We have studied the chemical vapour deposition growth rates of copper
films by H-2 reduction of Cu(hfac)(2) in a horizontal axial flow react
or, under reaction conditions that span the transition from transport-
limited to reaction-limited growth. At high temperature and H-2 pressu
re (350 degrees C and 760 Torr), the growth rate becomes transport lim
ited, resulting in highly non-uniform axial film thickness profiles. A
s the H-2 pressure is lowered to 40 Torr, the rate of convective and d
iffusive transport increases while the intrinsic rate decreases, leadi
ng to reaction-limited growth and more uniform films. At lower tempera
tures (250 degrees C), film growth is essentially reaction-limited at
all H-2 pressures. We analyze the measured growth rate profiles using
a reactor transport model to calculate the reactant concentration prof
iles and unmask the intrinsic growth rates. The results are used to op
timize the kinetic parameter estimates for two recently proposed rate
expressions for Cu(hfac)(2) reduction.