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III-V Compound Semiconductor

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Crystal Growth
overpressure

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Phase Diagrams: # and types of phases


Phases: The physically or chemically distinct material regions. Rule 1: If we know T and Co, then we know:
--the # and types of phases present.

Examples:
A(1100C, 60): 1 phase: B(1250C, 35): 2 phases: L +

T(C)
1600

L (liquid)
B (1250C,35) 1500 1400 1300 1200
liq u u id
s

L (FCC solid
solution)
A(1100C,60)

s du oli

Cu-Ni phase diagram

Adapted from Fig. 9.3(a), Callister 7e. (Fig. 9.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH, 1991).

1100 1000 0 20 40

60

80

100

wt% Ni

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Phase Diagrams: composition of phases


Rule 2: If we know T and Co, then we know:
--the composition of each phase. Cu-Ni system A L (liquid) B
L +
tie line dus i liqu

Examples:
Co = 35 wt% Ni At T A = 1320C: Only Liquid (L) CL = Co ( = 35 wt% Ni) At T D = 1190C: Only Solid ( ) C = Co ( = 35 wt% Ni)

T(C) TA
1300

L+

TB
1200

TD
20

D CLCo

(solid)
4043 50

us olid s

At T B = 1250C: Both and L CL = C liquidus ( = 32 wt% Ni here) C = C solidus ( = 43 wt% Ni here)

30 35 32

C wt% Ni

Adapted from Fig. 9.3(b), Callister 7e. (Fig. 9.3(b) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH, 1991.)

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Phase Diagrams: weight fractions of phases


Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%). Cu-Ni system A L (liquid)
tie line dus i liqu

Examples:
Co = 35 wt% Ni At T A : Only Liquid (L) W L = 100 wt%, W = 0 At T D: Only Solid ( ) W L = 0, W = 100 wt% At T B : Both and L

T(C) TA
1300

TB
1200

B R S D CLCo

+ L

(solid)
50

us olid s

TD
20

WL = W =

43 35 S = = 73 wt % R + S 43 32

30 35 32

40 43

C wt% Ni

R = 27 wt% R +S

Adapted from Fig. 9.3(b), Callister 7e. (Fig. 9.3(b) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH, 1991.)

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The Lever Rule


Tie line connects the phases in equilibrium with each other essentially an isotherm
T(C)
1300 tie line dus i liqu

L (liquid) B
L +
R

How much of each phase? Think of it as a lever (teeter-totter)


ML M

+ L

TB
1200

(solid)
S
50

us olid s

20

30C C 40 C L o

M S = M L R
C CL R = 0 R + S C CL
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wt% Ni

Adapted from Fig. 9.3(b), Callister 7e.

WL =

C C0 ML S = = M L + M R + S C CL

W =

LEC-liquid encapsulation Czochralski

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Heteroepitaxy of GaAs/AlGaAs
Lattice constant: GaAs: 5.654 AlAs: 5.661 AlAs properties: Indirect, Eg = 1.26 eV Unstable in air GaAs properties: direct, Eg = 1.42 eV AlGaAs properties: Stable for x < 0.8 Variable gap depending on x x < 0.34 direct x > 0.34 indirect
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Epitaxy

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Why use MOCVD to grow the epitaxial layer ?


(1) (2) (Quaternary P-Containing Compounds)MOCVD (3)

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Metalorganic Chemical-Vapor Deposition


LP-MOCVD of Thomas Swan
H2 Hydride Line MFC AsH3 MFC PH3 MFC SiH4 MFC DMZ MFC Reactor Substrate MO Line Heater MFC H2 Exhaust MFC: Mass Flow Controller MFC H2 MFC H2 MFC H2 TMI TMG TMA P Pressure Controller Rotator

1.

2. 3. 4. 5.

Reaction Chamber & Heating System Gas Delivery System Low-Pressure System Epifold & APC System Gas Exhaust System.

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LP-MOCVD of Thomas Swan Cont


Graphite Susceptor & Heater

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LP-MOCVD of Thomas Swan Cont


Reaction Chamber

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LP-MOCVD of Thomas Swan Cont


Reaction Chamber (Top Part)

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LP-MOCVD of Thomas Swan Cont


Reaction Chamber (Bottom Part)

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LP-MOCVD of Thomas Swan Cont


Gas Delivery & Epifold System

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LP-MOCVD of Thomas Swan Cont


Graphite Susceptor & Display Panel

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Growth Mechanism (1)


Normally, MOCVD process is mostly dominated by the diffusion of the MO compounds and thus called diffusion-controlled (mass-transport limited) growth. The growth rate of Rg can be expressed as:

Rg p MO ptot

pMO: the MO partial pressure v: the gas velocity Ptot: the total reactor pressure

For InP: 265 A/min For InGaAs: 500 A/min

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Growth Mechanism (2)


For InP growth: In(CH3)3 + PH3 InP + 3CH4
H 3C In H 3C CH 3 H H P H
H

In

H H

For GaxIn1-xAs growth: xGa(CH3)3 + (1-x) In(CH3)3 + AsH3 GaxIn1-xAs +3CH4 For GaAs growth: AsH3x + Ga(CH3)3 GaAs +3CH4 Generally, the V/III ratio is much higher than 1 to supply a large amount of group V sources at the surface and to avoid thermal decomposition..
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Linear GRINSCH 1.55 m InGaAsP/InP SMQW laser diode grown by substrate temperature control

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Why linear GRIN-SCH structure ?

Steps GRIN-SCH Linear GRIN-SCH


1.05 PQ 1.23 PQ 1.05 PQ 1.2 PQ 1.23 PQ

Well 0.85CS In0.738 Ga0.262 As0.812P0.188(5nm) Barrier =1250nm InGaAsP unstrained


5 1 0 18

Material Gain (1/cm)

1 1 0 18 0 .8 1 0 1 8

Modal Gain (1/cm)

34.5 34

Modal Gain (1/cm)

1 1 i + ln( ) 2L R1R 2 g th = opt , w h ( I I th ) Pout = d q

0 .6 1 0 1 8
N = 0 .5 1 0 1 8 c m - 3

, opt,w

gth

W a v e le n g th ( m )
36 35.5 35

45 44.5 44 43.5 43

33.5 33

Pout

, at same injected current

opt,w = 0.85%
1.51
1.52

42.5 42

opt,w = 1.1%
1.51
1.52

1.5

1.53

1.54

1.55

1.56

1.5

1.53

1.54

1.55

1.56

Wavelength (m)

Wavelength (m)

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Why InxGa1-xAsyP1-y materials hard to grow linear GRINSCH structure ?


100 6

Source Flow-Rate (SCCM)

80

fPH3 fTMIn = 430 SCCM

4 60 3 40

Mole fraction of As (y)

Growth Rate (m/h)

fAsH3 Flow-Rate (SCCM)


According to the experimental source flows rate the growth of InxGa1-xAsyP1-y materials can be formulated as:

fTMGa fAsH3
0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7

20

Ga1-x= 0.0173fTMGa Asy= 0.1154 e 0.041 f AsH3


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Material Wavelength (m)

1150

2000

In 0.873 Ga 0.127 As 0.314 P 0.687 In 0.876 Ga 0.124 As 0.282 P 0.718 Emission Wavelength (nm)
1100

PH 3 = 75 AsH 3
1000

Lattice Mismatched rate a/a) PPM (

In 0.878 Ga 0.122 As 0.26 P 0.74 In 0.882 Ga 0.118 As 0.241 P 0.759

1050
Normalized Intensity 660 620

PH3 /AsH3 Ratio

Growth Temper -ature () 620 630 640 650 660

1000

-1000

PL Peak Wave length (m) 1.239 1.200 1.176 1.158 1.142 1.133 1.101 1.080 1.064 1.048

Lattice Mismatch (ppm)

Solid Composition in In1-xGaxAsyP1-y x y 0.204 0.466 0.196 0.428 0.195 0.407 0.192 0.389 0.190 0.373 0.127 0.313 0.124 0.282 0.122 0.260 0.118 0.241 0.115 0.224

900

1000

1100

1200

In 0.883 Ga 0.115 As 0.224 P 0.776


-2000

36

758 52 -568 -968 -1352 1158 320 -254 -582 -1058

Wave Length (nm)

950 610 620 630 640 650 660 670

Deposition Temperature (
1250

)
2000

In0.796Ga0.204As0.466P0.534 In0.804Ga0.196As0.428P0.572

PH 3 = 36 AsH 3
Lattice Mismatched rate (a/a) PPM
1000

Emission Wavelength (nm)

In0.805Ga0.195As0.407P0.593
1200

75

620 630 640 650 660

In0.808Ga0.192As0.389P0.611
0

In0.81Ga0.19As0.373P0.627
1150
Normalized Intensity
660 620

-1 000

1050

1100

1150

1200

1250

1300

Wave Length (nm)

1100 610

620

630

640

650

660

-2 000 670

Deposition Temperature ( )

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In

Ion Signal Intensity (arb. units)

Ga

As

0.1

0.2

0.3

0.4

0.5

0.6

Depth (m)

SIMS depth profiles for InGaAsP linearly GRINSCH SMQW structure


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Steps GRIN-SCH
10
10

Linear GRIN-SCH
Light Output Power (mW)
30 40 50 60

Light Output Power (mW)

As cleaved LDs

20

As cleaved LDs
8

20 30

40 50 60 70 80

70
2

0 0 10 20 30 40 50 60 70 80

0 0 10 20 30 40 50 60 70 80

Injection Current (mA)

Injection Current (mA)

The dependence of light output power on drive current at various heat-sink temperatures

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20

60

Inverse Differential Efficiency (1/ext)

45 40

Threshold Current (mA)

i = 72.5 Steps GRINSCH i = 14.4 cm-1


Linearly i = 72.5 GRINSCH = 10.3 cm-1 i

i = 65 i = 34 cm-1 i = 70.1 i = 23.6 cm-1

60

35 40 30 35 25 30 20
25

T0= 63 K (<50C) T0= 50 K (>50C)

24 22 20 18 16 14

20
3

15 20 10 15
10 20 30 40 50 60 70 80

12 10

Temperature (C)
1

200

400

600

800

1000

1200

1400

40 35

Linear GRINSCH
T0= 65 K (<50C) T0= 57 K (>50C)

30

Threshold Current (mA)

Cavity Length (m)

d = i

m i + m

35 30 30 25 25 20 20 15 15 10 10 5

, i
) , T0

d
(temperature insenstive)

25

I th = I th 0 exp(

Tj T0

20

15 10 20 30 40 50 60 70 80

Temperature (C)

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Front Facet Slope Efficiency (%)

Front Facet Slope Efficiency (%)

Steps GRINSCH

20

Intensity (dB)

LDs with a coating facet Light Output Power (mW)


15

20 30 40

1.57

-30

-40

Lasing Wavelength (m)

50 60

-50

1.56

-60

-70

1.525

10

70 80

1.545 1.535 Wavelength (m)

1.55

90 95

1.54

1.53 10 20 30 40 50 60 70 80 90
80

0
0 10 20 30 40 50 60 70

Injection Current (mA)

Heat Sink Temperature ( )

Red-shift rate 0.45 nm/K

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