MOCVD

Micro and Nano- Processing Technologies
EPITAXIAL
GROWTH Mahdad Sadeghi
mahdad.sadeghi@mc2.chalmers.se
031-7721902
VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Processing Technologies
CONTROL
BY OF
Growth temperature Thickness
Gas flow rate- Flowmeter Composition
Source temperature Throughput (growth rate)
Flux cutoff – valves/shutters Uniformitiy
X-tal orientation Doping concentration
Geometry/ Environment Junctions
Source/Gas purity (X-tal) Quality, defects
Precleaning Reproducibility
Epitaxy is a well-controlled phase transition

which leads to a (single crystalline) solid.
Epitaxy techniques - the spectrum of options
Chemical Vapour Deposition (CVD)

• Atmospheric pressure – APCVD
• Low pressure CVD – LPCVD
• Plasma enhanced CVD – PECVD
Vapor phase Epitaxy (hydrodynamic flow)
• Hydride
• Chlorine
Metallo-Organic CVD (MOCVD)
Liquid Phase Epitaxy
Molecular Beam Epitaxy (MBE) (ballistic flow)

• Solid source
• Gas source
• Chemical beam
• Organo-metallic source

LPE VPE MBE
GaAs/AlGaAs 750- - 600-
825oC 700oC
InP+related 600- 500- 480-
660oC 650oC 560oC


• Hydride
• Chlorine

• Solid source
• Gas source
• Chemical beam

CVD Applications
• Thin insulating films

oxides, silicon nitride
• Polysilicon (gates/conductors)
• Epitaxial silicon (single crystal on wafer)
• Silicide materials
• III-V compounds

Chemical reactions (Gas phase reactions) in a reactor to
create a thin film layer at surface

CVD Important film parameters
• Stoichiometery: exact composition of film

• Physical parameters: hardness, optical density
• Electrical parameters:
dielectric constant, breakdown voltage
• Purity of film: lack of contamination
• Thickness and uniformity
• Conformality and step coverage
• pin hole and particle free
• Adhesion

Four main CVD Reactions
• Pyrolysis: heat driven break down
• Reduction: usually react with Hydrogen
• Oxidation: react with oxygen to form oxides
• Nitradation: create nitrides with nitrogen compounds

Major CVD Processes
• Reactants diffuse to surface
• Chemical reaction(s) at surface
• Film reformed at surface
• Products desorbed and diffuse from surface
CARRIER GAS
+ UNREACTED
CARRIER GAS REACTANTS
+ REACTANTS + PRODUCTS
TRANSFER OF TRANSFER OF
REACTANTS TO PRODUCTS TO
SURFACE ADSORPTION DESORPTION MAIN FLOW
OF REACTANTS OF PRODUCTS
SURFACE DIFFUSION
SURFACE REACTION
SUBSTRATE
Sequence of events in thermal CVD or VPE reactor

TYPE OF CONTROL RATE LIMITING
STEPS
MASS TRANSFER Input rate of reactants to
TYPE 1 epitaxial growth region
Inpu Rate Limited
Equilibrium Process
MASS TRANSFER Transfer of reactants or
TYPE 2 products between main
Diffusion Controlled gas streaqm and sbstrate
surface by physical
Mass Transfer Limited processes such as
diffusion or convection
Kinetics Control Adsorption of reactants

Surface Limited Desorption of products
Chemically Controlled Surface reaction
Site incorporation
After D.W. Shaw, Mechanisms in Vapour Phase epitaxy of Semiconducors,

Crystal Growth Vol1, Ed. C.H.L. Goodman, Plenum press, NY, 174

MASS TRANSPORT MASS TRANSPORT KINETICS
EXPERIMENTAL TYPE 1 TYPE 2 (Chemical Control,
PARAMETERS (Eqm. process) (Diffusion control) Surface Limited)
Growth temperature Dependence predicted by Slight dependence due to Rate increases

thermodynamics concentration gradient exponentially with
changes increasing temperature
Total flow rate (constant Rate increases with total Rate increases with flow
partial pressure and tube flow rate due to increase rate increase Independent
diameter) in total mass input rate
Gas stream velocity Rate increases with
(Constant mass input rate Independent increasing veocity Independent
and partial pressure)
Crystalloraphic Independent Independent Dependent
orientation
Geometric orientaion of Independent Dependent Independent
substrate
Surface area Total amount deposited Dependent on apparent or Dependent on true or
independent of surface geometrical surface area actual surface area
area

Atmospheric & Low Pressure CVD
Atmospheric Pressure Low pressure
Cold wall Hot wall
Horizontal Plasma enhanced
Vertical Vertical isothermal
Pancake
Hot wall
Photochemical
VPE
MOCVD
Overview of CVD systems
VPE: Vapour Phase Epitaxy (Si single crystal)

MOCVD: Metalo-organic CVD (III-V compounds)

Plasma Enhanced CVD (PECVD)


• Hydride
• Chlorine

• Solid source
• Gas source
• Chemical beam

Vapour Phase Epitaxy (VPE)
A process used for depositing thin films on monocrystalline
substrates using gases.

VAPOUR PHASE EPITAXY of III-V materials
EXAMPLE: InP can be deposited using phosphine and indium
chloride gases:
InCl (g) + PH3 (g) = InP (s) + HCl (g) + H2 (g)
Hydride VAPOUR PHASE EPITAXY

(HVPE) for depositing GaInAsP
III-sources: InCl and GaCl
V-sources: PH3 and AsH3 (hydrides of phosphorus and arsenic)
Chloride VAPOUR PHASE EPITAXY

(Cl-VPE) for depositing GaInAsP
III-sources: InCl and GaCl
V-sources: PCl3 and AsCl3 (chlorides of phosphorus and arsenic)

Hydride VPE
Advantages: Disadvantages:
+ Purity - No Al or Sb alloys
+ High growth rate - Complex process/reactions
+ Throughput - Difficult to control thin layer
+ Versatile for selective growth - Hazardous gases


• Hydride
• Chlorine

• Solid source
• Gas source
• Chemical beam

Liquid Phase Epitaxy (LPE)
Liquid phase epitaxy (LPE) is the solidification from a liquid phase of a

Crystalline layer onto a parent substrate such that the crystallinity of the
substrate is maintained in the grown layer.
Used for initial demonstration and production of most optoelectronic devices

Near-equilibrium technique
Advantages: Disadvantages:
+ Simple, inexpensive equipment - Difficult to control thin layer
+ High utilization efficiency of thickness
precursor materials - Composition problematic
+ High purity material - Poor uniformity
+ In-situ etching possible - Poor morphology

LPE Growth Procedure
GaAs LPE introducted by H. Nelson (1963)

1) Heat to T>Tsat(saturation temperature)
2) Lower T and introduction of seed crystal (Tipper, Dipper, Slider …)
3) Withdraw of the sample from the melt
Growth rate will depend on:

- Composition of solution
- Degree of supersaturation
- Cooling rate
- Contact period
- Subsrate orientation

Requirements in epitaxial growth
• Improved crystallinity
• Reduced defects
• Higher purity
• Precise control of thickness
• Precise control alloy composition
• “Lattice matched” compounds
• Abrupt or graded interfaces
• Ability to engineer unique device structures
• Nanostructures
• Superlattices
• Strained layers
• New materials: Quarternaries
• AlGaInAs (MBE), InPAsSb (MOCVD)

How accurate is the control needed?
• Source temperature: < 0.2 deg

• In/Ga ratio control in InGaAs < 1 %
to avoid dislocations
• 1.5 mm InGaAs/InGaAsP QW (l=±10 nm)
Control of QW thickness < 6 %
Control of Comp. InGaAs < 0.5 %
• Bragg mirrors thickness control < 1 % mm


• Hydride
• Chlorine

• Solid source
• Gas source
• Chemical beam

Metal Organic Vapor Phase Epitaxy (MOVPE)
• Growth in “reactor”
• Pressure 10s-100s of torr
• Metal organic group III source material
• Trimethyl Gallium Ga(CH3)3
• Trimethyl Indium In(CH3)3
• MO vapor transported by H2 carrier gas
• Hydride group V source gas
• Arsine AsH3
• Phosphine PH3
• Thermal cracking at growth surface

MOCVD- Surface Chemistry

Example: OMCVD growth of GaN and related materials
Special problems for GaN

and related materials. Ga(CH3)3+NH3 GaN+3 CH4
• No suitable substrate
• Difficult to obtain p-type
epilayer

MOCVD- Gas Handling System

MOCVD Summary
• Growth rates 2-100 micron/hr

• high throughput
• P-type doping
• Zn (Diethyl Zinc), high diffusivity
• C (CCl4, CBr4), amphoteric
• Complex growth kinetics

• Delicate interaction between injected gasses,
temperatures
• High background pressure

• Parasitic incorporation
• Intermixing of atoms at interfaces


• Hydride
• Chlorine

• Solid source
• Gas source
• Chemical beam

Molecular Beam Epitaxy (MBE)
Cho, JVST 8, s31 (1971)
• Homo-epitaxy and heteroepitaxy of semiconductor and compounds

• Growth rate: 1µm/hr
• Growth in high vacuum chamber
• Ultimate vacuum < 10e-10 torr
• Pressure during growth < 10e-6 torr
• Elemental source material

• High purity Ga, In, As (99.9999%)
• Sources individually evaporated in high temperature cells
• In situ monitoring, calibration

• Probing of surface structure during growth
• Real time feedback of growth rate

Molecular Beam Epitaxy (MBE)
Variations
• SSMBE solid evaporation sources
• GSMBE metals + group V hydrides
• MOMBE metalorganics + conventiona grop Vs
• CBE all gas sources

MBE Growth Mechanism
- Absorption to the surface,
- Surface migration
- Incorporation into the crystal lattice
- Thermal desorption

Molecular Beam Epitaxy

MBE- EPI930 System

MBE- In Situ Surface Analysis
• High energy (10-30 keV) electron beam

• Reflection High Energy Electron Diffraction (RHEED)
• Shallow angle of incidence
• Beam reconstruction on phosphor screen

MBE- In Situ Growth Rate Feedback
Monitoring RHEED image intensity versus time

provides layer-by-layer growth rate feedback

MBE- Summary
• Ultra high vacuum, high purity layers

• No chemical byproducts created at growth surface
• High uniformity (< 1% deviation)
• Growth rates 0.1-10 micron/hr.
• High control of composition
• In situ monitoring and feedback
• Mature production technology
Low P large mean free path beam nature of flux (molecular flow)
Mechanical shutters fast switching abrupt interface
Low T limited interdiffusion

Gas Source MBE
• Combines advantages of MBE with gas source

delivery of group V atoms (as used in MOCVD)
• PH3, AsH3 used for group V sources
• Thermally cracked at injector into P2, As2 and H2
• P2, As2 dimers arrive at growth surface along with Ga, In
• MBE surface kinetics maintained

Gas Source MBE
• Advantages of GSMBE
• More abrupt junctions than in SSMBE
• PH3 a more mature method for phosphorus MBE growth
• Improved dynamic range of switching state
• As, P molecules travel around shutter in solid source MBE
• Increased control of As/P ratio by adjustment of gas flow
• Can replenish group V source material without breaking
vacuum
• Disadvantages
• Requires gas handling system
• Requires extra vacuum pumping to remove hydrogen
• Arsine and Phosphine highly toxic

Comparison of epitaxial growth techniques

III-V Compound Semiconductors

Limits to Strained Layers: Critical Thickness


MOCVD

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Micro and Nano- Processing Technologies

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Epitaxy is a well-controlled phase transition

Chemical Vapour Deposition (CVD)

Molecular Beam Epitaxy (MBE) (ballistic flow)

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Chemical Vapour Deposition (CVD)

Molecular Beam Epitaxy (MBE) (ballistic flow)

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

• Thin insulating films

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

• Stoichiometery: exact composition of film

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Kinetics Control Adsorption of reactants

After D.W. Shaw, Mechanisms in Vapour Phase epitaxy of Semiconducors,

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Growth temperature Dependence predicted by Slight dependence due to Rate increases

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VPE: Vapour Phase Epitaxy (Si single crystal)

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Chemical Vapour Deposition (CVD)

Molecular Beam Epitaxy (MBE) (ballistic flow)

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Hydride VAPOUR PHASE EPITAXY

Chloride VAPOUR PHASE EPITAXY

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Chemical Vapour Deposition (CVD)

Molecular Beam Epitaxy (MBE) (ballistic flow)

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Liquid phase epitaxy (LPE) is the solidification from a liquid phase of a

Used for initial demonstration and production of most optoelectronic devices

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

GaAs LPE introducted by H. Nelson (1963)

Growth rate will depend on:

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

• Source temperature: < 0.2 deg

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Chemical Vapour Deposition (CVD)

Molecular Beam Epitaxy (MBE) (ballistic flow)

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Special problems for GaN

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

• Growth rates 2-100 micron/hr

• Complex growth kinetics

• High background pressure

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

Chemical Vapour Deposition (CVD)

Molecular Beam Epitaxy (MBE) (ballistic flow)

VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth

• Homo-epitaxy and heteroepitaxy of semiconductor and compounds

• Elemental source material

• In situ monitoring, calibration