MSE 550 - CVD

Chemical Vapor Deposition

• Chemical vapor deposition (CVD) is a widely used method for
depositing thin films of a large variety of materials. Applications of
CVD range from the fabrication of microelectronic devices to the
deposition of protective coatings. In a typical CVD process, reactant
gases (often diluted in a carrier gas) at room temperature enter the
reaction chamber. The gas mixture is heated as it approaches the
deposition surface, heated radiatively or placed upon a heated
substrate. Depending on the process and operating conditions, the
reactant gases may undergo homogeneous chemical reactions in the
vapor phase before striking the surface. Near the surface thermal,
momentum, and chemical concentration boundary layers form as the
gas stream heats, slows down due to viscous drag, and the chemical
composition changes. Heterogeneous reactions of the source gases
or reactive intermediate species (formed from homogeneous
pyrolysis) occur at the deposition surface forming the deposited
material. Gaseous reaction by-products are then transported out of
the reaction chamber.
 What is CVD?
• Thin film formation from vapor phase reactants.
Deposited films range from metals to
semiconductors to insulators.
• An essential process step in the manufacturing
of microelectronic devices. High temperatures
and low pressures are the most common
process conditions, but are not necessary.
• All CVD involves using an energy source to
break reactant gases into reactive species for
deposition.
Chemical Vapor Deposition:
CVD is the formation of a film on a surface from a volatile precursor (vapor or
gas), as a consequence of one or more chemical reactions which change the
state of the precursor. Many different films can be deposited: elements and
compounds, crystalline, polycrystalline, and amorphous. Most films can be
deposited from several different precursor systems. Plasma discharges can
be used to help things along, or the substrate and/or the gas can be heated or
cooled. Different deposition techniques, process conditions, and treatment
after deposition produce films with differing
characteristics, suitable for different applications. Each film has an optimal set
of characterization techniques.

In every case, CVD processes must:

provide a volatile precursor containing the constituents of the film
transport that precursor to the deposition surface
encourage or avoid reactions in the gas phase
encourage surface reactions that form the film
and do it rapidly, reproducibly,
and uniformly for industrial applications.
Advantages:
• high growth rates possible
• can deposit materials which are hard to evaporate
• good reproducibility
• can grow epitaxial films

Disadvantages
• high temperatures
• complex processes
• toxic and corrosive gasses
 Examples of CVD

• Metals/Conductors - W, Al, Cu, doped poly-Si

• Insulators (dielectrics) - BPSG, Si3N4, SiO2
• Semiconductors - Si, Ge, InP, GaAsP
• Silicides - TiSi2, WSi2
• Barriers – TiN, TaN
Types of CVD reactions
• Pyrolysis - thermal decomposition
• AB(g) ---> A(s) + B(g)
• ex: Si deposition from Silane at 650 C
• SiH4(g) ---> Si(s) + 2H2(g)
• use to deposit: Al, Ti, Pb, Mo, Fe, Ni, B, Zr, C, Si, Ge, SiO2, Al2O3, MnO2, BN, Si3N4,
GaN, Si1-xGex, . . .
• Reduction
• often using H2
• AX(g) + H2(g) <===> A(s) + HX(g)
• often lower temperature than pyrolysis
• reversible => can use for cleaning too
• ex: W deposition at 300 C
• WF6(g) + 3H2(g) <===> W(s) + 6HF(g)
• use to deposit: Al, Ti, Sn, Ta, Nb, Cr, Mo, Fe, B, Si, Ge, TaB, TiB2, SiO2, BP, Nb3Ge, Si1-
xGex, . . .
• Oxidation
• often using O2
• AX(g) + O2(g) ---> AO(s) + [O]X(g)
• ex: SiO2 deposition from silane and oxygen at 450 C (lower temp than thermal oxidation)
• SiH4(g) + O2(g) ---> SiO2(s) + 2H2(g)
• use to deposit: Al2O3, TiO2, Ta2O5, SnO2, ZnO, . . .
• Compound formation
• often using ammonia or water vapor
• AX(g) + NH3(g) ---> AN(s) + HX(g)
• AX(g) + H2O(g) ---> AO(s) + HX(g)
• ex: deposit wear resistant film (BN) at 1100 C
• BF3(g) + NH3(g) ---> BN(s) + 3HF(g)
• use to deposit: TiN, TaN, AlN, SiC, Al2O3, In2O3, SnO2, SiO2, . . .

• Disproportionation
• compounds involving elements with multiple valence states
• 2AB(g) <===> A(s) + AB2(g)
• use to deposit: Al, C, Ge, Si,
III-V compounds, . . .

• Reversible Transfer
• ex: use to deposit: GaInAs,
AlGaAs, InP, FeSi2, . . .
• Mass transport in gas
• goals
• deliver gas uniformly to substrate (uniform films)
• optimize flow for maximum deposition rate
• Two flow regimes
• Molecular flow
– diffusion in gas
• D ~ T3/2 / P from Kinetic Theory of Gasses
• reduce Pressure for higher D and higher deposition rate
• Viscous flow
– low flow rates produces laminar flow (desired)
– high flow rates produces turbulent flow (avoid)

laminar flow: simple case: flow past a plate

near plate velocity = 0 ==> stagnant layer

 – diffuse gas through stagnant layer to surface
• mass transport depends on:

fundamental parameters experimental parameters

reactant concentration
diffusivity
boundary layer thickness
pressure
gas velocity
temperature distribution
reactor geometry
gas properties (viscosity . . .)
 Generic CVD Steps
Five steps occur during all CVD processes:
– Reactants pumped through reactor.
– Reactants diffuse across boundary layer to surface.
– Reactants adsorb on surface (adatoms).
– Surface reactions; pos. formation of islands or clusters.
– Pos. surface diffusion of adatoms.
– Diffusion of by-products away from surface.
• Simple model (Grove, 1967)
– AB(g) ---> A(s) + B(g)
• F1 = flux to surface
• F2 = flux consumed in film
• CG = concentration of AB in gas
• CS = concentration of AB at surface
– F1 = hG (CG - Cs)
• where hG = gas diffusion rate constant
• F2 = kS Cs

• where kG = surface rate constant

• in steady state: F1 = F2 = F

• growth rate of film is proportional to F

• NOTE: Two rate-limiting cases
• mass transfer limited
– small hG
– growth controlled by transfer to substrate
– hG is not very temperature dependent
– common limit at higher temperatures
• surface reaction limited
– small kS
– growth controlled by processes on surface
» adsorption
» decomposition
» surface migration
» chemical reaction
» desorption of products
– kS is highly temperature dependent (increases with T)
– common limit at lower temperatures
– often preferred
Stagnant layer model

o assume transport depends only on diffusion across stagnant layer (mass

transfer limited)
 variations along flow direction

Consider flow into and out of a volume (as in Chapter 1)

apply boundary conditions

• all gas reacts at substrate
– C = 0 at y = 0
• initial concentration is constant
– C = Ci at x = 0
• no flow out of the top
– dC/dy = 0 at y = b
• SOLVE differential equation subject to these
boundary conditions

• C(x, y) = a mess (see equation 4-41)

• ASSUME large flow rate or large chamber
– vaveb >> D¹
• examine this solution:
• proportional to Ci
• at y = b, sin = 1
– C decreases exponentially with x
• tricks to improve uniformity
– tilt substrate into flow
– increase T continuously along x
– single wafer processing
• often using a flow of gas normal to
sample

Deposition depends on:

• materials: gas, film
• geometry (b, substrate orientation)
• process conditions (Ci, pressure,
velocity)
• temperature and temperature
distribution (D . . .)
 Variables Affecting Steps
– Diffusion of reactants to & by products away from surface.
•Gas flow rates, pressure, reactor configuration
– boundary layer formation
•Temperature
– diffusion is a mildly activated process

– Surface reaction and surface diffusion

•Temperature (both are affected exponentially by temperature)
•Surface interactions (reactive and “overall” sticking coefficient of a
species)
•Rate of incoming reactants and out going by-products
Molecule/Surface Interactions
Physisorption
– No electron transfer occurs between adatom & surface
– Binding energies ≈ 0.1 eV
– Essentially condensation
• Substrate/adsorbate independent
– Doesn’t occur at temperatures much above the boiling
point of the adsorbate

Chemisorption
– Electronic interactions between surface & adspecies
– Binding energies ≈ 1 eV
– This is a chemical reaction
• Substrate/adsorbate selective
 Nucleation and Growth
• Initial formation of clusters (nuclei)
• Can grow or shrink until a critical size is
reached
– Above critical size, increasing nuclei size
lowers the overall surface energy
– Clusters can grow at the expense of sub-
critically sized clusters
• Clusters impinge and grow together to
form continuous film (coalescence)
 Limiting Cases

Assuming steps occur sequentially, then the

slowest step determines the deposition rate.
• Reactions
• Mass Transport
 Surface Reactions
• Reaction rate strong function of temperature

• Reactant species must first be adsorbed on

substrate (wafer) for deposition to take place.
• After adsorption, the reactive species can
remain fixed at the surface site or migrate along
the surface. This is temperature dependent and
affects step coverage.
Mass Transport Limited Depositions
– Processes are run in laminar flow regime
• Re=UL/ < 2100
– Boundary layer forms next to wafer surfaces
• Due to viscous forces in the gas
– Reactants must diffuse across the boundary layer to
reach wafer surface
– Boundary layer thickness decreases with increasing
gas velocity
• Rate increases with decreasing boundary layer
• Maximizes when reaction becomes reaction rate limited
 Why Epi?
– Bipolar devices
• Add a lightly doped layer on a heavily doped
substrate increases breakdown voltage of the
collector/substrate junction
• Deposited over patterned heavily doped areas
called buried layers
– CMOS
• No SiOx precipitates, unlike substrates
– Less junction leakage due to defects
• Smoother surface leads to better gate oxide
 Silicon Precursors
• SiCl4- Silicon tetrachloride (1150-1250 °C)
• SiHCl3-Tricholorosilane (1110-1150 °C)
• SiH2Cl2-Dichlorosilane (1020-1120 °C)
• SiH4- Silane (650-900 °C)
– Gas phase nucleation a problem
• Si2H6- Disilane (400-600 °C)
– Pyrogenic and toxic
 Doping an Epi Layer
Add dopant gas to deposition reaction
 PH3, AsH3, B2H6
 Added in ppm levels in H2
Outdiffusion from doped substrate
 High deposition temperature drives diffusion out of highly
doped substrates into growing epi films
Auto doping
 Deposition temperature evaporates dopants from
substrates or from chamber walls
 Dopants are then incorporated in growing film
–Types of pressure dependent CVD
processes
• Atmospheric Pressure CVD (APCVD)
• Sub-atmospheric CVD (SACVD)
• Low Pressure CVD (LPCVD)
–In general, APCVD is controlled by the
rate of reactant transport to the wafer,
LPCVD is controlled by the reaction rate
 LPCVD

– Lower Pressure
• Increases diffusivity by about 1000x
• Increases boundary layer thickness by ≈ (P) 0.5
(factor of about 25 for 1 torr vs. 760 torr)
• Results in a net mass transport increase by more
than an order of magnitude
– Reaction rate limited
• Temperature control critical
 Depletion Effects
– Batch reactors prone to reactant depletion
• Due to deposition on wafers nearer the gas entrance
– Increase gas flow
• Reduces fraction of reactant depleted
– Distributed feed
• Adds fresh reactant along length of reactor
– Temperature gradient
• Increase temperature along length to compensate for lower
reactant concentration
• Can significantly affect film properties (grain size, stress, etc.
 PECVD
• Film growth involves surface reactions
with incoming gas radical molecules.
• Most radicals are electrically neutral so
their transport to the wafer surface is by
gas phase diffusion.
• Radical concentration gradient drives the
diffusion process.
 PECVD
Process Control Parameters

1. RF power, frequency, and bias

2. Gas composition and flow rate
3. System pressure and reactant partial
pressure
4. Deposition time
5. Temperature