q'

ELSEVIER

D|AMOHD
AND
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MATER|AL$
D i a m o n d and Related Materials 6 ( ! 997 ) 7 i 2-716

Gap density of states in CVD diamond films from photoconducfivity and

photoluminescence data
M.C. Rossi, S. Salvatori, F. Galluzzi
Dipartimento di Ingegneria Elettronica, Universitfi degli Studi Roma Ill. Roma Via Vasca Navale 84, 00146. Roma, ltah'

Abstract
Spectral photoconductivity (PC) and photoluminescence (PL) have been used to investigate the nature and distribution of
defect states in CVD-grown polycrystalline diamond films. PC measurements at 300 K reveal an onset close to 1 eV and two
broad bands peaking at 2.2 and 3.6 eV, which are mainly attributed to photoionization of impurities. Transitions between localized
energy levels are responsible for a PL vibronic band peaking at 1.68 eV. Excitation spectra monitored at this energy exhibit at
77 K a sharp resonance at 1.95 eV. Starting from these results a possible picture of the defect density distribution is suggested and
a simple model for the electronic structure of the 1.68 eV optical center is proposed. 1997 Elsevier Science S.A.
Keywords: Photoconductivity; Diamond defects; Photoluminescence; Impurities

I. Introduction
Diamond is a very attractive material for several kinds
of semiconductor devices, showing desiderable properties for high temperature and high power electronics,
such as wide band gap, high breakdown fields and high
thermal conductivity [1]. Nevertheless, due to the polycrystalline structure of CVD diamond films, structural
defects, non-diamond phases, and impurities strongly
affect optical and electronic properties of the material,
giving rise to localized electronic states within the gap.
In order to get a better insight into this field a comparative investigation of defect states is reported here, based
on experimental data from photoconductivity (PC) and
photoluminescence (PL) spectroscopies. Each technique
gives information on different electronic transitions: PC
in the subgap region is related to transitions between
localized and extended electronic states, while PL mainly
reflects transitions between localized levels.

kept at 2200 C. Following the procedure described in

Ref. [2], polycrystalline diamond films with grain size
in the range 1-5 ~tm were obtained. Interdigitated aluminum contacts with 5 ~tm electrode gap were thermally
evaporated on the diamond surface. This inter-eleclrode
spacing was chosen in order to optimize carrier collection efficiency. Free-standing diamond films were realized by chemical etching of the silicon substrate in a
HF + HNOs solution. In order to remove non-diamond
surface layers, some films were also chemically cleaned
in sulphochromic acid at 100 C for 5 min. Spectral
photoconductivity was measured by a standard lock-in
technique using mechanically chopped light from Zn,
Cd and Hg low pressure lamps, and from a 250 W
tungsten lamp. The photon flux was measured by calibrated InGaAs and UV-grade Si photodiodes below
and above 1.5 eV, respectively. Emission spectra were
measured at 77 K and excited with different lines either
of an Argon or a dye laser and detected by a cooled
RCA 7102 photomultiplier.

2. Experimental
3. Results
Samples used in this study have been grown by hot
filament chemical vapour deposition (HFCVD) on
p-type (100) oriented Si substrates, previously treated
with diamond paste. The gas mixture consisted of 0.8%
CH4 and 99.2% H2, and the filament temperature was
0925-9635/97/$17.00 1997ElsevierScienceS.A. All rights reserved.
PlI S0925-9635 (96) 00752-2

3.1. Photocurrent spectra

HFCVD diamond films with coplanar contacts exhibit

a measurable photorespon~e under illumination at

M. (. Rossi el at. /: Diam+md and Rehaed Materials 6 (1997) 712-7/6

photon energies lower than the diamond band gap

(5.5 eV} down to 1 eV. lln this spectral range the photocurrent yield decreases by about four orders of magnitude, as shown in Fig. 1, exhibiting significant structure
at 2.2 and 3.6 eV
In diamond-on-silicon structures a contribution of Si
substrate to the photoelectric signal cannm in principR
be ruled out (and indeed the photocurrent threshold is
very close to the silicon band gap), but a comparison
with free standing diamond films does not present any
significant difference in the subgap photoresponse (see
Fig. 2(a)). Actually this result is not surprising, since
10:

....

i , , ~ , I , , , r - i ~ , , , g', , , , i , , , , i , + , ,~
E n e c t H c F i e l d = 5 mO 3 V c m - I

10

lO ~

a-,

10:
10 .3

10 4

i0 s
0

{eV )

Energy

Fig. I. P i m t o c u r t e n t s p e c t r a l r e s p o n s e o f a H F C V D d i a m o n d tihn with

c o p h m a r o h m i c c o n t a c t s , at a field s t r e n g t h o f 5 10 3 V cnl I in the
p h o t o n e n e r g y r a n g e 1 6 eV.

(a)

10 "3

T .......

0
0
0

0
@

I 0 "4 I~-

O 0 0 0 0 (3
@ @

10

I ''

I-- ~ 1 - - - - - - - r

o~ll~olll

freestanding 1
on silicon

tt@@0w o o 0 0 0 v ,
@
0

:
II

-4

00

i0 s
@

-3

_ooooe: o~::

O@

10

carriers photogenerated in silicon before colIecion at

front electrodes should cross the strongly detected
silicon/diamond interface and travel through the polycrystalline diamond film, where diffusion lengths are
shorter than 0.5 ~m.
Another possible extrinsic source of photocurrent is
represented by surface layers containing amorphous
carbon phases. Their presence is clearly revealed not
only by Raman spectroscopy, but also by dark electrical
measurements, where strong shunting effects are
observed in as-grown samples [3]. Since surface chemical
and thermal treatments are able to reduce these electrical
effects [4], we measured subgap photoresponse in both
as-grown and treated diamond films, without observing
any signal reduction in treated samples (see Fig. 2(b)),
at variance with photosignal reduction in the visible
range obtained by means of an annealing procedure in
methane and air [5].
The preceding results clearly sugges: that photocurrent spectra in the subgap region reflect real
characteristics of polycrystalline diamond, such as grain
boundaries, intragrain defects and impurities, indeed,
the observed spectral response is due to optical transitions between localized gap states and extended band
states and its shape is determined by the e~ergy dependence of both gap state distribution and optical cross
sections. A clear discrimination between these contributions is not an easy task and in the following we shall
present possible interpretations for the various spectral
features.
In the threshold region (0.8-1.5 eV) quite different
spectral details can be measured in different samples, as
shown in Fig. 3. In some samples, particularly after
chemical post-treatment with sulphochromic acid, a
sharp band, peaked at about l.! eV, is observed.
Actually, XPS measurements [6] show that alter this

0 0 0

o o @@@OOO@

713

o
oooO

li@@ll@

0 o

I
1.8

,_.L
2.2

"

(.)

I 0 -G

~'il~

@ @ II O

10 -,l
1.4

-i

L?

(b)

@01100 cO
o

O(D 0 0 O 0
~)c?
(~o

treated

I
2.6

lO-Z

I
3.0

__
0.7

Energy (eV)

I
0.8

~O.t~
o 'lbl::r

~o :

6)oO

I
0.9

I
I

o-

i,

I
1.1
Energy

I
1.2

1.3

1. . . . .

1.4

1.5

(eV)

Fig. 2. P h o t o c u r r e n t yield v e r s u s p h o t o n e n e r g y for: (a) f r e e - s t a n d i n g

d i a m o n d a n d d i a m o n d - o n - s i l i c o n film; ( b ) a s - g r o w n a n d s u r f a c e -

Fig. 3. C o m p a r i s o n b e t w e e n I R p h o t o c u r r e n t yield for a s - g r o w n ( o p e n

dots} a n d c h e m i c a l l y t r e a t e d (full d o t s ) d i a m o n d films with c o p l a n a r

t r e a t e d d i a m o n d film.

ohmic contacts.

M. C Rossiet aL Ditmumd and Rt,htted Materials 6 (1997) 712,716

714

treatment oxygen is bonded to the diamond film surlace,

so that a relation between the PC band at 1.1 eV and
an oxygen defect level cannot be ruled out. On the other
hand, this feature has been previously reported by
Gonon et al. [7] and assigned to the photoionization of
acceptor states lying 1 eV above the valence band and
responsible for the pinning of the Fermi level in undoped
diamond films. These authors describe the photoionization cross section by means of a Gaussian line shape,
expected in the presence of strong electron-phonon
interactions:

a(E) -,-exp[- ( E - EoJ2/2A 2 ]

(I )

where Eo is the effective ionization energy and/I is the

standard deviation, proportional to the temperature.
Owing to the asymmetry of the band (see Fig. 4), the
fitting of our data with Eq. ( 1) is not particularly good,
although the estimated values of Eo = 1.09 eV and A =
24 meV are in fair agreement with those reported in
Ref. [7]. We also tried to fit the low energy photocurrent
peak with theoretical lineshapes for photoionization
processes in the absence of electron-phonon coupling.
In the frame of the effective mass approximation and
using the quantum-defect method, the photoionization
cross-section can be approximated by [8]:

a(E) ~ ( E - Eo )l/2/[ 1 + C(E- Eo )]k

(2 )

where Eo is the ionization energy, C is a proper constant

and the exponent k depends on the effective potential
seen by the defect in the initial state (for a Coulombic
potential k=4 while for a delta-function potential
k = 2). Eq. (2) gives a reasonable fit to the experimental
data, with Eo = !.06 eV and k =4.
Photocurrent spectra of other HFCVD samples do

510

----,--T--..

,"

'

'

0 10

N.

.*., ,d'
I

1.05

1.1

1.15

not exhibit any sharp low-energy peak but only a

monotonic response growth at increasing photon energies, up to about 2.5 eV. Actually, in this region other
photoconductivity peaks have been reported at about
1.4 and 2.0 eV in both CVD and natural diamond [7],
but our data do not allow the resolution of any s~ructure.
At high energies the majority of samples show a continuous growing response with a broad shoulder but
without sharp features, up to the band edge onset. It
seems reasonable to assume that a similar spectral profile
can result from the superposition of photoionization
processes of various centres, according to the equation

Y(E),,, ~ Ni ~ d(Ei)G(Ei)cr~(E~,E)

(3)

where N~ is the concentration of the i-th center,

G(EO dEi is the probability for the i-th center to have
an ionization energy between E~ and E~+dEi and
ai(E~,E) is the photoionization cross section for the i-th
center with ionization energy Ei. The distribution G(E~)
was introduced in order to account for defect site
inhomogeneity in the polycrystalline matrix.
Going back to the discussion of photoresponse data
presented in Fig. 1, we can now give a tentative attribution of the distinct features detected. Even if our samples
were nominally undoped, photoionization of isolated
substitutional nitrogen having donor-like properties with
ionization energy around i.7 eV [9] could be responsible
for the observed photoconductivity band. A photoconductivit5 band centered at 2.2 eV with an energy threshold at 1.7 eV has also been reported by Farter [10]. On
the other hand, the PC band peaking at about 3.6 eV
could be ascribed to photoionization of carbon vacancies, which act as deep acceptors with ionization energy
of about 2.85 eV [11]. Actually, the theoretical calculation by Pugh [12] shows that a narrow defects band
below the center of the diamond gap is introduced by
surface states, which could also make a contribution in
this photon energy range. PC signals related to the
2.2 eV band seem to be due to extrinsic defects, while
intrinsic defects mainly affect the intensity of the PC
band located at 3.6 eV, even if a contribution from Ns
centers cannot be ruled out [13]. At photon energies
higher than 4.5 eV [ 11 ], photoionization of N2 centers
could be responsible for the detected PC signal, as
suggested previously [13]. Nevertheless, such a large
concentration of Nz centers is not expected in our
nominally undoped samples, while the existence of an
Urbach-like absorption tail is more reasonable.

1.2

Energy (eV)
Fig. 4. Spectral dependence of photocurrent yield for a chemicaUy
treated diamond film. The dashed line represents a Gaussian fit of
experimental data (dots) according to Eq. (1), while the continuous
line is the theoretical prediction for the optical cross-section
following Eq. (2).

3.2. Photoluminescence spectra

Photoluminescence spectra of HFCVD diamond
films, excited in the range 1.9-2.7 eV, are dominated by
a sharp band peaked around 1.68 eV (see Fig. 5, curve
a). This energy is generally related to the zero-phonon

Diam.m/ aml Rchm'd Malert'al.~ 6 ~1997~ 712 7/6

M. C R,.'.'.~'i~'1 ul.

d~e GR1 system, which is generally assigned ~o a aeatral

vacancy optical cemre [14]. Ahhough a ~'u~Pdi:;c~ssion
of these r.suhs wilt be given dsewherc, here xve can
suggest that beth 1.672 and 1.681 eV emission compohems ace related to a very shnilar defect, wilh a slightly
differem environment. This imerpretation is at variance
w'ith a recem analysis by Bergman and Nemanich. [|9},
which exctuded the coexistence of 1.673 and |.681 eV
lines in CVD diamond films {excited at 2.41 eV). suggesting Hie observed band asymmetries to be related to
the non-uniform concentration of silicon impurities.
In order to gain more information on the electronic
structure of the centers giving rise to the 1.68eV
emission band, we measured the corresponding excitation spectrum in 1.7---2.0 e\' and 2.5-2.7 eV regions. As
shown in Fig. 5, dashed curve, a sharp resonance is
observed around 1.95 eV. Such a resonance can be
attributed to the transition by the radiationless relaxation to the first excited stale and finally by the radiative
transition to lhe ground state, as depicted in Fig. 7.
It is worth noting that transition energies of 1.68 cV
{emission band) and !.95 eV (excitation band l are in
lair agreement with a simple hydrogenic model [211] fl~r
the electronic energy levels E,, of the optical center.
giving the well-known equation:

]~=77 K

.4
~==..
.==,
0~

il
,I

i,

,==

/
I

.,=,=,_,~..~ J ~ . - ' .

1.2

1.4

J
,

.,

\.

/ " /
-=

1.6

1.8

2.2

2.0

2.4

2.6

2.8

Energy te~')

Fig. 5. Photolumincscencc spectrum of HFCVD samples under la~cr

"5 cV Icontinous linc): and excilalion spectra ol the
excitation at =._
1.68 eV band (dashed lincL
emission peak of an optical center induced by siliconvacancy complexes [14]. The !.68 eV emiss,ml band has
been extensively studied by several authors [14--19]. In
particular, it has been shown that this emission band
dominates PL spectra of untextured film, while it is
hardly detectable in highly oriented films [15]. It has
also been reported that methane concentration, stress
and temperature strongly affect the 1 6 8 e V emission
[17]. Nevertheless, although some information has been
deduced from the temperature dependence of the 1.68 eV
emission Ivtnd [I 7], no definitive model of the structure
of this optical center has yet been proposed. The line
shape of the 1.68eV band slightly depends on the
excitation energy and a careful specl,:al analysis ai!ows
us fit of the observed beh:wiour by introducing two
close symmetric components, peaked at !.672 and
1.681 eV, respectively (see Fig. 6). The former energy
peak is nearly coincident with the zero-phonon peak of
I

(a)
A

E,, = -- R * / n 2 ( w i t h

n = 1.,...1
"~

Here, R* is the Rydberg constant, given by

R * = ( 2~2 e4 Ul* /2h 2 )

15)

where m* is the e l e c t r o n e | t ~ c t i v e m a s s , c' is t h e e l e c t r o n i c

charge, ~- the local dielectric constant and h Ihc Planck
constant. R* represents the ionization encrgs, which is
abottl 2.23 cV in our system. Asstinling m* m,, w e can
then estimate the local dielectric constant value, obtaining e = 1.7. Such a small value can be related to a less
dense environment surrounding the defect. Indeed, a
preferential distribution of the defects responsible Ibr

T = 77 K

j,-e~p

kex= 457 nm

/t

g
8

715

T=77K
;k x = 649 r,m

(b)

3"
d
U
o

.E
E
O
O
cO.

e.

o.
!

1.66

,.

1.67

1.68
Energy

1.69
(eV)

1.7

......

1.65

7 .....

1.66

"["

" I

1.67

1.68

Energy

(eV)

"'-'-'_2_.3

1.69

1.7

Fig. 6. Lineshapes of the 1.68eV photolummescence band at different excitation energies: (a) 2.71 eV, (b) 1.91eV. Dashed lines rcprcscnt
deconvolution of spectral data with a Loremzian component peaked at 1.672eV and with a Gaussian component at 1.681 cV.

716

3 C Rossi et al, / Diamomt aml Rehm,d MateriaL~6 (1997) 712-716

band edge

2nd excited state

0.25 eV (*)

! st excited state

0.56 eV (*)

!.95 eV

ground state

1.68eV

ductivity spectra at 2.2 and 3.6 eV, which can be related

to photoionization of isolated substitutional nitrogen
and to photoionization of intrinsic defects, namely
vacancy and surface states, respectively.
On the other hand, PL measurements revealed the
presence of silicon-vacancy opt cal centres located at
1.68 eV, whose electronic levels are in fair agreemem
with a simple hydrogenic model. At photon energies
higher than 2.23 eV such a centre can also give a
contribution to photoconductivity through photoionization processes.

2.23 eV

Energy
(*) calculated energies from
hydrogenic model
Fig. 7. Schematic representation of electronic energy levels and
transitions in the optical center emitting around 1.68 eV.

the PL band at i.68 eV at grain boundaries has been

observed previously by Raman filter imaging [21].
Following the hydrogenic model we can locate the
electronic ground state of the investigated optical centre
in the diamond gap, 2.23 eV far from the band edge
(see Fig. 7). Photons with energy higher than 2.23 eV
are able to ionize the centre, exciting carriers within the
band. Such free carriers can be trapped again by the
center, relaxing down to the first excited state and then
undergoing the radiative transition to the ground state.
This process accounts for the observation of i.68 eV
photoluminescence under excitation above 2.23 eV.

4. Conclusions
In summary, an extensive investigation on the defect
density distribution in polycrystalline diamond film has
been performed. Different origins of the subgap absorptiov~ have been analyzed, discussing in particular the
contribution of the silicon substrate and of non-diamond
phases to sub-band gap photocenductivity. Both can be
discarded as a possible origin of the photoconductivity
signal in the 1.5-3 eV photon energy range, while after
chemical treatement in sulphochromic acid a defect or
impurity level showing an ionization energy of 1.1 eV
becomes evident.
Significant features have been detected in photocon-

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