-Nicolin V.,Garambelli S., Maurel V., Desfonds G., Jacquot J.F., Tardif S., Structure and magnetism of Ge3Mn5

clusters, J. Appl. Phys. (2011) 109, 013911-1-437. Katcho N.A., Richard M.I., Proietti M.G., Renevier H., Leclere C., Favre-Nicolin V., Zhang J.J., Bauer

G., Composition and strain of Ge domes on Si(001) close to the dome/susbtrate interface, Europhys.Lett. (2011) 93, 66004

38. Lacaze E., Apicella A., De Santo M.P., Coursault D., Alba M., Goldmann M., Barberi R., Orderedinterfaces for dual easy axes in liquid crystals, Soft Matter (2011) 7, 1078-1083

39. Laszlo K., Fluerasu A., Moussaıd A., Geissler E., Kinetics of jammed systems: PNIPA gels, Macromolec-ular Symposia (2011) 306-307, 27-32

40. Le Bourhis E., Faurie D., Renault P.O., Geandier G., Thiaudiere D., Castelnau O., Goudeau P., X-ray elastic response of metallic thin film supported by polyimide substrates, J. of Strain Analysis forEngineering Design (2011) 46, 639-649

41. Livi S., Duchet-rumeau J., Gerard J.M., Nanostructuration of ionic liquids in fluorinated matrix: Influ-ence on the mechanical properties, Polymer (2011) 52, 1523-1531

42. Manet S., Lecchi A., Imperor-Clerc M., Zholobenko V., Durand D., Oliveira C.L.P., Pedersen J.S., GrilloI., Meneau F., Rochas C., Structure of micelles of a non-ionic copolymer determined by SANS and SAXS,J. Phys. Chem. B (2011) DOI: 10.1021/jp200212g

43. Manet S., Schmitt V., Imperor-Clerc M., Zholobenko V., Durand D., Oliveira C.L.P., Pedersen J.S.,Gervais C., Baccile N., Babonneau D., Grillo I., Meneau F., Rochas C., Kinetics of the formation ofa 2D-hexagonal silica nano-structures materials by non(ionic copolymer templating in solutionJ. Phys.Chem. B 2011 DOI: 10.1021/jp200213k, J. Phys. Chem. B (2011) DOI: 10.1021/jp200213k

44. Maret M., Liscio F., Makarov D., Simon J.P., Gauthier Y., Albrecht M., Morphology of epitaxial magneticalloy nanostructures grown on WSe2(0001) studied by grazing-incidence small-angle X-ray scattering, J.Appl. Cryst. (2011) 44, 1173-1181

45. Medjoubi K., Hustache S., Picca F., Berar J.F., Boudet N., Bompard F., Breugnon P., Clemens J.C.,Dawiec A., Delpierre P., Dinkespiler B., Godiot S, Logier J.P., Menouni M., Morel C., Nicolas M., PangaudP., Vigeolas E., Performance and Applications of the CdTe- and Si-XPAD3 photon counting 2D detector.,J. Instrum. (2011) 6, C01080

46. Mourier E., David L., Alcouffe P., Rochas C., Mechin F., Fulchiron R., Composition Effects of Thermo-plastic Segmented Polyurethanes on Their Nanostructuring Kinetics with or without Preshear, J. PolymerSc. B: Polymer Phys. (2011) 49(11), 801-811

47. Osorio-madrazo A., David L., Trombotto S., Domard A., Highly crystalline chitosan produced by multi-steps acid hydrolysis in the solid-state, Carbohydrate Polymers (2011) 83(4), 1730-1739

48. Pacheco N., Garnica-Gonzalez M., Gimeno M., Barzana E., Trombotto S., David L., Shirai K., Structuralcharacterization of chitin and chitosan obtained by biological and chemical methods, Biomacromolecules(2011) 12(9), 3285

49. Paineau E., Bihannic I., Baravian C., Philippe A.M., Davidson I., Levitz P., Funari S.S., Rochas C.,Michot L.J., Aqueous suspensions of natural swelling clay minerals. 1. Structure and electrostatic inter-



actions, Langmuir (2011) 27, 5562-557350. Pansu B., Lecchi A., Constantin D., Imperor-Clerc M., Veber M., Dozov I., Insertion of Gold Nanopar-

ticles in Fluid Mesophases : Size Filtering and Control of Interactions , J. Phys. Chem. C (2011) 115,17682-17687

51. Perrier M., Deschamps A., Donnadieu P., De Geuser F., Danoix F., Bouaziz O., Brechet Y., PrecipitationSequence and Kinetics in an Fe-Si-Ti Alloy, Solid State Phenomena (2011) 172, 833-838

52. Porto L.C., Aissou K., Giacomelli F.C., Baron T., Rochas C., Pignot-paintrand I., Armes S.P., SoldiV., Borsali R., Nanostructured films made from zwitterionic phosphorylcholine diblock copolymer systems,Macromolecules (2011) 44, 2240-2244

53. Reibstein S., Wondraczek L., De Ligny D., Krolikowski S., Sirotkin S., Simon J.P., Martinez V., Cham-pagnon B., Structural heterogeneity and pressure-relaxation in compressed borosilicate glasses by in situsmall angle X-ray scattering, J. Chem. Phys. (2011) 134, 204502-1

54. Renault P.O., Krauss C., Le Bourhis E., Geandier G., Benedetto A., Grachev S.Y., Barthel E., In situthermal residual stress evolution in ultrathin ZnO and Ag films studied by synchrotron X-ray diffraction,Thin Solid Films (2011) 520, 1390-1394

55. Roeser J., Moingeon F., Heinrich B., Masson P., Arnaud-Neu F., Rawiso M., Mery S., Dendronizedpolymers with peripheral oligo(ethylene oxide) chains: Thermoresponsive behavior and shape anisotropyin solution, Macromolecules (2011) 44, 8925-8935

56. Scott C., Remy B., Collet J.L., Cael A., Bao C., Danoix F., Malard B., Curfs C., Precipitation strength-ening in high manganese austenitic TWIP steels, Int. J. of Mater. Res. (2011) 102, 538-549

57. Serrero , Trombotto S., Bayon Y., Gravagna P., Montanari S., David L., Polysaccharide-Based Adhesivefor Biomedical Applications:Correlation between Rheological Behavior and Adhesion, Biomacromolecules(2011) 12, 1556

58. Simeone D., Baldinozzi G., Gosset D., Zalczer G., Berar J.F., Rietveld refinements performed on meso-porous ceria layers, J. Appl. Cryst. (2011) 44, 1205-1210

59. Soldo-Olivier Y., Lafouresse M. C., De Santis M., Lebouin C., De Boissieu M., Sibert E., Hydrogen Electro-Insertion into Pd/Pt(111) Nanofilms: An in Situ Surface X-ray Diffraction Study, J. Phys. Chem. C(2011)

60. Soules A., Ameduri B., Boutevin B., David G., Perrin R., Gebel G., Soules A./Ameduri B./BoutevinB./David G./Perrin R./Gebel G. - Proton conducting sulphonated fluorinated poly(styrene) crosslinkedelectrolyte membranes, Fuel Cells (2011), s 11, 611-619

61. Steuwer A., Dumont D., Altenkirch J., Birosca S., Deschamps A., Prangnell P.B., Withers P.J., A com-bined approach to microstructure mapping of an Al-Li AA2199 friction stir weld, Acta Materialia (2011)59, 3002-3011

62. Stoclet G., Seguela R., Lefebvre J.M., Morphology, thermal behavior and mechanical properties of binaryblends of compatible biosourced polymers: Polylactide/polyamide11 , Polymer (2011) 52, 1417-1425

63. Stoclet G., Seguela R., Lefebvre J.M., Li S., Vert M., Thermal and strain-induced chain ordering in lacticacid stereocopolymers: Influence of the composition in stereomers, Macromolecules (2011) 44, 4961-4969

64. Tertre E., Ferrage E., Bihannic I., Michot L.J., Pret D., Influence of the ionic strength and solid/solutionratio on Ca(II)-for-Na+ exchange on montmorillonite. Part 2: Understanding the effect of the m/V ratio.Implications for pore water composition and element transport in natural media, J. Colloid Interface Sci.(2011) 363, 334-347

65. Toth J., Torocsik A., Tombacz E., Olah E., Heggen M., Li C., Klumpp E., Geissler E., Laszlo K.,Interaction of phenol and dopamine with commercial MWCNTs, J. Colloid Interface Sci. (2011)

66. Vazquez-santos M. B., Martinez-alonso A., Tascon J.M.D., Rouzaud J. N., Geissler E., Laszlo K., Com-plementary X-ray scattering and transmission electron microimagery of nanostructure development inthermally treated PBO fibers, Carbon (2011) 49, 2960-2970.

67. Wiemer C., Lamperti A., Lamagna L., Salicio O., Molle A., Fanciulli M., Detection of the Tetragonal andMonoclinic Phases and their Role on the Dielectric Constant of Atomic Layer Deposited La-doped ZrO2Thin Films on Ge (001), ECS Trans. (2011) 35 (3), 481-490

68. Wiemer C., Lamperti A., Lamagna L., Salicio O., Molle A., Fanciulli M., Detection of the tetragonalphase in atomic layer deposited La-doped ZrO2 thin films on germanium, J. Electrochem. Soc (2011)158, G194-G198

69. Zappone B., Lacaze E., Hayeb H., Goldmann M., Boudet N., Barois P., Alba M., Self-ordered arrays oflinear defects virtual singularities in thin smectic-A films, Soft Matter (2011) 7, 1161-1167

Proceedings 2011 not cited in Conferences lists

1. Krauss C., Geandier G., Conchon F., Renault P.O., Le Bourhis E., Benedetto A., Grachev S.Y., GoudeauP., Barthel E., Thermal residual stress relaxation in sputtered ZnO film on (100) Si substrate studied in



situ by synchrotron X-ray diffraction, Mater. Sci. Forum (2011) 681, 127-132

Other publications 2011

1. Maillet P., Levard C., Larquet E., Mariet C., Spalla O., Menguy N., Masion A., Doelsch E., Rose J., ThillA., Evidence of double-walled Al-Ge imogolitelike nanotubes. A cryo-TEM, AFM and SAXSinvestigation,ESRF Highlights (2011) Structure of materials, 29-30

Articles 2012

1. Agulhon P., Robitzer M., David L., Quignard F., Structural regime identification in ionotropic alginategels: Influence of the cation nature and alginate structure, Biomacromolecules (2012) 13, 215-220

2. Alvarez-Murga M., Bleuet P., Hodeau J.-L., Diffraction/scattering computed tomography for three-dimensionalcharacterization of multi-phase crystalline and amorphous materials, J. Appl. Cryst. (2012) 45, 1109-1124

3. Antav V., Simonot L., Babonneau D., Camelio S., Pailloux F., Guerin P., Monitoring the reactivity of Agnanoparticles in oxygen atmosphere by using in situ and real-time optical spectroscopy, J. of nanophotonics(2012) 6, 061502-1-061502-13

4. Bauer C., Bauduin P., Dufreche J.F., Zemb T., Diat O., Liquid/liquid metal extraction: Phase diagramtopology resulting from molecular interactions between extractant, ion, oil and water, Eur. Phys. J-Spec.Top. (2012) 213, 225-241

5. Bourgeat-Lami E., Farzi G.A., David L., Putaux J.L., Mckenna T.F.L., Silica encapsulation by miniemul-sion polymerization: Distribution and localization of the silica particles in droplets and latex particles,Langmuir (2012) 28, 6021-6031

6. Brombacher C., Schletter H., Daniel m, Matthes P., Johrmann N, Maret M., FePtCu alloy thin films:Morphology, L10 chemical ordering, and perpendicular magnetic anisotropy , J. Appl. Phys. (2012) 112,073912

7. Candau N., Chazeau L., Chenal J.M., Gauthier C., Ferreira J., Munch E., Rochas C., - Characteristictime of strain induced crystallization of crosslinked natural rubber, Polymer (2012) 53, 2540-2543

8. Chen p., Nishiyama Y., Mazeau K., Torsional entropy at the origin of the reversible temperature-inducedphase transition of cellulose, Macromolecules (2012) 45, 362-368

9. Cheng y., Gray K.M., David L., Royaud I., Payne G.F., Characterization of the cathodic electrodepositionof semicrystalline chitosan hydrogel, materials letters (2012) 87, 97-100

10. Combet J., Lorchat P., Rawiso M., Salt-free aqueous solutions of polyelectrolytes: Small angle X-ray andneutron scattering characterization, Eur. Phys. J-Spec. Top. (2012) 213, 243-265

11. Cushen J.D., Otsuka I., Bates C.M., Halila S., Fort S., Rochas C., Easley J.A., Borsali R., Oligosaccharide/silicon-containing block copolymers with 5 nm features for lithographic applications, ACS Nano (2012) 6, 3424-3433

12. Czakkel O., Szekely E., Koczka B., Geissler E., Laszlo K., Drying of resorcinol formaldehyde gels withCO2 medium, Micropor. Mesopor. Mat. (2012) 148, 3442

13. Czakkel O., Geissler E., Szilagyi I.M., Laszlo K., TiO2-doped resorcinol-formaldehyde (RF) polymer andcarbon gels with photocatalytic activity, Nanomaterials and the Environment (2012) 2, 23-30

14. Dal Bo A.G., Soldi V., Giacomelli F.C., Travelet C., Jean B., Pignot-paintrand I., Borsali R., FortS., Self-assembly of amphiphilic glycoconjugates into lectin-adhesive nanoparticles, Langmuir (2012) 28,1418-1426

15. Dal Pont K., Gerard J.F., Espuche E., Modification of α-ZrP nanofillers by amines of different chainlength: Consequences on the morphology and mechanical properties of styrene butadiene rubber basednanocomposites, Eur. Polym. J. (2012) 48, 217-227

16. Dasgupta D., Thierry A., Rochas C., Ajayaghosh A., Guenet J.-M, Key role of solvent type in organogela-tion, Soft Matter (2012) 8, 8714-8721

17. Da Silva-Cadoux C., Hazemann J.-L., Testemale D., Proux O., Rochas C., Influence of monovalent ionson density fluctuations in hydrothermal aqueous solutions by small angle X-ray scattering, J. Chem. Phys.(2012) 136, 044515-1-044515-10

18. Delhorbe V., Thiry X., Cailleteau C., Mourier E., Bathfield M., Chikh L., Espuche E., Gebel G., MorinP., Fluorohexane network and sulfonated PEEK based semi-IPNs for fuel cell membranes, J. of MembraneScience (2012) 389, 57-66

19. Deschamps A., Fribourg G., Brechet Y., Chemin J.L., Hutchinson C.R., In situ evaluation of dynamicprecipitation during plastic straining of an Al-Zn-Mg-Cu alloy, Acta Materialia (2012) 60, 1905-16

20. Deschamps A., Sigli C., Mourey T., De Geuser F., Lefebvre W., Experimental and modelling assessmentof precipitation kinetics in an Al-Li-Mg alloy, Acta Materialia (2012) 60, 1917-28



21. Deschamps A., De Geuser F., Quantitative Characterization of Precipitate Microstructures in MetallicAlloys Using Small-Angle Scattering, Metallurgical and Materials Trans. (2012)

22. De Boissieu M., Atomic structure of quasicrystals, Structural Chemistry (2012) 23(4), 965-97623. De Boissieu M., Phonons, phasons and atomic dynamics in quasicrystals, Chem. Soc. Rev. (2012) 41,

6778-678624. De Geuser F., Bley F., Deschamps A., A new method for evaluating the size of plate like precipitates by

small angle scattering, J. Appl. Cryst. (2012) 45, 1208-121825. Dora C.L., Silva L.F.C., Putaux J.L., Nishiyama Y., Pignot-paintrand I., Borsali R., Poly(ethylene glycol)

hydroxystearate-based nanosized emulsions: Effect of surfactant concentration on their formation andability to solubilize quercetin, J. of Biomedical Nanotechnology (2012) 8, 202-210

26. Dupre L., Buttard D., Leclere C., Renevier H., Gentile P., Gold contamination in VLS-grown Si nanowires:Multiwavelength anomalous diffraction investigations, Chemistry of Materials (2012) 24, 4511-4516

27. D Arrigo g., Di Meo C., Geissler E., Coviello T., Alhaique F., Matricardi P., Hyaluronic acid methacrylatederivatives and calcium alginate interpenetrated hydrogel networks for biomedical applications: Physico-chemical characterization and protein release, Colloid and Polymer Science (2012) 290, 1575-1582

28. Euchner H., Yamada T., Schober H., Rols S., Mihalkovic M., Tamura R., Ishimasa T., De Boissieu M.,Ordering and dynamics of the central tetrahedron in the 1/1 Zn6Sc periodic approximant to quasicrystal,J. Phys. Cond. Mat. (2012) 24, 415403

29. Favre-Nicolin V., Proietti M.G., Leclere C., Katcho N.A., Richard M.I., Renevier H., Multiwavelengthanomalous diffraction and diffraction anomalous fine structure to study composition and strain of semi-conductor nanostructures, Eur. Phys. J-Spec. Top. (2012) 208 , 189-216

30. Galimberti P., Lay S., Antoni-Zdziobek A., Precipitation and age-hardening in the Fe-27Co-8Mo alloy,Intermetallics (2012) 22, 33-40

31. Gamys , Beyou E., Bourgeat-Lami E., David L., Alcouffe P., Tunable morphologies from bulk self-assemblies of poly(acryloxypropyl triethoxysilane)-b-poly(styrene)-b-poly(acryloxypropyl triethoxysilane)triblock copolymers, Macromol. Chem. Phys. (2012) 213, 10-18

32. Gamys , Beyou E., Bourgeat-Lami E., David L., Oberdisse J., SAXS and SANS characterization of gelablepolystyrene-b-poly(acryloxy propyl triethoxysilane) (PS-b-PAPTES) diblock copolymer micelles before andafter hydrolysis-condensation, Soft Matter (2012) 8, 6564-6572

33. Ghezzi G., Morel R., Brenac A., Boudet N., Audier M., Fillot L.A., Maitrejean S., Hippert F., Crystal-lization of Ge2Sb2Te5 nanometric phase change material clusters made by gas-phase condensation, Appl.Phys. Lett. (2012) 101, 233113-1-233113-4

34. Gondikas A.P., Masion A., Auffan M., Lau B.L.T., Hsu Kim H., Early-stage precipitation kinetics of zincsulfide nanoclusters forming in the presence of cysteine, Chemical Geology (2012) 329, 10-17

35. Goycoolea F.M., Valle Gallego A., Stefani R., Menchicchi B., David L., Rochas C., Chitosan-basednanocapsules: physical characterization, stability in biological media and capsaicin encapsulation, Col-loid and Polymer Science (2012) 290, 1423-1434

36. Hosokawa S., Pilgrim W.-C., Berar J.F., Kohara S., Anomalous X-ray scattering studies on semiconduct-ing and metallic glasses, Eur. Phys. J-Spec. Top. (2012) 208, 291-304

37. Hosokawa S., Pilgrim W.-C., Hohle A., Szubrin D., Boudet N., Berar J.F., Key experimental informationon intermediate-range atomic structures in amorphous Ge2Sb2Te5 phase change material, J. Appl. Phys.(2012) 111, 083517-1-083517-9

38. Humbert S., Lame O., Chenal J.M., Seguela R., Vigier G., Memory effect of the molecular topology oflamellar polyethylene on the strain-induced fibrillar structure, Eur. Polym. J. (2012) 48, 1093-1100

39. Katcho N.A., Richard M.I., Proietti M.G., Renevier H., Leclere C., Favre-Nicolin V., Zhang J.J., BauerG., Diffraction Anomalous Fine Structure study and atomistic simulation of Ge/Si nanoislands, Nucl.Instr. and Meth. B (2012) 284, 58-63

40. Lanneluc R., Bounor-Legare V., Fulchiron R., Katena J., Otaigbe J.U., Toward forced assembly of insitu low-density polyethylene composites reinforced with low-Tg phosphate glass fibers: Effects of matrixcrystallization and shear deformation, Polymer Engineering & Science (2012) 52, 2090-2098

41. Leroy F., Cheynis F., Passante T., Muller P., Dynamics, anisotropy, and stability of silicon-on-insulatordewetting fronts, Phys. Rev. B (2012) 85, 195414-1-195414-6

42. Maret M., Brombacher C., Matthes P., Makarov D., Boudet N., Albrecht M., Anomalous X-ray diffractionmeasurements of long-range order in (001)-textured L1-0 FePtCu thin films, Phys. Rev. B (2012) 86,024204

43. Osorio-madrazo A., Eder M., Rueggeberg M., Pandey J.K., Harrington M.J., Nishiyama Y., Putaux J.L.,Rochas C., Burgert I., Reorientation of cellulose nanowhiskers in agarose hydrogels under tensile loading,Biomacromolecules (2012) 13(3), 850-856

44. Otsuka I., Isono T., Rochas C., Halila S., Fort S., Satoh T., Kakuchi T., Borsali R., 10 nm Scale Cylinder-



Cubic Phase Transition Induced by Caramelization in Sugar-Based Block Copolymers , ACS Macro Letters(2012) 1, 1379-1382

45. Palancher H., Bos S., Berar J.F., Margiolaki I., Hodeau J.-L., - X-ray resonant powder diffraction, Eur.Phys. J-Spec. Top. (2012) 208, 275-289

46. Piskorska E., Holy V., Caha O., Wolska A., Gust A., Kruse C., Kroncke H., Falta J., Hommel D.,Complementary information on CdSe/ZnSe quantum dot local structure from extended X-ray absorptionfine structure and diffraction anomalous fine structure measurements, J. Alloys and Compounds (2012)523, 155-160

47. Poulos A.S., Constantin D., Davidson P., Imperor-Clerc M., Pansu B., Rouziere S., The interaction ofcharged nanoparticles at interfaces, Europhys. Lett. (2012) 100, 18002 1-5

48. Roberts D., Rochas C., Saiani A., Miler A.F., Effect of Peptide and Guest Charge on the Structural,Mechanical and Release Properties of beta-Sheet Forming Peptide, Langmuir (2012) 28, 16196-16206

49. Sabard D., Gouanve F., Espuche E., Fulchiron R., Seytre G., Fillot L.A., Trouillet-fonti L., Influenceof film processing conditions on the morphology of polyamide 6: Consequences on water and ethanolasorption properties, J. Membrane Science (2012) 415-416, 670-680

50. Schmidt T., Borsali R., Giacomelli F.C., Nanostructure of polystyrene-b-poly(2-hydroxyethyl methacrylate)and derivatives with phosphonic diacid groups, J. Braz. Chem. Soc. (2012) 23, 747-752

51. Simeone D., Baldinozzi G., Gosset D., Le Caer S., Berar J.F., Grazing incidence X-ray diffraction for thestudy of polycrystalline layers, Thin Solid Films (2012)

52. Stoclet G., Seguela R., Vanmansart C., Rochas C., Lefebvre J.M., WAXS study of the structural reorga-nization of semi-crystalline polylactide under tensile drawing, Polymer (2012) 53, 519-528

53. Vachoud L., Pochat-bohatier C., Chakrabandhu Y., Bouyer D., David L., Preparation and characteriza-tion of chitin hydrogels by water vapor induced gelation route, Int. J. of Biological Macromolecules (2012)51, 431-439

54. Vazquez-santos M. B., Martinez-alonso A., Tascon J.M.D., Rouzaud J. N., Rochas C., Geissler E., Nanos-tructure evolution in heat-treated porous carbons derived from PBO polymer , J. Alloys and Compounds(2012) 536S, 464-468

55. Venault A., Pochat C., Bouyer D., Vachoud L., David L., Faure C., Preparation and characterization ofcomposite chitosan/active carbon physical hydrogels for wound-dressing materials, Carbohydrate Polymers(2012)

Articles 2013

1. Antad V., Simonot L., Babonneau D., Tuning the surface plasmon resonance of silver nanoclusters byoxygen exposure and low-energy plasma annealing, Nanotechnology (2013) 24, 045606-1-045606-7

2. Blanc n., Diıaz-Sanchez L.E., Ramos A.Y., Tournus F., Tolentino H.C.N., Proux O., Tamion A., BardottiL., Dupuis V., Tuaillon-Combes J., Element-specific quantitative determination of the local atomic orderin CoPt alloy nanoparticles: Experiment and theory, Phys. Rev. B (2013) 87, 155412-1-155412-5

3. Bourgeois F., Gergaud P., Renevier H., Leclere C., Feuillet G., Low temperature oxidation mechanisms ofnanocrystalline magnetite thin film , J. Appl. Phys. (2013) 113, 013510-1-013510-8

4. Collette F.M., Thominette F., Mendil-jakani H., Gebel G., Structure and transport properties of solution-cast Nafion R©membranes subjected to hygrothermal aging, J. Membrane Science (2013) 435, 242-252

5. Decreus B., Deschamps A., De Geuser F., Donnadieu P., Sigli C., Weyland M., The influence of Cu/Liratio on precipitation in Al-Cu-Li-x alloys, Acta Materialia (2013) 61, 2207-2218

6. Decreus B., Deschamps A., De Geuser F., Sigli C., Influence of natural ageing and deformation onprecipitation in an Al-Cu-Li alloy, Adv. Eng. Mat. (2013) 15, 1082-1085

7. Delhorbe V., Cailleteau C., Chikh L., Guillermo A., Gebel G., Morin P., Fichet o., Influence of the mem-brane treatment on structure and properties of sulfonated poly(etheretherketone) semi-interpenetratingpolymer network, J. Membrane Science (2013) 427, 283-292

8. Deschamps A., De Geuser F., Quantitative Characterization of Precipitate Microstructures in MetallicAlloys Using Small-Angle Scattering, Metallurgical and Materials Trans. (2013) A 44, 77-86

9. Desormes M., Montembault A., Lucas J.M., Rochas C., Bouet T., David M.L., Spinning of hydroalcoholicchitosan solutions, Carbohydrate Polymers (2013) 98, 50-63

10. Djaziri s., Faurie D., Renault P.O., Geandier G., Le Bourhis E., Goudeau P., Yield surface of polycrys-talline thin films as revealed by non-equibiaxial loadings at small deformation, Acta Materialia (2013) 61,5067-5077

11. Dupre L., Gorisse t., Letrouit Lebranchu A, Bernardin T., Gentile P., Renevier H., Buttard D., Ultra-dense and planarized antireflective vertical silicon nanowire array using a bottom-up technique, NanoscaleResearch Letters (2013) 8, 123-1-123-7



12. Dupuis V., Blanc n., Diaz-sanchez L.E., Hillion A., Tamion A., Tournus F., Pastor G.M., Specific localrelaxation and magnetism in mass-selected CoPt nanoparticles, Eur. Phys. J. B (2013) 86, 83-1-83-4

13. Faurie D., Geandier G., Renault L., Renault P.O., Le Bourhis E., Thiaudiere D., Sin2 Ψ analysis in thinfilms using 2D detectors: Non-linearity due to set-up, stress state and microstructure, Thin Solid Films(2013) 530, 25-29

14. Fiorentino B., Fulchiron R., Duchet-rumeau J., Bounor-Legare V., Majeste J.C., Controlled shear-inducedmolecular orientation and crystallization in polypropylene/talc microcomposites - Effects of the talc nature,Polymer (2013) 54, 2764-2775

15. Frederix C., Beauchene P., Seguela R., Lefebvre J.M., Kinetics of the non-isothermal fusion-welding ofunlike ethylene copolymers over a wide crystallinity range, Polymer (2013) 54, 2755-2763

16. Gebel G., Structure of membranes for fuel cells: SANS and SAXS analyses of sulfonated PEEK mem-branes and solutions, Macromolecules (2013) 46, 6057-6066

17. Goncalves P.F., Lalatonne Y., Melro L., Badino G., Ferreira M.F.M., David M.L., Geraldes C.F.G.C.,Motte L., Martins J.A., New dextrin nanomagnetogels as contrast agents for magnetic resonance imaging,J. Mater. Chem. (2013) B 1, 5853-5864

18. Greasty R.J., Richardson R.M., Klein S., Chems D., Thomas R., Pizzey C., Terrill N., Rochas C.,Electro-induced orientational ordering of anisotropic pigment nanoparticles R. J. Greasty, R. Richardson,D.Cherns, R. Thomas, Phil. Trans. R. Soc. A 371, (2013)., Phil. Trans. R. Soc. (2013) 371

19. Guilbaud J.B., Rochas C., Miller A.F., Saiani A., Effect of enzyme concentration of the morphology andproperties of enzymatically triggered peptide hydrogels, Biomacromolecules (2013) 14, 1403-1411

20. Hosokawa S., Koura A., Berar J.F., Pilgrim W.-C., Kohara S., Shimojo F., Does the 8-N bonding rulebreak down in As2Se3 glass?, Europhys. Lett. (2013) 102, 66008-1-66008-6

21. Isono T., Otsuka I., Kondo Y., Halila S., Fort S., Rochas C., Satoh T., Borsali R., Sub-10 nm nano-organization in AB2- and AB3-type miktoarm star copolymers consisting of maltoheptaose and polycapro-lactone, Macromolecules (2013) 46, 1461-1469

22. Isono T., Otsuka I., Suemasa D., Rochas C., Satoh T., Borsali R., Synthesis, self-assembly, and ther-mal caramelization of maltoheptaose-conjugated polycaprolactones leading to spherical, cylindrical, andlamellar morphologies, Macromolecules (2013) 46, 8932-8940

23. Kreuer K.D., Portale G., A critical revision of the nano-morphology of proton conducting ionomers andpolyelectrolytes for fuel cell applications, Adv. Functional Materials (2013) 23, 5390-5397

24. Leclere C., Fellmann V., Bougerol C., Cooper D., Gayral B., Proietti M.G., Renevier H., Daudin B., Strainassisted inter-diffusion in GaN/AlN quantum dots, J. Appl. Phys. (2013) 113, 034311-1-034311-10

25. Muller W., Dejugnat C., Zemb T., Dufreche J.F., Diat O., Muller W. , Dejugnat C. , Zemb T. , DufrecheJ.F. , Diat O. - How do anions affect self-assembly and solubility of cetylpyridinium surfactants in water,J. Phys. Chem. B (2013) 117, 1345-1356

26. Ndong G., Picardi G., Licitra C., Rouchon D., Eymery J., Ossikovski R., Ndong G. , Picardi G. , LicitraC. , Rouchon D. , Ossikovski R. - Determination of the biaxial stress in strained silicon nano-stripesthrough polarized oblique incidence Raman spectroscopy, J. Appl. Phys. (2013) 114, 164309-1-164309-8

27. Nguyen Thanh T., Robert C., Giudicelli E., Letoublon A., Cornet C., Ponchet A., Rohel T., Balocchi A.,Micha J.S., Quantitative study of microtwins in GaP/Si thin film and GaAsPN quantum wells grown onsilicon substrates, J. Cryst. Growth (2013) 378, 25-28

28. Nguyen Thanh T., Robert C., Letoublon A., Quinci T., Giudicelli E., Almosni S., Boudet N., PonchetA., Synchrotron X-ray diffraction analysis for quantitative defect evaluation in GaP/Si nanolayers, ThinSolid Films (2013) 541, 36-40

29. Otsuka I., Tallegas S., Sakai Y., Rochas C., Halila S., Fort S., Bsiesy A., Baron T., Borsali R., Control of10 nm Scale Cylinder Orientation in Self Organized Sugar-Based Block Copolymer Thin Films, Nanoscale(2013) 5, 2637-2641

30. Pierret A., Bougerol C., Murcia-Mascaros S., Cros A., Renevier H., Gayral B., Daudin B., Growth,structural and optical properties of AlGaN nanowires in the whole composition range, Nanotechnology(2013) 24, 115704-1-115704-9

31. Pochat-bohatier C., Venault A., Bouyer D., Vachoud L., David L., Faure C., Development and character-ization of composite chitosan/active carbon hydrogels for a medical application, J. Appl. Polymer Science(2013) 128, 2945-2953

32. Quinci T., Kuyyalil J., Nguyen Thanh T., Wang Y.P., Almosni S., Letoublon A., Rohel T., TavernierK., Chevalier N., Dehaese O., Boudet N., Cornet C., Wang Y.P. , F. , Durand - Defects limitation inepitaxial GaP on bistepped Si surface using UHVCVD-MBE growth cluster, J. Cryst. Growth (2013) 380,157-162

33. Roux R., Ladaviere C., Montembault A., David L., Delair T., Shear thinning three-dimensional colloidalassemblies of chitosan and poly(lactic acid) nanoparticles, J. Phys. Chem. B (2013) 117, 7455-7464


5.3 Conferences 5 SCIENTIFIC PRODUCTION 2009-2013

34. Saiani A., Miller A.F., undefined, undefined, Controlling network topology and mechanical properties ofco-assembling peptide hydrogels, Biopolymers (2013), DOI: 10.1002/bip.22435

35. Schmitt J., Imperor-Clerc M., Michaux F., Blin J.L., Stebe M.J., Pedersen J.S., Meneau F., Formation ofnanostructured silica materials templated with nonionic fluorinated surfactant followed by in situ SAXS,Langmuir (2013) 29, 2007-2023

36. Tallegas S., Baron T., Gay G., Aggrafeil C., Salhi B., Chevolleau T., Cunge G., Tiron R., Aissou K.,Otsuka I., Halila S., Fort S., Borsali R., Block copolymer technology applied to nanoelectronics, PhysicaStatus Solidi (2013) 10, 1195-1206

37. Thevenon A., Fulchiron R., Evolution of polypropylene morphology in the rubbery state under uniaxialstrain, Macromolecular Materials & Engineering (2013)

38. Xiong B., Lame O., Chenal J.M., Rochas C., Seguela R., Vigier G., In-situ SAXS study and modelingof the cavitation/crystal-shear competition in semi-crystalline polymers: Influence of temperature andmicrostructure in polyethylene , Polymer (2013) 54, 5408-5418

39. Yamada T., Euchner H., Gomez C.P., Takakura H., Tamura R., De Boissieu M., Short- and long-rangeordering during the phase transition of the Zn6Sc 1/1 cubic approximant, J. Phys. Cond. Mat. (2013)25, 205405-1-205405-13

5.3 Conferences

Invited Conferences 2009

1. Deschamps A., Small-Angle scattering techniques: tools for the understanding of the kinetics of complexprecipitation phenomena in metallic alloys. , International Conference on Advanced Materials (ICAM2009 ) , sept. 2009 Rio de Janiero, Brazil. Proceedings: to be published in Journal of Materials Science

2. Maitrejean S., Jousseaume V., Olivier S., Haumesser PH., Chevalier N., Mariolle D., Bleuet P., Ger-gaud P., Advanced characterizations for materials process and integration. Selected examples, AdvancedMetallization Conference 2009 (AMC 2009). Oct. 13-15 2009, Baltimore ,

3. Paineau E., Michot L.J., Bihannic I., Baravian C., Davidson P., Liquid Crystal Phases in Aqueous Sus-pensions of Natural Beidellite. L. J. Michot, , International Clay Conference , Italie

Other Conferences 2009

1. Gloaguen , Lefebvre J.M., Stoclet G., Miri V., Peurton F., Seguela R., Devaux J., Sclavons M., Spatialorganization and mechanical behavior of polymer clay nanocomposites, POLYCHAR17 (POLYCHAR17), 20-24 Avril 2009 Rouen

2. Mourglia E., Long L., Odoni P., Sotta P., Rochas C., Nanocomposites & , ,3. Paineau E., Michot L.J., Baravian C., Bihannic I., Levitz P., Davidson P., Sol-Gel And Isotropic/Nematic

Transitions In Aqueous Suspensions of Swelling Clay Minerals: a Structural And Rheological Study OnSize-Selected Particles. L. J. Michot, IACIS, New York 2009, IACIS (IACIS) , 2009 New York

4. Paineau E., Michot L.J., Baravian C., Antonova K., Dozov I., Davidson P., Imperor-Clerc M., Proprietescristal-liquide des suspensions d’argile naturelle., CFCL , Orsay

5. Stoclet G., Seguela R., Lefebvre J.M., Etude des arrangements locaux dans la phase amorphe de Poly(acidelactiques) de differentes puretes optique, Journee Jeunes Polymeristes du Nord , 2-12-2009 Villeneuved’Ascq

6. Stoclet G., Seguela R., Lefebvre J.M., Rochas C., Chenal J.M., Etude in-situ par diffraction et diffusiondes rayons X de l’evolution structurale en traction uni-axiale de l’acide polylactique, Colloque analyse despolymeres par rayonnement , 5-6 Fevrier 2009 Nancy

7. Stoclet G., Seguela R., Lefebvre J.M., Comportement mecanique et evolution structural du Poly(acidelactique) en relation avec la deformation plastique, Deformation des Polymeres Solides (DEPOS 22) ,18-20 Mars 2009 La Colle sur Loup


1. Guenet J.-M, Thermoreversible polymer gels as hosts to functional self-assembled systems, 2nd Interna-tional workshop on soft matter and biological systems , 28-30 avril 2010 Fes, Maroc

2. Guenet J.-M, Functional self-assembled systems hosted by a thermoreversible polymer gel , MACRO 2010, 15-17 Decembre 2010 New-Delhi, Inde

3. Stoclet G., Seguela R., Lefebvre J.M., Rochas C., In situ WAXS and ex situ DSC characterization of thestrain-inducedstructural evolution of poly(D,L-lactide) under tensile drawing, 4th International Conferenceon Polymer Behavior, IUPAC , 20-23 Septembre 2010 Lodz (Pologne)


5.3 Conferences 5 SCIENTIFIC PRODUCTION 2009-2013

Published Conferences 2010

1. Marlaud T., Deschamps A., Lefebvre W., Evolution of the Nanostructure of a 7xxx Alloy during retorgres-sion and Re-ageing as investigated by ASAXS and atom probe tomography, 12th Internation conference onAluminium Alloy (12th ICAA) , 5-9 Sept 2010 Yokohama, Japan. Proceedings: Proceedings of the 12thInternational Conference on Aluminium Alloys, 2010 The Japan Institute of Light Metals, pp. 1690-1695


1. Bigarre J., Galiano H., Gebel G., Niepceron F., Marechal M., Composite PVDF-HFP-based proton-exchange membranes embedding sulfonated , International Society of Electrochemistry , 26 Septembre -1er octobre 2010 Nice

2. Dahmani M., Rochas C., Measurement of the agarose gel pore size using static light scattering, 8thInternational Conference on Polymer-Solvent Complexes and Intercalates , 5-8 juillet 2010 Strasbourg

3. Geze , Putaux J.L., Nishiyama N., Yameogo J., Rochas C., Structured nanoparticles from self-assembledcyclodextrin derivatives., 15th International Cyclodextrin Symposium , 9-12 Mai 2010 Vienne, Autriche

4. Gloaguen , Lefebvre J.M., Peurton F., Seguela R., Stoclet G., Devaux J., Sclavons M., Structural orga-nization and Mecahnical Behavior of PLA Nanocomposites with untreated Clay, International Conferenceon Nanostructured Polymers and Nanocomposites , 28 - 30 April 2010 Madrid

5. Kamar Z., Mesini P., Dahmani M., Fethi F., Rochas C., Guenet J.-M, Complexation of iPS gel fibrils bynanotubules, 8th International Conference on Polymer-Solvent Complexes and Intercalates ,

6. Stoclet G., Seguela R., Lefebvre J.M., Rochas C., In situ WAXS and DSC characterization of thestrain-induced structural evolution of polylactid, International Conference on Nanostructured Polymersand Nanocomposites , 28 - 30 April 2010. Madrid

7. Stoclet G., Seguela R., Lefebvre J.M., Lefebvre J.M., Rochas C., , Conference Nationale ”MATERIAUX2010”, Nantes , Nantes

8. Marechal M., Niepceron F., Bigarre J., Mendil-jakani H., Gebel G., Crystallinity and morphology ofPVDF-HFP-based proton-exchange membranes embedding polytyrenesulfonic acid-grafted silica particles,International Symposium of Polymer Electrolytes , 29 aout- 3 septembre 2010 Padoue

9. Marechal M., Niepceron F., Bigarre J., Mendil-jakani H., Gebel G., Hybrid membranes for medium-temperature PEMFC: PVDF-HFP-based proton-exchange membranes embedding polytyrenesulfonic acid-grafted silica particles, Solid State Proton Conductors , 15-19 aout 2010 Santa Barbara

10. Michot L.J., Paineau E., Bihannic I., Baravian C., Davidson I., Levitz P., Repulsive interactions inaqueous dioctahedral swelling clay minerals at low ionic strength., Trilateral Meeting on Clay , Seville

11. Paineau E., Bihannic I., Baravian C., Philippe A.M., Davidson P., Levitz P., Michot L.J., Electrostaticsinteractions in charged colloidal clay suspensions., ECIS , 2010 Prague

12. Stoclet G., Seguela R., Lefebvre J.M., Rochas C., Caracterisation par WAXS in situ et DSC de l’evolutionstructurale d’un poly(D,L-lactide) induite par etirage, Deformation des Polymeres Solides (DEPOS 23) ,29/09 - 01/10 2010 Lorient

13. Stoclet G., Lefebvre J.M., Seguela R., In situ WAXS Characterization of the Strain-Induced StructuralEvolution of Poly(D,L-Lactide) based nanocomposites, Material Research Society Fall Meeting 2010 , 28Novembre - 4 December Boston (USA)


1. Guenet J.-M, Polymer hosting self-assembled systems for preparing functional materials , II InternationalConference on functional polymers , 28-30/01/2011 National Institute of Technology, Calicut, Kerala,India

2. Morfin I., Two-Photon Fluorescence Microscopy and Small Angle X ray and Neutron Scattering : Struc-tural characterization of complex polymer architectures, european polymer congress (june 2011) , Grenade


1. Deschamps A., Bastow T.J., De Geuser F., Hill A.J., Hutchinson C.R., Revisiting the microstructurechanges during rapid hardening of an Al-Cu-Mg alloy using in situ synchrotron Small angle X-ray Scat-tering and Nuclear Magnetic Resonance, EUROMAT , Septembre 2011 Montpellier (France)

2. De Geuser F., Mourey T., Sigli C., Deschamps A., Precipitation of delta’ in Al-Li-Mg : modelling andcharacterisation by SAXS and DSC. EUROMAT, Montpellier (France), Septembre 2011., EUROMAT ,Septembre 2011 Montpellier (France)

3. De Geuser F., Malard B., Deschamps A., SAXS mapping of the microstructure in a friction-stir weldedAl-Li-Cu alloy, THERMEC , Aout 2011 Quebec (Canada)


5.4 Books and chapters 5 SCIENTIFIC PRODUCTION 2009-2013

4. Imperor-Clerc M., Self-assembly in solution of silica-based hybrid materials, UK colloids 2011 , july 20115. Malard B., De Geuser F., Ruis-santos W., Deschamps A., A combined approach to microstructure mapping

on an Al-Cu-Li 2050 friction stir weld, EUROMAT , Septembre 2011 Montpellier (France)6. Malard B., De Geuser F., Ruis-santos W., Deschamps A., A combined approach to microstructure mapping

on an Al-Cu-Li 2050 friction stir weld, THERMEC , Aout 2011 Quebec (Canada)


1. Berar J.F., Materiaux reels : defauts et diffraction, diffusion., Journees de la Matiere Condensee (JMC13), 28/8/2012 Montpellier

2. David L., Agulhon P., Robitzer M., Rochas C., Quignard F., Structural regimes in alginate ionotropichydrogels,, 9th International Symposium on Polyelectrolytes ( (9-14th July 2012)) , Lausanne Switzerland

3. Deschamps A., De Geuser F., Precipitation in Al-Cu-Li alloys: From kinetics to Friction Stir Welding,13th International Conference on Aluminium Alloys , Pittsburgh, PA

4. Deschamps A., De Geuser F., Characterization of complex precipitation pathways using Small AngleScattering, ”Neutron and X-Ray Studies of Advanced Materials V: Centennial” symposium of the 2012TMS conference , Orlando, Florida

5. De Geuser F., Gault B., Deschamps A., Role of atom probe tomography in small-angle X-ray scatteringinvestigations of phase separation in alloys: interplay between direct and reciprocal spaces, InternationalField Emission Symposium , Tuscaloosa, Alabama

6. Goycoolea F.M., Chitosan-based nanomaterials for advanced drug delivery and nanotechniology, 6thIberoamerican Chitin Symposium & 12th International Conference on Chitin and Chitosan , Septem-ber 02-05 2012, Fortaleza, Brasil

7. Maitrejean S., Ghezzi G., Gourvest E., Beneventi G.B., Fantini A., Phase Change Memories challenges:A material and process perspective, 15th International Interconnect Technology Conference IITC 2012 ,San Jose, CA (June 4-6)

8. Maret M., Tiron R., Chevalier N., Gergaud P., Dubray J., Gharbi A., Lapeyre C., Pradelles J., JousseaumeV., Fleury G., Boudet N., GISAXS study of directed self-assembly of block copolymers , GISAS2012,satellite conference of SAS2012 , Kyoto, 13-16 nov 2012

5.4 Books and chapters

Books 2012

1. Etienne S., Introduction a la Science Physique des Polymeres, Deuxieme edition revue et augmentee ,Dunod, Paris (2012)

Books 2013

1. Boulle A., Conchon F., Guinebretiere R., The micro- and nanostructure of imperfect oxide epitaxial films,Modern Diffraction Methods , editors: Mittemeijer E.J. (Eds.) Welzel U. (Eds.) , Wiley-VCH VerlagGmbH & Co. KGaA , Germany (2013) doi: 10.1002/9783527649884.ch9

2. Renevier H., Proietti M.G., Grazing incidence diffraction anomalous fine structure in the study of struc-tural properties of nanostructures, Characterization of Semiconductor Heterostructures and Nanostruc-tures. 2. , editors: Lamberti C. (Eds.)Agostini G. (Eds.) , Elsevier (2013)

5.5 Softwares

bm2hkl from image to reciprocal space (language IDL)available on beamline or contact [email protected]

bm2img an image preprocessing tool with grid corrections allowing to extract radial distribution (language c,Linux, MSWindows)ftp://ftp.grenoble.cnrs.fr/pub/xnd/BM2 or http://perso.neel.cnrs.fr/jean-francois.berar/bm2img (bm2img 1.25release)

bm2py From images to high resolution powder pattern, (language Python)http://perso.neel.cnrs.fr/jean-francois.berar/bm2py (preliminary release)

guifit multilayer fit program (language IDL)available on beamline or contact [email protected]

spec2grace tool for converting spec files (language c, Linux)ftp://ftp.grenoble.cnrs.fr/pub/xnd/BM2 (spec2grace 2.21 release)


5.5 Softwares 5 SCIENTIFIC PRODUCTION 2009-2013

xnd a rietveld program (language c, Linux, MSWindows)ftp://ftp.grenoble.cnrs.fr/pub/xnd or http://perso.neel.cnrs.fr/jean-francois.berar/xnd (xnd 1.41 release)


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