-
.. , ..
3-
2
2003
-
621.382(075.8) 32.852 73
82
: , -
..
.. 82 : . . -
. 3 . . 2. / .. -, .. . : , 2003. 76 .: .
ISBN 985-444-493-7 (. 2).
,
. .
621.382(075.8) 32.852 73
1: .. .
3 . . 1. . .: , 2001. 48 .: .
ISBN 985-444-493-7 (. 2) .., .., 2003 ISBN 985-444-308-6 , 2003
-
, , . , , . , , , .. , 1000 , .
, , , , - - . , . , . , . , .
1.
,
, . - .
1.1.
. , , . , , . , -, , .
-
, , .
. , -, -- . (CH3) (C2H5) . . 1.1. . -, , - () . , .
.1.1 , GaAs GaAlAs.
. 1.1.
((CH3)3Ga) ((CH3)3Al)
. , AsH3, . . 1.2. -
reactor
manifold substrates
heated holder
H2 H2H2
H2
AsH3
(CH ) Al3 3(CH ) Ga3 3 dopant
bublers
-
, . , , :
650 oC
(CH3)3Ga + AsH3 GaAs + 3CH4. (1.1) , Zn Cd,
, , Si, S, Se, . (AlN, GaN, InN) (NH3).
1.1
,
a (logP =
= A B/T)
-
-,
-, C A B
1 2 3 4 5 6 7 Be (C2H5)2Be
(Diethylberyllium) 17 C, 85 C
14,496 5102
Mg (C2H5)2Mg (Diethylmagne-sium)
17 C, 175 C
9,121 2832
Mg (C5H4CH3)2Mg (Ditolilmagnesium)
logP = 0,2T 20 C logP = 1,8T 70 C
Zn (CH3)2Zn (Dimethylzinc)
29,2 44,0 7,802 1560
Zn (C2H5)2Zn (Diethylzinc)
30,0 117,6 8,280 2109
Cd (CH3)2Cd (Dimethylcadmium)
4,5 105,5 7,764 1850
Al (CH3)3Al - (Trime-thylaluminum)
15,4 126,1 8,224 2135
-
. 1.1
1 2 3 4 5 6 7 l (C2H5)3Al
(Triethylaluminum) 52,5 185,6 8,999 2361
l iso-(C4H9)3Al - (Triisobu-tylaluminum)
4,3 7,121 1710
l (CH3)2NH2CH2Al - (Trime-thylaminealuminum)
Ga (CH3)3Ga (Trimethylgallium)
15,8 55,7 8,070 1703
Ga (C2H5)3Ga (Triethylgallium)
83,2 142,8 8,224 2222
In (CH3)3In (Trimethylindium)
88,4 135,8 10,520 3014
In (C2H5)3In (Triethylindium)
32 144 8,930 2815
In (C3H7)3In (Tripropylindium)
51 178
Si (CH3)4Si - (Tetramethylsilicon)
99,1 26,6
Si (C2H5)4Si (Tetraethylsilicon)
153,7
Ge (CH3)4Ge - (Tetra-methylgermanium)
88 43,6
Ge (C2H5)4Ge - (Tetra-ethylgermanium)
90 163,5
Sn (CH3)2Sn (Dimethylstanum)
7,445 1620
Sn (C2H5)2Sn (Diethylstanum)
17 C, 150 C
6,445 1973
P (CH3)3P (Trimethylphosphin)
37,8
P (C2H5)3P (Triethylphosphine)
127
-
. 1.1 1 2 3 4 5 6 7
P (t-C4H9)3P (Tertiarybutyl-phosphine)
215 7,586 1539
As (CH3)3As (Trimethylarsine)
51,9 7,405 1480
As (C2H5)3As (Triethylarsine)
140
As (CH3)4As2 - (Tetramethyldi-arsine)
170
As (C4H9)4As (Tetrabutylarsine)
7,500 1562
Sb (CH3)3Sb (Trimethylstibium)
80,6 7,707 1697
Sb (C2H5)3Sb (Triethylstibium)
160
Te (CH3)2Te (Dimethyltellurium)
10 82 7,970 1865
Te (C2H5)2Te (Diethyltellurium)
137,5
Fe Fe(CO)5 (Ferumpenta-carbonyl)
21 102,8
Fe (C5H5)2Fe (Ferrocene)
17 C, 179 C
a P ; T K; logP = A B/(T 73,82); logP = A B/(T 73,82).
. .
-
. , 3060 . .
1.2
,
,
C ,
C
-, C
Si SiH4 (Silane)
185 111,9 450
Si2H6 (Disilane)
132,5 14,5
Si3H8 (Trisilane)
117,4 52,9
Si4H10 (Tetrasilane)
108 84,3
Ge GeH4 (Germane)
165 88,5 350
Ge2H6 (Digermane)
109 29 215
Ge3H8 (Trigermane)
105,6 110,5 195
P PH3 (Phosphine)
133 87,8
As AsH3 (Arsine)
116 62,5
S H2S (Hydrogen Sulfide)
85,5 59,6
Se H2Se - (Hydrogen Selenid)
65,7 41,3
-
, AIIIBV . , AIIBVI, . , .
. , . , , .
1.2. -
-
. , 10-7 , 10-11 . ( ) .
- . . , . , , , .. , .
- , (.. ), . . , . .
- . 1.2. . .
-
. 1.2. -
, , . . : - (Auger electron spectrometry AES), (low energy electron diffraction LEED), (reflection high energy electron diffraction RHEED), (x-ray and ultraviolet photoemission spectroscopy XPS and UPS), - (secondary ion mass spectrometry SIMS). in situ*.
(RHEED). 1015 . , .
* in situ , . . ,
-
, .
- . , . , - . , , - , ( ) . .
2. ,
. . . , .
2.1.
, ,
, (scanning tunneling microscopy STM) (atomic force microscopy AFM). .
1981 ., IBM . , 1986 ., .
, . , , . , , .. 0,10,3 , ,
-
, , . W , , z V
)22exp(~ meVzW , (2.1)
, m e . .
, , - . , , .
(. 2.1).
)22exp(~ m eVzI
tip
scanning
V
)22exp(~ m eVzI
. 2.1.
, ,
, . ,
-
, , xy, .
, V. V(x,y) , ( ) . , , , . , . 0,010,05 , 0,3 . . , .
-. , . 2.2.
Force( )F
cantileverdeflection
substrate
F
deflection sensor
contact
repulsive force
attractive force
non-contactTip-to-surface
distance
0
. 2.2. () ()
. (, ) (, ) . , , .
-
, , . , .
, . 109. , . (515 ) , , () .
, , . , , 109 / 107 /2. , , - .
, .
2.2.
. . . . . , . . , .
-
. . . , , . 1/10 1/3 , 0,011,0 .
, . 3050 /. . . , , . )(rE :
)(rEp += + , (2.2)
, E(r) .
)()()(21)()( rErErrErU = . (2.3)
(. 2.3,), , , . , .
(. 2.3,) , . , , (. 2.3,). .
. .
-
, .
tiptip
adsorbed atom
Pot
entia
l ene
rgy
Lateral position
E r( ) = 0
a
. 2.3. , ,
. 2.4.
. , . . , , , , .
adsorbate
substrate
a
tip tip
. 2.4. :
; ; ;
-
, . , , . , .. , . . , , .
. , , , . , , .
. . , .
,
. . , , , . , , , . , .
. , . ,
-
. . , , .
. , , , . . , , , .
, . .
. , , , , ( ), . , . , , .
, . , . . , .. .
, , . 2.5.
. , , , .
-
. 2.5. , 48 Cu(111) . 7,13 .
(http://www.almaden.ibm.com/vis/stm)
. , . , , .
2.3.
. , . . . 2.6.
. . . c: H2O H+ + OH, H+ OH-. , OH- . , . ,
-
, . .
MeSiO
2
Sisubstrate
MeOx
DCbias
+
-tip
Sisubstrate
+
-tip
SiO2
DCbias
scanning scanning
. 2.6. () ()
. , , . 110 , , , 1 10 /. , . 1 .
2.4.
, , . . , .
, -. . .
-
, , .. . , . 35 . 3 3/.
. . - . , .
, , . , 10 . . . , . (1000 ) .
3.
,
, . , - . . , - . , , , 100 . ,
-
, . , , , , .
3.1. -
- , .
- , , . 20100 , 11,5 . , . , , . (polymethyl methacrelate PMMA), . , , , . 5x104 /2.
* -, . , . 3.1. 1 . , . 20 , PMMA. .
(~50 ) , * p- (MC6AOAc)
-
. 5 , 10 .
. 3.1. ,
PMMA 6 , . , 210 . ,
, , SiO2, AlF3, LiF NaCl, . 5 , , 0,1 /2, .
SiO2 . 1 . . 720750 C. in situ , , SiO2- .
-
. . , , (lift-off process). . 3.2.
substrate
scanningelectronbeamPMMAresist
a
material left after lift-off broad beam evaporation
exposed resist removedduring development
. 3.2. ():
- , , ,
, . . , . , . , , , . . ,
-
.
- . . . , , , . , .
3.2.
,
. ( ) . , - .
. , , , . 520 . - . 30 6070 .
. - . , , .
, , , , , . .
-
, - .
3.3.
,
, , . . , , . , , . - , , .
. 3.3.
substrate
master (stamp)
ink
. 3.3. : , , ; ,
.
, . , , .
(). . , .
-
, , , . , , , , . , , 10 , , .
. , , . . . 100 .
, . . 3.4.
substrate
master (mold)
thermoplastic polymer
a
residual polymer
. 3.4. : ;
, ,
. , .
-
. , , ( ), . . . . .
PMMA, , - . 105 C, 190200 C. 50 C. 10 .
, . , , - . . , , .
3.4.
,
101000 , . 3.5, .
, . 50 /, 1 2/c. .
10100 2/ . ,
-
, . . G- (436 ) I- (365 ) , : KrF (248 ), ArF (197 ), F2 (157 ). 100 . 50 , .
1 10 100 1000 10000
nanoimprinting
. 3.5.
. . 100 30 -. , - , .
-
, .
, 1 , . (1:1). . 5070 . . , .
- . 103102 2/, - . 30 5 . , . . , I2/3, . 10 /2. ( ) , .
- - . 20 . . - . 50100 , , , . , . , .
, , .
-
, , .
, . 3050 . . .
, , 104106. . , .
, 10100 , . .
4.
. , . , , .
4.1.
. , . , . .
, , ,
-
. . .
, , . . , , , . .
, , RSiX3 (R = CH3, C2H5, ), (OH) , , , . X , , -, . . , (RSH).
. (, CH2-) . , , .
. , (NH2) . (, .) , . . , , . . .
, , . 4.1.
-
. 4.1.
[1]: ;
; ;
HF. , , , , , . C18H37Cl3Si, C6H5CH2CH2(CH3O)3Si, - ClCH2CH6H3(CH3)3Si, - ClCH2C6H3CH2CH2(CH3O)3Si . , 1 , , . 210 , , , . , . . .
biased tip
Sisubstrate
Pd PdPd
Ni Ni
a
-
, . . 1520 , .
4.2.
. (), , , .
, . . , . . - , , , . .
g = gam gcr, gcr, gam. . g, , r *
G = 4r2* 4/3r3g. (4.1)
()
, . 4.2.
, .
rcr = 2*/g. (4.2)
-
surface contribution~ r2
bulk contribution~ r3
0rrcr
Gcr
G
. 4.2.
, . . . vn , :
vn ~ exp(Gcr/kBT)exp(Ea/kBT), (4.3)
Gcr , kB
, T . exp(Ea/kBT) . Ea. Gcr T2, exp(-1/T3). , , , .
. .
-
, , , , .
, , - , . . . , , Tglass < T < Tmelt, Tglass , Tmelt . 550 C 700 C .
. - AIIBVI AIBVII 110 .
--, . . 1100 . . . . , . -- . -- .
. Si(OR)4, R CH3, C2H5, C3H7, .. --. () Si(OC2H5)4, .
, , . -- OH-,
-
. OH-
OR OH
ROSiOR + 4 H2O HOSiOH + 4 ROH.
OR OH
(4.4)
(Si(OH)4)
, , , Si-O-Si .
OH OH OH OH
HOSiOH + HOSiOH HOSiOSiOH + H2O.
OH OH OH OH
(4.5)
400 oC. , , --. 20 . . . ( ), , , . .
- (NaCl, KBr, KI), , (CuCl, CuBr, CuI). , , NaCl CuCl 1 .% NaCl. 600 C CuCl 25 .
-
Al-O-Si - 1 . , . CdS, PbI2 . 100 .
-- . , SiO2 CaF2.
, / , , - , . , . .
. SiO2. , . , , . , SiO2. .
AIIBVI , , .
. , .
-
( 200 C). , , . , . (PMMA). , , .
4.3.
. . 4.3.
substrate
deposited material
Frank-van der Merwegrowth
Volmer-Webergrowth
Stranski-Krastanovgrowth
. 4.3.
( ) ,
--, ( ) -, -, , . () , . , . ,
-
, . , , . , , , , , , .
, , . , , ( ), --. . . , ( ). , (001) (311) . . 4.4 .
(001)
a
. 4.4. :
; ; ; ; ,
-
, . . , . , . , . , . , , . , . , , , , , . , . , , () .
, . , . -. . (2D3D ) , , . , . , . , .
, , , , *. * , . 4.3 4.4, [2]
-
. 4.5. , , , X. , A, B C.
stable2D
metastable2D
Stranski-Krastanow morphology2D + 3D
A B C
X
Y Z
Ea
Time
Ener
gy
. 4.5. , [2]
A
. . . tcw , . , -. E.
B, 2D3D-, .. , , X. , , , 2D3D- , , . B . . , , , . , ,
-
. , .
. . . 4.6.
Loca
l stra
in e
nerg
y de
nsity
0
compressivearea wetting layer
before during islandformation
x
. 4.6. [2]
,
. , . .
, . . {11n} (n = 0, 1, ~3), . {113} {110} . , , .
-
C . , . . .
- 240 AIIIBV, AIIBVI, SiGe, Ge. . , . , , - .
. , InAs, . 4.7.
GaAs
Ga As In
GaAs
As
GaAs
STMtip
GaAs
GaAsInAs
GaAs
GaAs
. 4.7. InAs/GaAs, ,
[3]
GaAs . , .
610 C, GaAs. GaAs , GaAs .
-
. InAs. . . 4.8 - .
. 4.8. InAs GaAs, . 6
30 [3] GaAs InAs
InAs, GaAs. , .
, , , , - , - .
4.4.
(LangmuirBlodgett films)
- , - ( ) . . 1917 . .. 1935 . LB- (
-
) , , LB-. , , , . ( ).
, LB- ( ), , . , ( ), , . , , , . , ( ). (17352), (1735) , () (2) . (head ), (tail ), , - -. surfactants -.
LB- . . , (retraction) . , , , , , ( , , 123/1), , (, .). , 30%- (30:70 .%) 90 30 . . . LB- Au-.
- . , . , , . 4.9.
-
. 4.9. : ; ; ; -,
( ) ( ). , . , , . , , . , (head) (, 32 .), () .
. Y- , Y-. , , . , (, ) , .
-
, . X- , , , -. : -, ; -, ; , - , . , , . 4.10.
Y-type X-type Z-type
hydrophilic head
hydrophobic tailamphiphilic
molecule
. 4.10. Y-, X- Z- ,
. , -,
. X- Y- , . , Y- .
, , , -. , ( Z-).
, ( ), (, NO2). , , Y- . , , - , , , Y-
-
. , X- Z- , NLO- ( ). , , X-, Y-, Z- X-, Y-, Z- .
. , , , . l/As, As , , Al , ( ). Y- , ( ). X- , . .
. 4.11 LB-. : , ; , ; -, ; , ; ; ( ); . .
. 4.11.
( ). , , , : , , ,
-
, , , , , . . . , , , . , , , . , , , , . , , .
, LB- , . ( , , , .
LB- (Schaefer's method), 1938. () . (1, . 4.12). (2, 3, . 4.12). , (4, . 4.12), , , (-).
- . , - .
, . , , , . -, . , , .
, , ,
-
.
. 4.12.
( ) , . , , , , , .
- , LB- . , .
-
5. ,
. , . .
5.1.
,
, , (HF). , . , , , , - . , . , . , SiC, SiGe, GaAs, GaP, InP. , , .
, HF, . () . , , . , , , . . , - . , . .
-
. . 5.1.
HFsolution
Si
tefloncellPt
grid
mixer cathode
anode
. 5.1.
, . ( ) . . , , .
, HF, (h+)-(e) , :
Si + 2HF + lh+ SiF2 + 2H+ + (2 l)e,
(5.1)
SiF2 + 2HF SiF4 + H2,
(5.2)
SiF4 + 2HF SiH2F6, (5.3) l ,
. HF ( ) ( ).
-
. n- ( 1018 -3) p-. SiH2F6 . HF , . - . , 15 %. , pH .
, , ( ), , , . : , , HF , pH , , , , . .
. . 5.2.
. 5.2. : , ;
, ( . . )
-
, . n- .
, p- . , ( 0,05 ) 10 , (. 5.2,a). 60 %. . , p- n- , 24 (. 5.2,). . n-, , . 10 %.
n- , . , , , , . 10 200 /2. HF . , . Si3N4 HF .
. , . , . - . . , - .
-
5.2.
, , , , , , , . : ; (1000) ; ; .
, . , . , , , , , , , , , .
() Al+3 O-2 . : 1) ; 2) ; 3) . (SO42, HSO4, PO43, C2O42, OH), , , . (, ) (, H2SO4 SO2 ), , (SO42) , . 1
2Al + 3H2O Al2O3 + 6H+ + 6e (5.4)
, 1 - (. 5.3):
-
1 13+ + 3-. (5.5)
,
. 13+ ( ) .
, , -,
H2O 2H+ + O2-, (5.6)
2 2+ + + 2-. (5.7) ,
(5.7), .
1,4 / , 5,5, . (Uf /h) = = (78) 106 /, , , .
( ) , , .. . 1,0 / .
, , , , , , . , , . , . .
,
-
. , , . , , , , . , . , (), , . , (), .. .
, ( ) , . .
( ) . . , , , , , . (.. ).
, tmin, . 2 , 3%- (pH = 5,5) tmin = 12 , (pH = 7,0) 90 . tmin . (Uf = const) . ( ~ 1,0 /) () , (). , .
, . .
-
d/1,31 h ln (d/1,31 + h)h = K(t t0), (5.8) d , h , t ,
t0 , K .
(47 ) , . (47 ), ().
- ( ). / .
( ) , , . , . , (. 5.3).
. 5.3. (d ,
D , h ( ))
-
, , .
. . , , , . . .
. () - , .
, , , ( ). , -, .
, , , ( ). . , (3%- , 15%- , 4%- , 2%- ) .
, , , .
, () , , , .. .
, - 1 , , 3%- . ( ~90 ), ,
-
., .
, - - , , , . 5.3, , (~32 ) , , (. 5.3, ).
( ) . 8 (). - , . - . . , .
:
; ; - ; -
( ); - .
() . . , .
. , , , , , .
.
, 0 , ( ), (
-
). 160 .
. . 5.4 () [4] () [5] .
. 5.4.
() (): 1 ; 2 ,
; 3 , ; 4 ,
5 ; 6
, (. . 5.4), (). (). () () () . , , , , (); () ().
-
(), ( ). 40 100 [5].
(SiC Mold), . 5.5. () (B). (C). - . , ( ) .
. 5.5. ,
1 SiC- (, , ) - , : ;
() [6]
-
, . . . 5.6 , Ag, Si , . , . (, ) , ( ).
. 5.6. - () Ag-
, () [6]
. 5.7 [7], . 5.8 , 4 [8]. : , , . , , , , , .
-
, , , . Pt- : Ni(OSO2NH2)24H2O (330 /), NiCO3 (0,5 /) H3BO3 (30 /) . Ni- 10 , 70 . 123 , , Pt-. , .
. 5.7. Ta2O5 :
; , ; , Al2O3;
( ) .
160 535 .
-
, , .
. 5.8. - , [8]
. 5.9 ()
(F), - Pt-, [9]: 160 0 0,3- 40 (). , .
(), (), 5 .% - (). .
10%- NaOH (D) (E). - (F). , .
-
. 5.9. (F) - : (
); ( ); [9] 10%- NaOH (D)
(E). - (F). , .
, , , , , - .
5.3.
. . ,
-
. . , . 5.10.
, . , , sp2- (. 5.10,a). k-, . 5.10,. , , . , ( x . 5.10,a), , ( y . 5.10,a).
(. 5.10,) . , CC- , , . , , , . , , CC-, . , , . , , , CC-, , , .
1,21,4 . 0,4 0,7 . , . . .
, . 1040 . . - . 250 4,2 , 60 .
-
. 5.10. [10]: ,
k- , , , , - () y, -
() .
, , , , . - - http://www.pa.msu.edu/cmp/csc/nanotube.html http://shachi.cochem2.tutkie.tut.ac.jp/Fuller/Fuller.html.
, , . , . . SiO2 .
-
.
, . , . , , , . , 500700 C. , , , . , . . 9001000 C , . , .
. . 5.11.
. 5.11. :
, -; - SiO2
, (. 5.11,a). , . , , , , ,
-
. , -- . , .
(. 5.11,). , . . .
110 , 200 . , , , , .
, , . , , . , .
, , . . . - , -. . , , , , . , , . .
, . , , .
-
, . , . , , 1013 /2. . . . , - - AIIIBV. , .
-
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