Physica C: Superconductivity and its applications 555 (2018) 28–34

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Physica C: Superconductivity and its applications

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Tc suppression and impurity band structure in overdoped superconducting T

Boron-doped diamond films
Dinesh Kumara, Maneesh Chandrana,b, D.K. Shuklac, D.M. Phasec, K. Sethupathid,
M.S. Ramachandra Rao ,a
⁎

a
Department of Physics, Nano Functional Materials Technology Centre (NFMTC) and Materials Science Research Centre (MSRC), Indian Institute of Technology Madras
(IITM), Chennai 600036, India
b
Department of Physics, National Institute of Technology (NIT), Kozhikode 673601, India
c
UGC DAE Consortium for Scientific Research, Khandwa Road, Indore 01, India
d
Department of Physics, Low Temperature Physics Laboratory, Indian Institute of Technology Madras, Chennai 600036, India

ABSTRACT

Our work investigates the impurity band and the core excitonic level evolution of a series of systematically boron doped diamond (BDD) films using Raman and X-ray
absorption (XAS) spectroscopies. The resistivity versus temperature data shows that Tc of the BDD films achieves a peak at a maximum gaseous phase boron to carbon
ratio, , beyond which Tc drops gradually as a result of excess defect formation, revealing a dome-shaped behaviour. Study of lattice expansion clearly shows
B
C max

the unambiguous presence of substitutional boron atoms beyond . Direct probe of the impurity band using XAS show a systematic increase in the absorption
B
C max

intensity of the bandgap states which ultimately degrades as the limit of is exceeded. The binding energy of the BDD 1s core exciton reveal a shallow
B B
C
> C max
measured value of 0.11 eV. This is less than earlier found values of 0.19 - 1.2 eV, in various reports for intrinsic diamond.

1. Introduction
Intrinsic diamond has a bandgap of 5.49 eV with the Fermi level
located at the middle of the bandgap. As carbon atoms are tetrahedrally
bonded, nitrogen doping leads to a deep donor state at 1.7 eV, this is
because nitrogen introduces Jahn-Teller type of distortion in the dia-
mond lattice [1]. This is also one of the reasons why heavy nitrogen
doping has remained unpopular among researchers. On the other hand,
carbon is easily substituted by boron in the diamond lattice. Boron
creates a shallow acceptor level at 0.36 eV [2,3]. Discovery of super-
conductivity in boron doped diamond (BDD) has made this an attractive
material of research [4,5]. Just like the high Tc superconductors [6,7],
the proposed mechanism governing superconductivity in BDD has re-
mained controversial [8–12]. The general consensus is that two holes
generated by the substitutional boron atoms are coupled together by
the zone centre phonon (ZCP), resulting into the Cooper pairs. Cooper
pairing is subject to the condition that Mott’s criteria for the critical
1
concentration is achieved (aB nc 3 = 0.25). Superconductivity sets in as
substitutional boron atoms in the sp3 bonded grains of BDD exceeds
nc = 4.5 × 10 20 cm 3 [13–16].
Upon heavy doping, the impurity band merges with the valence
band creating a condition favourable for the Cooper pair formation at
low temperatures. Thus, the extent of doping dictates the Tc of this
superconductor. Upper limit for the solubility of boron in diamond,
under the chemical vapor deposition (CVD) condition, is proposed to be
about 38% [17,18]. The experimentally achieved doping limit (2 to
4%), however, is far away from the theoretical prediction. Clearly, most
of the boron atoms are consumed in the form of defects that are inactive
with respect to active carrier concentration in BDD. Stress accumulated
as a result of heavy boron doping can result into 2D defects such as
dislocations and twin boundaries. Such defective sites are boron rich
regions within an individual grain that are non-productive and perhaps
even detrimental with respect to superconductivity. It was also found
that grain boundaries in BDD are boron rich regions indicating that a
large percentage of boron atoms were consumed in the grain bound-
aries [11,12,15,19–21]. In addition, point defects such as boron ag-
gregates, boron-vacancy complex and boron interstitials form either
deep acceptor level or even donor levels in BDD and could be a source
of carrier compensation [22,23]. It will be interesting to see such effects
under extreme doping conditions. Density of states N(E) of the impurity
band, as formed by the isolated substitutional boron atoms, determine
Tc in BDD. By monitoring the evolution of the impurity band as a
function of gaseous phase boron to carbon ratio, C , one can obtain
B
valuable information regarding the onset of defect formation in BDD.

⁎
Corresponding author. msrrao@iitm.ac.in
E-mail address: msrrao@iitm.ac.in (M.S. Ramachandra Rao).

https://doi.org/10.1016/j.physc.2018.09.005
Received 11 June 2018; Received in revised form 8 September 2018; Accepted 24 September 2018
Available online 25 September 2018
0921-4534/ © 2018 Published by Elsevier B.V.
D. Kumar et al. Physica C: Superconductivity and its applications 555 (2018) 28–34

Defects formed in heavily doped diamond can give rise to new exotic
phases. Interplay among the parameters such as Tc, grain size and the
doping concentration can lead to many exciting phenomena in BDD.
For example, existence of a Bosonic state just at the onset of the su-
perconducting state and finding of ferromagnetism in superconducting
diamond are a clear indication of the role of boron induced defect in
diamond[24–28].
Here we use Raman spectroscopy and X-ray absorption spectroscopy
(XAS) to probe the evolution of the impurity band in underdoped to
overdoped superconducting BDD films. After confirming the semi-
conducting and the superconducting nature of the BDD films using re-
sistivity (ρ) versus temperature curves, Fano analysis of the ZCP mode is
used to demonstrate how Tc is related to N(E) in the BDD films. We have Fig. 1. (a) Resistivity versus temperature curves of boron doped diamond
also carried out direct probe of the impurity band using XAS. Although (BDD) films with various boron concentration in the temperature range of 2 to
binding energy of the core exciton in BDD remained constant at 20 K. (b) Representation of the experimental phase diagram of the BDD films
0.11 eV, full width half maximum (FWHM) of the core exciton peak indicating the normal and the superconducting regions, superconducting tran-
sition temperature Tc (spheres) is plotted on the left y-axis. The right y-axis
changes with doping concentration, pointing out the role of shallow
indicate the Hall concentration nh versus the gaseous phase boron to carbon
donor-type defect formation under extreme doping conditions. The
ratio. Error bars on the spheres indicate the difference between the onset and
experiment was initially intended to maximize doping efficiency and the offset Tc obtained from the first derivative of the resistivity curves and Tc is
thereby obtain a maximum limit for the substitutional boron con- the inflection point of the curves. Blue curves and the blue symbols represents
centration beyond which a saturation of Tc in the BDD films would data for the samples grown with boron to carbon ratio where Tc starts to de-
occur. The experimental results, however, revealed that beyond a crease. (For interpretation of the references to colour in this figure legend, the
maximum gaseous phase boron to carbon ratio, C
B
, the impurity reader is referred to the web version of this article.)
max
band and the Tc decrease simultaneously.
temperature Hall effect measurements were carried out using physical
property measurement system (PPMS) from Quantum Design. To ensure
2. Experimental ohmic contacts, four gold pads of 0.5 mm diameter were sputtered onto
the films and copper wires were attached to the gold pads using ad-
Granular intrinsic diamond film and BDD films were deposited on Si hesive silver paint. For XAS, after loading the samples, the chamber was
substrate using a hot filament chemical vapour deposition (HFCVD) evacuated to UHV (base pressure of 10 10 Torr). The spot size of the
reactor [16]. Deposition of each film was carried out for 3 h. The incident X-ray beam is ∼ 0.5 mm. To ensure the homogeneity and data
substrate temperature was 850 °C and the chamber pressure during the reproducibility, measurements were taken from several spots of the
deposition was maintained at 7 Torr. The flow rates of H2 and CH4 samples. For reference, highly oriented pyrolytic graphite (HOPG) was
during the deposition process were maintained at 3000 sccm and 80 also measured along with the BDD films. Pre and post edge correction
sccm, respectively. Boron doping was achieved by inletting B(CH3)3 gas and the fittings of normalized XAS data were performed using Athena
during the depositions. Several depositions were carried out by sys- [29]. The measurements were obtained at room temperature in the
tematically varying the concentrations of boron in the gaseous phase total electron yield (TEY) mode at soft x-ray absorption spectroscopy
(Table 1). (SXAS) beamline (BL-1) of the Indus-2 synchrotron radiation source,
Crystallinity of the deposited films was monitored using SmartLab India.
X-ray diffractometer (Rigaku) in 2θ configuration. Thickness and
morphology of BDD films were evaluated using a field emission scan-
ning electron microscope (FESEM, Quanta 3D, FEI). The thicknesses of 3. Results and discussion
the deposited films were found to be ∼ 1.5 μm with grain sizes between
200 nm - 800 nm. Room temperature Raman spectra of the BDD films 3.1. Transport properties, lattice constant and vibrational properties
were recorded using a confocal Raman spectrometer (Witec). The ex-
citation wavelength was 488 nm and the spectra were collected using a Fig. 1shows the resistivity versus temperature curves of the BDD
1800 gr/mm grating. Temperature dependent resistivity and room films grown using various B ratio. Clearly, at low B ratios (2500 and
C C
5000 ppm), the films remain semiconducting (D1 and D2). As B
ratio is
Table 1 C
further increased, Tc=7 K is achieved at (10000 ppm). The blue
B
Summary of the B
ratio, Hall concentration (nh), asymmetry parameter (q), C max
C
Fano linewidth (Γ) and critical frequency (ω) of the BDD films. curves indicate ρ versus T curves for the samples under extreme doping
where Tcs of the films decreases as B is tuned beyond C . Inter-
B
Samples B nh q Γ ωc C max
C
(ppm) (cm 3) (cm 1) (cm 1) esting evolution of Tc as a function of gaseous phase B can be seen in
C
Fig. 1(b), where Tc (left y-axis) and nh (right y-axis) achieves a max-
D1 2500 1.7 × 1020 -6.5 18.1 1320 imum at C
B
, beyond this, due to excess defect formation and carrier
D2 5000 2.5 × 1020 -5.7 20.6 1313 max
D3 5750 5.1 × 1020 -4.7 22.9 1300 compensation Tc begin to decline gradually. Hole concentrations (nh) as
D4 6250 8.0 × 1020 -4.2 24.1 1299 obtained from the Hall effect measurement are listed in Table 1. In
D5 7500 1.3 × 1021 -3.9 25.3 1295 accordance with Tc, nh drops beyond C
B
, revealing a dome-shaped
D6 8000 1.8 × 1021 -3.1 25.6 1290 max
D7 8750 2.0 × 1021 -2.7 26.2 1287 behaviour. Till date, homoepitaxial (111) films have demonstrated
D8 9500 2.2 × 1021 -2.1 27.1 1285 highest offset superconducting transition temperature of up to Tc,
D9 10000 3.0 × 1021 -1.9 28.3 1283 zero=10.2 K [30]. However, for the granular BDD films the transition
D10 10750 1.5 × 1021 -3.7 22.5 1296 temperatures are usually less. Tc, zero for the highest doped sample D9
D11 11250 1.2 × 1021 -3.5 22.6 1298
with nh=3.0 × 1021 cm 3 is 6.4 K in our case, similar results have
D12 12000 4.9 × 1020 ⋅⋅⋅ ⋅⋅⋅ ⋅⋅⋅
D13 12500 4.5 × 1020 ⋅⋅⋅ ⋅⋅⋅ ⋅⋅⋅ been reported by several other groups. For example, using microwave
assisted CVD (MWCVD), Takano et al. reported Tc, zero=4.2 K with

29
D. Kumar et al.
Fig. 2. (a)Lattice parameter versus the gaseous phase boron to carbon ratio
plot. Blue half circles are the lattice parameters of BDD films deposited with
high gaseous phase boron to carbon ratio where the Tc begin to decrease as a
result of extreme doping. (b) X-ray diffraction pattern of a boron doped dia-
mond film, D1(2500 ppm) to D13 (12500 ppm).
nh=3.1 × 1021 cm 3 for the polycrystalline BDD films [5]. Again,
Wang et al. showed a relatively higher Tc, zero of 6.2 K for
nh=4.8 × 1021 cm 3, in the HFCVD grown BDD microcrystalline films
[31]. Doi et al. also reported a Tc, zero ∼ 4 K for the HFCVD grown BDD
microcrystalline films with nh=1.1 × 1021cm 3 [32].
It is certainly possible that excess boron content in the gaseous
phase has minimal effect during the deposition, such that boron atoms
do not actively take part in the doping process, rather it is lost in the
complex gas dynamics towards extreme doping. To confirm this we
further carried out XRD studies. XRD patterns of the films revealed no
discernible feature except that the diffraction peaks showed systematic
shift towards higher angle as B ratio is increased and beyond C
B
,a
C max
saturation of lattice parameter (a) is achieved. This suggest that boron
is doped in the system even under extreme doping concentration.
Fig. 2(a) shows a versus B plot. Lattice parameters of samples D1
C
and D2 were found to be close to that of the intrinsic diamond, a =
3.566(4) Å. Further increase in B lead to a monotonic increase in the
C
lattice parameter. It is noteworthy that beyond
B
, a saturates
C max
suggesting the presence of substitutional boron atoms and boron pairs
in these films [33]. Lattice parameter expansion can also be seen from
the shift in the XRD peaks to higher angles, the shift in (220) diffraction
peak can be clearly seen in Fig. 2(b). Increase in a may be influenced by
the presence of free carrier concentration via the deformation potential
as pointed out by Brunet et al. [34], in addition to the linear lattice
expansion according to Vegard’s law [35,36].
Fig. 3depicts the Raman spectra of BDD films deposited at different
B
ratios. Raman spectra in BDD consist of the peaks at 450, 1200, 1332,
C linewidth due to Fano resonance, respectively. VE is the discrete-con-
1350 and 1560 cm 1. Peak at ∼ 1200 cm 1 is attributed to the maxima
in the phonon density of states (pDOS) of diamond [16,37,38] and the
broad peaks at ∼ 1350 cm 1 and ∼ 1560 cm 1 are due to the graphitic
grain boundaries. The A1g stretching mode which are Raman active
vibrational modes of the nearest neighbour boron pairs forms a broad
maximum around 450 cm 1. Boron pairs form an impurity level at
0.6 eV above the valence band maximum (VBM), which do not con-
tribute to superconductivity as it forms deeper acceptor levels
[22,39,40]. Again, 450 cm 1 and the zone centre phonon (ZCP) mode of
BDD undergo a systematic redshift until C is attained. Thus for the
B
max
samples D10 - D13, the 450 cm 1 peak and the ZCP peak show sudden
increase in frequency due to lesser active carrier concentration as listed
in Table 1. Surprisingly for the samples D12 and D13, the intensities of
the graphitic peaks at 1350 and 1560 cm 1 increases drastically sug-
gesting enhanced formation of graphitic components in the grain
boundaries.
30
Physica C: Superconductivity and its applications 555 (2018) 28–34
Fig. 3. Concentration dependent Raman curves of the boron doped diamond
films. Blue curves signify the overdoped regime where the superconducting
transition temperature starts to decrease.
Intrinsic diamond has a ZCP mode at 1332 cm 1 . For BDD, however,
this mode interfere with impurity band (with density of states, N(E))
resulting into Fano resonance phenomena [41]. An expression relating
a discrete state transition with the energy continuum was described in a
seminal work of U. Fano [42]. Fano lineshape is given by,
(q + ) 2
I( )
1+ 2 (1)
where ϵ and q are the Fano parameters dependent on the continuum
background.
Furthermore, using the Raman scattering tensors for electron (Te)
and phonons (Tp), and also considering the quasi-continuum nature of
the impurity band in the expressions for Fano parameters [43], ex-
pressions for Fano parameters, ϵ, q and Γ are described as,
=
(N (E )) (2)
(N (E )) = |VE |2 N (E ) (3)
Tp
VE T +
q= e
(N (E )) (4)
where, q is the asymmetry of the ZCP mode. As |q| → ∞, asymmetry
vanishes and the ZCP mode in BDD achieves a Lorentzian line shape
and as |q| → 0, the ZCP mode undergoes a ‘window resonance’. Here,
ω, Δω and Γ(ρ) represent the critical frequency of the Fano resonance,
shift in the frequency as a result of Fano interference and the modified
tinuum interaction matrix.
In order to extract the Fano parameters we carried out least square
fittings using a Fano and Gaussian profiles as shown in Fig. 4. The fittings
were carried out in the wavenumber range of 900 cm 1 - 1700 cm 1 after
the linear background subtraction. Fano profile in BDD is also affected by
the neighbouring Gaussian profiles, hence to correctly estimate Fano
parameters, a wider wavenumber range has been taken into consideration
in the present analysis. The resulting Fano parameters are listed in Table 1.
As described in (3), the width (FWHM) of the Fano resonant peak is
proportional to N(E) [43]. In Fig. 5, we show Γ(N(E)) as a function of C ,
B
clearly, Γ(N(E)) increases monotonically upto
B
as indicated by the
C max
dotted line. Beyond this Γ(N(E)) decreases, suggesting a decrease in N(E)
of the BDD films in concomitant with our earlier result of the ρ versus T
data. Note that for the samples D12 and D13, graphitic peaks (1350 cm 1
and 1560 cm 1) begins to dominate making it difficult to extract the Fano
parameters for these curves.
D. Kumar et al. Physica C: Superconductivity and its applications 555 (2018) 28–34

Fig. 4. Raman spectra in the wavenumber range of 900 - 1700 cm 1 of the
selected BDD films. Filled Gaussian profiles at 1140 and 1440 cm 1 are the
peaks due to trans-polyacetylene [16,44,45] and the filled asymmetric profile is
Fano resonant ZCP peak. A Gaussian peak at 1000 cm 1 is due to the pDOS [37].
Fig. 5. Fano linewidth (Γ) versus
fitting of the Raman curves. Dotted line indicate
film (D9) is maximum.
289.6 eV and the VBM at 283.2 eV [48]. HOPG C K edge was also
measured together with these samples. Energy axis of these spectra are
corrected according to the position of π* peak found in HOPG at
285.4 eV [49]. In the present samples, π* peak is due to the graphitic
components in the grain boundaries, which is also seen as a broad G
band in the Raman spectra of the films around 1560 cm 1. In addition
to the π* peak, two localized peaks are found at 282.5 eV (labelled as
H) and 283.9 eV (labelled as I). Since these localized bands are absent
in the XAS spectrum of intrinsic diamond (labelled as NCD), they are
attributed to the boron impurities in the host network. Such peaks were
first reported by Nakamura et al. [50]. In their publication, absorption
spectra of semiconducting samples were compared with that of a su-
perconducting sample. For the superconducting BDD film, existence of
absorption peaks at 282.5 eV and 284 eV was reported below and above
the VBM (283.8 eV), respectively. Such unoccupied states were also
reported by Morar et al. as due to unoccupied surface states [51]. A
recent work by Glans et al. [52], although no superconductivity was
reported in their samples, further supported the work of Nakamura et al.
It was shown that H and I bands originate from the sp3 bonded network.
Thus, it was argued in both works that peak H is a consequence of a
core level shift [53,54] as indicated in the schematic of Fig. 6. In con-
tradiction to the above concept, and though there has been a general
consensus that BDD is a BCS type superconductor [50,52,55,56], Bas-
karan hinted the importance of strong electron correlation in the rigid
impurity band and suggested that peak H and I are the correlated mid-
gap band the upper Hubbard band [10]. ARPES study carried out by
Yokoya et al. [55], however, showed the absence of isolated impurity
band contradicting Baskaran’s theory of Resonating Valence Bond
(RVB) superconductivity. Therefore, it is important to carry out mea-
surement of these in-gap states for a series of systematically doped
samples all the way up to the regime of extreme doping where effects
due to defects begin to dominate.
Our result shows that (1) no in-gap states exist for the intrinsic
diamond (NCD), (2) the integrated absorption intensities of the two in-
gap states (H and I) follows the behaviour of Tc and nh (3) peak centres
of H and I remain constant (within the instrumental resolution limit of
0.17 eV) with increase in nh and (4) the core exciton peak at 289.5 eV is
sharper for NCD as compared to that of the sample D9. In our result, H
and I are separated by 1.4 eV, suggesting that core level shift is 1.4 eV.
B
ratio as obtained from the Fano profile In Fig. 7(a), we show the isolated hole states H and I, for NCD and
C
B
, where Tc of the BDD
BDD films. Clearly, intensities of the states H and I increases with in-
C max
crease in the substitutional boron content in the films, as can be seen for
the samples D1 to D9. However, as the B ratio is increased further
C

3.2. X-ray absorption spectroscopy

The expression for the x-ray absorption cross-section can be derived

from the Fermi’s golden rule. Under the dipole approximation, for a
transition from an initial state |1s⟩ to a final continuum state |f⟩, the x-
ray absorption cross-section is given by,
4 2e 2
= f |e. p|1s (E )
a
m2c
f
(5)
Here, δf(E) indicate the transition of the electron to a continuum
state, the term ⟨f|e.p|1s⟩ is the dipole matrix element. According to the
one-electron transition model, a core electron is excited to the available
empty states upon collision by the x-ray photon and the multi-electron
effects are passive with respect to such transition. Thus, XAS intensity
Fig. 6. Normalized carbon K edge absorption spectra of nanocrystalline dia-
maps the conduction band and also the available empty states in
mond and boron doped diamond (D9) film. Dotted lines represents the bandgap
semiconductors. Here, intensity of the XAS spectra directly depends on
of diamond and spectra were shifted according to the π* peak as indicated in
the hole concentration, I(E)∝N(E) [46,47]. Therefore, evolution of the figure. The states H and I represents the impurity band states.The width of
empty states with B can be effectively and directly probed using XAS. the core exciton peak at 289.5 eV widen as the concentration of boron is in-
C
To understand the evolution of the impurity band as a function of B creased in the films. The schematic on the right represents the density of states
C
ratio and Tc, XAS spectra were recorded for the BDD films. Figure 6 of boron doped diamond films where the two peaks at 282.5 eV and 283.9 eV
shows the XAS spectra for undoped nanocrystalline diamond (NCD) and are shown by transitions H and I. Here, VB and CB represent valence band and
a BDD film (D9). The dotted lines represent conduction band edge at conduction band, respectively.

31
D. Kumar et al.
Fig. 8. Full width at half maximum, Γcore, (half circles) and binding energy,
BEcore, (half squares) of the core exciton versus gaseous phase boron to carbon
ratio of the boron doped diamond films. The red dashed line indicate the core
exciton binding energy of 0.11 eV. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article.)
B
beyond [ C ] max as seen in the case of samples D10 to D13, intensities of
the hole states decreases gradually (blue curves). In order to make this
clearer, we plot the integrated absorption intensity (IH+II) and Tc
versus B ratio on the left y-axis and the right y-axis, respectively, in
C
Fig. 7(b). Integrated intensities of the peaks were estimated by fitting
the two peaks using Gaussian profiles after a linear background sub-
traction in the region between 281.7 eV to 284.7 eV. Intensities of the
peaks follow the behaviour of Tcs of the BDD films, we find that beyond
the sample D9, the absorption intensities as well as the Tcs decreases
gradually. This was also seen from the Raman spectroscopic studies
where Fano linewidth first increase followed by a decrease as B ratio is
C
tuned towards extreme doping.
In Fig. 7(c), we show the overview of the C 1s absorption edge of
BDD film (D9). The sharp edge at 289.5 eV is due to the core exciton in
diamond. The spectra dominantly consist of secondary and Auger
electrons as a result of cascades of inelastic collisions when the X-ray
photon are incident on the specimen [57]. We reproduce the spectrum
using a combination of a Lorentzian function, an arctangent function
and several Gaussian curves. Here, the Lorentzian function represents
the core exciton state in BDD. Edge-jump at E0 = 289.5 eV is followed
by a smooth arctangent rise which represents the continuum
32
Physica C: Superconductivity and its applications 555 (2018) 28–34
Fig. 7. (a) Normalized total electron yield of the impurity
band states (H and I), curves in blue represent data for the
samples with boron to carbon ratio where the superconducting
transition temperature (Tc) degrades (b) integrated intensities
of the impurity band states versus the boron to carbon ratio
(upper half triangle) and Tc (lower half triangle). Dotted line
indicate the maximum boron to carbon ratio in the gaseous
phase where Tc is maximum and (c) enlarged absorption data
of the sample D9, solid curve in red represents the fitted curve
obtained using an arctangent, Lorentzian and multiple
Gaussian functions. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web
version of this article.)
absorption. The zero of energy is the inflection point of this arctangent
function and it was found at E0T = 289.6 eV.
Core excitons are the bound electron-hole pair formed as a result of
excitation of the core electron. In doing so, defect states are pushed in
to the primary band gap just below the conduction band minimum
(CBM). For sp3 diamond structures localized shallow l = A1 (s-like) and
deep l = T2 (p-like) states are formed below the CBM [58]. Depending
on which defect level does the core electron occupies, the core exciton
forms either a tightly bound Frankel type exciton with binding energy
(BE) of ∼ 1 eV or a loosely bound Wannier type core exciton with BE
∼ 0.2 eV. Interestingly, reports on BE of diamond core exciton has
revealed puzzling and at the same time intriguing results [59–63]. For
example, core exciton in diamond was found to be of Frankel type with
BE of 1.2 - 1.5 eV [61,63], suggesting an s-type nature of the excitonic
level. On the other hand a loosely bound electron-hole pair of Wannier
type was reported with BE energies ranging from 0.19 - 0.32 eV
[59,60,62], indicating a transition to a p-like defect state.
As our data clearly shows the distinction between the core excitonic
features of undoped diamond and doped diamond (Figure 6), we fur-
ther examine the core-exciton peak of the BDD samples. In Fig. 8, we
show the FWHM of the core exciton peak (Γcore) versus the B ratio, we
C
also show the core excitonic BE (BEcore) on the right y-axis. Core-exciton
BE remains constant at 0.11 eV (BE = E0T E0 ) whereas Γcore of the
core excitonic peak is seen to follow the behaviour of Tc. Core-excitonic
features appears to broaden with increasing nh, and beyond C
B
,
max
FWHM remains constant. This may be due to creation of new defect
states leading to lifetime degradation of the core - exciton as pointed
out by Chang et al. [64]. The Gaussian peak at 288 eV represents the
surface C-O/C-H states [65], and several peaks across the conduction
band states fitted using Gaussian profiles represent the high symmetry
points in diamond[66]. Clearly, the basic structure of the extended
empty states replicates the structure of the intrinsic host network,
suggesting that, despite heavy boron doping, sp3 nature of the host
network remains uncompromised.
4. Conclusions
In summary, we have probed the impurity band evolution in a
carefully deposited series of semiconducting and superconducting BDD
films starting from the moderately doped region to the region of
D. Kumar et al.
extreme doping, using a chemical vapor deposition method. The films
showed systematic increase in Tc, with Tc = 7 K for the sample grown
with a maximum gaseous phase boron to carbon ratio, C =
B
max
10000 ppm. Further increase in the gaseous phase , showed
B B
C
> C max
gradual degradation of Tc. The saturation of a beyond points to
B
C max
the fact that, isolated substitutional boron atoms and the boron pairs
increases the lattice constant to certain level beyond which the boron
atoms becomes detrimental to active carrier concentration contributing
to superconductivity. Detailed analysis of the Fano asymmetric peak of
the BDD films revealed a systematic increase of the Fano linewidth
(Γ∝N(E)) upto C , beyond this, Γ decreased gradually. Also, direct
B
max
probe of the impurity band using XAS showed similar behaviour of N(E)
as found from the Fano line shape analysis of the BDD films. C 1s core
exciton binding energy (BEcore) was found to be 0.11 eV, in marked
contrast to the earlier results of intrinsic diamond. Although no dis-
cernible effect of defect formation under extreme doping conditions can
be seen in the core exciton BE, full width at half maximum (Γcore) fol-
lows the behaviour of N(E).
Acknowledgments
Authors would like to thank the financial support from Department
of Science and Technology (DST) that led to the establishment of Nano
Functional Materials Technology Centre (NFMTC)(SR/NM/NAT/02 -
2005) and the Department of Atomic Energy (DAE).
Supplementary material
Supplementary material associated with this article can be found, in
the online version, at 10.1016/j.physc.2018.09.005
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