Thermodynamic of GaN grow

th by HVPE method
Prepared by: Kawan
Anil
Thermodynamic:
• Chemical thermodynamics is the study of the interr
elation of energy with chemical reactions and che
mical transport and with physical changes of state
within the confines of the laws of thermodynamics.

• Zeroth law
• First
• Second
• Third
 GaN
• Gallium Nitride is a wide-bandgap, compound semiconductor. Due
to its unique material properties, GaN is a disruptive technology acr
oss a wide range of electronic applications.
• Deriving from its inherent material properties, devices based on gall
ium nitride can deliver vastly superior performance compared to cu
rrently available silicon and III-V solutions, the most important of w
hich are the ability to operate with:
• High Power (V*I)
• High Voltage
• High Temperature
• High Speed
• High tolerance to Radiation
• Low Noise
 Properties:
Property GaN SiC Si Ga GaAs
Bandgap (eV) Direct Indirect Indirect Indirect Direct
3.42 3.2 1.1 0.66 1.43
Thermal 1.8-2.4 3.6-4.9 1.3 0.58 0.46
conductivity
(W/cm k)
Melting point 2500 3100 1412 937 1240
(° C )
 HVPE:
• 1st: 1966; Tietjen & Amick
 Thermodynamic of GaN
• Partial pressures of gaseous species in equilibrium with GaN are calculated for temperatures, input GaCl partia
l pressures, input V/III ratios and mole fractions of hydrogen relative to the inert gas atoms.

• GaCl, GaCl3, NH3, HCl, H2 and inert gas(IG)

• Ga precursors are obtained by following reaction:

• Galiq+HClg ⇔ GaClg +½H2g

• GaClg+2HClg ⇔ GaCl3g+H2g

Two thermodynamic reaction pathway for deposition of GaN:

• GaClg+NH3g ⇔ GaN +HClg+H2g

• 3GaClg+2NH3g ⇔ 2GaN + GaClg+3H2g

• K1= (PHClPH2)/(PGaClPNH3)

• K2=(PGaCl3PH2)/(PGaClPHCl)

• ΣPi= PGaCl + PGaCl3 + PNH3 + PHCl+ PH2 + PIG

• P°GaCl - PGaCl = P°NH3 - PNH3

• A=½(PGaCl + 3PGaCl3 + PHCl) / (3/2PNH3 + ½PHCl+ PH2 + PIG)

• F= ½(3PNH3 + PHCl+ 2PH2) / (3/2PNH3 + ½PHCl+ PH2 + PIG)

• NH3(g)→(1-α)NH3(g)+ α/2N2(g)+3 α /2H2(g)

Equilibrium partial pressures Equilibrium partial pressure over
over GaN as a function of GaN as a function of input
growth temperature. partial pressure of GaCl.
Equilibrium partial pressures Driving force for the GaN
over GaN as a function of deposition as a function
hydrogen partial pressure in of growth temperature
the carrier gas, parameter F. with various parameters F.
 Comparison between
calculated growth rates
and experimental data.
 Values of gas flows used for the HVPE gro
wth of GaN

Gas Flow in SCCM

HCl source 20-30a
N2 source 83-73a
Additional HCl 0-200b
N2 Carrier gas 1480-2000b
NH3 300
 Major problems:
• Dislocation
• the substrate of choice has been sapphire (Al2O3), which has a 14% la
ttice-size mismatch and a 34% mismatch in thermal expansion coeffic
ient. As a result of growth along (0001) GaN on Al2O3, high concentra
tions of misfit and threading dislocations are formed. The main conce
rns are threading dislocations because they will propagate to the acti
ve parts of devices grown on top of the underlying GaN layers, due t
o the fact that dislocations cannot terminate inside the material unles
s they form half-loops. One of the growth techniques that give small
er dislocation density is hydride vapor-phase epitaxy (HVPE). The low
er density is due to the fact that large thickness of GaN can be grow
n, allowing more interactions between dislocations and lowering their
density