27.

3 Transient Diffusion in a Finite-Dimensional Medium 503

equal to zero because the net flux is equal to zero at the centerline. Consequently, the
following boundary condition at z ¼ L/2 also holds:
@cA
¼0
@z
Recall from Section 25.3 that the mathematical boundary condition also arises when the flux at
a boundary is equal to zero because of the presence of barrier that is impermeable to the
transfer of diffusing species A. Consequently, equation (27-16) can also be used for the
physical situation where a slab of corresponding to a thickness x1 of has an imperme-
able barrier at the boundary z ¼ x1.
The following examples illustrate processes that are governed by one-dimensional
unsteady-state diffusion of a dilute solute into semi-infinite or finite-dimensional media.
The phosphorous doping of silicon wafers illustrates molecular diffusion into a semi-infinite
medium, whereas the timed drug release from a spherical capsule illustrates molecular
diffusion from a finite-dimensional medium. We take a little extra time at the beginning of
each example to describe the interesting technology behind the process.

EXAMPLE 1 In the fabrication of solid-state microelectronic devices, semiconducting thin films can be made by
impregnating either phosphorous or boron into a silicon wafer. This process is called doping. The doping
of phosphorous atoms into crystalline silicon makes an n-type semiconductor, whereas the doping of
boron atoms into crystalline silicon makes a p-type semiconductor. The formation of the semiconducting
thin film is controlled by the molecular diffusion of the dopant atoms through crystalline-silicon matrix.
Methods to deliver phosphorous atoms to the silicon wafer surface include chemical vapor
deposition and ion implantation. In one typical process, phosphorous oxychloride, POCl3 , which
has a normal boiling point of 105.38C, is vaporized. The POCl3 vapors are fed into a chemical vapor
deposition (CVD) reactor at elevated temperature and reduced system pressure (e.g., 0.1 atm), where
POCl3 decomposes on the silicon surface according to the reaction
Si(s) þ 2POCl3 (g) ! SiO2 (s) þ 3Cl2 þ 2P(s)
A SiO2 coating rich in molecular phosphorous (P) is formed over the crystalline-silicon surface. The
molecular phosphorous then diffuses through the crystalline silicon to form the Si–P thin film. So
the coating is the source for mass transfer of phosphorous, and the silicon wafer is the sink for mass
transfer of phosphorous.
As one can see in Figure 27.2, the process for making Si–P thin films can be quite complex with
many species diffusing and reacting simultaneously. But consider a simplified case where the P-atom

POCl3 Cl2 POCl3 vapor

SiO2 + P(s) CVD coating

P Si wafer

Si(s) + 2 POCl3(g) SiO2(s) + 3 Cl2 + 2 P(s)

P-rich layer (source)

z=0
CAs
P Si (sink)
Figure 27.2 Phosphorous doping of
a silicon wafer.