.. , ..

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. , .

1. Snow E.S., Campbell P.M., Perkins F.K. Nanofabrication with proximal probes // Proceedings of the IEEE. 1997. 85 (4). . 601611. 2. Seifert W., Carlsson N., Johansson J., Pistol M.-E., Samuelson L. In situ growth of nano-structures by metal-organic vapour phase epitaxy // J. Cryst. Growth. 1997. 170 (14). . 3946. 3. Kohmoto S., Nakamura H., Ishikawa T., Asakawa K. Self-controlled self-organization of individual InAs dots by scanning tunneling probe-assisted nanolithography // Appl. Phys. Lett. 1999. 75 (22). . 34883490. 4. Vorobyova A.I., Sokol V.A., Outkina E.A. SEM investigation of pillared microstructures formed by electrochemical anodization // Appl. Phys. A. 1998. 67. . 489492. 5. Masuda H., Saton M. Fabrication of gold nanodot array using anodic porous alumina as an evaporation mask // Jpn. J. Appl. Phys. Lett. 1996. 35 (NIB). P. L126L129. 6. Masuda ., Yasui ., Sakamoto Y., Nakao . Ideally Ordered Anodic Porous Alumina Mask Prepared by Imprinting of Vacuum-Evaporated Al on Si // Appl. Phys. 2000. 40. . L1267-L1269. 7. Vorobyova A.I., Outkina E.A. Study of pillar microstructure formation with anodic oxides // Thin Solid Films. 1998. 8. .. // . 2001. 6 (30). . 445458. 9. Masuda ., Fukuda . Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb Structures of Anodic Alumina // Science. 1995. 268 (9). . 14661468. 10. McEuen P.L. Singl-wall carbon nanotubes // Physics Word. 2000. 13 (6). . 3136.

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