This document investigates thermally induced dissociative adsorption of molecular deuterium on polycrystalline diamond films, highlighting the formation of C-D bonds and their thermal stability through high-resolution electron energy loss spectroscopy (HR-EELS). It compares the bonding configurations and stability of hydrogenated and deuterated diamond surfaces, revealing differences in C-D and C-H modes as a function of annealing temperatures. The findings emphasize the significance of deuterium adsorption phenomena in understanding the physicochemical properties of diamond surfaces.

1. Part of Topical Section
Recent Advances on Diamond Surfaces and Devices
Dissociative adsorption of molecular
deuterium on polycrystalline diamond
films activated by medium surface
temperature
Shaul Michaelson, Tiran Berkovitz, Roza Akhvlediani, and Alon Hoffman*
Schulich Faculty of Chemistry, Technion, Haifa 32000, Israel
Received 13 March 2014, revised 24 August 2014, accepted 27 August 2014
Published online 18 September 2014
Keywords diamond, dissociative adsorption, hydrogen bonding, polycrystalline materials, surfaces, thin films
* Corresponding author: e-mail choffman@tx.technion.ac.il, Phone: þ972-4-8293747, Fax: þ972-4-8295703
In this work we report on an investigation of thermally induced
dissociative adsorption of molecular deuterium onto hydroge-
nated and bare polycrystalline diamond film surfaces studied by
high resolution electron energy loss spectroscopy (HR-EELS).
Hydrogenated diamond films (grown from CH4 and H2 gases)
were heated at various temperatures in molecular D2 ambient at
5 Â 10À6
Torr and then studied by HR-EELS. This study clearly
shows the formation of C–D bonding on hydrogenated
polycrystalline diamond surface and gradual disappearance
of C–H mode as a function of annealing temperature. The C–D
bonding configurations and thermal stability of adsorbed
deuterium resulting from dissociate adsorption were compared
to those occurring on deuterated diamond films (grown from
CD4 and D2 gases). We report and assign at least three
contributions to C–D stretching HR-EELS mode associated to
(111), (100) crystallographic orientations as well as grain
boundary associated vibrations in accordance with similar
vibrations of C–H stretching vibrations, reported previously.
ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1 Introduction The physical and electronic properties
of diamond film surface are largely determined by the
adsorbed molecules, their chemical nature, thermal stability
and particular bonding configuration [1–3]. Diamond films
of polycrystalline character prepared by hot filament
chemical vapor deposition (HF CVD) consist of a high
ratio of surface-to-bulk atoms, while their grain boundary
region contains hydrogen in different bonding configura-
tions [4–10]. The films surface possess a high extent of low-
hybridized C atoms (sp2
or sp) [11], which can be
responsible for the greater reactivity of these surfaces
towards terminating molecules. Chemisorption of environ-
mental molecules, such as water or oxygen, onto hydroge-
nated surface is believed to be responsible for surface
conductivity [12]. For example, physisorbed water induce
p-type conductivity of diamond surfaces terminated by
chemisorbed hydrogen [2, 12–15]: surface resistivity increases
by few order of magnitudes following in situ annealing of
water exposed diamond surface above 300 8C [16], most likely
associated to H2O desorption. Moreover, it was reported that
photon induced electron emission (the absolute quantum
photo-yield) from H-terminated diamond surface exposed to
environmental conditions significantly decreases with time [3].
In order to manipulate and control these fundamental
physicochemical properties the adsorption/desorption phe-
nomena of basic chemical species on diamond surfaces
should be understood.
Particularly, adsorption of hydrogen, its bonding
configuration and thermal stability onto diamond surfaces
is mostly important from applied and basic perspectives.
Nearly in all ultra-high vacuum (UHV) studies diamond
films undergo exposition to surrounding conditions for
different times, giving rise to uncontrolled adsorption of
water, CO2, oxygen, hydrocarbon, and other ambient
species. These species undergo low temperature desorp-
tion [17, 18], resulting in surface degradation to some extent.
Thus, in order to compare results obtained in different
laboratories, a well-established physicochemical treatment
prior to the UHV studies is required. Also, chemical species
can terminate different crystallographic planes of diamond
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2. with unequal reactivity. For example, activated oxygen
preferentially terminates and etches diamond (111) facets as
compared to (100) planes [19–21]. To understand the effect
of the in situ annealing on reactivity and properties of
hydrogenated diamond surfaces prepared by CVD the
careful study is required.
To eliminate ambient contamination and induce hydro-
gen termination the common procedure is 300–500 8C
annealing at UHV conditions following by surface exposure
to activated hydrogen [17, 18]. In this study we investigated
the deuterium adsorption phenomena and C–D thermal
stability on HF CVD diamond film surface in situ heated in
UHV conditions in molecular deuterium. In order to study
deuterium bonding configuration films also were grown
from CD4/D2 ambient. The thermal stability of the C–H/C–D
bonding was assesses by performing HR-EELS measurements
following gradual vacuum thermal annealing up to 1000 8C.
2 Experimental Hot filament chemical vapor deposi-
tion (HF CVD) was carried for 1 h from CD4/D2 (1/99) or
CH4/H2 (1/99) gas mixture [22]. Deposition from hydroge-
nated gas mixture results in polycrystalline film with the
thickness of 700 nm and $300 nm grain size (at the film’s
surface), while deposition from deuterated gases results in
$300 nm film thickness and $150 nm grain size (in our
previous work we reported a detailed study of the impact of
isotopic gas mixture exchange on diamond film growth [23]).
Samples were cooled to room temperature (RT) at the
termination of the CVD process by switching off the hot
filament and the heater of the sample holder, while keeping a
steady flow of the CH4/H2 gas mixture. Then the CVD
chamber was vented and the samples were transferred under
ambient conditions to the UHV system where the HR-EELS/
X-ray photoelectron spectroscopy (XPS) measurements were
carried out.
In situ deuteration was carried out by exposure of the
sample surface to non-activated molecular D2 at pressure
5 Â 10À6
Torr for 30 min, while the sample holder was
resistively heated at different temperatures. After heating the
sample was cooled in D2 ambient to RT, then D2 flow was
stopped and UHV conditions were restored. Chemical and
phase characterization was done by XPS using Mg Ka line
(Ephoton ¼ 1256.6 eV, data not shown) by analyzing the C (1s)
photoelectron line and plasmon losses. Vibrational characteri-
zation was done by HR-EELS system consisting of a double
monochromator and a single analyzer housed in an UHV
system with base pressure of $8 Â 10À10
Torr. The HR-EELS
spectra were recorded at RT up to loss energies of 600 meV.
The primary electron energy was 5 eV and the spectra were
recorded in the specular geometry with an incident angle of 558
from the surface normal. The full width half maximum
(FWHM) of elastically scattered beam was 9–10 meV.
3 Results and discussion We start this discussion
with phase purity analysis of HF CVD deposited diamond
sample that underwent annealing at 800 8C, studied by XPS
and shown in Fig. 1.
This figure shows C (1s) photoelectron loss spectrum
where well defined diamond bulk ($33 eV) and surface
(23 eV) plasmon losses signify well defined diamond matrix of
the upper surface region. Annealing at 1000 8C (discussed
below in the case of HR-EEL spectra) results in hydrogen
desorption and surface bond rearrangement: as a result
plasmon peaks slightly decrease in intensity alongside with the
appearance of a $6 eV loss associated with a p!pÃ
interband
transitions of reconstructed surface, which has a partial
graphitic character data was published previously [24, 25].
Figure 2 shows HR-EELS of HF-CVD diamond film
deposited from CH4/H2 and CD4/D2 gas mixtures and UHV
annealed at 800 8C and 1000 8C. TA ¼ 800 8C guarantees
desorption of any environmental contaminations, which can
be adsorbed onto the sample surfaces during the transfer
from the deposition chamber to the HR-EELS system. This
annealing temperature results in desorption of non-diamond
bonded hydrogen termination, while annealing at 1000 8C
results in a bare surface (complete desorption of hydrogen
atoms) and surface reconstruction. These spectra were
widely studied in our previous works [11, 26–28] while
herein we briefly describe these spectra for convenience. For
the CH4/H2 grown sample (Fig. 2(a)), the vibrational mode at
$155 meV is an overlapping of a C–C stretch and a C–H
bending vibrations. The peak centered at $360 meV energy
loss is attributed to C–H stretching mode, while the mode at
$510 meV is a coupling of this C–H stretch mode
($360 meV) and the 155 meV band. Figure 2(d) shows a
detailed fit procedure of the C–H stretching HR-EELS mode.
This mode was split into three contributions positioned at
$350, $360, and $373 meV. Mode centered at $350 meV
is most likely attributed to diamond (111) C–H, $360 meV
mode can be associated with diamond (100) C–H stretch-
ing [29], while $373 meV positioned mode can be assigned
to sp2
-hybridised carbon located in the grain boundary
region and at the film surface [11]. The modes at $300 and
$450 meV energy losses are pure C–C vibrations; most
likely the first and second overtones (or multiple losses) of
the diamond optical phonon positioned at $150 meV [26].
Figure 1 Plasmon scattering of CH4/H2 grown HF CVD diamond
and annealed at 800 8C. Data was derived from C (1s) photoelectron
peak recorded during XPS measurements.
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3. We showed in our previous studies that peaks centered at
300, 450, and 600 meV can be associated to first, second and
third diamond optical phonon overtone (or multiple loss),
correspondingly. These modes appear only in the spectrum
of well-defined and defects free hydrogenated diamond
surface [26, 27]. The relative intensities of pure C–H to pure
C–C peaks serve as indication of surface purity and are also
affected by diamond crystalline size. For example, the
relationship between pure C–H to pure C–C modes (I360/
I300) depends on diamond grain size: this ratio decreases in
transfer from sub-micron to nanodiamond films [30].
Alternatively, high I360/I300 ratio on well-defined diamond
surface indicates ambient contaminations: CHx species
adsorbed from atmosphere depress intensity of diamond
overtone at 300 meV and increase C–H peak at 360 meV.
Because of its extremely high surface sensitivity, HR-
EEL spectroscopy is best utilized for studying bonding
configuration of molecular adsorbates on well-defined solid
surfaces [31]. Particularly, in the case of ambient
contaminated diamond there are conceptual difficulties to
distinguish the adsorbed hydrocarbon vibrations from
diamond C–H bonding. In our previous works we studied
different aspects of hydrocarbon contaminations and their
bonding configuration and thermal stability on differently
treated diamond surfaces [17, 18].
In order to distinguish between peaks associated to
ambient originated carbon from those originating from the
CVD process, diamond films were grown from deuterated
gas mixture, CD4 and D2. However, C–D bonding configura-
tion on deuterated diamond surface was studied to much less
extend. HR-EEL spectrum of well-defined polycrystalline
diamond film grown from CD4/D2 species is shown in Fig. 2
(b). This spectrum shows pronounced C–D features: the C–D
bending mode at 108meV and C–D stretching centered at
$270 meV. The broad band at $370–380 meV may be
attributed to coupled losses of these two vibrations. The small
peak at $220 meV is attributed to multiple losses of the C–D
bending vibration at 108 meV. The pure carbon vibrations are
positioned at 150 meV and $300 meV: the appearance of
diamond optical phonon multiple loss at 300meV is clearly
seen in the spectrum, which is highly overlapped with C–D
stretching mode centered at $270 meV. Higher diamond
optical phonon harmonics (450 and 600 meV) are strongly
overlapped with C–D originated modes.
The spectrum of bare diamond surface obtained by UHV
film annealing at 1000 8C for $5 min is shown in Fig. 2(c).
This high-temperature annealing results in the desorption of
hydrogen-associated features (360 and 510 meV peaks) and
the emergence of a peak at $90 meV characteristic to the
CÀÀÀÀC dimer and associated to surface reconstruction of the
upper carbon layer, and, as seen in spectrum 2(c), it
completely shields the bulk diamond vibrational structures,
such as optical photon and its harmonics at 300 and
450 meV. These results confirm the remarkable surface
sensitivity of electronic vibrational spectroscopy to the
chemical bonding configuration of the upper atomic layer.
Figure 3 shows HR-EEL spectra of HF CVD films
deposited from deuterated CD4/D2 ambient. In this figure
deuterium/carbon bonding is monitored as a function of
annealing temperature (TA), indicated on the plot. Small
hydrogen peak shown on the spectrum (a) can be attributed
to ambient adsorbed hydrocarbon contaminations, that
disappears at TA ¼ 500 and 800 8C. As shown in Fig. 3,
C–D bonding is stable up to TA ¼ 800 8C, which agrees well
with previous studies of hydrogen thermal desorption from
well-defined diamond films [32–35]. The small contribution
at $85 meV (Fig. 3(c)) is most likely attributed to CÀÀÀÀC
dimer, produced by thermal desorption of non-diamond
bonded carbon. Detailed analysis of C–D stretching region
(shown in Fig. 3(d)–(f)) reveals at least three different
contributions to C–D stretching region in similar way, as was
detected for C–H stretching mode and shown in Fig. 2(d).
Now we concentrate on the detailed peak fitting of the
C–D mode of 800 8C annealed sample, shown in Fig. 3(f).
Figure 2 (a) HR-EEL spectrum of polycrystalline HF CVD
diamond films deposited from CH4/H2 gas species upon annealing
at 800 8C. (b) Spectrum of polycrystalline HF CVD diamond films
deposited from CD4/D2 gas species upon annealing at 800 8C.
(c) Spectrum of the sample as in (a) annealed at 1000 8C. Bare
(hydrogen free) diamond surface is characterized by peak at
$90 meV, associated to CÀÀÀÀC dimer and peak at 150 meV
associated with C–C stretching vibration. (d) Detailed view of
C–H stretching mode (data derived from spectrum (a)). Note the
splitting for at least three different modes at 350, 360, and 373 meV,
associated to hydrogen bonding to (111), (100) surfaces and (sp2
)
C–H, respectively.
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4. According to peak fitting, three different contributions are
positioned at 259, 270, and 280 meV and most likely could
be associated to diamond (111), (100) and sp2
hybridized
carbon, correspondingly, in similar manner as their
“analogous” vibrations on hydrogenated diamond facets at
$350, $360, and 373 meV (Fig. 2(d)). Adsorption of
deuterium on bare and hydrogenated poly- and single
crystalline diamond surface was studied to some extend [36–
42]. However, to the best of our knowledge these three
components on deuterated diamond films were not reported
hitherto. Our present results show that the three C–D
stretching components appear on the spectrum of as-
deposited polycrystalline diamond surface (i.e. grown from
deuterated gases, CD4/D2), while sp2
associated contribution
at 280 meV is absent from the spectrum of deuterium
terminated hydrogenated poly- and single-crystalline surfa-
ces (Figs. 4 and 5). This difference is due to the fact that
surface termination by activated deuterium results in
multiple bond opening of low hybridized carbon. This most
likely results in the appearance of the 259 and 270 meV
components only (sp3
hybridized carbon). Therefore, the sp2
related 280 meV feature is absent from such spectrum
suggesting that in situ deuteration (or hydrogenation) does
not result in C(sp2
)–D (or H) surface species. We will use
this data to analyze C–D bond formation upon molecular
deuterium expose of the hydrogenated diamond surface. In
addition, HR-EELS of well-defined diamond surface should
exhibit diamond phonon overtone (or multiple losses) at
300 meV, highly overlapped with C–D stretching peak.
Spectra which do not have this overtone cannot be
considered as representing chemical configuration of
diamond related bonding.
Figures 4 and 5 show a series of experiments, in which
as-deposited hydrogenated HF CVD diamond film was
heated in situ and exposed to molecular deuterium during the
heating.
After heating, the sample was cooled down in deuterium
ambient, and following vacuum renewal, the HR-EEL
spectrum was recorded at room temperature (spectra 4(d),
5(a), 5(d)). In each case the thermal stability of adsorbed
deuterium was verified by subsequent UHV annealing up to
800 8C (spectra 4(e), 5(b) and (e)). This temperature was
chosen as high enough for desorption of all non-diamond
bonded H/D, while H/D bonded to diamond matrix is stable
at these conditions [43]. Spectra shown in Fig. 4(a)–(c)
display gradual thermal desorption of ambient contamina-
tion from hydrogenated diamond surface extensively studied
by us previously [11, 26, 27, 44]. Spectrum 4(c) corresponds
to well-defined diamond surface, with contribution of sp2
hybridized carbon, detected in spectrum 4(m). Spectrum
of annealed sample in D2 ambient at 500 8C is shown in
Fig. 4(d), (i), and (n).
Clear contribution of C–D mode is distinguished as a
peak at 274 meV (spectrum 4(n)). According to previous
discussion this peak most likely belongs to C–D bonding on
diamond (100) facets. We suggest that molecular deuterium
terminates low hybridized carbon positioned on the as-
deposited diamond surface. Subsequent annealing in UHV
conditions at 800 8C (Fig. 4(e), (j), and (o)) reveals high
thermal stability of this 274 mode, although its intensity
relative to C–C overtone slightly decreases. These results
clearly suggest that annealing at TA ¼ 500 8C in molecular
D2 ambient leads to diamond surface termination by C–D
bonding, that is stable up to elevated temperatures.
Similar annealing procedure in D2 ambient at TA ¼ 800 8
C and TA ¼ 900 8C followed by UHV annealing at 800 8C is
shown in Fig. 5. Appearance of the C–D mode at 268 meV is
clearly distinguished in spectrum 5(k), although its relative
intensity to 300 meV overtone decreases for some extent
following UHV annealing at 800 8C (spectrum 5(l)). Peak
fitting reveals 275 meV position of C–D stretching,
suggesting bonding to (100) facets. In the spectrum 5(n),
following TA ¼ 900 8C in D2, both (111) and (100)
components can be distinguished. UHV annealing at
TA ¼ 800 8C (spectrum 5(o)) does not affect the spectrum
shape, suggesting a diamond character of C–D bonding.
C–D adsorption can be explained by C–H abstraction/
adsorption dynamics, studied by Thoms et al. [39]. Abstrac-
tion/adsorption probability ratio of H onto hydrogenated
polycrystalline diamond surface was reported to equal 0.06
with activation barrier for abstraction $0.434 eV (10 kcal/
mol [39]). The ratio of abstraction to adsorption rates
determined in their experiments places the maximum surface
coverage at about 0.95 monolayers, that is, about 5% open
sites after a saturation hydrogen atom exposure. Obviously,
heating the substrate increases the fraction of desorbed
hydrogen atoms, creating more sp/sp2
carbon states and thus
Figure 3 HR-EEL spectrum of polycrystalline HF CVD diamond
films deposited from CD4/D2 gas species: (a) as-deposited sample
recorded as-loaded, (b) annealed at 500 8C, (c) annealed at 800 8C.
(d)–(f) Detailed view of C–D bending mode (data derived from
spectra (a)–(c)).
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5. increasing C–H/C–D exchange reaction, in agreement with
present results. However, in their work Thoms et al.,
monitored C–H/C–D exchanged reactions using atomic
deuterium in situ activated by hot filament heated at
1800 8C [39].
Figure 6 shows an experiment advanced according to a
little different scenario. The hydrogenated sample was
annealed in UHV conditions at TA ¼ 1000 8C, cooled to RT
and then exposed to molecular D2. Pronounced C–D
vibration signifies room temperature dissociative adsorption
of D2 on highly reactive bare diamond surface. According to
Fig. 2(c) bare surface is characterized by CÀÀÀÀC dimers (most
likely CÀÀÀÀC monolayer induced by hydrogen desorption,
peak at $90 meV), which is suggested to be highly
chemically reactive. D2 adsorption and D-termination most
likely occur at these sp2
hybridized carbon states, opening
carbon double bonds. The observed position of C–D bond
(264 meV) suggests sp3
carbon hybridization. Thus, D2
treatment itself converts sp2
hybridized carbon to sp3
, as, for
example, in an alkene hydro- genation mechanism. Re-
appearance of low intensity diamond overtone at 300 meV
(spectrum 6(e)) suggests partial diamond structure recon-
struction. However, as can be studied from subsequent
800 8C annealing, most of the adsorbed deuterium desorbs
(spectrum 6(b)), suggesting defective and non-diamond C–D
bonding. We conclude from these results that annealing at
TA ¼ 1000 8C produces surface defects that cannot be
reduced by dissociative adsorption of molecular deuterium
Figure 6 (a) TA ¼ 1000 8C and cooling to RT in UHV, followed by
D2 exposure at RT. (b) UHV annealing at TA ¼ 800 8C. (c)–(d) and
(e)–(f) Detailed view of 70–200 and 200–400 meV region,
correspondingly.
Figure 5 (continuation of Fig. 4). (a) TA ¼ 800 8C and cooling in
molecular deuterium, (b) TA ¼ 800 8C, (c) TA ¼ 900 8C, (d)
TA ¼ 900 8C and cooling in molecular deuterium, (e) TA ¼ 800 8C.
(f)–(j) and (k)–(o) Detailed view of 70–180 and 200–400 meV
region, correspondingly (data derived from spectra (a)–(e)).
Figure 4 HR-EEL spectra of CH4/H2 grown HF CVD diamond as
a function of annealing temperature and exposure to molecular
deuterium: (a) as-loaded sample, (b) TA ¼ 300 8C, (c) TA ¼ 500 8C,
(d) TA ¼ 500 8C and cooling in molecular deuterium (see
experimental section), (e) TA ¼ 800 8C. (f)–(j) and (k)–(o) Detailed
view of 70–200 and 200–400 meV region, correspondingly (data
derived from spectra (a)–(e)).
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6. at RT. This effect can be associated with defective structure
of polycrystalline diamond surface.
4 Summary In this work dissociative adsorption and
bonding configuration of molecular deuterium on hydroge-
nated and bare polycrystalline HF CVD diamond film
surface were studied by HR-EELS. Fine vibrational analysis
of C–D stretching mode reveals that a sample grown from
CD4/D2 ambient display at least three contributions
positioned at 259, 270, and 280 meV that most likely could
be associated to diamond (111), (100) and sp2
hybridized
carbon, correspondingly. Heating of partially hydrogenated
sample deposited from CH4/H2 ambient in molecular D2
evidently results in decomposition of D2 molecule and
creation surface C–D bonding at TA as low as 500 8C.
Created C–D vibration has stretching energy around 260 and
270 meV, thereby, characteristic to diamond (111) and (100)
facets. We suggest that molecular deuterium decomposition
occurs at low hybridized carbon, resulted in D termination
and sp3
bonding formation. These bonds are stable up to
TA ¼ 800 8C, signifying good diamond character of the
surface. On the other hand, bare diamond surface reacts with
molecular deuterium already at room temperature, however,
leading to non-diamond C–D bonding.
Acknowledgements Financial support of the European
Community Seventh Framework Programme Prometheus (FP7,
grant agreement no’ 308975) is greatly acknowledged.
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2318 S. Michaelson et al.: Dissociative adsorption of molecular deuterium on polycrystalline diamond films
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