Vapor Metalation of Porphyrin by ALD In-situ QCM analysis of site selective ALD Conclusions In-situ...
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Transcript of Vapor Metalation of Porphyrin by ALD In-situ QCM analysis of site selective ALD Conclusions In-situ...
Vapor Metalation of Porphyrin by ALD
In-situ QCM analysis of site selective ALD
Conclusions
In-situ GISAXS analysis
In-situ Form Factor Analysis of Site-Selective Atomic Layer Deposition of Metal Oxide Nanoclusters on Vapor Metalated Porphyrin
Jason R. Avila, Jonathan D. Emery, Omar K. Farha, Michael J. Pellin, Alex B. F. Martinson, and Joseph T. Hupp
Department of Chemistry, Northwestern University and Argonne Northwestern Solar Energy Research Center (ANSER) 2145 Sheridan Road, Evanston, IL, 60208, USA
Using a modular ALD reactor developed at Argonne national laboratory, we can perform high X-ray scattering experiments at Argonne National Laboratory’s Advanced Photon Source to probe the nanoparticle form factor during ALD nucleation and growth in-situ.
UV-Vis confirms the successful vapor metalation of free-base porphyrin Mn using a reactive ALD precursor and a O2/H2O mix to present isolated OH nucleation sites.
In-situ QCM and an island growth model shows MnO nucleation is limited to the OH site on the porphyrin and grows as a hemisphere until its radii exceeds the porphyrins.
In-situ GISAXS shows a significant form factor difference between MnO grown on porphyrin over MnO grown on Si substrates.
Acknowledgements Using an island growth model previously used to quantify the ALD nucleation and growth of metal oxides in SAM films, this study aims to confirm the growth of monodispersed MnOx clusters knowing the fixed radius of the porphyrin and assuming a hemispherical growth geometry.
Model assumes 1) a monondispersed array of nucleation events that will nucleate and grow uniformly and 2) initial growth is limited by a fixed geometry, followed by coalescence to film growth.
Background
The increasing focus on implementing photocatalysts for future sustainable fuel generation has driven many to look toward nature for the ideal system. Examination of enzymatic catalysts indicate the critical property for catalytic activity are nanoscale metallo clusters. Mimicking these cluster systems is synthetically challenging because conventional solution-based methodology can cause aggregation or require capping the cluster, thereby limiting its catalytic active sites. In this work we use site-selective atomic layer deposition (ALD) to grow metal oxide clusters that are spatially isolated and easily controlled. By implementing a tetra-acid free base porphyrin (H2TCPP) nucleation platform we demonstrate the ability to metalate a porphyrin with Mn by ALD precursor exposure to form a spatially isolated hydroxide which acts as a nucleation point for MnO cluster growth. Using in-situ quartz crystal microbalance (QCM) analysis we show through an analytical island growth model that the growth of these clusters is hemispherical with a convergence radii near that expected of the porphyrin platform (0.8 nm). Finally, through in-situ synchrotron GISAXS measurements we find that the structure of MnO grown on porphyrin platforms mirrors the growth behavior determined by QCM measurements. Using this methodology developed in this study we show it is feasible to grow a wide range of well-controlled metallo clusters using the self-limiting nature of ALD.
Abstract
2.5
2.0
1.5
1.0
0.5
0.0
Abs
orba
nce
(a.u
.)
700650600550500
wavelength (nm)
H2TCPP
25 pulse MnEtCp
20 pulse H2O
1 pulse O2/H2O1 cycle MnO
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Abs
orba
nce
(a.u
.)
700650600550500
wavelength (nm)
ZnTCPP
20 pulse MnEtCp
0.5
0.4
0.3
0.2
0.1
0.0
Abs
orba
nce
(a.u
.)
700650600550500
wavelength (nm)
H2TCPP
2 pulse TMA
Using a wall mounted QCM we can measure the nucleation and growth of MnOx clusters grown by ALD with nanogram resolution
Once metalated, the growth of MnO on the Mn porphyrin shows a hemispherical growth up to 20 cycles before a linear growth rate is observed, similar to what is expected from the island growth model.
Fitting to the model gives a convergence radii similar to the radii of the porphyrin and a linear growth rate similar to that measured by ellipsometry
Vapor metalating with DEZ to form ZnTCPP (which does not have an axial ligand) shows a higher convergence radius indicating the axial OH ligand on the porphyrin is required for growth.
Evolution of thickness (µ) – growth of hemisphere normal to the surface
Radius of convergence (Rcov) – fixed radii before cluster
coalescence.
Nucleation density (Nd) – density of nucleation at defect sites in the
SAM film (pin holes).
thic
knes
s ev
olut
ion/
mas
s ga
in
AB ALD cycles
Rcov
Coalescence
and film gro
wth
Hem
isph
eric
al is
land
gro
wth
Nilsen, O.; et.al. J. Appl. Phys. 2007, 102, 24906Avila, J. R.; et. al. Appl Mater. and Inter.2014, 6, 11891
O2/H2O mix
MnII(CpEt)2 X ALD cycles
Free base porphyrin loaded substrate
ALD clusters of metal oxides/sulfides
Metalated with isolated OH nucleation site
N
N N
N
OH
O
HO
O
O
OH
OH
O
Mn
OH
~1.5 nm diameter Rcov = 0.75 nm Riha, S. C.; et.al. Rev. Sci. Instrum. 2012, 86, 94101
O O
=
Porph
yrin
func
tiona
lized
subs
trate
Passiv
atio
n
of in
ters
titia
l
spac
ed
Met
alat
ion
by A
LD
Model fitted growth
Yanguas-Gil, A.; et.al. Chem. Mater. 2013, 25, 4849-4860
Effect of Interstitial spaces
To establish if the interstitial spaces play a role in the growth morphology of MnO on porphyrins, acetylacetone (AcAc) was vapor deposited to poison any surface hydroxyls before the vapor metalation step.
The Mn metalated case shows no difference in cluster growth with or without AcAc
Once H2TCPP is functionalized on a surface it was then exposed to the Mn(CpEt)2 ALD precursor in order to metalate the porphyrin
UV-Vis shows once exposed to the Mn ALD precursor there is a reduction in the number of Q bands from 4 to 2, and the formation of 2nd soret peak at 475 nm characteristic of a MnIII metalated porphyrin with a ligand normal to the porphyrin ring
UV-Vis was also examined in a N2 environment to determine the mechanism of metalation and ligation using the MnII ALD precursor. Once metalated with MnII water exposure does little to properly oxidize the porphyrin.
O2/H2O mix is needed to oxidize the Mn porphyrin and ligate a hydroxo group for the desired isolated nucleation site
Some degradation of H2TCPP and ZnTCPP porphyrin is observed due to the reactivity of the Mn(CpEt)2 precursor
Can also metalate using diethylzinc (DEZ) and trimethylaluminum but can severely degrade the porphyrin due to high reactivity
UV-Vis under N2
Rochford, J.; et.al. J. Am. Chem. Soc. 2007, 129, 4655-4665
Characterization of MnOx Clusters with Island Growth Model
Porphyrin Nucleation Platform
1 cycle 5 cycle 10 cycle 20 cycle
SiMnO
N
N N
NO
OO
O
O
O
O
O
Mn
OH
Surface Binding Geometry
Using a tetracarboxyphenyl porphyrin with carboxylic acid groups functionalized to the meta positions of the phenyl moiety achieve a binding geometry presents an isolate nucleation sites (-OH) separated by the diameter of the porphyrin ring (~1.5 nm).
Using a solution loaded ZnTCPP shows faster nucleation and film growth than the Mn metalated case indicating the interstitial spaces nucleate quickly.
With AcAc we see a long nucleation delay confirming the interstitial spaces are the primary growth mechanism without an axial ligand on the porphyrin
The difference between the vapor (above) and solution (right) metalated is attributed to increased steric and hydrophobic effects from unreacted precursor ligands
Guinier–Porod fitted radii
Thanks to Jeffery Klug, Matthew Weimer, and Angel Yanguas-Gil for their assistance in setting up and using the in-situ tool.
Scattering for the MnO grown on Mn porphyrin indicates a rougher surface over the bare Si control substrate, with scattering at the high scattering angle indicating particle formation.
MnO grown on Si shows an increase in scattering intensity with minimal comparable roughness
In-plane cuts (qy) shows the peak formation for the MnTCPP indicating discrete particle formation with increasing ALD cycles.
MnO grown on Si does not observe formation of a peak, only observing an increase in scattering intensity with increasing MnO deposition.
Taking out-of-plane cuts (qz) near the q = 0.2 of the scattering signal allows to approximate a particle radii using Guinier-Porod fit.
Assuming a truncated sphere, fitting for radii shows two growth regimes MnO grown on porphyrin. A shallow increase in radii from 1-5 cycles, followed by a second growth regime that matches the growth of MnO on Si.
Further examination as to the discrepancy between the MnO cluster development measured by QCM and GISAXS are ongoing.
Metalation effect on ZnTCPP Metelation with TMA
SiMnO