Lesson 1 Introduction of magnetism I

Neutron Scattering grope, Quantum Beam Unit, NIMS

Hideaki KITAZAWA

“Advanced Materials and Technologies (NIMS Lecture) II: Materials and characterization for energy and informatics, Woloska141, Room 215, Oct. 27-Oct. 28, 2015

Magnetic properties of rare earth compounds - basics and application

1

Syllabus: Lesson 1 – Lesson 5

Magnetic properties of rare earth compounds - basics and application

Lesson 1. Introduction of magnetism I Lesson 2. Introduction of magnetism II Lesson 3. High-field study of rare earth compounds Lesson 4. Introduction of neutron scattering Lesson 5. Some example of neutron scattering study for rare earth compounds

2

Outline of lesson 1 Oct. 27(Tue) 9：30～10：20

0-1. Introduction of International Joint Graduate Program with WUT 0-2. Self-introduction 1-1. What are rare earth elements? 1-2. Magnetism in an isolated magnetic ion

Introduction of magnetism I

3

0-1.Introduction of International Joint Graduate

Program with WUT

4

What is NIMS?

5

Budget: 21.5 billion JPY (15.6 million Euro) Personnel : 1,503 (1,138 research staff)

including 289 staff from abroad Plus 428 students

National Research Institute for Metals (since 1956)

National Institute for Research in Inorganic Materials

(since 1966)

Independent Administrative Institution National Institute for Materials Science

Established in April 2001

(as of April 2014)

Academic Achievements N

umbe

r of P

ublis

hed

Pape

rs

Aver

age

Impa

ct

Fact

ors

Publications

6

1,238 1,292

1,361

1,128 1,179

1,159

1,293 1,329 1,266

2.01 2.2 2.16 2.24

2.42

2.89

3.32

3.74 3.64

0

0.5

1

1.5

2

2.5

3

3.5

4

0

200

400

600

800

1,000

1,200

1,400

1,600

Compiled from the ESI database, Thomson Reuter, as of March, 2014

Citation Ranking (Mat. Sci.)

Jan. 2008 – Dec. 2012 Ranking Institution Citations

1 (grp) Chinese Acad. Sci. 63,429

2 (grp) U. of California System 43,427

3 (grp) CNRS 42,839

4 (grp) US DOE 41,937

5 (grp) Max Planck Society 20,974

6 (grp) ETH Domain 20,139

7 Natl. Univ. Singapore 18,469

8 MIT 15,523

9 Northwestern Univ. 14,916

10 Tsing Hua Univ. 14,567

11 Nanyang Tech. Univ. 14,445

12 NIMS 14,393

Dual Ion Beam Interfaced High-

Voltage TEM

7

Advanced Facilities and Equipment

A Large Synchrotron

Radiation Facility

Spring-8

World Class Facilities & Equipments

2-D Nano-Patterning Foundry &

3-D Nano-Integration Foundry

Bio-Organic Materials Facility

930 MHz High Resolution

Solid-States NMR Magnet

35T Hybrid Magnet

Clean Room Electron Beam

Lithography System Focused Ion Beam

System

Polymer and Organic Materials Lab.

Ultra High Resolution TEM

Organic Synthesis Laboratory

8

Moscow State Univ.

Charles Univ.

Univ. of Pardubice

Univ. of Tribuvan

Warsaw Univ. of Tech.

Budapest Univ. Economic & Tech.

Anna Univ.

City Univ. Hong Kong

Flinders Univ.

Kyushu Univ.

Hokkaido Univ.

Waseda Univ.

Univ. Tsukuba

25 Other Univ.

E-JUST

National Taiwan Univ.

Univ. of Melbourne

Univ. of Auckland

Univ. of Rennes 1

Institute of Materials Science

National Tsing Hua

Univ.

Universiti Teknologi, Malaysia

17 Overseas 29 Domestic

International Joint/Cooperative Graduate Program -NIMS Graduate Partners-

International Cooperative Graduate School International Joint Graduate School

Joint Graduate Program with WUT -Number of the Students in 2014-

9

Name Number of Students

Warsaw University of Technology (Poland) 9 Anna University (India) 5 National Taiwan Tsing Hua University (Taiwan) 2 Flinders University (Australia) 2

National Taiwan University (Taiwan) 2

Xi’an Jiaotong University (China) 1

Pardubice University (Czech) 1

Charles University (Czech) 1

Inst. of Materials and Science (Vietnam) 1

Total 24

10

Joint Graduate Program with WUT -Faculty Members-

Materials Degradation Group

Krzysztof J. KURZYDŁOWSKI

Seiji KURODA

Makoto WATANABE Coating Materials Group

Hideaki KITAZAWA Neutron Scattering

Group

Yoko MITARAI Functional Structure

Materials Group

Małgorzata LEWANDOWSKA Characterization of

Nanomaterials Group

Halina GARBACZ Nanomaterials Group

[NIMS] [WUT]

11

Joint Graduate Program with WUT -Faculty Members-

[NIMS] [WUT]

Katsuhiko ARIGA Supermolecules Group

Akiko YAMAMOTO Biometals Group

Anna BOCZKOWSKA Polymeric and Composite

Materials Group

Wojciech ŚWIĘSZKOWSKI

Biomaterials Group

Marcin LEONOWICZ Powder Metallurgy and

Composites Group

12

Researchers Classification by Materials

General*: Computational Science, Analytical Science, Characterization, etc.

Prof. Kuroda Prof. Watanabe

Prof. Yamamoto Prof. Ariga

Prof. Mitarai Prof. Kitazawa

WUT faculties in NIMS Prof. Yamamoto

Prof. Ariga

Prof. Ariga Prof. Kitazawa

13

Summer Training Program -Outline of the Program-

- Program started in FY 2011 - Experience of staying NIMS and participating in the state-of-the-art project - Training at NIMS: Approx. 10 students, 2month under the supervision of NIMS professors [Schedule in 2014] Jul. 1: Orientation Jul. 4: Welcome Reception Jul. 10-16: Lectures by NIMS professors (7 lectures by 6 profs.) Jul. 8: Study tour to Hitachi (Hitachi High Technologies corp.) Aug. 28: Presentation Seminar & Farewell Party

14

Summer Training Program -Activity in NIMS-

Final Presentation Seminar with NIMS President

15

Mt. Rysy 2,500m Mt. Fuji 3,776m

Experience of Japanese Culture and Nature

1-0. Self-introduction

16

Nationality: Japanese Family : a wife and 2 children Position : Unit director of Quantum Beam Unit Affiliation: Neutron Scattering Group, Quantum Beam Unit, NIMS E-mail: KITAZAWA.Hideaki@nims.go.jp Research topics: Magnetism, Single-crystal growth, Neutron scattering, High-field

science, TOF-SIMS, Cs-decontamination Education: April 1983, Entrance of the doctor course of Physics Department, Tohoku University, Japan March 1988, Doctorate of Science from Tohoku University, Japan Research and professional experience: 1987- 1995 : Researcher, The Institute for Physical and Chemical Research (RIKEN) 1995- 2001 : Senior Researcher, National Research Institute for Metals (NRIM), 2001-present : Group leader-Unit director, National Institute for Materials Science (NIMS) Hobbies : Singing, reading mystery novels and recording of TV programs

CURRICULUM VITAE: Hideaki Kitazawa 英明 北澤

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In the Quantum Beam Unit, we are carrying out synthetic R & D of neutron beams, high-brightness synchrotron radiation and ion beams for material science. In particular, we focus on developments of various quantum beam technologies for crystal structure analysis with X-ray and neutron diffraction, novel analytical methods and instruments with advanced brilliant X-ray sources, fabrication of nanoparticles and nano-structured materials by ion-laser co-irradiation apparatus in order to establish the basis of quantum beam technologies for Energy, Environment, Resource Field and Nano-scale Materials.

Quantum Beam Unit (QBU) in NIMS

Group Group Name GL Number of Permanent

staff

Number of Temporary

staff Group 1 Neutron Scattering

G Dr. H.

Kitazawa 7 12

Group 2 X-Ray Physics G Dr. K. Sakurai

1 5

Group 3 Ion Beam Group Dr. Y. Takeda

5 2

Group 4

Synchrotron X-ray G (after Oc. 1, 2013)

Dr. O. Sakata

3 5

18

QBU: Synthetic R&D of Energy, Environment, Resource Field and Nano-scale Materials

19 Courtesy of KEK/JAEA J-PARC Center

Domestic and Overseas Quantum Beam Facilities

Ion beam G

J-PARC, JRR-3

ナノアレイ Nano-array

3D analysis of thin films

5040

3020

100 0

100

200

300

Inten

sity [

Coun

ts]

X-ray Energy [keV]

KEK, SPring-8

Neutron scattering G X-ray physics G Synchrotron X-ray G

Time-resolved analysis of multi-scale structures under manufacturing process / conditions Powder diffraction analysis by WPF method

Ultra trace elements Surface and buried interfaces Advanced X-ray imaging X-ray and neutron small angle scattering

Surface and thin film X-ray diffraction crystallography Hard X-ray photoelectron spectroscopy Atomic-scale and electronic structures revealed using In-situ measurement or under device operation

Novel functional materials controlled by ion-beam and kinetic external fields Advanced characterization of photonic nanomaterials Assembling nanostructures

Extreme Particle Field Generator (EPF)

Group Leader Researcher

Research Fellow & Office Assistant

Dr. Hideaki KITAZAWA Senior researcher Dr. Masashi HASE

Principal Researcher Dr. Hiroyuki SUZUKI

Senior Researcher Dr. Naohito TSUJII

Senior Researcher Dr. Seiichi KATO

Principal Researcher Dr. Hiroaki MAMIYA

Senior Researcher Dr. Noriki TERADA

Dr. Fujio IZUMI NIMS Special Researcher Dr. Osamu YANAGIMACHI NIMS Special Researcher Dr. Masahiko KATAGIRI NIMS Special Researcher Mr. Maki MUSHIAKE Technical Staff Ms. Sumie HASHIMOTO Techinical Staff

Ms. Seiko MATSUMOTO Technical Staff Md. Rumiko NAKAMURA Techinical Staff Mr. Seisuke NIGO Visiting Researcher Dr. Giyuu KIDO Visiting Researcher Mr. Shingo HOSOYA Visiting Researcher

Neutron Scattering Group

20

NIMS the 8th Advisory Board Meeting

- 21 -

Multi-scale Characterization Using Neutron Scattering

Public release of RIETAN-FP for powder diffraction data Direct observation of hydrogen (6wt. ppm) in steel by SANS

Neutron Scattering Group

3D-visualization of migration pathway for mobile ions in a doped Pr2NiO4-based mixed conductor by

a MEM-based pattern fitting method which we develop.

TEM image and small angle neutron scattering (SANS) profile of steel with and without hydrogen

charging

Fig

Nonosized NbC R=2.6 nm

Steel

TEM image SANS profile

Extreamly small amount of hydrogen

Steel

TiO2 fiber Al2O3/Al2TiO5 matrix

Fig

Hydrogen embrittlement Oxygen separation permeability

21

Tetra-arc furnace for the Czochralski pulling method

High-temperature furnace for the Bridgman method

Infrared-image furnace for the floating zone method

Single crystal of CeSb

Single crystal of TbNiAl

0 10 20 30 40 500

1

2

3

0 10 20 30 40 500

1

2

3

0 50 100 150 200 250 300 35002468

10121416 H=9 T

H//cH=0 T

Resis

tivity

(µΩ

cm

)

T (K) H=9 T

H=0 TH//ab

Resi

stiv

ity (µΩ

cm

)

T (K)

H=0 T

Resis

tivity

(µΩ

cm

)

Temperature (K)Single crystal of MgB2

Growth of single crystals with high quality

22

(a) polymers and FRP (fiber reinforced plastics) (b) ceramics coatings (c) heat resistant alloys and intermetallic compounds (d) heat-resistant steel.

(a) polymers and FRP

(b) ceramics coatings

(c) heat resistant alloys and

intermetallic compounds

(d) heat-resistant steel

For future’s commercial aircrafts and thermal power generation

Enhancement of energy efficiency Reduction of CO2 emission

Targets of SIP-IMASM

Innovative Measurement and Analysis for Structural Materials (SIP-IMASM) FY2014-FY2018)

Synchrotron Radiation

3D Atom Probe & Nanocharacterization Ion Beam Analysis

Positron microprobe & Superconducting X-ray

analysis

Acquisition of hidden informative data of structural materials

1. Stress & Cracks 2. Trace Light Elements

3. Heterogeneous Boundaries 4. Vacancy Defects

Four groups for hidden data and one for integrated analysis

KEK Integrated analysis

Measuring range

μm

nm

mm

Inner layer Surface layer (static)

TEM, HIM,SPM 3D-AP

Conventional observation technology

FIB-SEM

SIMS SAXS

New method XAFS-CT

Real operating environment (high temperature, stress-strain field)

Base materials

Heterophase interface

Coating

HIM,SPM

TOF-SIMS

TEM

SAXS

, XAFS-CT

Target materials: (a) polymers and FRP, (b) ceramics coatings, (c) heat resistant

alloys and intermetallic compounds, (d) heat resistant steel

3D multiscale characterization

Operand measurement

Initial precipitation

aging

26

Nanotech Career-up Alliance (Nanotech CUPAL)

Single Dopant Eu Atom

Eu dopant

Short-term NIP course:

NIMS Advanced Measuring Technologies Introductory Course

Intensive and practice courses for 3 days will be held for 4 times per year.

1. Advanced transmission electron microscopy (TEM) course 2. Advanced surface analysis course ( STM, He ion microscope ad PEEM/SPEEM) 3. Advanced structure analysis course ( X-ray & neutron diffraction, small angle scattering, reflectometry, solid-state NMR) The certificate of the completion of attending each course will be given at the end.

Mid- to Long-term NIP Course NIMS Advanced Measuring Technologies

Advanced Course The applicants after completion of the introductory course or

professionals can chose your preferred course from the following advanced course.

1. Advanced transmission electron microscopy course 2. Advanced surface analysis course 3. Advanced structure analysis course The applicants can choose the training days (about 10 days) from

3 periods in a year. The NIP persons can apply to your own research interest while discussing with the host researchers.

Advanced transmission electron microscopy(TEM)

There are three theme as follows; a) Materials research by high-level methods in advanced TEMs b) Materials research by multidisciplinary-integrated analysis in advanced TEMs c) Development of new TEM techniques combined with advanced TEMs

Two aberration corrected TEMs are available for your researches

Micro vacuum gauge

Heating chip

Gas nozzle

Development of special sample holder

Education&training

1 nm

Good sample results in good image

Discussion

Dr. M Yakeguchi Dr. K. Mitsuishii

1-1. What are rare earth elements?

30

What are 4f electrons?

3d-electron system

4f-electron system

5f-electron system

The lanthanides elements from La to Lu which are located at the bottom of the periodic table are often called as rare earth elements. Despite their name, rare earth elements (with the exception of radioactive promethium) are relatively plentiful in Earth’s crust. 31

Localization or Delocalization (Itinerant) ?

1. 3d-electron system mainly itinerant : band theory

2. 4f-electron system mainly localized : RKKY model

3. 5f-electron system localized / itinerant ?

3d orbit 4f orbit 5f orbit

Electronic states of electrons in an incomplete shell

Since their electronic states of in the substance mostly prefer to the trivalent state in the substance, rare earth compounds often show the similar chemical properties. However, their magnetic properties are quite variable depending on lanthanides elements 32

Are materials with rare earth elements useful?

Physical mechanism Application Materials

Ferromagnetism

Magnetic Kerr effect

Magnetostriction

Magneto-caloric effect

Luminescence

Superconductivity

Double exchange interaction

Permanent magnet

Magneto-optical disk

Magnetic actuator

Magnetic refrigerator

Phosphor material

Superconducting wire

Giant magnetoresistance device)

Sm-Co, Nd-Fe-B etc.

Fe-Tb system

TbFe2

Gd, Gd-Si(Ge) system

BaMgAl10O17; Eu2+

RBa2Cu3O7 etc.

LaCaMn3

33

1-2. Magnetism in an isolated magnetic ion

34

Magnetic moment of the electron

Spin magnetic moment of the electron

sg Bs µµ −=

erg/G100.9274J/T109274.02

20-23 ×=×== −

mce

BµBohr magneton：

g-factor of an electron： 0023.2=g

s

sµ

Orbital magnetic moment of the electron （ H =0 ）

r v

cevr

cIS

2==µ （current X area）

( )rveI

π2−

=

[ ] [ ]

[ ] llmcepr

mce

vmrmcevr

ceH

B

µ

µ

−=−=×−=

×−=×⋅−==

22

221)0(

Areal velocity

Gauss Unit

Classical theory → Quantum theory 35

)(rAcepvm

+=

Vector potential

[ ]rHrA ×=

21)(

Momentum of an electron

[ ] [ ] [ ]rHrHrmcelpr

mcevr

ce

Borb )(

4222

2

2

⋅−−−=×−=×−= µµ

Lentz’s law

Induced magnetic moment by magnetic field

Quantization of the orbital angular momentum ,2,,0

When the magnetic field is changed, the induced current in a closed circuit flows in the opposite direction to cancel the change of field. The 2nd term is caused by this origin.

Orbital magnetic moment of the electron （ H = 0）

Orbital magnetic moment of an electron

36

Magnetic interaction between µorb and H and diamagnetic moment due to electron motion

Magnetic interaction between µorb and H

222

2

0dia 8

HrmceHlHdE

H

B ⊥+⋅=⋅−= ∫ µµ

： component normal to the magnetic field for the position vector of the electron from the nucleus

⊥r r

Diamagnetic moment due to electron moment

Hrmc

enNyxHmc

eNdH

dEM e 22

2atom

electron

222

2atom

electron

dia

64−=+−=−= ∑∑

Diamagnetic susceptibility 22

2atom

dia 6r

mcenN

dHdM e−==χ

A12 ≈r )1001(emu/mol103 6dia −=×−= −

ee nnχ

Nucleus

Electron

r

⊥r

37

Electronic configuration of the magnetic ion

Electronic configuration of the magnetic ion

Electronic states are governed by the following quantum numbers

Principal quantum number (n) Orbital angular momentum (l), component along the quantized axis (lz) Spin angular momentum (s), component along the quantized axis (sz)

n l lz sz

1 0 (s-orbit) -l ～ +l （2(2l+1)

degeneracies）

+1/2,-1/2 2 0,1 (s,p-orbit)

3 0,1,2 (s,p,d-orbit) 4 0,1,2,3 (s,p,d,f-orbit)

magnetic moment of the magnetic ion

),()( LSglsg BiiB

+−=+−= ∑∑ µµµ ∑∑ == ii lLsS

,

Total atomic spin (orbital angular) momentum

38

(1)The maximum total atomic spin S = Σm s is obtained (Coulomb interaction) without violating the Pauli exclusion principle

(2)The maximum value of the total atomic orbital angular momentum L = Σm L is obtained, while remaining consistent with the given value of S (from the experimental results)

(3)The total angular momentum J is equal to |L-S| when the shell is less than half shell, and is equal to |L+S| when the shell is more than half full. When the shell is exactly half full L = 0 so that J = S .

Hund’s rule ground state in multi-electron system

39

Hund’s rule

3d1

3d-trnasition element series (l = 2)

Degeneracy : 2l +1 = 5

3d2 3d5 3d7 3d9 3d10

L = 2, S = 1/2

lz

L = 0, S = 5/2 L = 0, S = 0

-2

+2 +1 0

-1

L = 3, S = 1 L = 3, S = 3/2 L = 3, S = 1/2 40

6-2-7. Ground LS multiplets of the 3d transition metal series

Question 1：Fill the following table according to obtain the ground LS multiplets in the 3d transition metal series.

Ti4+ Ti3+,V4+ V3+ Cr3+,Mn4+

Mn3+ Fe3+,Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Cu+

ne 0 1 2 3 4 5 6 7 8 9 10

S

L

41

Ti4+ Ti3+,V4+ V3+ Cr3+,Mn4+

Mn3+ Fe3+,Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Cu+

ne 0 1 2 3 4 5 6 7 8 9 10

S 0 1/2 1 3/2 2 5/2 2 3/2 1 1/2 0

L 0 2 3 3 2 0 2 3 3 2 0

Answer 1：Fill the following table according to obtain the ground LS multiplets in the 3d transition metal series.

6-2-7. Ground LS multiplets of the 3d transition metal series

42

Hund’s rule

4f1

4f-trnasition element series (l = 3) Degeneracy of l : 2l +1 = 7 Total degeneracy : 2*(2l+1) =14

4f2 4f7 4f10 4f14

L = 3, S = 1/2

lz

L = 0, S = 7/2 L = 0, S = 0

-2

+2 +1 0

-1

L = 5, S = 1 L = 6, S = 3/2 +3

-3

Summary of lesson 1

1. The rare earth elements are rather expensive than the other important elements , H, C, O, Si, Fe and etc. However they are very important to sustain our modern life.

2. Most of magnetism can be understood by quantum mechanics. 3. The Hunt’s rule is governed in the ground state of unpaired electron system.

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Bardzo dziękuję !

45

Thank you for your kind attention!