Mocvd

ADVANCED INSTITUTE OF TECHNOLOGY
MOCVD
- Basics and Applications Photonics Lab
-Tutorial (2004.4.23)
Photonics Lab
Outline
BASICS OF MOCVD PROCESS Introduction to MOCVD/MOVPE/OMVPE Systems and Reactors Precursors Basic transport and growth mechanisms Applications Summary
-Tutorial (2004.4.23)
Photonics Lab
Introduction to MOCVD / MOVPE / OMVPE
-Tutorial (2004.4.23)
Photonics Lab
MOCVD / MOVPE / OMVPE

MOCVD: Metal Organic Chemical Vapor Deposition Metal Organic Vapor Phase Epitaxy Organo Metallic Vapor Phase Epitaxy
MOVPE: OMVPE:
Often all three expressions are used interchangeably
-Tutorial (2004.4.23)
Photonics Lab
What is MOCVD?
MOCVD is a method to grow/deposit thin solid films, usually semiconductors, on solid substrates (wafers) using organometallic compounds as sources. The films grown by MOCVD are mainly used for the fabrication of electronic and optoelectronic devices. The electronic and optoelectronic devices produced by MOCVD are used in cell phones (HBTs), optical communication, optical storage (CD, DVD, HD-DVD/BDLDs), traffic lights, bill boards (LEDs), lighting and satellites (solar cells). Major MOCVD vendors are AIXTRON, Thomas Swan, VEECO (Emcore), Nippon-Sanso, etc.
-Tutorial (2004.4.23) 5 Photonics Lab
Overview of Epitaxy Techniques

Technique LPE HVPE Strengths Simple High purity Well developed Large scale Simple process Uniform, Abrupt interface In-situ monitoring Most flexible, Large scale production Abrupt interface Simple reactor, High purity
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Weaknesses Scale economies Inflexible, Non-uniformity No Al alloys Complex process/Control difficult, Hazardous sources As/P alloy difficult Expensive Low throughput Expensive sources Most parameters to control Accurately Hazardous precursors
Photonics Lab
MBE
MOCVD/ OMVPE
-Tutorial (2004.4.23)
Why MOVPE?
Very high quality of grown layers (high growth rate and doping uniformity/reproducibility) High throughput and no ultra high vacuum needed (compared to MBE), therefore economically advantageous, high system up-time Different materials can be grown in the same system, therefore highest flexibility Growth of sharp interfaces possible - therefore very suitable for hetero-structures, e.g., multi quantum wells (MQW)
-Tutorial (2004.4.23)
Photonics Lab
Simplified Presentation of a Crystal Growth Process
-Tutorial (2004.4.23)
Photonics Lab
Crystal Structures
(1) (2) (3)
a a c
The group III nitrides GaN, AlN and InN can crystallize in the following three crystal structures: : (1) Wurtzite (2) Rock-salt and (3) Zinc-blende
The World of Semiconductors

III IV V
Traditional semiconductors Si: DRAMs, Processors Compound semiconductors III-Vs: GaAs, AlGaAs, GalnP, AlGaInP, GaN, InGaN Speciality: SiC Enabling technology for: Advantages of compound semiconductors: faster, higher frequencies visible light, infrared high efficient photovoltaics heat and high power resistant
How MOCVD Works
-Tutorial (2004.4.23)
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Photonics Lab
Components of a LP-MOCVD System
gas blending unit
reactor with heated susceptor
control unit
vacuum system
scrubbing system
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-Tutorial (2004.4.23)
Basic Principles of the MOVPE Process
Step 1: A gas mixture containing the precursors needed for growth, and if necessary for doping, is passed over a heated substrate. Step 2: The precursor molecules pyrolyze leaving the atoms, e.g., Ga and As atoms on the substrate surface. Step 3: The atoms bond to the substrate surface and a new crystalline layer is grown, in this case GaAs.
Systems and Reactors
-Tutorial (2004.4.23)
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Photonics Lab
AIXTRON MOCVD System

transfer cabinet wafer handler vacuum pump (inside)
reactor + heater gas mixing system computer electronic control rack

Gas Blending System
run/vent stack Lauda bath for bubblers H2 purifier (Pd-cell)
-Tutorial (2004.4.23)
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Photonics Lab
AIX 2600G3 MOCVD Reactor
-Tutorial (2004.4.23)
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Photonics Lab
Vacuum System Vacuum pump - Ebara dry pump
-Tutorial (2004.4.23)
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Photonics Lab
AIXTOX Scrubbers: Principle

Chemical reaction between a liquid and a Gas in a counter-flowsetup Typically no reaction with carrier gas (e.g. H2 is not treated) A fast reaction is essential for efficient scrubbing
-Tutorial (2004.4.23)
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Photonics Lab
Planetary Reactor AIX 2600 G3 Susceptor (horizontal type)
wafer handler 4 wafer on rotating satellite main susceptor disk collector ring
-Tutorial (2004.4.23)
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Photonics Lab
RF Heater in G3 Systems
-Tutorial (2004.4.23)
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Photonics Lab
Horizontal Tube Reactor AIX 200RF
-Tutorial (2004.4.23)
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Photonics Lab
Thomas Swan MOCVD system (Vertical type)
CCS(Close Coupled Showerhead) Reactor

Veeco(Emcore) MOCVD system (Vertical type)
Turbo Disc system
-Tutorial (2004.4.23)
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Photonics Lab
Precursors
-Tutorial (2004.4.23)
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Photonics Lab
Example: Precursor Molecules
AsH3
DMZn - (CH3)2Zn
TMGa - (CH3)3Ga H C As Zn Ga
-Tutorial (2004.4.23)
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Photonics Lab
Precursors - Definitions Pyrolysis:

Chemical decomposition of (metal)organic materials by heat in the absence of oxygen. E.g., for TMGa the decomposition takes place in steps from TMGaMMGa Ga. Each decomposition needs higher activation energy. The organic materials are transformed into volatile components (e.g., CH3 molecules in the case of TMGa or DMZn).
Ligand:
A molecule, ion, or atom that is bonded to the central metal atom of the metalorganic molecule (e.g., the CH3 molecules in the case of TMGa or DMZn).
-Tutorial (2004.4.23)
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Photonics Lab
Precursors - Chemical Bonds Chemical bond strength

Determines: Pyrolysis temperature and long term stability, both increase with increasing bond strength The more C atoms are attached to the central metal atom, the weaker the bond The bond strength decreases with increasing molecule size (bond crowding effect) Precursor pyrolysis temp. increases from TBAs TEAs TMAs AsH3 or TEGa TMGa Decomposition sequence: TMGa MMGa Ga
General:
Example:
-Tutorial (2004.4.23)
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Photonics Lab
Precursors - Reaction Types

Homogeneous Reactions
Reactions in the gas phase, e.g., in boundary layer May occur without or with collision of additional molecule (unimolecular or bimolecular)
Heterogeneous Reactions
Reactions at reactor walls or substrate surface The bonds of adsorbed molecules are weakened, e.g., the H bonds of AsH3 at the substrate surface Occur mostly at lower temperatures than homogeneous reactions
-Tutorial (2004.4.23)
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Photonics Lab
Precursors - Precursor Properties Desirable properties of precursors:

Low toxicity Liquid at room temperature Suitable vapor pressure at room temperature Low carbon contamination in grown layer (avoid CH3 radicals), however, for some applications C doping is desired No parasitic reactions with other sources Good long term stability (should not decompose in bubbler) Pyrolysis temperature should match growth temperature Inexpensive for industrial mass production
Precursors - Carbon Incorporation Carbon contamination

Unintentional C doping from C containing precursors is called carbon contamination CH3 radicals (mostly available in methyl precursors) are responsible for C contamination of the growing film C2H5 from ethyl groups causes significantly less carbon contamination than CH3 radicals C contamination from MO source can be reduced by increasing AsH3 partial pressure (higher V/III ratio), more H to react with CH3 However, in some cases p-type doping with C from MO sources is desired
Group III MO Precursors

Precursor Symbol
TMGa TEGa (CH3)3Ga (C2H5)3Ga
Advantages
liquid, high vapor pressure liquid, low carbon contamination, decomposes by -hydride elimination reaction, used in LP MOVPE systems solid, good vapor pressure for MOVPE, also exists as solution TMIn
Disadvantages
low vapor pressure, less stable than TMGa, strong parasitic reactions low vapor pressure
TMIn
(CH3)3In
TEIn TMAl TEAl
(C2H5)3In (CH3)3Al (C2H5)3Al liquid, good vapor pressure, good long term stability liquid, low carbon contamination
very unstable oxygen contamination low long term stability
TM = Trimethyl, TE = Triethyl (Ga = Gallium, In = Indium, Al = Aluminum)

Group V Precursors
Precursor Symbol
Arsine AsH3
Advantages
good pressure control for MOVPE, inexpensive good pressure control for MOVPE, inexpensive liquid, good vapor pressure for MOVPE, very low carbon contamin., good stability, low pyrolysis temperature (T1/2 = 380C) liquid, used to grow C doped GaAs liquid, good vapor pressure for MOVPE, good stability, low pyrolysis temperature (T1/2 = 450C) good stability, only practically available nitrogen precursor
Disadvantages
very toxic, high pyrolysis temperature (T1/2 = 600C) very toxic, high pyrolysis temperature (T1/2 = 850C) expensive for many applications
Phosphine
PH3
TBA
(C4H9)AsH2
TMA TBP
(CH3)3As (C4H9)PH2
expensive for many applications high pyrolysis temperature
Ammonia (for nitrides)
NH3
TM = Trimethyl, TB = Tertiarybutyl (A = arsine, P = phospine)

Dopant Precursors
Precursor
DMZn (p-dopant) Carbontetrachloride (p-dopant in GaAs)
Symbol Advantages
(CH3)2Zn liquid, high vapor pressure, very common Zn precursor liquid, C is shallow acceptor in GaAs, C has low diffusion coeff., used for sharp interfaces, e.g., for high p-type doping in HBTs used in similar applications as CCl4 used as n-dopant for electronic devices used in similar applications as SiH4, but lower pyrolysis temp., better doping uniformity than SiH4 liquid, used in LED production
Disadvantages
Zn often has very high diffusion coefficient in solid, diffuses via interstitials usage might be subject to legal regulation due to ozone depleting character of chemical same as for CCl4 gaseous, flammable, high pyrolysis temperature gaseous, flammable
CCl4
Carbontetrabromide (p-dopant ) Silane (n-dopant) Disilane (n-dopant)
CBr4 SiH4 Si2H6
DETe (n-dopant)
(C2H5)2Te
DM = Dimethyl, DE = Diethyl (Zn = Zinc, Te = Tellurium)

Doping Example: Doping of Silicon
undoped Si (intrinsic)
Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si
Arsenic doped Si (n-type)

Si Si Si Si Si Si As Si Si Si Si Si Si Si Si Si
Boron doped Si (p-type)

Si Si Si Si Si Si B Si Si Si Si Si Si Si Si Si
bonding electron (covalent bond)
additional free electron As = donor
missing electron (hole) B = acceptor
-Tutorial (2004.4.23)
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Photonics Lab
Basic Transport and Growth Mechanisms
-Tutorial (2004.4.23)
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Photonics Lab
Principle of LP-MOVPE
H 2
gas blending
reactor
scrubbing system
H , N P=10-200 mbar 2 2
Ga (CH ) + AsH 3 3 3 Ga (CH ) + NH 3 3 3
GaAs GaN
+ 3CH + 3CH
4 4
vacuum pump
TMGa, AsH
TMAl, TMGa, TMIn , PH
5 - 100 rpm
throttle valve
TMGa, NH
filter unit GaAs , InP , sapphire substrate, T ~ 400 - 1200C
high purity, precise mixing
crystal quality, thickness uniformity, reproducibility
safety
-Tutorial (2004.4.23)
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Photonics Lab
MOVPE Growth Mechanisms

(simplified) horizontal gas flow
CH3 H2 H H2
H N
H
H2
Ga
CH3 CH3
CH3
H2
gas phase
boundary layer
CH3 -radical H H H
Ga
CH3 CH3 CH3radical CH4 = CH3 + H
N
H + H = H2
mass transport to the surface by diffusion precursor decomposition adsorption wafer surface
atomic step
-Tutorial (2004.4.23)
surface diffusion and reaction

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incorporation and growth

Photonics Lab
Boundary Layer Model

D p * pi J= RT 0
Mass transport limited growth regime:
rg = const (PTMGa (v/ptotal)1/2) J

Flux
pi = 0
Temperature dependency of growth rate for mass transport limited growth:
D Diffusion coefficient
p * Input partial pressure of group-III precursor p i Group-III partial pressure at the interface
Thickness of boundary layer Growth rate
D = D (T ) 0 = 0 (T , v)
R Gas constant
rg
v T
Gas velocity Temperature
-Tutorial (2004.4.23)
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Photonics Lab
Transport Mechanisms in Horizontal System

boundary layer
Convective transport by flow
Diffusion in cross-flow direction
longitudinal depletion is governed by:

consumption of nutrients development of boundary layer
rg
... can be controlled by, e.g.

total flow rate gas density and diffusion properties reactor aspect ratio & inlet design
wafer
Depletion profile of growth rate

Growth Rate Uniformity

inlet
fer rota tion
wa
outlet
Viewgraphs: predicted growth rate profiles of AlGaAs on the AIX200 susceptor (T=700C, p = 20 mbar); static wafer vs. rotated wafer
longitudinal non-uniformity (1) lateral non-uniformity (2)
depletion of nutrients parabolic flow profile in rectangular duct
lateral non-uniformity only partially compensated by rotation

Example: GaAs Growth Rate
3 Growth Rate [m/hour]
5 Group III flow rate [mole/min]
10
In the mass transport limited regime the growth rate is almost independent of temperature. It mainly depends on the group III molar flow rate. Changing the group III flow rate will change the growth rate, but not the V/III ratio at the interface, and not the solid stoichiometry.
-Tutorial (2004.4.23)
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Photonics Lab
Example: GaAs Growth Efficiency

Growth Efficiency [m/mole]
104 B C 103 A A - Kinetically limited growth B - Mass transport limited growth
102 0.6
1.0 1000/T [K-1]
1.4
-Tutorial (2004.4.23)
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Photonics Lab
Wafer Surface Orientation

CH3
CH3 CH3
Ga
CH3
Ga
CH3
CH3
Ga As
on-axis substrate
misoriented substrate, net surface diffusion of atoms to the left - from high to low steps
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MOVPE growth of conventional III-V semiconductors is usually performed on substrates misoriented by 2-3 toward a certain crystallographic direction (e.g., <100> 2 <110>. This yields better quality films and higher growth rates, since atoms easier incorporate at step edges.
-Tutorial (2004.4.23)
Photonics Lab
Surface Diffusion
The diffusion of atoms on a surface is affected by atomic steps on the surface:
Atoms preferentially move from high to low steps Wide steps allow long diffusion, while narrow steps reduce the diffusion coefficient (step width depends on degree of misorientation)
-Tutorial (2004.4.23)
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Photonics Lab
What is important for successful Epitaxy?

Thermal management in the reactor effects
Transport coefficient Reaction rates Incorporation of dopants Composition of multi-component material systems
Composition of the gas phase

For InxGa1-xN LEDs, the In/Ga-ratio determines the color of the LED. Therefore calibrated and stable MFCs and PCs are needed for reproducible LED colors. Bubbler temperature determines vapor pressure of MO
-Tutorial (2004.4.23)
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Photonics Lab
Applications
-Tutorial (2004.4.23)
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Photonics Lab
Products made by MOVPE

Semiconductor AlGaInP InGaN Application displays, DVD, automotive, traffic lights blue LED, Violet LD displays, BD, White-LED automotive, Indoor/outdoor lighting LD CD, telecomm., solar cells satellites, transistors, ICs cellular phones, radar
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Device LED, LD
AlGaAs GaAs GaInP
-Tutorial (2004.4.23)
Materials and Applications
-Tutorial (2004.4.23)
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Photonics Lab
LEDs 15000 LEDs on a 2-Wafer Chip size : 0.35 x 0.35mm

The optoelectronic properties of the different compound semiconductors determine the illuminated color of an LED: red to yellow/green green/blue AlGaAs, AlGaInP (In)GaN
White light is generated by combining blue LEDs with fluorescent dyes.

LED - Colors
-Tutorial (2004.4.23)
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Photonics Lab
GaN LED Test Structures grown by MOCVD
-Tutorial (2004.4.23)
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Photonics Lab
LED Media Boards

~ 1000 m2 LEDs
= 19 mil. LEDs
Times Square, New York

Cost Comparison
Incandescent No. of lamps Cost of lamps Power requirements Energy consumption (kWhr/yr) Annual electrical bill (at $0.10/kWhr) Payback period 1 $2.50 150 W 788 $78.80 LED 280 $42.00 20 W 105 $10.50
< 1 year
Source: European Semiconductor, Vol. 22, No. 1, Jan. 2000
Standard in several US states; pilot projects in UK, S, CH, Au, F Germany: pilot projects in Munich, Frankfurt, Aachen
LEDs for Lighting

(1998)
(Siemens - Osram)
signal/traffic interior lighting

(1996) (Hewlett Packard - Philips) signal/traffic interior lighting
-Tutorial (2004.4.23)
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Photonics Lab
SAITs InGaN LEDs and LDs
1st LD operation (98. 12)
LED lamps (98. 10)
30mW-InGaN LD (03. 10)

Laser Diodes
Three main wavelength ranges: short wave length 360nm to 475nm - InGaN/AlGaN mid wave length 635nm to 1060nm AlGaInP, GaAs / AlGaAs long wavelength 1250nm to 1650nm - InP / InGaAsP / InGaAs Particular wavelengths are achieved by changing the alloy composition and, in the case of quantum well designs, the thickness of the active layer.
-Tutorial (2004.4.23)
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Photonics Lab
Enabled by Compound Semiconductors
LED blinker
LED dashboard illumination
GPS CD-Player Wireless com. (GSM) LED stop lights Fiber optic data transmission Distronic
-Tutorial (2004.4.23)
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Photonics Lab
HBT and HEMT Transistors

HBT - Heterojunction Bipolar Transistor HEMT - High Electron Mobility Transistor HBT products :
Small High Speed High Power Low Noise

N on P Ga0,51In0,49P/GaAs-tandem solar cell
Cell 1: spectral absorption between 300 - 660 nm
Cell 2: spectral absorption between 660 - 890 nm
-Tutorial (2004.4.23)
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Photonics Lab
GaAs Space Solar Cell

MOCVD: AIX 2600G3
TiO2/MgF2 ARC Grid contact AlGaAs window GaAs emitter GaAs base
Conversion Efficiency: AM 1.5 AM 0

30
= 24.2 % = 21.9 %
Current (mA)
20
AlGaAs/GaAs DBR Substrate
10
FF = 85.1 %
0,2 0,4 0,6 0,8 1,0
0 0,0
Back side contact
Voltage (V)
Solar Cell Structure

-Tutorial (2004.4.23) 61
I-V curve at AM 1.5 one sun

Photonics Lab
Requirements of Compound Semiconductor Industry

Uniformity of layer thickness and composition of 1% on the wafer Temperature uniformity on wafer T = 1C within a wide temperature range Wafer to wafer and run to run reproducibility Low cost of ownership, high wafer capacity, high uptime ratio
-Tutorial (2004.4.23)
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Photonics Lab
Summary
Discussed topics:
MOCVD systems and reactors Properties of commonly used precursors Fundamental MOVPE growth principles Devices made by MOVPE
-Tutorial (2004.4.23)
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Photonics Lab

Mocvd

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ADVANCED INSTITUTE OF TECHNOLOGY

ADVANCED INSTITUTE OF TECHNOLOGY

ADVANCED INSTITUTE OF TECHNOLOGY

Introduction to MOCVD / MOVPE / OMVPE

ADVANCED INSTITUTE OF TECHNOLOGY

MOCVD / MOVPE / OMVPE

Often all three expressions are used interchangeably

ADVANCED INSTITUTE OF TECHNOLOGY

ADVANCED INSTITUTE OF TECHNOLOGY

Overview of Epitaxy Techniques

ADVANCED INSTITUTE OF TECHNOLOGY

ADVANCED INSTITUTE OF TECHNOLOGY

Simplified Presentation of a Crystal Growth Process

ADVANCED INSTITUTE OF TECHNOLOGY

ADVANCED INSTITUTE OF TECHNOLOGY

The World of Semiconductors

ADVANCED INSTITUTE OF TECHNOLOGY

How MOCVD Works

ADVANCED INSTITUTE OF TECHNOLOGY

Components of a LP-MOCVD System

gas blending unit

reactor with heated susceptor

ADVANCED INSTITUTE OF TECHNOLOGY

Basic Principles of the MOVPE Process

ADVANCED INSTITUTE OF TECHNOLOGY

Systems and Reactors

ADVANCED INSTITUTE OF TECHNOLOGY

AIXTRON MOCVD System

reactor + heater gas mixing system computer electronic control rack

ADVANCED INSTITUTE OF TECHNOLOGY

Gas Blending System

run/vent stack Lauda bath for bubblers H2 purifier (Pd-cell)

ADVANCED INSTITUTE OF TECHNOLOGY

AIX 2600G3 MOCVD Reactor

ADVANCED INSTITUTE OF TECHNOLOGY

Vacuum System Vacuum pump - Ebara dry pump

ADVANCED INSTITUTE OF TECHNOLOGY

AIXTOX Scrubbers: Principle

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Planetary Reactor AIX 2600 G3 Susceptor (horizontal type)

ADVANCED INSTITUTE OF TECHNOLOGY

ADVANCED INSTITUTE OF TECHNOLOGY

Horizontal Tube Reactor AIX 200RF

ADVANCED INSTITUTE OF TECHNOLOGY

Thomas Swan MOCVD system (Vertical type)

CCS(Close Coupled Showerhead) Reactor

ADVANCED INSTITUTE OF TECHNOLOGY

Veeco(Emcore) MOCVD system (Vertical type)

Turbo Disc system

ADVANCED INSTITUTE OF TECHNOLOGY

ADVANCED INSTITUTE OF TECHNOLOGY

Example: Precursor Molecules

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Precursors - Definitions Pyrolysis:

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Precursors - Chemical Bonds Chemical bond strength

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Precursors - Reaction Types

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Precursors - Precursor Properties Desirable properties of precursors:

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Precursors - Carbon Incorporation Carbon contamination