Industrial ApplicationsElectronicsGate oxide films for LSIThin films for storage devices, etcmaterialsSafety tire, fibersMetal coats, etcEnergy & environmentsDetection of metals in human hairbatteryJASRI Satoshi Komiya01

Industrial Applications of SR Characterization of materialsProduction technologyStructure, Chemical state, Contamination, etc.thin films for electronic devices;LSI, HDD, lasersmetalspolymers, batteries,catalyseshigh brilliant source, x-raybig machinelithography, photo-assisted etching or depositionhigh flux source, ultra-violet-soft x-ray; small machine02

Synchrotron radiation Industrial ApplicationselectronicsMetals & Soft materialsEnergy & EnvironmentBatteries: fuel cell & Li-ion Analysis of contamination elementsCatalysts for environmentTiresFibersOthersBuilding materialsCatalysis InsectsFilms for ULSI, semiconductorsHDD, DVDSemiconductor laserSteel & Coats on steel Al included bubblesLife sciencemedicine 03

CMOS Structurecross sectionkey points for R&D:gate & lines04

Grazing incident x-ray reflection and diffractionIncidenceReflectionHigh brilliant x-ray

Structural analysis of thin filmsDiffractionthin films05

X-ray reflectivity analysisInformation obtainedby reflectivity analysisIncidence angle()Reflection Intensity06

X-ray reflectivity profiles of oxide films on silicon substratesAccuracyThickness0.01nmDensity0.01g/cm3Roughness0.02nm07

X-ray reflectivity profile and interference components (calculation)SiO2 on Sithickness4nmSi=2.33 g/cm3Interference componentsSubtraction technique of the interference component derive easy analysis.SiO2 > Si

SiO2 < Si

R=log10(R/Rave)

Rave:reference

08

Analysis with the interference component4nm thin SiO2 on Si fabricated by thermal oxidationSingle layer modelDouble layer modelInterfacial layer09

Generation of high dense interfacial layeron thermal oxidation process TemperatureTemperaturewetdry SiO2SiInterfacial layer high dense, 1nm thickN.Awaji et al., JJAP 35(1996)L67.10

Development of measurement technique N.Awaji in Fujitsu Labs.Si(002) SiO2 1.0 nm BL16XU BL16B2 Accurate evaluation of ultra-thin filmsBL16XU:undulator beamlineBL16B2:bending magnet beamlineSame region11

X-ray Crystal Truncation Rod ScatteringSiO2/Sicrystalline SiO2Observation of crystalline SiO2 in thermal oxides a-SiO2SiI.Takahashi et al., Physica B245(1998) 306.high dense interfacial layer1.1nmInterference fringes12

N.Awaji Appl. Phys. Lett., 74(1999)2669.In-situ observation of CTR scatteringduring thermal oxidation interface layer = oxidation front : 1 nm at RTfundamental phenomena on thermal oxidation13

J.H. Oh et al., Phys. Rev. B63, 205310 (2001)0.14nmTransition layersTransition layer model3rd Si3+/Si4+ (Si3+

Hard Disk DriveHeadyearMemory density (Mbit/in2) MO HDD15

X-ray reflectivity analysis of multi-layersIncidence angle (deg)Reflection intensityY.Kitade in Fujitsu Labs.16

layered

structure

thickness

(nm)

rouphness

(nm)

Ta2O5

2.0

0.6

Ta

9.3

0.5

PbPtMn

24.3

0.5

CoFe

2.2

0.4

Cu

2.5

0.5

CoFe

2.3

0.4

NiFe

3.8

0.3

Ta

4.8

0.4

I.L.

7

0.2

Si

OpticsFluorescence spectra from spin-valve multi-layers with grazing incidenceWavelength dispersive X-ray fluorescence17

Standing wave is induced into multi-layersincidencereflectionTaPtFeCuX-ray fluorescenceGrazing Incidence X-ray Fluorescence Technique18

Ta2O5TaPdPtMnCoFeCuCoFeNiFeTaT.L.Si substrate

Broadening of the interfaces in GMR multilayers 3584713Depth profiles of elements analyzed from GIXF and reflectivity data(magnetic properties degraded after annealing)N.Awaji Fujitsu scientific & technical journal 38 (2002) 82.19

aa-C cover layerCo alloy recording layerCr buffer layerAl substratecross sectionHccircularradialcoercive forceCo alloy : hcp crystalhard disk texturediffractionc:magnetization axis control the orientationrecord along a circle and in-plane magnetizationmagnetization along a circlealong a radiusalong a circle20

Grazing incidence x-ray diffraction profiles2 (deg)Textured-Al/NiP/Cr/Co-alloy(20nm)/a-CCo(002)Cr(110)Co(002)Co(100)Co(101)Cr(200)=0.5=0.2from Cr buffer layer2 (deg)Intensity (a. u.)circleradiuspreferential orientationof c-axis due to texturealong a circle from only a Co layerunder grazing incidence21

Textured sub.(Ra50)Preferential c-axis orientation dependence of coercive magnetic forceIncrease in coercive force due to preferential c-axis orientation along a circle T.Hirose IEEE Trans. Mag. 33. (1997) 2971. 22

Blue: Ga1-xInxNRed: GaAlAsHow is local structure in GaInN with low In composition less than 20% which is the critical composition for the phase separation?Blue laser for DVD optical storage devices23

InN composition dependence of GaInN XAFS24

wurtzite crystal structure(a=3.189, c=5.185 for GaN)InN composition dependence of radial distribution functionsMonotonic decrease in the second peaks from In-Ga(In) 25

InN composition dependence of the local structure Change of bond anglesInN composition dependence of atomic distances26

Deviation from random distribution of Ga and In atoms in GaInN mixed crystalIn composition dependence of the 2nd neighbor coordination numbersT. Miyajima phys. Stat. Sol. (b) 228, 45 (2001).27

What materials are excellent in high speed record/elimination and reliabilityPhase transition storage materials for DVDRecorded markPhase transition materialsDebye-Scherrer cameraAuGeSnTeGeSbTeAgInSbTeAccurate structure analysis with a Debye-Scherrer camera28

Ag3.4In3.7Sb76.4Te16.5With a laboratory sourceX-ray powder diffraction with SR sourceExcellent resolutionX-ray power diffraction with SR29

R32/R3mTemperature dependence of lattice parameteresAt low temperatureAt high temperatureRandom occupancy of Ag, In, Sb, TeSimple cubic unitsFine crystalline structure of AgInSbTeAg3.4In3.7Sb76.4Te16.530T. Matsunaga Phys. Rev. B64 (2001)184116.

A

B

C

a

b

c

o

11.276A

4.355A

0.2357

rl = 3.343A

rs = 2.955A

A7, R3m

rl

rs

r

z

o

x

r

86.8

y

3a

z = 0.25

zyxxxzzyy GeTe-Sb2Te3 Au25Ge4Sn11Te60 Ag3.4In3.7Sb76.4Te16.5 Unique crystalline phasePoor package :simple cubic, allowance of many vacanciesRandom occupancy of component atoms at lattice sitesCommon properties on three materials31

A package process for fabrication of lasers with various wavelengthDevelopment of laser diodes for optical communicationsControl of wave lengthDFB laser diode integrated with wave length modulator for WDM optical communications systemNarrow-strip selective metal-organic vapor phase epitaxy (MOVPE)32

X-ray micro-beammFormation of x-ray micro-beam with asymmetric diffraction33

Determination of process condition40% up on emission efficiency of semiconductor laserS.Kimura et al., APL 77(2000) 1286.IntensityMask width (m)Composition (x,y)In composition (x)As composition (y)Mask width dependence of lattice parameterMask width dependence of composition (x,y)InxGa1-xAsyP1-x34

X-ray fluorescence analysisSample (Si wafer)Reflected X-rayIncident X-rayDetectors (SC, FPC)Wave dispersiveAnalyzing crystals:LiF(200), PET(002), multi-layersSolar slitEnergy dispersiveSSDPCSROpticsHigh sensitivityLow energy resolutionlow sensitivityhigh energy resolution35

x106 atoms/cm2 = 4 atoms/100m2ITRS road mapUltra-low detection limitatoms/cm2M. Takemura in TOSHIBA36

2002200520082011size(nm)1301007050production(bit)1G2G-16Gallowance(x108 atoms/cm2)4.42.52.11.8

Before concentrationAfter concentrationNi5x1084x106Cu5x1084x106Al2x10118x108

Direct observation of fibers in safety tireSEM imageicetireFibers stick into iceDirect observation of fibers sticking into ice pressfiberR&D on safety tire on iceX-ray tubeSR sourceRefractive contrast imageDifference of absorptionSharp edge image37

spacefiberstireicetireiceicetireFibers stick into iceFibers slip from icepresspullH. Kishimoto in Sumitomo Rubber Industries 38

Observation of crush of babbles in AlCCDCrush from the bottom side X-ray Shock absorber for crushImages stored during 2 secCrush from the both sides Crush all1mmT. Watanabe in Kobelco Research Institute39

In-situ observation of alloying of galvanized steel by ZnLamp heaterRust preventive coatDiffractmeter40

Alloying process of Zn on steelAmount of 1 crystals t (integrated intensities)

Controlled by diffusion processZn-0.14mass%AlFeZn101480Variation of diffraction profiles on alloying41A. Taniyama SPring-8 User Experiment Report 2002A0658.

Characterization of inner stress in coats on turbine bladesVariation of diffraction profiles on heatingGas turbineCoat to protect blades from high temperature gasDiffractometerfurnaceNi3Al(311)

42K. Suzuki SPring-8 User Experiment Report No.8 2001B0063.

Temperature dependence of residual stress in bond-coatZSurface normalDiffract plane nomalTc=0.24mm2constant Ksin2K=(tan0) 2(1+)/ETemperature dependence of residual stress in bond-coatPoissons ratio EYoungs modulaus43

X-ray micro-beam with zone plateFocus with zone platem44

Structural analysis of a single fiberStress-strain of a PBO single fiber 0.01mm in diameterStructural change at local parts in complex fibers.Kodera in JASRI45

(1 fg = 10-15 g)2-D mapping of a very small amount of metals with x-ray fluorescence analysisInfluence of special water from deep sea on the body46.Kagoshima Nucl. Instrum. & Methods. A 467-468 (2001) 872.

Capacity fading on Li ion battery during charge/discharge cyclesCathode:LiNi0.8Co0.2O2In-situ XAFS study on cathode during cycling of batteryX-rayCoin cellNi K-edge XANES spectra of LiNi0.8Co0.2O2Coin cell47

Decrease in capacity due to no return of Li into cathodeNiONiO6Li+capacitycapacity48

Mechanism of the capacity fadingInitial:distorted NiO6 octahedronAfter fading:regular NiO6 octahedronNiO6Li+Jahn-Teller distortionT.Nonaka J. Synchrotron rad., 8 (2001) 869.49

Request to analysis on material science in industryNo detectable with other techniquesHow situation : Research, Development, ProductionR&DExcellent characterizationDevelopment of process : regular measurement according to planTestQuality & Quantity & Time Response to trouble : SpeedHow can we (SR) reply on request?50

Situation in JapanNo detectable with other techniquesHow situation : Research, Development, ProductionR&DExcellent characterizationStructural analysis of thin films of electronic devicesDevelopment of process : Determination of process conditions for laserImaging of tire and bobbled AlTestQuality & Quantity & Time Not actualized in Japanese facilitiesResponse to trouble : SpeedNo answer 51

Industrial Applications in JapanFilms for ULSI, semiconductorsHDD, DVDSemiconductor laserelectronicsMetalsSoft MaterialsEnergy & EnvironmentSteel & rust preventive coat Various coats to prevent heat, stress, etc.Al including bubblesBatteries: fuel cell & Li-ion Analysis of contamination elementsCatalysts for environmentTiresFibersOthersBuilding materialsCatalysis InsectsSynchrotron radiationXAFS, XPS Diffraction; GIXD, Powder Reflectivity, Grazing incidence x-ray fluorescence techniqueFluorescence analysisImaging, Micro-beam52