The electronic states of boron and phosphorus in diamond have been studied
by infrared absorption and photo-thermal ionisation spectroscopies. High qu
ality boron doped synthetic diamond (p-type conductive) and phosphorus-dope
d CVD diamond film (n-type conductive) were used for this study. In the cas
e of boron-doped diamond, the four main excited states of the bound hole fo
llow a Rydberg series, suggesting that boron has a hydrogen-like behaviour.
with a weak splitting of the excited states. The consistent values of the
optical ionisation energy (E-0 = 382 meV), of an "average" effective mass (
m* = 0.74m(0)) and of the Bohr radius of the ground state (a* = 4.1 Angstro
m) deduced from the Rydberg series support this suggestion. The comparison
with the effective mass approximation, applied for acceptor states in diamo
nd, suggests that the top of the valence band of diamond is different from
that of silicon and germanium. In the case of phosphorus-doped diamond, two
excited states of the bound electron have been observed for the first time
, at 523 and 562 meV from the ground level. The good agreement with the eff
ective mass approximation suggests that phosphorus is a shallow donor, and
allows us to propose a first value of the optical ionisation energy of phos
phorus in diamond of about 600 meV, consistent with Hall effect measurement
s.