3. Dynamic SIMS 김경중.ppt [호환 모드]

1

Dynamic SIMS의 원리 및 응용

김 경 중한국표준과학연구원

산업응용측정본부

표면분석교육2019/5/8 (수)

Division of Industrial Metrology 2

SIMS 개요- SIMS의 개요 및 범위

- SIMS의 역사

- SIMS의 산업 응용

SIMS 기본 원리- SIMS 장비 구성

- 이온화율 및 상대감도인자

- 이온빔 스퍼터링 효과

SIMS 응용- 원소분석

- 미량성분 정량분석

- 주성분 정량분석

- 깊이분포도 분석

- 박막두께측정

- 공간분포도 분석

내 용

2

Division of Industrial Metrology

PhotonIon

Electron

PhotonIon

Electron

3

Secondary Ion Mass Spectrometry(SIMS)

Introduction

이차이온질량분석법의 원리이차이온질량분석법의 원리

Out

InPhoton Ion Electron

PhotonIR, Raman XRF, XRD

LAMMAPSD, TPD

XPS, UPS

Ion PIXESIMS, ISS RBS, MEIS

IIE

ElectronIPES

SEM/EDS ESDAES, LEEDTEM, SEM


~ eV

~ keV

~100 keV

~ MeV

Ion Beam Deposition

Sputtering (SIMS)Ion Beam Analysis (ISS)

Ion ImplantationIon Beam Analysis (MEIS)

Ion Beam Analysis (RBS)

DamagedRegion

이온빔 상호 작용이온빔 상호 작용

4

Introduction

3


Primary Ion (~10 keV)Secondary Ion (~10 eV)

Penetration Depth (~ 10 nm)

Information Depth (~ 1 nm)

Surface

Introduction

이차이온질량분석법의 원리이차이온질량분석법의 원리

Secondary Ion Mass Spectrometry (SIMS)


Introduction

이차이온질량분석법의 분석 범위이차이온질량분석법의 분석 범위

4


◈ Discovery of Electron - 1905, J. J. Thomson- Crooks tube- cathode rays

◈ Discovery of Ion- 1907, J. J. Thomson- anode ray tube- canal ray

◈ Separation of Ions - 1913, J. J. Thomson- composition of canal rays (ionized Ne)- through a magnetic and an electric field

History of SIMS

C A B

D

E

이차이온질량분석법의 역사이차이온질량분석법의 역사

7


H. J. Liebl, J. Appl. Phys. 38, 5277 (1967)

History of SIMS

◈ Prototype of SIMS - 1949, Herzog and Viehböck- improved vacuum technology

◈ Magnetic sector SIMS- 1967, Liebel and Herzog- American NASA project- analysis of moon rocks

◈ Quadrupole SIMS- 1970s, K. Wittmack and C. Magee - quadrupole mass analyzer

◈ ToF-SIMS- the 1970s, Benninghoven- time-of flight mass spectrometer

이차이온질량분석법의 역사이차이온질량분석법의 역사

5


◈ Magnetic sector SIMS

◈ Quadrupole SIMS

◈ ToF-SIMS

Quad 4550

IMS7F NanoSIMS50

TRIFT5

Cameca Cameca

Cameca

Ulvac PHIIONTOF

TOF-SIMS5

◈ HR-SIMS

이차이온질량분석기 개발 (상용장비)이차이온질량분석기 개발 (상용장비)

IMS1280-HR

Cameca

History of SIMS

SHRIMP-II

ASI

ADEPT-1010™

ULVAC-PHI

◈ Nano SIMS

Cameca

NanoSIMS 50L

9


◈ Geology - isotopic ratio measurement- trace analysis- radiometric geochronology

◈ Metallurgy and Material sciences- quantification of major components (metal alloy)- quantification of minor components (C, N, O, S)- localization and identification of precipitates

◈ Semiconductor and Solar cell industry- quantification and in-depth distribution of dopants - quantification of major components (reference)- impurities bulk analysis

◈ Organic and Biology- image of elements in cells and tissues- identification of molecular peak

Industrial Application

이차이온질량분석법의 산업 응용이차이온질량분석법의 산업 응용

6


2.0 nm SiO2

1 08 1 06 1 04 10 2 10 0 98 96

1 k

2 k

3 k

4 k

5 k

6 k

7 k

S iS iO

2

B ind in g E n e rg y (eV )

Oxide Thickness

Dist. of N in Oxide

Nano Shape (SEM, AFM)

Quant. of major comp.

Depth Dist. Of Dopants

Nano area strain Activated comp.

405 400 395 390

1k

2k

3k

4k

5k

6k

7k

N 1s

Binding energy (eV)

0 15 30 45 60 75

110 108 106 104 102 100 98 96 940

1k

2k

3k

4k

5k

6kSi 2p

XP

S In

ten

sity

(cp

s)

Binding energy (eV)

0 15 30 45 60 75

0 50 100 150 200 250 300 3501015

1016

1017

1018

1019

1020

10B

Co

nce

ntr

atio

n (

ato

ms/

cm3 )

Sputter Depth (nm)

Qunat. of minor comp.

0 50 100 150 200

0

20

40

60

80

100 Si Ge

Co

nce

ntr

atio

n (

%)

Depth (nm)0 50 100 150 200

100

101

102

103

104

105

106

Si Ge

Inte

nsi

ty (

cps)

Depth (nm)


11

차세대 반도체 분석 응용차세대 반도체 분석 응용


Total Area Spectrum

Primary Ion Beam

Total Ion Image

m/z

Sample

m/z

Region 1 Spectrum

m/z

Region 2 Spectrum

Chemical Map 1

Chemical Map 2


유기 및 바이오 분자 분석유기 및 바이오 분자 분석

12

7



- SIMS의 역사





SIMS를 이용한 다양한 분석법- 원소분석






내 용


Instrumentation

Schematic Diagram of SIMS Instrument

Mass analyser

Ion gun

Detector

8


Cs sourceDuoplasmatron

source

Accel-Decel

PBMF

Isolation valve

Primary Faraday cup

Airlock system

Cs source isolation valve

E.S.A Energy slit

Exit slit

E.M.

Post Acc.

Faraday cup

Channel plate

Fluorescent screen

Sample-10 to +10 kV

Fieldaperture

Lens

Diaphragm, slit (automation option)

Electrostatic sector

Magnetic sector

Deflector

Stigmator

Entrance slit

N.E.G.Isolation valve

Contrast aperture

Laminated magnet

Instrumentation

Cameca IMS-7f SIMS

Primary Ion gun

Mass analyser

Detector


Instrumentation

Primary Ions

Duoplasmatron (Ar+, O2+) Surface Ionization (Cs+)

- Argon : sputtering, surface cleaningAES, XPS sputter depth profiling

- Oxygen : positive SIMSEnhanced ion yield for positive elements

- Cesium : negative SIMSEnhanced ion yield for negative elements

9


- Quadrupole :Relatively inexpensiveFast switchingControl of incidence angle : ultra high depth resolution

- Magnetic Sector :High transmission : ultimate detection limitHigh mass resolution : no mass interference

- Time-of-Flight :High molecular weight determinationRapid surveyUltra low dose: surface contamination analysis

Instrumentation

Mass Analyzer


U+Vcos(wt)

- relatively cheap- fast switching fast analysis- high incidence angle high depth resolution- insulator analysis

Instrumentation

Quadrupole Mass Analyzer

- poor mass resolution- poor transmission low detection limit

- low mass range

10


K.E. = 0.5 mv2 = eV

mv2 / r = Hev

mveHr =

1H

=me2V

me

H2r2

2V=

double focusing electorostatic / magnetic sector:- high transmission : ultimate detection limit, impurity bulk analysis- high mass resolution : no mass interference- ion microscope, higher mass range

Instrumentation

Magnetic Sector Mass Analyzer


Ion Gun

Spectrum

Ion Mirror

Focusing

Raster

Target

PulsingDetector

Transport Optics

Extractor

Electron Flood Gun

- high sensitivityhigh transmission

- high mass resolution10,000

- high mass rangeup to 10,000uorganic & bio molecule anal.

- rapid survey

K.E. = qV = 1/2 mv2

t = L/v = L / (2qV/m)1/2

m/q = (2V/L2)t2

Instrumentation

Time-of-Flight Mass Analyzer

Reflector의 역할

TOF의 특징

11


Instrumentation

Comparison of Mass Spectrometer


Electron Multipliers Faraday Cup

Instrumentation

Detectors

Micro-Channel Plate

12



- SIMS의 역사











내 용


Fundamentals

Dynamic SIMS vs Static SIMS

Dynamic SIMS and static SIMS are distinguished by the primary ion dose acceptable duringanalysis. The minimum dose in a dynamic SIMS measurement is ∼1017 ions/cm2.

For static SIMS, the probability of secondary ions being detected from sample surface alreadymodified by previous ion impact should be≪1.

In practice, the acceptable primary ion dose density is to <1013 ions/cm2 per experiment.

13


Fundamentals

◈ Working dynamic range (Dw) : around 10 orders of magnitudein concentration (i.e. from 5 × 1022 to 5 × 1012 atoms cm−3).

◈ Detection limit :1013 ~ 1016 atoms cm−3 for most impurities insemiconductors

◈ Lateral resolution : 20 nm

◈ Depth resolution : sub-nm

Dynamic SIMS


Fundamentals

Interaction of the Primary Beam

26

- : primary particle flux

- : sputter yield

- : ionization probability

- : fractional concentration

- : analysis system transmission

secondary ion current ( )I ms

14


0 5 10 15 20 25-6.0

-4.0

-2.0

0.0

2.0

4.0

Ionization Potential

Log

(Rel

ativ

e Io

n Y

ield

)

Ionization Potential

Fundamentals

27

Relative Sensitivity Factors (Positive Ion)


Fundamentals

28

Relative Sensitivity Factors (Positive Ion)

15


0 1 2 3 4-5

-4

-3

-2

-1

0

1

2

Electron Affinity

Log

(Rel

ativ

e Io

n Y

ield

)

Electron Affinity

Fundamentals

29

Relative Sensitivity Factors (Negative Ion)


Fundamentals

30

Relative Sensitivity Factors (Negative Ion)

16


O2+ Primary

Positive Secondary

Cs+ PrimaryNegative Secondary

Fundamentals

Relative Sensitivity Factors

31



- SIMS의 역사











내 용

17


Primary ions

Direct Recoils

Cascade Mixing

Collective relocation

Sputtering

Original Surface

Eroding Surface

Internal Plane

Fundamentals


33

◈ Preferential Sputtering

◈ Atomic Mixing

(Knock-on and Cascade)

◈ Radiation-induced Migration

(Diffusion, Segregation)

◈ Surface Topography

Interaction between the primary ion beam and the sample leads to complex masstransport effects, atomic mixing, radiation enhanced diffusion and segregation etc. in the nearsurface region, because of energy deposition by the beam and the accretion of probe atoms.

Collision Cascade Surface Change by Ion Sputtering


93 94 95 96 97 98 99 1000

50

100

150

200

250

300

350

400

450

500

2 nm

As Received (xxxx)After Sputtering (oooo)

W in

ten

sity

(co

un

ts)

Energy (keV)

800 600 400 200 0

Si 2s

W 4p3/2

in situ XPS W 31.3% Si 68.7%

W 4d

After sputteringW 52.9% Si 47.1 % Si 2p

W 4f

Inte

nsi

ty (

a.u

.)

Binding Energy (eV)

Fundamentals


34

Preferential Sputtering

18


Ion beam mixing

Fundamentals

작은 에너지 및 큰 입사각에 의해 이온빔 혼합이 효율적으로 감소함


78 80 82 84 86 88 90 92

0.0

0.5

1.0

1.5

2.0

2.5

Surface peak+ 0.6 nm

5.5 nm

clean Si(100)

0o

45o

60o

80o

Inte

nsity

( C

ount

s )

Energy ( keV )

500 eV O2+


Ra

tio

of

dec

ay l

eng

th

elements in Si

10 keV Ar+

oxygen leak

Heat of formation / mole of oxygen (kcal/mole)

12 keV O2+

2o incidence

Cu Si 200 keV, 1 x 1015 cm-1

5.5 keV O2+

64o incidence

Depth (nm)

63C

u+

Rel

ativ

e In

ten

sity

Surface Segregation

Fundamentals

108 106 104 102 100 98

XP

S In

ten

sity

(A

rb. U

nit

)

Binding Energy (eV)

Si 2p

5keV O2+

입사각 (o)

60

45

37

30

25

15

0

36


이온빔 스퍼터링에 따른 매질 물질의 화학상태 변화, 표면에너지 차이에 의한 물질 이동

19


7 keV O2+ Cr/Ni ML

Surface Topography (Ripple)

Appl. Phy. Lett., 60, 1178 (1992)

Ni Cr

Ni Cr

Cr Ni

Ni Cr

Cr

Si

Fundamentals

37


7 keV O2+ Fe/Si SL

Surface Topography (Hollow, Island)Fundamentals

20


7 keV O2+ Ta/Si

Appl. Phys. Lett. 69, 2483 (1996)

Surface Topography (Crater)Fundamentals


0 50 100 150 200 250 300100

101

102

103

104

105

106

Inte

ns

ity(

cps)

Sputter Depth(nm)

Si As

0 50 100 150 200 250 300100

101

102

103

104

105

106

Sputter Depth(nm)

Si AsSi

14.5 keV C600.5 keV Cs

“Hershey Kisses”Platelet like grain

Surface Topography (Hershey Kisses)

C60+ As-Si/Si ML

Appl. Surf. Sci. 252, 6521 (2006)

Fundamentals

21



- SIMS의 역사











내 용


Analysis Methods

Surface Spectroscopy Surface Imaging Depth Profiling

SIMS를 이용한 분석 기법SIMS를 이용한 분석 기법

22


Analysis Methods

SIMS를 이용한 분석 기법SIMS를 이용한 분석 기법

분석 장비 분석 기술

AES

XPS/UPS

SIMS / TOF-SIMS

XRR/XRD

Raman/FTIR

RBS/MEIS

TEM/SEM/EDS

주성분 정량 분석

미량 성분 정량 분석

깊이 분포 분석

공간 분포 분석

박막 두께 측정

전기적 특성 평가

화학 상태 분석

결정 구조 분석

성분 원소 분석


Survey Mass Spectrum

Analysis Method 1

SIMS 원소분석SIMS 원소분석

Mass spectrometry is inherently background free because the mass spectrum isdiscrete and not superimposed.

23


XPS survey spectrum of Si wafer AES survey spectrum of CuInSe2 film

EN(E) spectrum

EdN(E)/dE spectrum

SIMS 원소분석법 - XPS 및 AES와 비교SIMS 원소분석법 - XPS 및 AES와 비교Analysis Method 1


R=m/∆m

High Mass Resolution

46

원소분석 - 고질량분해능원소분석 - 고질량분해능Analysis Method 1

24


Even at a modest mass resolution (e.g. M/ΔM = 1000) a well set up magnetic or quadrupoleSIMS spectrometer should be capable of a rejection ratio (IM/I(M±1)) of >108, where I(M) is theintensity recorded at mass M, etc.

원소분석 - 고질량분해능원소분석 - 고질량분해능Analysis Method 1



- SIMS의 역사











내 용

25


미량성분 정량분석미량성분 정량분석

49

Analysis Method 2


CdIId

tCIRSF

bi

m

- RSF: relative sensitivity factor of the impurity withrespect to the matrix

- : ion implant fluence in atoms/cm2

- C: number of measurements or data cycles- d: crater depth in cm - ∑Ii : sum of impurity isotope secondary ion counts- Ib : background ion intensity of Ii in counts/cycle- t : analysis time in s/cycle

mii IRSFIX /][ - Xi : concentration of impurity- Ii : intensity of impurity- Im : intensity of matrix

0 100 200 300 4001015

1016

1017

1018

1019

1020

10B

Co

nce

ntr

atio

n (

ato

ms/

cm3 )

Sputter Depth (nm)

- Certification method: NDP

- Dose: 1.018 x1015 atoms/cm2

Uncertainty: 0.035 x1015 atoms/cm2

- Peak conc. of 10B: 8.37x1019/cm3

NIST CRM 2137

50

미량성분 정량분석미량성분 정량분석Analysis Method 2

26


0 200 400 600 800 1000 1200 1400100

101

102

103

104

105

106

107

108B

Ti

Ga

SnAg Si

Inte

nsi

ty (

cps)

Sputter Depth (nm)0 200 400 600 800 1000 1200 1400

100

101

102

103

104

105

106

107

108

A

Ti

Ga

SnAg Si

Inte

nsi

ty (

cps)

Sputter Depth (nm)

0 200 400 600 800 1000 1200 14001016

1017

1018

1019

1020

1021

B

A

P

Co

nce

ntr

atio

n (

ato

ms/

cm3 )

Sputter Depth (nm)0 200 400 600 800 1000 1200 1400

1016

1017

1018

1019

1020

1021

B

B

P

Co

nce

ntr

atio

n (

ato

ms/

cm3 )

Sputter Depth (nm)

51

미량성분 정량분석미량성분 정량분석

정상소자 불량소자

Analysis Method 2


0 200 400 600 800 1000100

101

102

103

104

105

106

107

10B+

29Si2

+

28Si2

+

Inte

nsi

ty

Sputter Time (s)0 200 400 600 800 1000

100

101

102

103

104

105

106

107

10B+

29Si2

+

28Si2

+

Inte

nsi

ty

Sputter Time (s)

Secondary Reference

Test Sample

Quantification of B in Si (ISO-14237)

0 100 200 300 4001015

1016

1017

1018

1019

1020

10B

Co

nce

ntr

atio

n (

ato

ms/

cm3 )

Sputter Depth (nm)

10B+

Primary Reference

RSF Tm

Sii

Ti

Ti IRSFIX /][ S

miiSi

Si IRSFIRSF /][

= ImS

= ImS

= ImT

= ImT

52

미량성분 정량분석미량성분 정량분석Analysis Method 2

27



- SIMS의 역사











내 용


◈ Pure Element-RSF (PE-RSF) : determined from pure elements(matrix effect, sputtering effect)

: 측정 시료 중 원소 A의 조성

: 측정 시료에서 측정된 원소 A의 세기

: 순수한 시료에서 측정된 원소 A 세기 (PE-RSF)

unkiXunkiI

iS

0 20 40 60 80 1000

20

40

60

80

100

Bulk Composition, Co at. %

Su

rfac

e C

om

po

siti

on

, Co

at.

%

0 20 40 60 80 1000

20

40

60

80

100

Bulk Composition, Au at. %

Co

mp

osi

tio

n b

y X

PS

, Au

at.

%

(a) Co-Ni alloy (c) Au-Cu alloy

0 20 40 60 80 1000

20

40

60

80

100

Co

mp

osi

tio

n b

y X

PS

(P

t at

.%)

Bulk Composition (Pt at. %)

(d) Pt-Co alloy

0 20 40 60 80 1000

20

40

60

80

100

Bulk Composition, Fe at. %

Co

mp

osi

tio

n b

y X

PS

(F

e at

.%)

(b) Fe-Ni alloy

54

)(

)(

1

n

j junkj

iunkiunk

iSI

SIX

주성분 정량분석주성분 정량분석Analysis Method 3

28


◈ Average Matrix-RSF (AM-RSF) : matrix effect correction(sputtering effect)

◈ Alloy Reference-RSF (AR-RSF) : from an alloy reference

3

)()(

)()(

A

B

BBAAB

AABABAAB a

a

EE

EEF

1

2

2 ln

E

D

E

CEEE p

j

n

j junkj

iiunkiunk

iFSI

FSIX

)(

)(

1

)(

)(

1

n

j

ARj

unkj

ARi

unkiunk

iSI

SIX

5555

주성분 정량분석주성분 정량분석Analysis Method 3


0 50 100 150 200101

102

103

104

105

106

58Ni

56Fe

Sec

on

dar

y Io

n C

ou

nt

(cp

s)

Sputter Depth (nm)

Average

ARRSF from a Fe51-Ni49 Alloy

INi

IFe

0 50 100 150 2000

20

40

60

80

100

50%

51%

56Fe

Co

mp

osi

tio

n (

Fe

At.

%)

Sputter Depth (nm)

Compositional DP of theFe51-Ni49 Alloy Film by C60

)( 51FeC

IR

Fe

FeFe

)( 51FeC

IR

Ni

NiNi

)( NiNiFeFe

FeFeFe RIRI

RIX

56

주성분 정량분석 (Fe-Ni 합금)주성분 정량분석 (Fe-Ni 합금)Analysis Method 3

29


0 20 40 60 80 1000

20

40

60

80

100

Co

mp

osi

tio

n b

y C

60 S

IMS

(F

e at

.%)

ICPMS C60

SIMS 27.61 26.87 50.59 50.59 77.80 78.21

m = 1.023 (0.005), C = -1.289 (0.274)

XC

60SIMS

=mXICPMS

+ C

Composition by ICP-MS (Fe at. %)

101

102

103

104

105

106

58Ni

56Fe

Sec

on

dar

y Io

n C

ou

nt

(cp

s)

101

102

103

104

105

106

58Ni

56Fe

Sec

on

dar

y Io

n C

ou

nt

(cp

s)

0 50 100 150 200101

102

103

104

105

106

58Ni

56Fe

Sec

on

dar

y Io

n C

ou

nt

(cp

s)

Sputter Depth (nm)0 50 100 150 200

0

20

40

60

80

100

79%78%

56Fe

Co

mp

osi

tio

n (

Fe

At.

%)

Sputter Depth (nm)

0

20

40

60

80

100

26%

27%

56Fe

Co

mp

osi

tio

n (

Fe

At.

%)

0

20

40

60

80

100

50%51%

56Fe

Co

mp

osi

tio

n (

Fe

At.

%)

Good linear relationship

Original SIMS DPsComposition DPsHomogeneity with depth Quantification

Fe28Ni72

Si(100)

Fe51Ni49

Si(100)

Fe78Ni22

Si(100)

Average

Average

Average

57

주성분 정량분석 (Fe-Ni 합금)주성분 정량분석 (Fe-Ni 합금)Analysis Method 3


0 20 40 60 80 1000

20

40

60

80

100

m = 1.022(0.019), c = -0.902(0.888)

XRBS

= mXICPAES

+ c

Nom. RBS66.3 66.639.8 40.318.3 17.5

Co

mp

osi

tio

n b

y R

BS

(P

t at

.%)

Composition by ICP-OES (Pt at. %)

Pt18Co82

Si(100)

Pt40Co60

Si(100)

Pt66Co34

Si(100)

Certification by ICP-OESSamples

0 20 40 60 80 1000

20

40

60

80

100

Nom. C60

SIMS 18.3 18.9 39.8 39.8 66.3 62.1

m = 0.898 (0.037), C = 3.039 (1.705)

XPt

SIMS=m XPt

nom+ C

Co

mp

osi

tio

n b

y C

60 S

IMS

(P

t at

.%)

Composition by ICP-OES (Pt at. %)

RSF from Pt40Co60 Alloy

58

주성분 정량분석 (Pt-Co 합금)주성분 정량분석 (Pt-Co 합금)Analysis Method 3

30


0

20

40

60

80

100 Si Ge

Co

nc

entr

ati

on

(%

)

0

20

40

60

80

100 Si Ge

Co

nc

entr

ati

on

(%

)

0

20

40

60

80

100 Si Ge

Co

nc

entr

ati

on

(%

)

0

20

40

60

80

100 Si Ge

Co

nc

entr

ati

on

(%

)

0 50 100 150 200 2500

20

40

60

80

100 Si Ge

Co

nc

entr

ati

on

(%

)

Depth (nm)

Average

Average

Average

Average

100

101

102

103

104

105

106

Si Ge

Inte

ns

ity

(cp

s)

100

101

102

103

104

105

106

Si Ge

Inte

ns

ity

(cp

s)

100

101

102

103

104

105

106

Si Ge

Inte

ns

ity

(cp

s)

100

101

102

103

104

105

106

Si Ge

Inte

ns

ity

(cp

s)

0 50 100 150 200 250100

101

102

103

104

105

106

Si Ge

Inte

ns

ity

(cp

s)

Depth (nm)

Average

RII

IX

GeSi

SiSi /

RII

IX

SiGe

GeGe

0 20 40 60 80 1000

20

40

60

80

100

Co

mp

osi

tio

n b

y S

IMS

(S

i at

%)

Composition by RBS (Si at %)

m = 0.932 (0.032) c = 4.827 (2.079)

XSIMS

=mXRBS

+ c

0 20 40 60 80 1000

20

40

60

80

100

Co

mp

osi

tio

n b

y S

IMS

(S

i at

%)

Composition by RBS (Si at %)

m = 1.039 (0.043) c = 0.009 (2.820)

XSIMS

=mXRBS

+ c

RBS 2keV

33.6 37.1

52.4 52.4

64.7 63.7

77.1 76.7

87.3 87.2

RBS 5keV

33.6 36.6

52.4 52.4

64.7 65.6

77.1 81.0

87.3 91.4

(a) 2 keV

(b) 5 keV

Ge13Si87

Si(100)

Ge23Si77

Si(100)

Ge35Si65

Si(100)

Ge48Si52

Si(100)

Ge66Si34

Si(100)

59

주성분 정량분석 (Si-Ge 합금)주성분 정량분석 (Si-Ge 합금)Analysis Method 3


Total Number Counting

composition of whole film

average composition

0 500 1000 1500 2000100

101

102

103

104

105

106

107

Sputter Depth (nm)

Se

GaCuIn

Inte

nsi

ty (

cp

s)

)( ARi

ARi

ARi CIS

Depth Profiling of an Alloy Reference Film

RSFs from the integrated intensities

Certification by ICP-MS

solution of whole film

average composition

CIGS

glass

glass

Film material is selectively dissolved in a solvent

solvent

The solution including film material is analyzed by ICP-

MS

Quantitative Analysis

Compositional Depth

Profiling

Quantitative Analysis

0 500 1000 1500 2000100

101

102

103

104

105

106

107

Sputter Depth (nm)

Se

GaCuIn

Inte

nsi

ty (

cp

s)

0 500 1000 1500 20000

20

40

60

80

100

Sputter Depth (nm)

Se

GaCu

In

Co

mp

osi

tio

n (

at%

)

100)(

)(

1

n

j

ARj

unkj

ARi

unkiunk

iSI

SIX

60

주성분 정량분석 (CIGS 박막)주성분 정량분석 (CIGS 박막)Analysis Method 3

31


Laboratory Country SIMS XPS AES EDX XRF

NMIand DI(9)

BAM Germany ○ ○

INPL Israel ○

KRISS Korea ○

NIM China ○

NIST USA ○ ○

NMIJ Japan ○

NMISA South Africa ○

NPL UK ○ ○

PTB Germany ○

nonNMI(6)

CNU Korea ○

NIMS Japan ○

KIST Korea ○

LSA UK ○

NNFC Korea ○

ZSW Germany ○

Number of Data 6 4 4 2 2

61

주성분 정량분석 (CIGS 박막) - 국제 RRT주성분 정량분석 (CIGS 박막) - 국제 RRTAnalysis Method 3


1 2 3 4 5 6 7 8 9 10 11 12 135.5

6.0

6.5

7.0

7.5

Ga

Ato

mic

Fra

ctio

n (

at%

)

1 2 3 4 5 6 7 8 9 10 11 12 1346

47

48

49

50

51

52

53

54

Se

Ato

mic

Fra

ctio

n (

at%

)

1 2 3 4 5 6 7 8 9 10 11 12 1321

22

23

24

25

26

27

Cu

Ato

mic

Fra

ctio

n (

at%

)

1 2 3 4 5 6 7 8 9 10 11 12 1316

17

18

19

20

21

22

In

Ato

mic

Fra

ctio

n (

at%

)

● SIMS ■ XPS ♦ AES ▲ XRF ▼ EPMA

%59.0=%46.2= atUref %47.0=%46.2= atUref

%16.0=%46.2= atUref %24.1=%46.2= atUref

62

주성분 정량분석 (CIGS 박막) - 국제 RRT주성분 정량분석 (CIGS 박막) - 국제 RRTAnalysis Method 3

32


Compositional Depth Profiling of Multi-element alloy film

0 500 1000 1500 2000100

101

102

103

104

105

106

107

Mo

Se

Ga

Cu

In

Inte

nsi

ty (

cps)

Sputter Depth (nm)0 500 1000 1500 2000

100

101

102

103

104

105

106

107

Mo

Se

Ga

Cu

In

Sputter Depth (nm)0 500 1000 1500 2000

100

101

102

103

104

105

106

107

Mo

Se

Ga

Cu

In

Sputter Depth (nm)0 500 1000 1500 2000

100

101

102

103

104

105

106

107

Mo

Se

Ga

Cu

In

Sputter Depth (nm)

0 500 1000 1500 20000

10

20

30

40

50

60

In

Ga

Cu

MoSe

Co

mp

osi

tio

n (

at. %

)

Sputter Depth (nm)0 500 1000 1500 2000

0

10

20

30

40

50

60

Sputter Depth (nm)0 500 1000 1500 2000

0

10

20

30

40

50

60

Sputter Depth (nm)0 500 1000 1500 2000

0

10

20

30

40

50

60

Sputter Depth (nm)

63

주성분 정량분석 (CIGS 박막)주성분 정량분석 (CIGS 박막)Analysis Method 3



- SIMS의 역사











내 용

33


◈ Destructive: Sputter Depth Profiling - Analysis of sputtered particle:

SIMS, SNMS, GD-OES, GD-MS

- Analysis of residue surface: AES, XPS, ISS

◈ Non-destructive Depth Profiling- RBS, MEIS- HI-ERDA- AR-XPS, XES

◈ Cross-Sectional Line Scan- SEM/EDX, SEM/WDX, TEM/EDX- SAM- TOF-SIMS

65

깊이분포도 분석법의 종류깊이분포도 분석법의 종류Analysis Method 4


◈ Special Features- High Sensitivity(ppm, ppb)

- Analysis of all Elements with Isotopes

- Rapid Analysis

- Good Depth Resolution

- Microanalysis with Focused Ion Beam

◈ Non-destructive Depth Profiling- Severe Artifacts

- Difficult Quantification

- Destructive

66

SIMS 깊이분포도 분석법의 특성SIMS 깊이분포도 분석법의 특성Analysis Method 4

34


0 50 100 150 200 250 300 35010

0

101

102

103

104

105

29Si

74Ge

Sec

on

dar

y Io

n C

ou

nt

Sputter Depth (nm)

0 50 100 150 200 250 300 350

0

20

40

60

80

100

29Si

74Ge

Rel

ativ

e C

om

po

siti

on

(%

)

Sputter Depth (nm)

0 100 200 300 400 500 600 700100

101

102

103

104

105

29Si

74Ge

Sec

on

dar

y Io

n C

ou

nt

Sputter Time (s)

0 50 100 150 200 250 300 350

0

20

40

60

80

10029Si

74Ge

Rel

ativ

e C

om

po

siti

on

(%

)

Sputter Depth (nm)

1. Calib. of depth scale

Stylus Profilometer, (Step-height Standardor multiple deltalayer)

2. Conversion to comp. Prof.

Si50Ge50 Alloy CRM

3. Calib. of etching rate

Si/Ge multilayer CRM

67

깊이분포도 분석깊이분포도 분석Analysis Method 4


Si/Ge 델타다층박막 CRM 두께 인증

Si layer 1 2 3 4 5 6

Thick. 39.5 39.6 39.1 39.0 39.1 37.8

Sm 0.27 0.35 0.24 0.19 0.50 0.45

Um 0.12 0.13 0.09 0.08 0.19 0.17

Ur 0.09 0.09 0.09 0.09 0.09 0.09

Uc 0.15 0.16 0.13 0.12 0.21 0.19

U (nm) 0.29 0.31 0.25 0.24 0.41 0.38

0 250 500 750 1000

-600

-400

-200

0

200

CB

A

Crater Size (m)

Cra

ter

Dep

th (

nm

)

0 100 200 300100

101

102

103

104

105

106

107

Sec

on

dar

y Io

n C

ou

nt

(cp

s)

Sputter Depth (nm)0 200 400 600 800 1000 1200

100

101

102

103

104

105

106

107

Interface

301.47 nm

Sec

on

dar

y Io

n C

ou

nt

(cp

s)

Sputter Time (s)

분석 깊이 단위 변환( s nm )

0 50 100 150 200 250 300100

101

102

103

104

105

29Si 74Ge

Inte

nsi

ty (

cou

nts

/sec

)

0 50 100 150 200 250 300100

101

102

103

104

105

29Si 74Ge

0 50 100 150 200 250 300100

101

102

103

104

105

29Si 74Ge

0 50 100 150 200 250 300100

101

102

103

104

105

Sputter Depth (nm)

Inte

nsi

ty (

cou

nts

/sec

)

29Si 74Ge

0 50 100 150 200 250 300100

101

102

103

104

105

Sputter Depth (nm)

29Si 74Ge

0 50 100 150 200 250 300100

101

102

103

104

105

29Si 74Ge

Sputter Depth (nm)

0 50 100 150 200 250 3000

50

100

150

200

250

300

6 Spectra - HMax

m = 0.985 (0.005)C = 2.544 (0.695) nm

dstylus

= mdnom

+ c

Dep

th b

y S

tylu

s, D

styl

us (

nm

)

Nominal Depth, Dnom

(nm)

일반적인 SIMS 분석 깊이 보정법

깊이분포도 분석 - 분석 깊이 보정깊이분포도 분석 - 분석 깊이 보정

◈ Depth Scale Calibration

Analysis Method 4

35


Nom 1 2 5 6 7 8 9 10 11 12 Ave. stdev RSD (%)

2nd 79.04 73.90 79.10 76.20 77.32 75.50 76.70 81.76 71.40 68.70 77.02 - - -

4th 157.22 151.00 157.30 152.17 153.91 153.80 155.80 163.12 147.80 145.80 157.12 - - -

6th 234.13 226.00 234.80 230.87 229.62 228.20 232.30 232.02 221.80 219.60 229.93 - - -

slope - 0.981 1.000 0.997 0.982 0.985 1.003 0.969 0.970 0.973 0.986 0.99 0.01 1.24

offset - -3.476 -0.345 -3.281 -0.358 -1.888 -2.380 7.022 -5.058 -7.866 0.081 - - -

◈ 실험내용- 3개의 SIMS 깊이분포도 분석 후 크레이터 깊이를 측정하여 델타 층의 위치 비교

◈ 참여업체 : 12기관- KIST, RIST, ETRI, LG-ELITE, Samsung SDI, SAIT, KBSI, Hynix Sem.,

Samsung Elec. Dongbu Elec., KRISS, Samsung LCD

◈ 공동분석 결과- 평균치가 1% 이내에서 인증 결과와 잘 일치함- 실험실 간의 결과가 2% 이내에서 잘 일치함


◈ Depth Scale Calibration

Analysis Method 4


Determination of sputtering rate in the surface region

(1) Calibration by sputtering rate

(2) Calibration by crater depth

(3) Uncertainty of calibrated depth

70


0 50 100 150 200 250 300100

101

102

103

104

105

106

107

10B+

11B+

29Si2

+

28Si2

+

Inte

nsi

ty

Sputter Time (s)

Transient Behavior

◈ Depth Scale Calibration : nm surface region

Analysis Method 4

36


◈ Factors Affecting on SIMS Depth Resolution

◈ Instrumental Factors- Edge Effect- Ion Beam Components (Impurities and Neutrals)

- Residual Gas Adsorption

◈ Ion Beam-Surface Interaction- Atomic Mixing - Preferential Sputtering- Sputter-induced Surface Roughness- Matrix Effects- Radiation-induced Migration (Diffusion, Segregation)- Chemical Effects (Decomposition, Compound Formation)

71

깊이분포도 분석 - 깊이분해능 평가깊이분포도 분석 - 깊이분해능 평가Analysis Method 4


◈ Depth Resolution

Measure of the ability to localize a concentration measurement at a depth anddistinguish between features at different depths. It is usually expressed as a parameterextracted from the measured profile of a thin plane of impurity grown by MBE or CVD.

Deltalayer FilmMultilayer Film

Depth ProfilingDepth ProfilingAnalysis Method 4

37


22

21

0

/5.0/)(exp1

/5.0/)(exp1)()(

0

0

TT

LLTL

zzerf

zzerfIzI

00 ],/)exp[()(fL zzzzAz L

2

2

2

)(exp

2)(

0

zzB

zg

Convolution of a double exponential with a Gaussian

2///)( ,2///)( 00 21 TL zzzzwhere M.G.Dowsett et al. JVST B12, 86(1994)

00 ],/)(exp[)(fT zzzzAz T

Exponential rising edge

Exponential trailing edge

Gaussian-like rounded top

135 140 145 150 155 160

T : 1.27 nm

L : 0.31 nm

: 0.81 nm

Sec

on

dar

y Io

n C

ou

nt

Sputter Depth (nm)

B-doped Si delta layer

leading edgedecay length

trailing edgedecay length

Gaussianbroadening

◈ Depth Resolution



0 10 20 30 40 50 60 70100

101

102

103

104

105

106

SIM

S In

ten

sity

(cp

s)

Sputter Depth (nm)10 20 30 40 50 60

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

FWHM

T

L

Sputter Depth (nm)

B-doped Si 델타 다층 박막 (500 eV O2+)


38



- SIMS의 역사











내 용


Definition of Interface in SIMS Depth Profiling

alloy reference film not practical

Interface

0 50 100 150 200 250 300 350 400 4500

20

40

60

80

100

Ato

mic

Fra

ctio

n (

at%

)

Sputter Depth (nm)

A

B

50 at%

General definition 50 at% definition

Analysis Method 5

76

39


Medium Intensity Ratio Definition

Raw Depth Profile

0 100 200 300 4000.0

0.2

0.4

0.6

0.8

1.0

1.2 iSnormi

F

norm

Sputter Depth (nm)

No

rmal

ize

d S

IMS

Inte

nsi

ty

0 100 200 300 4000

25

50

75

100r

Sr

F

Sputter Depth (nm)

Inte

nsi

ty R

atio

(%

)

0 100 200 300 400 500 600 70010

0

101

102

103

104

105

IS

plateauIF

plateau

iS

rawiF

raw

Sputter Time (s)

SIM

S In

ten

sit

y (c

ps

)

interface

Normalized Depth Profile Intensity Ratio Depth Profile

plateauF

rawF

normF Iii /

plateauS

rawS

normS Iii /

(%)100)/( normS

normF

normFF iiir

(%)100)/( normS

normF

normSS iiir

Medium Intensity

Ratio

no need of a reference film - internal reference

Analysis Method 5

77


0 200 400 600100

101

102

103

104

105

28SiCs2

58NiCs2

Sputter Time (s)

SIM

S In

ten

sity

(cp

s)

0 200 400 60010

0

101

102

103

104

105

28SiCs2

58NiCs2

Sputter Time (s)

0 200 400 60010

0

101

102

103

104

105

28SiCs2

58NiCs2

Sputter Time (s)

0 200 400 60010

0

101

102

103

104

105

28SiCs2

58NiCs2

Sputter Time (s)

0 200 400 60010

0

101

102

103

104

105

28SiCs2

58NiCs2

Sputter Time (s)

0 100 200 300 400 5000

20

40

60

80

100

28SiCs

2

58NiCs2

Sputter Depth (nm)

Inte

nsi

ty R

atio

(%

)

0 100 200 300 400 5000

20

40

60

80

100

28SiCs2

58NiCs2

Sputter Depth (nm)

0 100 200 300 400 5000

20

40

60

80

100

28SiCs2

58NiCs2

Sputter Depth (nm)

0 100 200 300 400 5000

20

40

60

80

100

28SiCs2

58NiCs2

Sputter Depth (nm)

0 100 200 300 400 5000

20

40

60

80

100

28SiCs2

58NiCs2

Sputter Depth (nm)

5.0 nm 182.7 nm

31.5 nm 208.6 nm

66.0 nm246.9 nm

102.3 nm290.2 nm

176.8 nm367.8 nm

0 200 400 60010

0

101

102

103

104

105

28SiCs2

58NiCs2

Sputter Time (s)

0 100 200 300 400 5000

20

40

60

80

100

28SiCs2

58NiCs2

Sputter Depth (nm)

241.1 nm429.4 nm

58NiCs2+

28SiCs2+ 28SiCs2

+

58NiCs2+ 58NiCs2

+

28SiCs2+ 28SiCs2

+

58NiCs2+ 58NiCs2

+

28SiCs2+ 28SiCs2

+

58NiCs2+

58NiCs2+

28SiCs2+ 28SiCs2

+

58NiCs2+ 58NiCs2

+

28SiCs2+ 28SiCs2

+

58NiCs2+ 58NiCs2

+

28SiCs2+ 28SiCs2

+

58NiCs2+

Crater formation by SIMS + Depth measurement by Stylus : ISO/TR-15969

Thickness Measurement of Films by SIMS

0 250 500 750 1000

-600

-400

-200

0

200

CB

A

Crater Size (m)

Cra

ter

Dep

th (

nm

)

0 50 100 150 200 250 300150

200

250

300

350

400

450

m : 1.057 c : 177.9

Dtotal

= mDsubst

+ C

To

tal

Cra

ter

Dep

th,

Dto

tal (

nm

)

Depth of Substrate, Dsubst (nm)

Crater A B C D E F

1 182.0 208.4 246.1 289.3 366.9 431.7

2 182.0 208.5 247.9 292.1 370.1 428.1

3 182.5 209.7 245.8 290.1 365.3 429.2

4 182.7 208.4 247.2 287.3 368.9 428.2

5 184.6 208.2 247.5 292.2 367.7 429.7

Average 182.7 208.6 246.9 290.2 367.8 429.4

RSD 0.906 0.936 0.410 0.664 0.761 0.787

CraterFe0.5Ni0.5

Total Subst.

A 182.7 5.0

B 208.6 31.5

C 246.9 66.0

D 290.2 102.3

E 367.8 176.8

F 429.4 241.1

m 1.057

c 177.9

A B C D E F

ABCDEF

Crater Depth Measurement Linear Fitting

Analysis Method 5

78

40


Single Metal Films on Si

0 20 40 60 8040

60

80

100

120

m : 0.804 c : 47.8

Dtotal= mDsubst+ C

To

tal C

rate

r D

epth

, Dto

tal (

nm

)

Depth of Substrate, Dsubst

(nm)0 50 100 150 200 250

150

200

250

300

350

400

m : 1.045 c : 194.2

Dtotal

= mDsubst

+ C


(nm)0 20 40 60 80 100

80

100

120

140

160

180

m : 0.679 c : 99.4

Dtotal

= mDsubst

+ C


(nm)

0 100 200 300 400 50010

1

102

103

104

105

28SiCs

2

+

74GeCs2

+

Sputter Time (s)

SIM

S In

ten

sity

(cp

s)

0 100 200 300 400 500 600 700101

102

103

104

105

28SiCs

2

+

58NiCs

2

+

Sputter Time (s)

0 100 200 300 400 500101

102

103

104

105

28SiCs2

+

74GeCs

2

+

Sputter Time (s)

Ge (50 nm) Ge (100 nm) Ni (200 nm)

Analysis Method 5

79


Multilayer Films on Si

0 300 600 900 1200100

101

102

103

104

105

106

28SiCs2

+74GeCs2

+

Sputter Time (s)

SIM

S In

ten

sity

(c

ps)

0 100 200 300 400 500 600 7000

25

50

75

100

Inte

nsi

ty R

atio

(%

)

28SiCs2

+

74GeCs

2

+

Sputter Depth (nm)

0 200 400 600 800100

101

102

103

104

105

106

28SiCs2

+

181TaCs

+

Sputter Time (s)

SIM

S In

ten

sity

(c

ps)

0 100 200 300 4000

25

50

75

100

Inte

nsi

ty R

atio

(%

)

28SiCs2

+

181TaCs

+

Sputter Depth (nm)

interface interface

0 200 400 600 800100

101

102

103

104

105

106

28SiCs2

+58NiCs2

+

Sputter Time (s)

SIM

S In

ten

sity

(c

ps)

0 100 200 300 4000

25

50

75

100

Inte

nsi

ty R

atio

(%

)

28SiCs2

+

58NiCs

2

+

Sputter Depth (nm)

interface

5 x (Ta2O5/Ta) / Si 5 x (Si/Ge) / Si 5 x (Cr/Ni) / Si

Analysis Method 5

80

41


Comparison of Film Thickness by SIMS and TEM

TTEM vs TSIMS TTEM vs TSIMS+∆I/2

SpecimenThickness (nm)

TTEM TSIMS ∆I/2 TSIMS+∆I/2Ge (50 nm)/Si 50.7 47.8 5.9 53.7

Ge (100 nm)/Si 101.4 99.4 5.9 105.3Ni (200 nm) /Si 210.7 197.8 8.2 206.1

Cr/Ni ML 257.9 244.9 8.0 252.9Ta/Ta2O5 ML 252 249.6 1.6 251.2

Si/Ge ML 397.1 392.2 5.4 397.6m - 0.988 - 0.985c - -3.829 - 2.947

0 100 200 300 4000

100

200

300

400

m : 0.988 c : - 3.829

TSIMS

= mTTEM

+ c

Th

ickn

ess

by

SIM

S, T

SIM

S (

nm

)

Thickness by TEM, TTEM

(nm)0 100 200 300 400

0

100

200

300

400

m : 0.985 c : 2.497

TSIMS+DI/2 = mTTEM+ c

Th

ickn

ess

by

SIM

S, T

SIM

S+

DI/2

(n

m)

Thickness by TEM, TTEM

(nm)

Analysis Method 5

81


Comparison of Film Thickness by SIMS and TEM

Ni/Si Cr/Ni M) Ta/Ta2O5 ML

82

42



- SIMS의 역사






- 미량성분 정량분석 - 주성분 정량분석




내 용


Secondary Ion Microprobe

Image display

Rasterscanplates

Detector

Massspectrometer

Secondary ioncollection optics

Sample

Electronicgating signal

Synchronizedscan generator

Ion gun

Focusing lens

Image display

Detector

Massspectrometer

Secondary ioncollection optics

Sample

Ion gun

Focusing lens

Optical gatingaperture

Secondary Ion Microscope

SIMS 공간분포도 분석법SIMS 공간분포도 분석법Analysis Method 6

43


3 µm 3 µm

1.5 µm 1.5 µm

Silicon dopant mapping in YAG(Ytrium Aluminium Garnet) sample.

Field: 20 µm x 20 µm (low magnification

Silicon dopant mapping of two YAGsamples: different segregation patternsafter thermal treatment.

Field: 10 µm x 10 µm (high magnification)

Maximum Silicon concentration at grain boundary: 0.1 at. % (<=> 50 counts).

■ Trace element imaging at 0.1µm lateral resolution, on bulk insulating sample.

Dopant imaging in ceramics: YAG samples

SIMS 공간분포도 분석법SIMS 공간분포도 분석법Analysis Method 6

순서 사용 표준시료 년도 내 용 참여기관

1 Ta/Ta2O5 다층 박막 1994년 SIMS, AES 스퍼터링율 LG종기원 등 8기관 분석능력 향상

2 Ta/Ta2O5 다층 박막 1995년 SIMS, AES 깊이분포도 LG종기원 등 8기관 ISO-14606

3 SiO2/Ta2O5 다층 박막 1996년 SIMS 깊이분포도 삼성반도체 등 7기관 분석능력 향상

4 Pt-Co 합금 박막 1996년 XPS, AES 정량 삼성종기원 등 7기관 분석능력 향상

5 Delta 다층 박막 1998년 SIMS 깊이분포도 현대반도체 등 8기관 분석능력 향상

6 Delta 다층 막막 1999년 SIMS 깊이분포도 현대반도체 등 8기관 분석능력 향상

7 B-doped Si 박막 2001년 SIMS 정량 (B) 하이닉스반도체 등 6기관 논문 JKVS

8 GaAs doped Si 다층 2001년 SIMS 깊이분포도 중국 등 3개국 ISO-20341

9 B-doped Si 박막 2002년 SIMS 정량 (B) 중국 등 3개국 분석능력 향상

10 B-doped Si 다층박막 2003년 SIMS 깊이분해능 하이닉스반도체 등10기관 ISO-20341

11 Si/Ge-delta 다층박막 2005년 SIMS 분석깊이 보정 삼성전자 등 12기관 논문 MST

12 Fe-Ni 합금 박막 2008년 XPS, AES 정량 분석 독일 등 5개국 CCQM KC

표준화연구역량표준화연구역량연구역량

◈ 국내외공동분석수행역량

감사합니다.

3. Dynamic SIMS 김경중.ppt [호환 모드]

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Transcript of 3. Dynamic SIMS 김경중.ppt [호환 모드]