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..

.. : Ni-Si --

..-.. .. ..-.. .. ()

..

2006

1. 1.1. -- () 1.2. 1.3. . 1.4. . 2. 2.1. 2.2. 2.3. 2.4. () 2.5. (, Low Energy Ion Spectroscopy, LEIS) 2.6. (Medium Energy Ion Spectroscopy, MEIS) 3. 33 3.1. in-situ 3.2. 3.3. MEIS-TUBA. 3.4. 3.5. . 3.6. - 3.7. - 4. 5. 6. 49 50 51 14 3 5

2

30 - (-), , - (. . ) . , , , , , , , . , SiO2 -- () , Si-SiO2, , . , , 40 , 1,5 , 6 (. . ), , 3-4 (~ 15 е) SiO2. SiO2 , . , SiO2, ( ) SiO2 . ( ), . , , , () -. . : 1) () -Si , ; 2) ; 3) -. , , , (
3

~0.3-0.5 [ 1 ], ). - 2007 [1]. Ni . , , , . , «» HfO2 [ 2 ], , , n- -Si. , - () , HfO2/Si(100), - .

4

1. 1.1. - - () (.1). . , , , . , n- - , . ( ) , ~10000C. 1.3). () , 1. , .

(.

. , , . , . - (5-10 е) SiO2, . SiO2 teq . , . SiO2. SiO2 Si 7 15е Muller et al. [
3

EELS,

], ,

SiO2. , Si-, «» , , , . , 10-12е . , poly-Si - ,
5

SiO2 / . SiO2 ( Si3N4 = 7), , [51-53]. Yang Lucovsky [56] , , SiO2:SixNy 1:1, teq=17A ~10-3е/2 1V. ~100 , SiO2. , teq~10е ,

1.2. , . :

=

0 A
t

,

( 1)

, 0 , , t ( t ). teq
eq

ox

SiO2, . SiO2, ( ). , .2.
.

, teq = 3.9 0 ( A ) , (C ) = 34.5 , teq = 10 A . C A 2

, ,

6

t

eq ox

=

t

high - k high - k

t

high-k

=

high- k

t

eq

ox

(2).

, , =16, t=40 teq=10A [
4

].

: 1. =10В30. 2. . -. (.3) - (() - n-,(b) p-)[9],[10]. , , . 3.
: () n- () -.

0. .

1. .2 [152].

7

3. . Si , Si, . ,

. Ta-Si-O Ti-Si-O .4. ()
Ta-Si-O, (b) Ti-Si-O, (c) Zr-Si-O

(.4). , Ta2O5 TiO2 ( Si) SiO2 Si. (a) (b) , Ta2O5 TiO2 Si SiO2, (MxOy, M ), (MxSiy). (.4) 700-9000, . Ta Ti, Zr-Si-O (.4()), , ZrO2 ZrSiO4 Si . .4() (ZrO2)x(SiO2) Si . 1 , . 1. SiO2 Si3N4 Al2O3 Y2O3 La2O3 Ta2O5 TiO2 HfO2 ZrO2 3.9 9 15 30 20 80 25 25 , eV 8.9 5.1 8.7 5.6 4.3 4.5 3.5 5.7 7.8
1-x

,

8

1.3. . poly-Si [ 5 ]. poly-Si : 1) () poly-Si , c ; 2) ; 3) .

, , ( ~0.30.5 , .5.
.

). . n- p- , n- - ( ). , . .5 , EF,m
CNL,d

,

m,eff

.
(E CNL , d =
m ,eff

CNL,d EF,m, , ,
m,vac
vac

-E

CNL , d

) . , q,
-
CNL , d

m,eff

: (3),

=

CNL , d

+ S (

m ,vac

)

S ,
[6] [7]

. 2

(SiO2, Al2O3, ZrO2, HfO2, Si3N4). .
9

, . , , ~0.5eV
[ 8 ] [ 9 ] [ 10 ]

. ,

, 2 . - .2.

. , , .7.

(3),
CNL,d

S Si3N4 [ 11 ].

.6.
.

SiO2, Al2O3, ZrO2, HfO2

n- p- . ,
10

, Si n- p- , . n- ~ 4.1eV, p- - ~ 5.1 eV. . : 1) 2) (Zr, Hf, Ti, Ta .). , , . N-

Ru Ta. Ta . .7.
Ru-Ta .

Ru - . RuxTa
y

40% [ 12 ]

.

. , , Ti1-xAlxNy (TiAlN) TaSixNy (TaSiN), , 1000. ~ 4-5 eV
[ 13 ]

.

4)

. : TaN Al , TaN .

1.4. . - .. poly-Si. -, , , . poly-Si
[ 14 , 15 ]

, , ,
11

n- p- .
2.5E-06 Capacitance [F/cm2] 2.0E-06 1.5E-06 1.0E-06 5.0E-07 0.0E+00 -1.5 -1 -0.5 0 0.5 1 1.5 Gate Voltage [V] PMOS WF shift NMOS CET decrease FUSI POLY

.8. C-V poly-Si NiSi SiON (EOT~9A).
WF ~0.26eV NMOS ~-0.26eV PMOS.

, poly-Si, , poly-Si . Id-Vg C-V (.8) Vg poly-Si, . Ni, Ni
[ 16 ]

. , WF

, . / .

poly-Si. -, - Ni-poly-Si. Ni Si:Ni=1.7 1.4 (. 9) Ni- . , Ni 350, NiSi.

12

100
Ni-rich NiSi

Atomic Concentration

90 80 70 60 50 40 30 20 10 00

(%)

Si:Ni~1.75
NiSi

Ni3Si2

Si Ni

Si:Ni~1.4
NiSi

a

O

Undoped poly

b

500 1000 1500 2000 2500 3000 3500 0 Sputter Time (s)

500 1000 1500 2000 2500 3000 3500 Sputter Time (s)

.9. . , , SiO2, HfO2 / [2]. , , / [2]. , HfO2. [ 17 ].

13

2

2.1. .

. <0,1 . - . - , . , . . , . , . . , , 1011-1015 -2-1, 0,01-0,1 е/. . , / . , . , , . - , , . . 1-10 . , 1-100 , . . .
14

, , , , , , 10-100 , 1014 -2-1. , , , , , .

2.2. () , . . 10.

Si

. 10. . . ( 1/ 50 ) , = 0,1-10 . . . , . 10-12 , , . . , .
[ 18 ]

15

T.k , q = . 2 A
T. , k , A = 1R (R ), = k/c , ( , 10-8 ). ,
[ 19 ]

q

.

~ 107 /2.

q , q ~ 108-109 /2 . , . q ~ 109 /2 ( = 10-8 ). 1012 25 . , . . , . , ~ 10-8 q ~ 109 /2 100
[ 20 ]

.

"" . . 200
[ 21 ]

Y(E) =

1,9 U0

Z

(

E - 0,09 U 0 ,

)

U0 (), Z , E (). , 1,
2

E 150 .

Y= 1

() = 750

U0 , Z

16

/ , . : , , , , , . ., , . : , . , , , .
2.3. ()

, 10 , . . : (UPS) (XPS). ,

, 10 , (13.6 ), 0.1 . , , . . , .
.

. 11 , MgK , . ,
17

S- . , - jj-. l>0 , j (j = l ± s). Ej "" "" . . Ej (n l ) Z, l n (, . 6 , 3p > 3d).

. 11. MgK ( MgK1,2),
, 100 ("" Ag3d MgK3,4).

(2j+1) (. . 3).

3. -

j s p d f 1/2 1/2 3/2 3/2 5/2 5/2 7/2 -- 1:2 2:3 3:4

18

. , . , MgK- AlK- . , () E, , , :

En - , Ep - Ea - . , " ". : , , .. :

Ei - i, E°i - , qi - i; i, " " j. , qi, qi/rv, rv - . () qi qi/rv. , . , rv qi . , , , ; , , ..
19

( i), ( j).
. ,

(0-20 ) .

. 12. D() (
) () () [59].

, . (. 12), (). , , () . (Ev), EF - Ev = , - . 12 , . , , , , , ( ), .. . , ; , . 12 4d , 4d-. , , , , .

20

, , .
-.

, (. . 13, , ).

. 13. - . - , ; - - L1, , L23 . , -; . -. KLL- KL2L3. LMM- , .. , L2 L3-, M23 M45. . L3M45M45 ( - ). MNN- : M45N45N45 M45N67N67 ( ( AgL 2984 ), .. ( >1660 - Hf M45-). :

Ek - , h - , EB - - " ". - :

Ei(Z) - i- Z, Ei(Z+1) .
21

, -, , , .. - . , , . . , -, (. ), . - ( 2 В 5 ). , .. , , . , , "" (shake-up) "" (shake-off) .
.

, (, ; 1s), 2p 4. 4. Mg Al [63]. K K K K K Mg 4.5 (1.0) 8.4 (9.2) 10.0 (5.1) 17.3 (0.8) 20.5 (0.5) 48.0 (2.0) Al 5.6 (1.0) 9.6 (7.8) 11.5 (3.3) 19.8 (0.4) 23.4 (0.3) 70.0 (2.0)
1,2 1/2,3/2

1s, 1,2,

(, 3,4).

()
1,2

(

= 100)

'

3 4 5 6

K

, . MgK
22

AlK

1,2

, - , , ,

( , ), 233.0 , MgK-. , CuK- . 323.9 (556.9 ) , MgK
1,2

(AlK1,2). ,

OK-, 728.7 (961.7 ) , MgK .
. ,
1,2

(AlK1,2)

. , Mn

2+

3d- , ( 6S). 3s- . 3- ( 7S), , , ( 5S). , ( - 3, .. -) , : E = (2S + 1)K3s3d , S - (5/2 ), K3s3d - (3s - 3d). , 3s- Mn2+ 1.4. , s-, - . , Mn
2+

3p- .

. 5.

23

5. 2p-- Co [65].

, Co 2p1/2 Co 2p3/2 2p1/2-2p3/2

Co(acac)2 Co(acac)3 (PEt2Ph)2Co(C6Cl5) )2
2

800.2 799.0 797.4 797.0

784.2 784.0 782.1 781.5

16.0 15.0 15.3 15.5

(PEt2Ph)2Co (2--1-

" " (shake-up).

. ( ), (""). , , , , , ( ""). "" / , "". ( , ).
.

(. . 13 ), "".
24

. , , , (. 14).

. 14. (4f) ()

, AlK-. [66]
"" (shake-off). , "",

, .. . , "", , . "" , , (.. ), .
2.4. ()

() . , , , . . , .
25

.15.

. 15. . (1) 1, . . Z1 0 (2), , 2 Z2. (3) (5), . , d (6), (4), . , 1-10 . , . 20 0 2, 1 2 :
2 M1 sin2 () + M1 cos( ) 1- M M 2 2 KM2 = M1 1+ M2 2

(4)

(1, 2, ...). , . 180° 1 2 3.
26

:
cos( ) + 1-M1 2 2 Z1Z2e 2Esin2 () M 1- 1 M2
2 sin2 () M2 2

d d

=

sin2 ()

2

,

(5)

, . , . , , . - - , . . , . d/d (+, d+ ++) (0,5--5 ) . 16. ; . ; , , . ,

E

dE E0 *t dx Et = E0 - E dE dx * t cos

(6)

s = (1 - K ) Et E
E1

. 16. , t: ; s ; . 1 = 0- -s-
27

, d/d 300 600 /. , t, t. ,
=
t

0

dE dE dx dx dx

*t

(7)

(d/d)| 0 0-t(d/d). t (t)=E0 -t*dE/dx| (8) (t), -- , (4). , ,
E1 (t ) = KE (t ) - t dE * cos dx

= -t ( K

dE dx

+

1 dE cos dx

) + KE

0

(9)

-- . , , t,

E = t(K

dE dx

+

1 dE cos dx

) = t[ S ]
(10)

"" "" , d/d [S] . d/d , , , t, . t <= 100 . d/d " ", (d/d) =0, (d/d)-- 0. 0 t

E = t[ S 0 ] = t[ K

dE dx

E0

+

dE 1 cos dx

]
KE
0

,

(11)

.

28

2.5. (, Low Energy Ion Spectroscopy, LEIS)

, He+ Ne+ c 0.5-3keV . [
22 ]

. .

, . , , , , . , , , «» . k, .
cos + M m k= 1 + - sin ( M m
2 2 2

)

2

(12)

, , m . . E = k E 0 . , , , «» , . , , . . 17 , He+ c 1keV , . , .

.17. He+ ~
1 , , .

« » , «» He+, . ,
29

, . , , ...., , ~2A ~1.5A, .. . , , . , , . , . , ,
[ 23 ]

. , , , . .18. «»
Ar+ 1keV, Cu 2.55A.

, , , . , . . , , . , , , , ; , , . . .18 Ar+ 1keV, Cu,
30

2,55е 25 30. . .19.
.

,

. , , : . . , , . , . , , , . .19. Ar+ + , ( ) , . , + 1keV , , , ..., , . , , , .

31

2.6. (Medium Energy Ion Spectroscopy, MEIS)

MEIS (RBS). . MEIS , , MEIS 200е. . , ~15 . MEIS 300 , . .20. MEIS.
.

,

, (.20). , 12, 20
[ 24 ]

.

, 120o. , , . , - . - , . ,
[ 25 ]

.

32

3.

3.1. in-situ

.21. : , , , . , , =950. , , , . , , .

.21. in situ . , . .

33

in-situ . -, , - , / . , (MgKa, AlKa), , , 100-3000 1 ( ), - .

3.2.

--
[ 26 ][ 27 ]

,

1,0-3,5 . .22. , . , (1) 90° , (2-3). 0,5-1 .

.22. : 1- , 2.3 , 4 , 5 , 6,7 , 8 , 9 , 10 , 11 , 12 . , , , . , ,
34

- . , , . . , ( ), . . -500, ~10-6 ... . - , (.23). , 0,02°, 0,07 . 1%. , , (5), - (6). , . 0.5°. . . . , . - (8), , (9). , .

35

.23. : ) , ) .
(1,2 - , 3 - , 4 - ).

36

.24. - . , , , . - - . , . , -
[ 28 ]

..24. RUMP

.

3.3.

MEIS-TUBA.

()

MEIS-TUBA -500 , , - . , keV . , « » (.25). , . , , .

37

.25. . , . - . . : A+ B B E= A+ B + + + + D C+D C C+D

=

. 90° . 0,5-1 . (.26). , , , 1 . , . . . , . .

38

.26. . , , . , , CAMAC, . 120 . 13, . 115. 13 ~16 . , .27 - 15 , , , , 2 . MEIS-TUBA , LEIS, (~100 ). 200 200 . . (.27) . -500.

39

3.4.

Si HfO2/Si . , , . He+ c 1000 125. . (. 28)
40

.27. , MEIS-TUBA,
13 , .

Si

, Si 1 . , 1 . (HfO2) , in situ Si/HfO2/Si(100) . , 5 . 1050 Hf, - Hf2 . 10 . 1100, HfO2 HfSi.

(He+, E0=1000 eV) (He Si O

+ 1100K,10' + 1100K,5' + 1050K,5' + 1000K,5' + 1.0 nm Si + 0.5 nm Si

Hf
7 6 5 4 3 2

HfO2/Si

1 400 500 600 700 800 900 1000 , eV
.28. , Si HfO2/Si(100) .

41

3.5.

Ni-Si Ni/Si

. (. 29) , () .

.29. .

, , - Ni Si . .

40 + He , E0=1.5 MeV 10
0

0

. 30. .

Ni Si , Ni, Si , .

42

6. . 1 3 5 7 9 11
Ni1Six, x= 2 2.4 1.8 1 1.1 1.1

,
25 40 40 50 70 70

9 Si
1 2 3 4 5 6 7 8

Ni
9 10 11

.31. Ni-Si/HfO2/Si.

(Ni-Si)/HfO2/Si(100) . -- . .30. He+ 1.5 . . (.32) , Ni Si 750 580 , , , . RUMP, . , .6.

43

(MeV) Energy (MeV)
50 0.4 0.6 0.8 1.0 1.2
Ni

40

Norm ield alized Y

Si

30

20

10

0 200

300

400

500

600

700

800

900

Ch annel
.32. , (Ni-Si)/HfO2/Si(100) (
Hf ).

3.6.

-

.33 , . (33()), , , , («») . - , «» . , , , , (binding energy, ) . , Si, (.33()).

44

sample

U

Si 2 p spectrometer EF p-Si E BEp-Si
k

100 e V

99.2 e V

W

2

W

1

EF n-Si BE
O

n++ - Si p++ - Si

Ek0 WFsam
pl e

BE

n-Si

?WF WFsp

ec

E

F

()

107.5

105

EB, eV

102.5

100

97.5

h?

BE0

BE

Ni/Si=x
W EF
NiSix NiSix

Ni/Si=y
W EF
NiSiy NiSiy

BE0=BE+WFsample U = ? WF = WF
spec-

WFsample

BE

Si2p

BE

Ni2p

BE=hv Ek WFspec
() Si Ni ()

BE

Si2p

BE

Ni2p

Si Ni

. 33. .

, Si2p n- p-Si ( ) , , , . , , , (.33()). .34 Si2 Ni2p, (NiSi)/HfO2/Si(100) ( Si2p ). , Ni2p , Si2p ( ) . , Ni2p , , 2- . Si2, , -, .

45

Si 2p (.)

Ni 2p

BE

1 3

5

7 9 11
104 102 100 98 96 , eV 857.5 855 852.5 850 , eV

.34. Si2p Ni2p, (Ni-Si)/HfO2/Si. . .35 - , 100. V, , ( ) ( ), . (, , , Ni-Si 5 , C-V , HfO2.) 0.3eV Ni:Si 1:2 1:1. C-V , , , , HfO2 3 .

46

1 0,9 0,8 0,7 0,6

C-V

i=3

4 (NiSi2)
i=5 i=6

C,

0,5 0,4 0,3 0,2 0,1 0 -1,0

WF=0.3 eV

i=7 i=9

11 (NiSi)

-0,8

-0,6

-0,4

-0,2

0,0

0,2

0,4

0,6

0,8

1,0

,

.35. C-V (Ni-Si)/HfO2/Si(100) , (. . 5).

3.7.

-

. 36 , - , , . WFNi=5.1 [ 29 ]. .36 , , , Ni . Ni:Si 1:2 WFNiSi2=4.4 , - Ni:Si 1:1 WFNiSi=4.8 . , , (WF).

47

5.0

Ni

.

p-Si

4.8

4.6 WF, eV

4.4

XPS WF+ Ni
4.2 NiSi 4.0
2

CV
NiSi

n-Si

0

2

4

6

8

10

12

14

16

18

20

22

x, mm

.36. , C-V- .

48

4.

1. (~1 ) Si, , . 2. , Ni . 3. - - (Ni-Si)/HfO2(3 )/Si(100) , WF=4.2В4.5eV Ni/Si 0,5 1, . 4. , Ni2p ( ) . * * *

- , .. , . - .. . - .. . .. .

49

5.

- MEIS-TUBA.

NIM Electronics

CAMAC Crate

a b c d
In out

ADC

, , .

6.
1

International Technology Roadmap for Semiconductors (Semiconductor Industry Association, San Jose, CA, 2003 http://public.itrs.net/Files/2003ITRS/PIDS2003.pdf).

2

K.Takahashi, K. Manabe, T. Ikarashi, N. Ikarashi, T. Hase, T. Yoshihara, H. Watanabe, T. Tatsumi, and Y. Mochizuki, Dual workfunction Ni-silicide/HfSiON gate stacks by phase-controlled fullsilicidation technique for 45nm-node LSTP and LOP devices, IEDM Tech. Dig., 2004. D.A. Muller, T.Sorsch, S.Moccio et al. Nature(London) 399, 758(1999) R.Rios and N.D. Arora, Tech.Dig.Int.Electron.Devices Meet. 1994, 613 (1994).

3 4 5

Yee-Chia Yeo, Tsu-Jae King, Chenming Hu Metal-dielectric band alignment and its implications for metal gate complementary metal-oxide-semiconductor technology, Journal of applied physics, vol 92, N 12, (2002)
6 7 8 9

W. Monch, J. Vac. Sci. Technol. B 14, 2985 (1996). W. Monch, Phys. Rev. Lett. 58, 1260 (1987). R. Garron, C. R. Hebd. Seances Acad. Sci. 258, 1458 (1964). R. E. Eastment and C. H. B. Mee, J. Phys. F: Met. Phys. 3, 1738 (1973). S. Berge, P. O. Gartland, and B. J. Slagsvold, Surf. Sci. 43, 275 (1974). J. Robertson, J. Vac. Sci. Technol. B 18, 1785 (2000).

10 11 12

Huicai Zhong, Shin-Nam Hong1, You-Seok Suh, Heather Lazar, Greg Heuss and Veena Misra, Properties of Ru-Ta Alloys as Gate Electrodes For NMOS and PMOS Silicon Devices, IEEE (2001) Dae-Gyu Park, Tae-Ho Cha, Kwan-Yong Lim, Heung-Jae Cho, Tae-Kyun Kim, Se-Aug Jang, YouSeok Suh#, Veena Misra#, In-Seok Yeo, Jae-Sung Roh, Jin Won Park, and Hee-Koo Yoon, Robust Ternary Metal Gate Electrodes for Dual Gate CMOS Devices, IEEE (2001) M.Qin et al., J.Electrochem.Soc., 148(5), p.G271, 2001

13

14 15

Kedzierski, J., D. Boyd, P. Ronsheim, S. Zafar, J. Newbury, J. Ott, C. Cabral, M. Ieong, and W. Haensch, Threshold voltage control in NiSi-gated MOSFETs through silicidation induced impurity segregation, IEDM Tech. Dig., 2003: p. 1331. W.P.Maszara et al., IEDM Tech.Digest, p. 271, 2002 Yu. Lebedinskii, A. Zenkevich and E.P. Gusev, Monitoring of Fermi level variations at metal/high-k

16

17

interfaceS with in situ X-ray Photoelectron Spectroscopy, NATO ARW "Defects in high-k dielectrics", Springer, Ed. E. Gusev, 2005. . . , . . , . . " " , . 315 (1975)
18

. . , . . , . . , . . " " 93, 500-507 (1987)
20

19

. . "- " 1997

21

P. C. Zalm "Some useful estimates for ion beam sputtering and ion plating at low bombarding energies" J. Vac. Sci. Tech., B2, 151-152 (1984)

22 ., . , «», (1989). ., . , «», (1989)
24 25 23

P.Zagwijn Ga.delta-doping layers in silicon,(1993)

M.Copel Medium energy ion scattering for analysis of microelectronic materials, IBM J.Res.Develop. vol.44 no.4, (2000) .., ., .., ., .. . 7. 1986. . 1(134). .75

26

27 .., .., .. . , . . . 1988. 88-57/76. 24 . 28 Doolittle L.R. Nucl. Inst. Meth. In Phys. Res. 1994. v.B84. p.497 . . .. , .. , , , 1991.
29

52