Mocvd
Mocvd
Mocvd
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
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MOVPE: OMVPE:
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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.
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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
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MBE
MOCVD/ OMVPE
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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)
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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
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control unit
vacuum system
scrubbing system
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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.
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wafer handler 4 wafer on rotating satellite main susceptor disk collector ring
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RF Heater in G3 Systems
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Precursors
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AsH3
DMZn - (CH3)2Zn
TMGa - (CH3)3Ga H C As Zn Ga
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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).
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General:
Example:
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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
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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
(C2H5)3In (CH3)3Al (C2H5)3Al liquid, good vapor pressure, good long term stability liquid, low carbon contamination
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
NH3
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
DETe (n-dopant)
(C2H5)2Te
undoped Si (intrinsic)
Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si
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Principle of LP-MOVPE
H 2
gas blending
reactor
scrubbing system
H , N P=10-200 mbar 2 2
GaAs GaN
+ 3CH + 3CH
4 4
vacuum pump
TMGa, AsH
5 - 100 rpm
throttle valve
TMGa, NH
safety
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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
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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
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wafer
wa
outlet
Viewgraphs: predicted growth rate profiles of AlGaAs on the AIX200 susceptor (T=700C, p = 20 mbar); static wafer vs. rotated wafer
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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.
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102 0.6
1.4
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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.
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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)
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Applications
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Device LED, LD
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LED - Colors
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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
Standard in several US states; pilot projects in UK, S, CH, Au, F Germany: pilot projects in Munich, Frankfurt, Aachen
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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.
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LED blinker
GPS CD-Player Wireless com. (GSM) LED stop lights Fiber optic data transmission Distronic
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= 24.2 % = 21.9 %
Current (mA)
20
10
FF = 85.1 %
0,2 0,4 0,6 0,8 1,0
0 0,0
Voltage (V)
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Summary
Discussed topics:
MOCVD systems and reactors Properties of commonly used precursors Fundamental MOVPE growth principles Devices made by MOVPE
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