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

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


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

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


Processing Technologies
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

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


Processing Technologies
CVD Applications

• Thin insulating films


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

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


Processing Technologies
Chemical Vapour Deposition (CVD)
Chemical reactions (Gas phase reactions) in a reactor to
create a thin film layer at surface

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
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

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


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

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


Processing Technologies
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

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


Processing Technologies
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)

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


Processing Technologies
VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth
Processing Technologies
VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth
Processing Technologies
VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth
Processing Technologies
VT 2004/5; Micro and Nano- Ch.14 : Epitaxial Growth
Processing Technologies
Plasma Enhanced CVD (PECVD)

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


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

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


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

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


Processing Technologies
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)

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
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

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


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

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
MOCVD- Surface Chemistry

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


Processing Technologies
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

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


Processing Technologies
MOCVD- Gas Handling System

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
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

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


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

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


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

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


Processing Technologies
Molecular Beam Epitaxy

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


Processing Technologies
MBE- EPI930 System

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


Processing Technologies
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

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


Processing Technologies
MBE- In Situ Growth Rate Feedback

Monitoring RHEED image intensity versus time


provides layer-by-layer growth rate feedback

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
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

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


Processing Technologies
Comparison of epitaxial growth techniques

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


Processing Technologies
III-V Compound Semiconductors

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


Processing Technologies
Limits to Strained Layers: Critical Thickness

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


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