化学气相沉积与薄膜材料

2265 5.21 9.0
32 (GPa) 1020 Decomposition of the Cr(C5H7O2)3 Cr
l、
HfO2 * 3310 10.0 9.4 150
109 HfCl4 + CO2 + H2 à HfO + CO + HCl
l
、
SiO2 cubic 1610 2.2 0.5 ZrO2 * 2700 5.4 10.2
Exhaust
Quarts reactor RF power
MFC: mass flow controller
MFC AsH3+H2 MFC H2Se+H2
MFC
DEZn
TMGa
MFC
MFC
MFC
TMAl
MFC
Dewar flash
Purified H2
Vacuum
Schematic diagram of a vertical atomspheric MOCVD reactor
Vapor pressure of OM precursor
a
b
8.224 2135
8.50 1824
9.17 2532
8.28 2190
7.76 1850 7.97 1865
Growth temperature
(℃) 700 1250 650~750 800 750 500~550 650~700
210 10 0.022
HfCl4 + N2 + 4H2 à 2HfN + 8HCl l l
NbN fcc 2330 8.3 10 140 200 0.04 NbCl4 + NH3 à NbN + 4HCl
l
Si3N4
1900 3.18 2.5 280 1014 0.45 W·cm
TiN fcc 2950 5.4 9.5 210 135 0.33
WCl6 + CH4 + H2 à WC + 6HCl
WF4 + CH3OH + 2H2 à WC + 6HF + H2O
ZrBr4 + CH4 à ZrC + 4HBr
16
CVD
Al2O3 Cr2O3
ºC g/cm3 10-6/K MPa 2015 3.9 8.3 191
W·cm 1016 AlCl3 + H2 + CO2 à Al2O3 + CO + HCl l
Ar or N2
l l l PECVD
CVD
(750-900ºC) 300ºC
SiH4 NH3 Si3N4
10
PECVD
l
l
l
l
(Al2O3)
l
DLC
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12
1.
(pyrolysis)
SiH4(g) → Si(s) + 2H2(g) Ni(CO)4(g) → Ni(s) + 4CO(g) CH4(g) → C(dia.) + 2H2(g)
(compound formation)
1400ºC
SiCl4(g) + CH4(g) → SiC(s) + 4HCl(g) TiCl4(g) + CH4(g) → TiC(s) + 4HCl(g)
1400ºC 1000ºC
BF4(g) + NH3(g) → BN(s) + 3HF(g) AlCl3 +CO2 +H2 → Al2O3(s) + CO +HCl
100
1021 SiCl2H2 + N2O à SiO2 + HCl + N2
l
SiH4 + O2 à SiO2 + H2O
SiH4 + O2 à SiO2 + H2
Si(OC2H3)4 + H2 à SiO2 + C2H4 + HO2
170
500 TiCl4 + CO2 + H2 à ZrO2 + CO + HCl l
650ºC 180ºC 750ºC
2.
(reduction)
SiCl4(g) + 2H2(g) → Si(s) + 4HCl(g)
1200ºC
WF6(g) + 3H2(g) → W(s) + 6HF(g)
300ºC
MoF6(g) + 3H2(g) → Mo(s) + 6HF(g)
300ºC
CH4 + nH2 → Cdia + (2+n)H2
BN
3000 2.25 1.2
c-BN fcc
1020 0.11 300
BCl3 + NH3 à BN + 3HCl
l
BF3 + NH3 à c-BN + 3HF
lX
B2H6 + NH3 + F2 à 2BN + 12HF
B(C2H5)3 + NH3 à c-BN + CnHm l
HfN fcc 3310 13.8 6.9
15
CVD
/ºC /g/cm3 /10-6/K
B4C rhl 2450 2.45 4.5
rhombohedral
MPa 500
/µW·cm /W/cm·K 5x106 0.35
Cr7C3 mcl 1780 6.9 10
mnoclinicl
HfC fcc 3890 12.6 6.6 290
84
0.11
Trimethyl-gallium (
)
(TMGa) arsenic indium
phosphorus
Triethyl-arsenic (
)
(TEAs) stibium zinc
Compound
AlAs AlN GaAs GaN GaP GaSb InAs InP ZnS ZnSe CdS
HgCdTe
50
0.08
NbC fcc 3500 7.1 6.0 240 60-150 0.14
-SiC cth 2700 3.21 3.9 280
107-8
1.25
TaC fcc 3880 7.1 5.5
240 40-175 0.22
TiC fcc 3250
7.6
Ti(C,N) 2950 5.4 9.3
320 60-250 0.17 21GPa 0.025 0.30
700
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13
3.
(oxidation)
SiH4(g) + 2O2(g) → SiO2(s) + 2H2(g)
450ºC
SiCl4(g)+2H2+O2(g) → SiO2(s)+4HCl(g)
1500ºC
C2H2(g)+1/2O2(g) → C(dia.)+CO(g)+H2(g)

4.
17 17
Si
Ge SiC AlN ITO ZnS CdS
Al2O3
SiO2 Si3N4 TiO2 TiC TiN BN DLC
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, GaAs, GaAs,
、 、
CVD
SiCl2H2, SiCl3H, or SiCl4 + H2 SiH4 + H2 GeCl4, or GeCl4 + H2 SiCl4, CH3SiCl3, or Toluene + H2 AlCl3 + NH3 + H2 In-chelate+(C4H9)2Sn(OOCH3)2+H2O+O2+N2 Zn + H2S + H2 Cd + H2S + H2 Al(CH3)3 + O2 AlCl3 + CO2 + H2 SiH4 + O2; SiCl2H2 + N2O
CdTe
Reactans
TMAl + AsH3 TMAl + NH3 TMGa + AsH3 TMGa + NH3 TMGa + PH3 TEGa+ TMSb TEIn + AsH3
TIn + PH3 DEZn + H2S DEZn + H2Se DMCd + H2S Hg + DMCd +
DMTe DMCd + DMTe
T ()
1050-1200 600-700 600-900
1100 1000 500 825 690 275-475 850-1100 450; 900
Ti(OC2H5)4 + O2 TiCl4 + CH4 + H2 TiCl4 + N2 + H2
450 1000 1000
C-H-O
18 18
(disproportionation)
CrCl + CnHm à Cr7C3 + HCl (1000ºC) Decomposition of Cr[(C6H5)C3H 7]2 (500ºC)
HfCl4 + CH4 à HfC + 4HCl HfCl4 + CH3Cl + H2 à HfC + 5HCl
Nb + CH4 à NbC + 4H2 2NbCl4 + 2CCl4 + 9H2 à 2NbC + 18HCl
(Sci. 226,623,1984)
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22
4-3
+ ⇋+
()
∆ = ( + )– ( + ) = +
∆ = ∆ + ln
, ∆ = 0,
0 = ∆ + ln
11/6/17
= ∆ 0 + ln
ai
(
1)
DG ~ DG0
k K=
k-1
∆ 0 =– = exp(– ∆ 0/ )
23
aA + bB « cC + dD
∆ = ∆ + ln
∆ = − ln
c
d
DG
=
RT
ln
æ çç è
aC aC¢
ö ÷÷ ø
a
æ × çç è
aD a¢D
ö ÷÷ ø
b
æ çç è
aA a¢A
ö ÷÷ ø
æ × çç è
aB a¢B
ö ÷÷ ø
For vapor deposition: vapor phase: ai ~ pi solid phase: ai ~ 1
u u u
11/6/17
Chemical Vapor Deposition (CVD) 。
2
l
l
l
l
(Al2O3)
l
DLC
11/6/17
3
PECVD PACVD
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CVD CVD CVD CVD CVD CVD CVD CVD CVD CVD
CVD
4
(a)
CVD
CVD
(b)
(c)
1.
-WC hex 2700 15.8 4.5 180 -WC fcc ZrC fcc 3450 6.57 6.0 200
17
0.28
57-75 0.20
4BCl3 + CH4 + 4H2 à B4C + 12HCl 4BCl3 + CH3Cl + 5H2 à B4C + 13HCl 4BCl3 + CCl4 + 8H2 à B4C + 16HCl 2B2H6 + CH4 à B4C + 8H2
SiCH3Cl3 à SiC + 3HCl SiH4 + C6H6 àSiC + 15H2 3SiH4 + C3H8 à 3SiC + 10H2 Ta + CH4 à TaC + 2H2 TaCl4 + CH3Cl + H2 à TaC + 5HCl
TiCl4 + CH4 à TiC + 4HCl TiCl4 + C + 2H2 à TiC + 4HCl 2TiCl4+2xCH4+(1-x)N2+4(1-x)H2à2TiCxN1-x+8HCl TiCl4 + 4CH3CN + 4H2 à Ti(CN)4 + 4HCl
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24
(
)Y2O3
(1): 2YCl3(g)+ (3/2)O2 DBiblioteka BaiduY2O3(s)+ 3Cl2(g) (2): 2YBr3(g)+ (3/2)O2 D Y2O3(s)+ 3Br2(g)
1 CO2(g) « CO(g) + 2 O2(g)
DG1 = −59.4 kcal/mol DG2 = −108 kcal/mol
CVD
(a) CVD (b) CVD (c)
CVD。
CVD
1100
11/6/17
6
11/6/17
CVD
(HT-CVD) >900
(MT-CVD) 700~900
7
CVD
()
T, C
(T)
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(C)
x
8
PECVD
~
l CVD
l l
PECVD
。 。
。
PECVD
rf ()
?
SiH4 + NH3
3SiCl4 + 4NH3 à Si3N4 + 12HCl l 3SiH4 + 4NH3 à Si3N4 + 12H2 l 3SiH4 + 2N2 à Si3N4 + 6H2
TiCl4 + H2 + N2 à TiN + HCl
l
TiCl4 + NH3 + H2 à TiC + HCl l
l
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1100ºC
2SiI2(g) D Si(s) + SiI4(g)
900ºC
900 SiI4 + Si 2SiI2
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1100 SiI4 + Si 2SiI2
19
CVD (MOCVD)
(CH3)3Ga + AsH3 g GaAs + 3CH4
log P(torr) = a – b/T(K)
DG = 46.7 kcal/mol
(3): 2YCl3(g)+ 3CO2(g) D Y2O3(s)+ CO(g) + 3Cl2(g) DG3 = DG1+ 3DG = 80.7 kcal/mol
1100ºC 1050ºC
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14
CVD
ºC g/cm3 10-6/K MPa µW·cm W/cm·K
AlN
2400e 3.28 4.3 123 >1014 3.2
AlCl3 + NH3 à AlN + 3HCl
l
W·cm
AlBr3 + NH3 à AlN + 3HBr
l
、
Al(CH3)3 + NH3 à AlN + 3CH4 l