Development of Hard X-ray Photoemission Spectroscopy for Advanced Materials Science and Technology

at BL-47XU/SPring-8(Development of 3D chemical states analysis)

Eiji IkenagaSPring-8/JASRI

Kouto 1-1-1, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan

20, May. 2009, HAXPES workshop

Hard X-ray Photoemission Spectroscopy ①

Hard X-ray Photoemission Spectroscopy

Collaborators

NIMS/SPring-8K. Kobayashi, S. Ueda, M. Kobata

JASRI/SPring-8Y. Watanabe, S. Komiya, K. Kinoshita, M. Machida, C. Son,K. Yan, S. Goto, I. Hirosawa, T. Matsushita, M. Yabashi

Nara Institute of Science and TechnologyH. Daimon, H. Matsuda

RIKEN/SPring-8 (Coherent X-ray Optics Lab.)T. Ishikawa, K. Tamasaku, Y. Nishino

VG SCIENTA

②

Fundamental Science

AppliedScienceIndustrial

application

( H. Tanaka et al. PRB accepted (2006) )

1.0

0.8

0.6

0.4

0.2

0.0

Nor

mal

ized

Inte

nsity

1846 1844 1842 1840 1838 1836 1834Binding Energy (eV)

HfO2/SiO2/Si(100) RTA

HfO2/SiO2/Si(100) as deposition

1.32 nmSiO2/Si(100)

h=5.95 keVTOA=30 deg

( K. Kobayashi, et al. Appl. Phys. Letters 83,1005(2003) )

Public BL47Ｘ U

Public BL47Ｘ U

Interface reaction of polyInterface reaction of poly--Si/highSi/high--k k insulator systemsinsulator systems

Typical result

The depth probe is analyzed in high accuracy.

Electronic Structure of Strained Manganite Thin Films Electronic Structure of Strained Manganite Thin Films with Room Temperature Ferromagnetism with Room Temperature Ferromagnetism （（LaBaMnLaBaMn33 /SrTiO/SrTiO33 ））

Typical result

The relation that corresponds to temperature-magnetization curve is experimentally clarified.

Organic Materials

Strained Manganite Thin Films

・In order to advance applications, we are continuously to carry out various developments.

・For material has nano structures, Request of observation in the microscopic area is enhanced.

③

Applied nanotechnology

( Kawai-Lab nano-bio-chip group)Manganite Thin Films

DNA chips

Outline

2. Introduce focusing optics

K-B Mirror

Present status of V: 40μm H: 30μm

・Wide acceptance angle: ±45°

・Present status of solid angle: ±7°

1. Development of Objective lens

After installation K-B Mirror,Status of beam spot size

⇒φ1μm～submicron

Electronic state of Electronic state of microscopic areamicroscopic area

Achievement the 3D analysis in the chemical states by taking depth profiles and sample scanning.

Purpose④

Development of Beamline SysytemDevelopment of K-B mirror system at BL47XU

In-vacuum" planar undulator, 5.9 ~18.9 keV Si (111) double crystal monochrometer liquid nitrogen cooling (not closed cycle system) Si (333) channel cut

10m

53 m

ID Mono

Front-end slit

0 29 m 36 m 51 m

1st hatch 2nd hatchOptics hatch

44 m 48 m

40.5m

Tc Slit sample

Hypothetical source point

⑤

Hard X-ray Photoemission Spectroscopy – K-B MirrorK-B mirror system

elliptical mirrors; figure errors ~ 2 nm; platinum coating;glancing angle ~ 3 mrad; incident slit: 300×300 μm

350

⑥

This large working distance make possible to realize wide space around sample

Hard X-ray Photoemission Spectroscopy – K-B MirrorFocusing Result

Beam size: 1.1μm (H) × 0.98μm (V)

Using Wire Scan monitor

⑦

Hard X-ray Photoemission Spectroscopy – Objective Lens

About withstanding voltage・・・・ Stable operation under 8kV application for 48 hrs

without discharge.

SIMION trace calculation (for 1kV)

(mm)

Development of Objective Lens

Main feature・・・・ Discharge prevention measures by simplification

of correction electrode part structure・ The shape mesh of a spheroid type・Working Distance=10mm・Magnification factor=5

In Collaborate with Drs. Daimon and Matsuda

⑧

Hard X-ray Photoemission Spectroscopy – Objective Lens

Au3d(3.2keV)Au3d(3.2keV)

Lens mode: angularPE=200eV,Slit:S4.0,FixedBeam Size200um(50W:Crkα

Lab X-ray source)Raster Scan(1mm×1mm)

2D detector Image2D detector Image

Total Acceptance angle of ±32degrees

Angle test device(VG SCIENTA)

X-ray Source

-1.0 0.0 1.0Emission Angle (deg)

3208eV

3206

3204

3202

3200

3198

3196

Kin

etic

Ene

rgy

(eV

)

0035 35

Separation between lines: 2.8degrees

- 35 0 35

Inte

nsity

(arb

.uni

ts)

Emission Angle (deg)Emission angle(deg) Peak width

0 1.1310 1.1725 1.1135 1.53

（Evaluation of acceptance angle）

⑨

X-ray

HAXPES SystemK-B Mirror

X-ray

Analyzer

Objective Lens

Wire scan System

Live showLive show

Objective Lens and K-B Mirror combined with HAXPES system

Hard X-ray Photoemission Spectroscopy in BL47XU2008.7.31

350mm

Translatio n

HAXPES system of BL-47XU

⑩

Hard X-ray Photoemission Spectroscopy（Evaluation of Intensity）

- decreased about 30 times

×10

6

Previous

×10

4

Energy relative to EF (eV)

With K-B

-90 -88 -86 -84 -820.0

0.5

1.0

1.5

2.0

×10

6

With K-B + Lens

- decreased about 0.5 times

Decreasing of flux efficiency by KDecreasing of flux efficiency by K--B mirror can be greatly B mirror can be greatly supplemented with objective lenssupplemented with objective lens

Au4f spectra

・ Attenuation by part Air path (About 1.5m). ※ The K-B system will be examined to replacement with He gas

⑪

3.5×106 1.8×1061.2×105

Photon Energy=7.94KeVPass Energy=200eVSlit:=C 0.5

Hard X-ray Photoemission Spectroscopy （Evaluation of Energy Resolution） Au Ef spectra

- 1 .0 - 0 .5 0 .0 0 .5

With K-B + Lens

Energy Resolution =255meV

Previous

Inte

nsity

(arb

. uni

ts)

Energy Resolution =237meV

Energy relative to EF (eV)

With K-B

Energy Resolution =217meV

–20meV

Resolution decreases when Object Lens is used.Resolution decreases when Object Lens is used.It results in the aberration (high degree side) due It results in the aberration (high degree side) due to the bend of spheroid shape mesh. to the bend of spheroid shape mesh. ※ Spheroid shape mesh making technology and Spheroid shape mesh making technology and the hole diameter shape are examined. the hole diameter shape are examined. 1

0-1

Emis

sion

Ang

le(d

eg)

7 86 0 eV7 8 567 8 5278 4 8

K ine tic E n erg y (e V)

25

-25

2D detector Image2D detector Image of Angular mode (Au4f)of Angular mode (Au4f)

⑫Photon Energy=7.94KeVPass Energy=200eVSlit:=C 0.5

Hard X-ray Photoemission Spectroscopy （Evaluation of Depth Probing）SiO2 (4nm)/Si spectra

TOA Dependence of Si Oxide

A oxide component increase is confirmed to the surface！

6090 6095 6100 6105

Nor

mal

ized

Inen

sity

Take Off Angle (deg)

Kineitic Energy (eV)

75 65 60 55 50 45 40 35 30 25

Si1s

SiO2

20 30 40 50 60 70 80

Nor

mal

ized

Inte

gral

Inte

nsity

TOA (deg)

1.0

0

-80

-70

-60

-50

-40

-30

-20

Emis

sion

Ang

le (d

eg)

6104610261006098609660946092Kinetic Energy (eV)

2D detector Image2D detector Image of Anglar mode (Si1s)of Anglar mode (Si1s)(Sample Angle 55deg fixed)

The emitted electron angle and depth information can be acquired without changing the angle of the sample.

TOA(deg)Kinetic Energy(eV)

10 min acquisition

TOA dependence of Si1s from SiO2Normalized by substrate Si1s intensity

One Detector Image

⑬Photon Energy=7.94KeVPass Energy=200eVSlit:=C 0.5

Hard X-ray Photoemission Spectroscopy

7800 7820 7840 78600

500

1000

1500

2000

2500

3000

3500Si2s

Au4f

Inte

nsity

(arb

.uni

ts)

Kinetic Energy (eV)

7800 7820 7840 78600

500

1000

1500

2000

2500

3000

Si2s

Au4f

Inte

nsity

(arb

.uni

ts)

Kinetic Energy (eV)

7800 7820 7840 78600

5001000150020002500300035004000450050005500

Si2s

Au4f

Inte

nsity

(arb

.uni

ts)

Kinetic Energy (eV)

Au(μ-dot) /Si

Au (t=20nm)

10μm

5μm

Si substrate

2D mapping of Au pattern on Si substrate by Sample Scanning2D mapping of Au pattern on Si substrate by Sample Scanning

⑭

Step size= 10μm

Hard X-ray Photoemission Spectroscopy （ 2D mapping）

140

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140

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100806040200

6500

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5000 4500 4000

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500

Au4f Si2s

X-axis (μm) Z-axis (μm) X-axis (μm) Z-axis (μm)

μm μm

Spatial Resolution= 1μm

⑮

Hard X-ray Photoemission Spectroscopy

(1) Objective Lens

・Total Acceptance angle = ±32 degrees

(2) K-B mirror

・Beam Size = Φ1μm

(3) Combination

・3D chemical states Mapping is possible now!

Summary

⑯