The chemistry of chlorine interacting with chemical-vapor deposited (CVD) d
iamond films and natural C(100) diamond has been investigated. High resolut
ion electron energy loss spectroscopy of polycrystalline CVD diamond reveal
s a strong band at 2900 cm(-1), with two maxima and a broad shoulder on the
energy loss tail. The two maxima represent monohydride stretches on {111}
and {100} crystal facets, while the broad shoulder is attributed to olefini
c stretches associated with defects on {111} surfaces. Reacting the CVD sur
face with atomic chlorine removes all monohydride vibrational structure exc
ept that associated with {111} defects, whose intensity remains unchanged.
Only a small feature at 800 cm(-1) is evident as a possible C-Cl stretch. A
uger spectroscopy confirms the presence of chemisorbed chlorine on both C(1
00) and CVD diamond and reveals a strong preference for chlorine addition t
o {100} facets. The only chlorine containing species observed by secondary
ion mass spectrometry on natural or polycrystalline diamond is C2H4Cl+. Thi
s ion is believed to originate from the same surface species regardless of
the sample under study. We suggest that chlorine preferentially adsorbs to
{100} surfaces by substituting for surface hydrogen, whereas sp(2) hydrogen
-terminated defects appear to be unreactive to chlorine substitution. (C) 1
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