X (XPS)

X-ray Photoelectron Spectroscopy

 .
1.
XPS ,

XPS 20 60 K.Siegbahn
20
K.Siegbahn 1981

 K.Siegbahn
(Electron Spectroscopy for Chemical Analysis), ESCA

70 40
XPS
XPS

 2. h

A+hA+*+e-




(Ek )

(h)

hv Eb Ek E E E
 Einstein

hv Eb Ek E E E
( 0.1ev)

hv Eb Ek hv Eb Ek sp
h

h
Eb
Ek

sp

 Eb hv Ek sp

sp
sp 4ev

xps

 Eb
3.

1s / 2 s 20

0.5~2nm 1.5~4nm 4~10nm

 xps d = 3

N
N0

d

d = 3 N 0 5%

d = 3 N 0 95% d
= 3

n : n n=1,2,3..
l :
l=0,1,2,..(n-1)
m : m=-l,l-1.,0,-1,-l
ms : ms=1/2 1/2

j :
j
j =l+ms= l1/2

l = 0 s j = 1/2 1s , 2s , 3s
l = 1 p j = 1/2
3/2 2p1/2 2p3/2
l = 2 d j = 3/2
5/2 3d3/2 3d5/2
l = 3 f j = 5/2
7/2 4f5/2 4f7/2
 4.

3 11 12 30 31 62 63 70 71 92
Li Na Mg Zn Ga Sm Eu Yb Lu U
1s 2p 3d 4d 4f

xps

 .
1. PHI 5000 Versaprobe

117



Quartz Crystal
Electron Gun Monochromator

Analyzer
Input Lens

Raster Scanned
Micro-Focused
Electron Beam
Raster Scanned
Al X-rays Micro-Focused
X-ray Beam

Analyzer
Input Lens

Al Anode Sample
1.
XPS X

X
 Mg Al
X
(eV) (eV)
K1 1253.6 67.0 1486.6 67.0
K2 1253.4 33.0 1486.3 33.0
K 1258.2 1.0 1492.3 1.0
K3 1262.1 9.2 1496.3 7.8
K4 1263.1 5.1 1498.2 3.3
K5 1271.0 0.8 1506.5 0.42
K6 1274.2 0.5 1510.1 0.28
K 1302.0 2.0 1557.0 2.0
 X

10

eV 10 keV

X (1010) Bragg
X X

Al/Mg X

X

(eV)
Y M 132.3 0.44
Zr M 151.4 0.77
Na K 1041.0 0.4
Mg K 1253.6 0.7
Al K 1486.6 0.8
Si K 1739.4 0.8
Ti K1 4511 1.4
Cr K1 5415 2.1
Cu K1 8048 2.5
2.

10 -6



3.

-4
10 -13 -9
~ 10 A 10 ~ 1A

PSD

10 9
4.

298K
10 -4Pa 1 10 -7Pa
1000
 .
1. wide scan or survey scan)
wide

F1s

O1s
FKLL
OKLL
intensity(a.u.)

Sn3p

C1s
Cu2p
Sn3s

Sn3d

P b4f
S2p

Si2p

O2s
1200 1000 800 600 400 200 0
Binding Energy (ev)
AlKa MgKa 0 1000ev
1200ev

H He

2.
C Sn
3d5/2
C1s

284.8 486.7
C1s 3d3/2

286.35
intensity(a.u.)

intensity (a.u.)
C1s

288.8

300 295 290 285 280 275

500 495 490 485 480
Binding Energy (ev)
Binding Energy (ev)

10 50ev




3.
wide

Ag3d5/2
Ag3p3/2

Ag3d3/2
O1s
Ag3p1/2
intensity (a.u.)

C1s

Ag4s

Ag4d
600 500 400 300 200 100 0
Binding Energy (ev)
n n
n l l
J J
( J = L S )
Au
 .
1.
XPS

X X X

V S
,



E c <0.1eV

(CH 2 ) n C 1s
284.6 eV 284.8 eV

Au4f 7/2
C1s

Ar Ar

2.

XPS



 C1s

F >O > C > H

4
3.
wide

F1s

O1s

FKLL
OKLL
intensity(a.u.)

Sn3p

C1s
Cu2p
Sn3s

Sn3d

P b4f

S2p

Si2p

O2s

1200 1000 800 600 400 200 0

Binding Energy (ev)

4.

http://www.lasurface.com/database/elementxps.php
5. -

Fe Fe2O3 Co CoO Ni NiO Cu CuO

2p1/2-2p3/2 13.1 13.6 15.0 15.2 17.3 17.5 19.8 19.9

0.2ev

 -

Ir 2(l 1 / 2) 1 / 2(l 1 / 2) 1 1 1 / l
Ca

2P 3/2

P3/2/P1/2 = 2:1

counts (c/s)
2P 1/2

d5/2/d3/2 = 3:2
f7/2:f5/2 = 4:3

355 350 345 340

Binding Energy (ev)
Sn Pb

3d5/2 Pb4f7/2

3d3/2 Pb4f5/2
counts (c/s)

counts (c/s)

500 495 490 485 480 150 145 140 135 130
Binding Energy (ev) Binding Energy (ev)
 wide

Ag3d5/2
Ag3p3/2

Ag3d3/2
O1s
Ag3p1/2
intensity (a.u.)

C1s

Ag4s

Ag4d
600 500 400 300 200 100 0
Binding Energy (ev)

3p 3d 4p 4d
4f
 Au

4p 4d 4f
6.

(shake-up)

(shake-off)


shake-off shake-up

Ne1s


3d 4f

 Cu Cu 2+ 2p

shake-up
shake-up

shake-up
shake-up
shake-up
 284.75

x 10

/
C 60

284.6
x5

x5

294 292 290 288 286 284 282

/ eV

sp 2
sp 2
C 60 5




plasmon)


XPS

(4 f ) 4 s

3 d 3 s

 Mn2+ 3s

MnF2 Mn3s

110 100 90 80
 Auger
XPS KLL, LMM, MNN NOO Auger

Auger

X
X X
XPS K 1,2

X
X X
X

Mg Al

O (K) 728.7 961.7

Cu (L) 323.9 556.9
Mg (K) - 233.0
Al (K) 233.0 -


C, O C, O
Auger C, O

p, d, f
p 1:2 d 2:3 f
3:4 p 4p 1:2
 .
1.

C O ,

2. (atomic sensitivity factor)

I nfyAT
n f x

y
A T

s fyAT
n1 I 1 / s1
n I /s
n2 I 2 / s2
 nx Ix / sx
Cx
ni Ii / si
i i
X
i
xps
xps 3 5nm

Atomic Concentration Table
--------------------------
C1s O1s Mg2p Cu2p3
1.000 0.733 0.167 2.626 RSF
48.945 17.215 4.500 150.493
Corrected RSF
2.88 59.71 34.07 3.34
 .
1.
Ar

1m
XPS ,
XPS

X 4
XPS X XPS



XPS
Ti, Mo, Ta

SiO 2 50nm/min

 SiO 2-SiON-Si

 Zalar Depth Profile with 500eV Ions
100

Ni 2p Cr 2p Ni 2p Cr 2p Si 2p
80
Atomic Concentration (%)

60

40 O 1s

20

0
0 Sputter Depth (nm) 185

Interface width (80/20%) = 3.8nm Depth

123.5nm
 .

,
x

10mm, 5 mm

XPS

X
X

 .XPS

XPSpeak , origin
XPS C. D. Wagner, W. M. Riggs, L. E. Davis, et al., Handbook of X-ray
photoelectron spectroscopy [M], (G. E. Muilenberg, editor) Perkin Elmer
Corporation (Physical Electronics), 1979

http://www.lasurface.com/database/elementxps.php
XPS XPS