J Mater Sci: Mater Electron (2017) 28:18075–18084
DOI 10.1007/s10854-017-7751-3
Effect of variation of thickness of ­TiO2 on the photovoltaic
performance of n-TiO2/p-Si heterostructure
Avijit Dewasi1 · Anirban Mitra1
Received: 29 April 2017 / Accepted: 18 August 2017 / Published online: 31 August 2017
© Springer Science+Business Media, LLC 2017
Abstract Fabrication of heterojunctions of Si along with
oxide based semiconductors like ­TiO2 is an alternative
method to produce cost effective solar cells. To study the
photovoltaic performance of the n-TiO2/p-Si heterostructure,
­TiO2 thin films of different thicknesses were deposited on p
type Si substrates using pulsed laser deposition technique.
All the films were characterized using XRD, AFM, Spec-
troscopic ellipsometry and I–V characteristics with solar
simulator and other monochromatic light sources of different
wavelengths. Optical properties of the thin films were cor-
related with the I–V characteristics under dark and illumina-
tion conditions. It has been shown that thickness plays a cru-
cial role on the photovoltaic performance of the n-TiO2/p-Si
heterostructure. Further, it has been observed that the optical
reflectivity of ­TiO2 thin film of particular optimized thick-
ness deposited on p type Si could be lowest. Consequently,
photocurrent of the n-TiO2/p-Si heterostructure is found to
decrease with an increment of the thickness of the T ­ iO2 thin
film. This is attributed to the increment of series and sheet
resistance with increase of ­TiO2 film thickness. Moreover,
increase of T­ iO2 film thickness can also create surface states
and defects in the n-TiO2/p-Si heterojunction which are also
responsible for poor efficiency of the photovoltaic cells.
* Anirban Mitra
mitrafph@gmail.com
1
High Power Laser Lab, Department of Physics,
Indian Institute of Technology Roorkee, Roorkee,
Uttarakhand 247667, India
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1 Introduction
Continuous increase in the demand of the modern society for
clean energy compels the researchers to focus on the devel-
opment of the high efficiency low cost solar cell. Till date,
crystalline Si is the most efficient (~25%) candidate for solar
cell. However, it is expensive due to the sophisticated fab-
rication of p–n junction at high temperatures (>800 °C) in
high purity furnaces. Therefore, Scientists are continuously
on the lookout for alternate cost effective ways to improve
the efficiency of the solar cell.
One alternate way to reduce the cost of Si solar cell
is the fabrication of heterojunction with oxide based
semiconductors. The use of heterojunction is an effective
method to improve the efficiency by combination of dif-
ferent semiconductors having different properties which is
not achievable with a single semiconductor. Among oxide
based semiconductors like ZnO, T ­ iO2, ­Cu2O, heterojunc-
tions have already been fabricated in proximity with Si
[1–3]. Oxide semiconductor at the nanoscale level can
significantly enhance the heterojunction effect and junc-
tion property of Schottky based sensors, metal–semicon-
ductor–metal, and homojunctions. Being a natural n type
material of band gap 3.2 eV, T ­ iO2 can form n-TiO2/p-Si
heterojunction by depositing on a p-Si substrate. Apart
from solar cells, such a simple cost effective structure is
suitable for various photovoltaic applications. Titanium
oxide based photodetectors were fabricated using ther-
mally oxidized ­TiO 2 nanostructure/p-Si heterojunction.
The effect of photoresponse on annealing temperature
was observed to be related with effective surface area of
quasi-one-dimensional ­TiO2 nanostructure [4]. Highly ori-
ented ­TiO2 nanorod based sensor were made by deposit-
ing on a fluorine-doped tin oxide substrate [5]. Structural
transformation of ­TiO2 films with deposition temperature
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18076 J Mater Sci: Mater Electron (2017) 28:18075–18084

and electrical properties of nanostructure n-TiO 2/p-Si 2 Experimental details

heterojunction diode were investigated in Ref. [6]. With
­TiO2 nanoarray, Schottky diode based UV detector was TiO2 thin films of various thicknesses were grown on com-
also fabricated [7]. Recently a comparative study for UV mercially available boron doped one side polished p type Si
detection property has been studied between the p-Si/n- (100) substrates with 380 μm thickness and a resistivity of
TiO2 heterojunction photodiodes grown by electron beam 1–10 Ω cm using PLD technique. All the substrates were
evaporation and sol–gel methods [8]. Niobium (Nb) doped cleaned in an ultrasonic bath in a solution of 1:1 mixture of
­TiO 2, with low electrical resistivity (~10 −4 Ω cm) and acetone and methanol. Sintered solid T ­ iO2 target was used
high optical transparency of more than 80% in the visible to deposit T­ iO2 thin film. ­TiO2 thin film was prepared from
region, was also found to be a suitable candidate for UV high purity (99.98%) T ­ iO2 powder (procured from Sigma-
detection [9]. Another advantage of heterojunctions is the Aldrich). Initially the powder was grinded for 1 h with
selective blocking of either hole (by valence band bar- the addition of five drops of 5 wt% polyvinyl alcohol (in
rier) or electrons (by conduction band barrier) [2]. There de-ionized water) and then again grinded for 3 h to obtain
are also several reports on heterostructures between two fine grains. ­TiO2 powder was then cold pressed with the
oxide semiconductors [10–12] and between doped oxide hydraulic press under the load of 20 tonnes to get solid disc
semiconductors and Si [9]. shaped (diameter 20 mm, thickness 6 mm) pellet. Following
Another way to enhance the efficiency of Si solar cell is pelletization, the target was sintered at 1200 °C in air for 5 h
the deposition of an antireflection
� coating material
� with and was ready to use as the solid target for PLD. Prior to
intermediate refractive index n n = nair nSi in between deposition, the chamber was initially evacuated to the base
√
pressure of 5 × 10−6 Torr and then oxygen gas was injected
refractive indices of Si (n Si = 3.939 at 600 nm) and air
with the flow rate at 1.5 SCCM (standard cubic centimeter
(nair = 1). The thickness of the antireflection coating for a
per minute) to attain the ambient partial oxygen gas pres-
particular wavelength should be λ/4n [13]. Having an aver-
sure of 20 mTorr. Third harmonic of a Nd:YAG laser was
age refractive index 1.98–2.5 in the region 600–1200 nm
used at 355 nm wavelength for ablation of T ­ iO2 target with
depending upon annealing temperatures, T ­ iO2 is a natural
repetition rate of 10 Hz and pulse width of 8 ns. All the films
choice as the antireflection coating material on Si. Double
were grown at room temperature following post deposition
layer coating of two different materials with two refractive
annealing at 400 °C for 2 h under vacuum. The substrate
indices can also be deposited to further reduce the reflectiv-
to target distance was kept constant at 3.5 cm for all the
ity of the solar cell over a broad range [14].
depositions. Thickness of the films were gradually increased
Though the variation of ­TiO2 thickness deposited on Si
with the increment of the number of laser pulses. Five ­TiO2
improves the antireflection property for photovoltaic applica-
thin-films were deposited on Si substrate with 1500, 2000,
tions, it may hinder the electrical properties due to several
3000, 5000 and 7000 pulses and denoted as S1, S2, S3, S4
other factors like interfacial defects, grain boundaries etc.
and S5, respectively.
So, it is important to simultaneously study the electrical and
Crystal structures of all the ­TiO2 samples were charac-
optical properties with the variation of thickness of ­TiO2 thin
terized using X-ray diffraction in Bragg–Brentano mode
film deposited on Si substrates, particularly for photovoltaic
(Bruker AXS, Model: D8 Advance). Surface morphol-
applications. ­TiO2 can serve the purpose of antireflection
ogy of the ­TiO2 thin film was studied using atomic force
coating as well as form the heterojunction with p type Si
microscopy (AFM) (NT-MDT, Model: NTEGRA, Prima).
for photovoltaic applications. T ­ iO2 will also act as the UV
The reflectance of the ­TiO2 thin films was measured using
absorber, with Si being the absorber of visible and infrared
V-650 UV–VIS spectrophotometer, JASCO. The thickness
light.
and refractive index measurements were carried out using
In this paper we have studied the optical and electrical
spectroscopic ellipsometer (J. A. Woollam Co., Model:
properties of ­TiO2 thin films of various thicknesses depos-
M-2000) in the range 350 nm to 1200 nm. Silver (Ag) metal
ited on p type Si substrates using pulsed laser deposition
contact was fabricated on the entire posterior of the p type
(PLD) technique. Photoresponse of the samples have been
Si substrate using thermal evaporation of high purity Ag
studied using laser and lamp sources at different wavelengths
wire. Following the deposition of ­TiO2 thin film, several alu-
from UV to visible region. Our results show that our samples
minium (Al) contacts each of 0.5 mm radius were formed on
can act as UV–visible photodetectors and solar cells. We
the top surface of the thin film using a metallic mask. Thick-
try to correlate the electrical, optical, structural and mor-
nesses of Ag and top Al contact were 150 nm each. The
phological properties of pulsed laser deposited ­TiO2 thin
schematic diagram of the device structure is shown in Fig. 1.
films with the photoresponse performance. We believe these
Electrical measurements of n-TiO2/p-Si heterostructure were
results would pave the way to fabricate n-TiO2/p-Si based
carried out under dark and illuminated condition with simu-
photovoltaic devices in future.
lated solar light, UV lamp and diode laser pointers at 405 nm

13

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J Mater Sci: Mater Electron (2017) 28:18075–18084 18077

are attributed to the planes (101), (004), (112), (200), (204),

(116) and (220), respectively. These planes belong to the
Al (150 nm) anatase phase of T ­ iO2. Other phases of T ­ iO2, rutile and
brookite were not found. Lattice spacing, dhkl, was calcu-
lated using Bragg’s equation [15]: dhkl = nλ/2sinθ, where h,
n-TiO
TiO2 (39-201nm)
k and l are the Miller indices of the corresponding planes, n
is the order of diffraction, λ is the wavelength of the X-ray
p-Si source CuKα (λ = 0.154 nm) and θ is the Bragg diffracted
angle. Anatase phase of ­TiO2 has tetragonal lattice structure,
in which, lattice spacing, dhkl, is connected to the lattice con-
stants by the equation [6]:
Ag (150 nm)
1 h2 + k 2 l2
Fig. 1  Schematic diagram of the n-TiO2/p-Si heterostructure with Al 2
=
a 2
+ 2,
c (1)
dhkl
and Ag as top and bottom electrode, respectively
where, a and c are the lattice constants of tetragonal unit
cell. Crystallite sizes of the thin films have been calculated
-0.15
using Debye–Sherrer’s equation [16–18]: l = 0.9λ/βcosθ,
-0.20
here β is the full width at the half maxima of the diffraction
Strain (%)

-0.25
peak. Crystallite size of the thin films increases from 35.4 to
C-Si

-0.30
40 nm with the increment of deposited ­TiO2 film thickness
(101)

-0.35
50 100 150 200
Thickness (nm) from 39 to 201 nm. It concludes that with the increment of
film thickness small crystallites coalesce with each other to
(004)
(112)

(200)
Intensity (a.u.)

(204)

(116)
(220)

20 30 40 50
2θ (degree)
Fig. 2  XRD spectra of T
­ iO2 thin films of various thicknesses depos-
ited on p-Si substrate. Variation of strain with T ­ iO2 thickness is
shown in the inset
(blue), 532 nm (green) and 670 nm (red), respectively, using
Keithley measurement unit Model No: 4200-SCS. External
quantum efficiency (EQE) was measured using SpeQuest
quantum efficiency measurement system.
3 Results and discussion
X-ray diffraction (XRD) pattern of ­TiO2 thin films depos-
ited with the increase of number of laser pulses on p type
Si substrates is shown in Fig. 2. XRD peaks are assigned in
comparison with the reference code: 01-086-1157 in X’Pert
HighScore software. The obtained Bragg diffracted peaks at
2θ angles ~25.3°, 37.8°, 38.6°, 48°, 62.7°, 68.8° and 70.3°
form a bigger cluster. The strain (ε) in the T ­ iO2 films has
S5, 201 nm
been calculated using the relation [15, 19]: ε = (ds − d0)/d0,
S4, 140 nm where, ds is the inter-planar spacing derived from the (101)
peak position and d0 is the corresponding inter-planar spac-
S3, 87 nm ing for the stress free material (0.3514 nm). The change in
the strain with the thickness is shown in the inset of Fig. 2
S2, 55 nm
and reveals that the stress in ­TiO2 thin films has been relaxed
S1, 39 nm with the increase of thickness.
Figure 3 shows the optical reflectance spectra of all the
60 70 80 ­TiO2 thin films deposited on p type Si substrates in the wave-
length range 350 to 800 nm. Due to the constructive and
destructive interference of light after multiple reflections
between the interfaces of ­TiO2/Si and ­TiO2/air, crests and
valleys have been observed in the reflection spectra. As a
consequence of the increase of thickness of the T ­ iO2 film,
the optical path length also increases causing the genera-
tion of larger number of crests and valleys in the reflection
spectra. Thinner film of T­ iO2 causes weak reflection of light
in broader range. So, optimization of thickness is required to
minimize the reflection in the particular wavelength range.
We have achieved a minimum reflection of 3.2% at 450 nm
and below 10% in the range of 400–800 nm for the 39 nm
thick ­TiO2 thin film.
Spectroscopic Ellipsometer was used to measure the real
(n) and imaginary refractive index (k) of the ­TiO2 thin film.
Variable Angle Spectroscopic Ellipsometer directly meas-
ures two ellipsometric angles ψ and Δ. Tangent of ψ is the
ratio of the amplitudes of reflected s and p polarized light
from the sample. Δ is the difference in phase change of the
reflected s and p polarized light. Now from ψ and Δ one

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18078 J Mater Sci: Mater Electron (2017) 28:18075–18084

70
S1, 39 nm 3.25 0.125 Surface morphology of the PLD deposited T ­ iO2 thin films
have been characterized using AFM and those results are

Extinction Coefficient (k)

S2, 55 nm
S1 0.100
S3, 87 nm

Refractive Index (n)

3.00 S2
60 S4, 140 nm S3 0.075 presented in Fig. 4 for different thicknesses of ­TiO2 thin
S5, 201 nm S4
2.75 S5
0.050 films. The AFM images were taken with the low dimen-
50
2.50 0.025
sion as 1 × 1 μm2 area and with low z scale at 10 nm, which
Reflectance (%)

2.25
40
400
30
20
10
0 from the electrical measurements in the subsequent text.
400 500
Wavelength (nm)
Fig. 3  Reflectance of ­TiO2 thin films for different thicknesses. Inset
shows the real and imaginary part of the refractive index for different
­TiO2 thicknesses
can measure n, k and the thickness of the film by modeling
accuracy. So, accuracy in measurement depends not only
on the instrument, but also on the model. To model the thin
film, we have used a native oxide layer of thickness 2.88 nm
on p type Si substrate. Since T
­ iO2 is optically transparent in
the wavelength range 400–1200 nm, we have used Cauchy’s
layer to initially guess the thickness of the film. Then we
have replaced the Cauchy layer with the double Lorentz
oscillator model to calculate the thickness, n (real refrac-
tive index) and k (imaginary refractive index) of the T ­ iO2
thin film. The values of parameters of the double Lorentz
oscillator model have been presented in Table 1. Thickness
of the sample deposited with 7000 pulses was verified with
the cross sectional FESEM image. Thicknesses of the other
samples obtained from the ellipsometric study are also con-
sistent with the number of laser pulses. Variation of n and k
with wavelength is shown in the inset of Fig. 3. Our results
show that the values of n and k are almost independent of
thickness of the ­TiO2 layer.
0.000
depicts that the surface of the T­ iO2 films are uniform and
600 800 1000
Wavelength (nm)
1200 smooth with dense nanostructure. It can be seen from Fig. 4
that roughness of the films increases with the increase in
thickness. root mean square (RMS) roughness of the films
was calculated and found to be below 1.55 nm. Smooth sur-
face plays a crucial role for charge transport. As the rough-
ness of the film increases with the increment of the thick-
ness, it hinders the charge transport as has been confirmed
600 700 800 As ­TiO2 is an undoped wide band gap semiconductor,
we expect that its resistivity should be very high. Thus,
resistivity measurements of ­TiO2 thin film with two probes
would not provide much error. Figure 5 shows the measure-
ment of sheet resistance of ­TiO2 thin films on Si for various
thicknesses. It shows that the resistivity of the film increases
almost linearly with the increase in thickness of ­TiO2 thin
film.
Ohmic contact is very important for the characterization
of a p–n junction device. It is well known that metal contact
with semiconductor forms Schottky barrier. If the potential
barrier height, Фb, is small, then the charge carriers would
travel through the barrier and are collected by the metal elec-
trode. For Ohmic contact, I–V curve shows a linear behavior.
In the present case Ag forms an Ohmic contact with p-Si,
so also Al with n-TiO2. This has been confirmed, as shown
in the inset of Fig. 5.
The current density–voltage (J–V) characteristic curves
of n-TiO2/p-Si heterojunction diode in the −5 to +5 V bias
range are shown in Fig. 6 under dark and illuminated con-
ditions with UV lamp, lasers (405, 532 and 670 nm) and
simulated sun light AMU 1.5G. Under dark condition, the
J–V characteristic curve shows rectification behavior as the
curve is asymmetrical and non-linear. The maximum diode
current density under forward bias condition is found to be
~0.2 A/cm2 at +5 V for the sample S2 which has 55 nm

Table 1  Determined lattice constants, average crystallite size, RMS roughness and ellipsometer fitting parameters including film thickness
Sample XRD AFM Ellipsometer: fitting parameters
a(Å) c(Å) Crystallite RMS Thickness (nm) εinf Amp1 Br1 En1 Amp2 Br2 En2 MSE
size (nm) roughness
(nm)

S1 3.7713 9.5126 35.41 0.504 39 1.64 0.504 0.2265 3.539 72.834 0.0201 3.807 1.38
S2 3.7729 9.4307 37.02 1.226 55 2.993 0.255 0.1764 3.519 11.829 0.0771 3.785 1.40
S3 3.7744 9.4768 35.88 1.528 87 2.126 0.357 0.2114 3.502 24.215 0.0468 3.768 2.85
S4 3.7796 9.4225 38.78 1.259 140 2.744 0.338 0.153 3.493 7.998 0.1032 3.739 2.84
S5 3.7804 9.4363 40.72 1.402 201 2.827 0.399 0.1354 3.485 7.930 0.1216 3.762 4.43

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J Mater Sci: Mater Electron (2017) 28:18075–18084 18079

Fig. 4  3D view of AFM micrographs (1 × 1 μm2) of T ­ iO2 thin films deposited on p-Si. a, b, c, d and e are the 3D surface view of the T
­ iO2 thin
films having thickness 39, 55, 87, 140 and 201 nm, respectively

thick ­TiO2 layer. With the increase of the thickness of ­TiO2
thin film to 201 nm, the maximum forward current density
gradually decreases to ~24 mA/cm2 at +5 V. This is due to
the increment of sheet resistance of ­TiO2 thin film with its
thickness. Rectification ratio (RR) of the J–V curve under
different ±bias conditions is shown in the inset of Fig. 6a–d
for different thicknesses of T­ iO2 thin films, respectively. Het-
erojunction n-TiO2/p-Si diodes exhibit excellent rectification
behavior with rectification ratio Jforward/Jreverse = 35 × 103 for
55 nm thick T ­ iO2 film at ±5 V. This rectification ratio also
drastically goes down with the increment of thickness to
201 nm probably due to the increase of sheet resistance.
Increase of sheet resistance of T
­ iO2 thin film means conse-
quent decrease of charge carriers leading to the reduction in
the rectification ratio.
J–V characteristics curves of heterojunction diodes are
characterized to analyze the carrier transport mechanism.
According to the modified Shockley equation, the cur-
rent–voltage (I–V) characteristic curve of a heterojunction
diode can expressed as [20, 21]:

13

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18080 J Mater Sci: Mater Electron (2017) 28:18075–18084

where, I0 is the reverse saturation current, Rs is the series

10 resistance and Rsh is the shunt resistance. Here, β = q/nkBT,
where q is the electronic charge, n is the ideality factor, kB
is the Boltzmann constant and T is the absolute temperature
8
Sheet resistance (MΩ/sq.)

in Kelvin. The reverse saturation current I0 is extracted from

the slope of the straight line of the semilog plot of the I–V
0.30 0.6
6 characteristic curve at zero bias condition. Reverse satura-
Si/Ag

Current (mA)
0.15 TiO2/Al 0.3 tion current I0 can be expressed as [6, 22]:

Current (μA)
( )
4 0.00 0.0 −q𝜑B
(3)
∗ 2
I0 = AA T exp ,
- 0.15 - 0.3 kB T
2 - 0.30 - 0.6 where, A is the contact area of the rectifier, A* is the effec-
-2 -1 0 1 2
Voltage (V)
tive Richardson constant which is 32 A/cm2 K2 for p type Si
50 100 150 200 [6], and φB is the apparent barrier height at zero bias condi-
Thickness (nm)
tion and it can be expressed as:
( ∗ 2)
Fig. 5  Variation of sheet resistance with thickness of T
­ iO2 thin films. k T AA T
𝜑B = B ln . (4)
Inset shows the ohmic nature of the Si/Ag and ­TiO2/Al contact q I0

( ) The ideality factor n is calculated from the equation [23]:

V − IRs
(2)
{ ( [ )} ] ( )
I = I0 exp 𝛽 V − IRs − 1 + , q dV
Rsh n= . (5)
kB T d(ln I)

Fig. 6  a, b, c and d represents 1 1

the current density–voltage (a) (b)
(J–V) characteristics of p-Si/n- 1E-1 1E-1
TiO2 heterojunction diode S2,
Current density (A/cm2 )

Current density (A/cm2 )

S3, S4 and S5 respectively hav- 1E-2 Dark Dark

1E-2
ing ­TiO2 thickness 55, 87, 140 UV
1.5 AMU
UV
1.5 AMU
and 201 nm respectively in dark 1E-3 405 nm 405 nm
and under the illumination with 532 nm 1E-3 532 nm
670 nm 670 nm
UV, 1.5 AMU solar simulator, 1E-4 40 8

blue, green and red laser light. 32 1E-4 6

RR (×103 )
RR (×103 )

The response of the rectifica- 1E-5 24

4
16
tion ratio (RR) with the applied 8 1E-5 2
respective ±bias voltage under 1E-6
0 0
0 1 2 3 4 5 0 1 2 3 4 5
dark condition is shown in the Respective ±Voltage (V) Respective ± Voltage (V)
1E-7 1E-6
inset, respectively -5.0 -2.5 0.0 2.5 5.0
-5.0 -2.5 0.0 2.5 5.0
Voltage (V) Voltage (V)

1E-1 1E-1
(c) (d)
1E-2
1E-2
Current density (A/cm2 )

Current density (A/cm2 )

1E-3
1E-3
1E-4

1E-4 1.0 1E-5 0.60

0.8 Dark 0.45
RR (×103 )
RR (×103 )

UV
Dark
0.6 1E-6 1.5 AMU 3.00
UV 0.4
1E-5 1.5 AMU 0.2
405 nm
0.15
532 nm
405 nm 1E-7 670 nm
0 0
532 nm 0 1 2 3 4 5 0 1 2 3 4 5
Respective ± Voltage Respective ± Voltage (V)
670 nm
1E-6 1E-8
-5.0 -2.5 0.0 2.5 5.0 -5.0 -2.5 0.0 2.5 5.0
Voltage (V) Voltage (V)

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J Mater Sci: Mater Electron (2017) 28:18075–18084 18081

The experimental values of n and φB are tabulated in
Table 2. It can be clearly seen in this Table that the ideal-
ity factor n has been considerably deviated from unity. It is
observed that with the increment of thickness of ­TiO2, the
ideality factor increases up to a thickness value of 140 nm
and then decreases. The deviation of the value of n from
ideal value infers the presence of surface states at the junc-
tion of the heterostructure n-TiO2/p-Si. There is also the pos-
sibility of oxide layer on top of p type Si which affects the
ideality factor. Rs and Rsh play a crucial role for deviation of
ideality factor from unity. Rs and Rsh at the interface defect
states in between T ­ iO2 and Si provide the forward leakage
path to the minority carriers and grain boundaries are the
source of defects in case of polycrystalline samples.
The differential resistance of the cells can be written
using Eq. (2) as:
dV 1
R0 = = Rs + { }.
(6)
dI [ ( )] 1
𝛽I0 exp 𝛽 V − IRs + Rsh
in Fig. 7. As under zero bias condition dark current is very
small compared to photocurrent, the contrast ratio reaches
its maximum value under zero bias condition. Under for-
ward bias condition, as bias voltage exceeds the open circuit
voltage (Voc) value of about 0.3 V, contrast ratio approaches
unity because of decrease of photocurrent.
The relative responsivity (R) of the device is defined as
the ratio of the photogenerated current (Iph) to the incident
power of light (Pinc). It can be expressed as [4]:
Iph Iillu − Idark
R= = , (8)
Pinc Pinc
where, Idark is the dark current and Iillu is the photogenerated
current under illumination with light. Responsivity versus
thickness of ­TiO2 curve as shown in Fig. 8 reveals the fact
that increase of thickness drastically reduces the responsivity
up to thickness 140 nm and then slowly to 201 nm. The rea-
son behind the decrement of responsivity is the deterioration
of both antireflection property as well as the increment of

At high voltages under forward bias, Eq. (6) simplifies to

1 10
R0 ≅ Rs + . (7)
𝛽I
UV
8 1.5 AMU
Hence, in the high voltage range, Rs can be extracted out 405 nm
from the plot of R0 versus 1/I. The current flowing through 532 nm
Contrast ratio ( ×103 )

670 nm
Rsh becomes important in the low voltage region. In this 6
voltage region Eq. (6) reduces to R0 = Rs + Rsh. Usually, in
the low voltage range, Rs ≪ Rsh. Hence, R0 approaches Rsh
4
under low bias condition. The obtained values of Rs and Rsh
are tabulated in Table 2.
Photoresponse characteristic curve of the n-TiO2/p-Si 2
heterostructure is studied under the illumination with UV
lamp, laser light (405, 532 and 670 nm) and simulated solar
0
light. Results for different thicknesses of T­ iO2 thin films -5.0 -2.5 0.0 2.5 5.0
have been shown in Fig. 6. In case of 55 nm thick ­TiO2 film Voltage (V)
under illumination with red light, maximum reverse current
increases up to a factor 7.45 × 102 times. The contrast ratio, Fig. 7  Variation of contrast ratio of n-TiO2/p-Si heterojunction diode
which is defined as the ratio of currents under illumination for ­TiO2 thickness 55 nm as a function of bias voltage under the illu-
to dark current, for 55 nm thick T ­ iO2 sample is presented mination with UV, 1.5 AMU solar simulator, blue, green and red
laser light

Table 2  Determined parameters of the diodes from I–V characteristic curve under dark and the solar cells parameters under illumination with
1.5 AMU solar simulated light
Sample Under dark condition Solar cell
Barrier n Rs (kΩ) Rsh (MΩ) Jsc (mA) Voc (V) Jmax (mA) Vmax (V) FF Efficiency (%)
height (eV)

S2 0.69 3.73 0.71 0.17 2.930 0.301 1.670 0.168 0.318 0.280
S3 0.67 5.74 1.2 0.15 1.840 0.252 1.007 0.130 0.283 0.130
S4 0.65 8.57 1.33 0.19 0.646 0.135 0.343 0.070 0.276 0.024
S5 0.64 5.09 1.52 0.21 0.299 0.104 0.169 0.050 0.270 0.008

13

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18082 J Mater Sci: Mater Electron (2017) 28:18075–18084

0.15 Voltage (mV)

UV 0.16
UV 0 50 100 150 200 250 300
1.5 AMU 1.5 AMU 0.0
405 nm 405 nm
0.12 532 nm

Responsivity (A/W)
532 nm 670 nm
0.12 -0.5
670 nm
0.08
-1.0
Responsivity (A/W)

Current density (mA/cm2)

0.09 0.04
-1.5
Voltage (mV)
0.00 0 50 100 150 200 250 300
-5 -4 -3 -2 -1 0 0
0.06 -2.0
Voltage (V) -50

Power (μW)
-100
-2.5 -150
S2, 55 nm
0.03 S3, 87 nm -200

-3.0 S4, 140 nm -250

S5, 201 nm -300

0.00
40 80 120 160 200 Fig. 9  The fourth quadrant I–V characteristics curve of the n-TiO2/p-
Thickness (nm) Si solar cells for different T
­ iO2 film thicknesses under illumination
(AMU 1.5G). Inset show the output power of the solar cells

Fig. 8  Responsivity graph of the n-TiO2/p-Si heterojunction diode

with variation of ­TiO2 thickness under the illumination with UV, 1.5
AMU solar simulator, blue, green and red laser light. Inset shows the
voltage dependent variation of responsivity under illumination with
the respective light sources for ­TiO2 thickness 55 nm
series and sheet resistance with the increase of thickness, as
discussed in the previous sections. Variation of responsivity
with respect to different reverse bias voltages for 55 nm thick
­TiO2 sample is shown in the inset of Fig. 8. The responsiv-
ity of n-TiO2/p-Si heterostructure increases almost monoto-
nously from very low value of ~0.04 A/W under UV light
illumination at zero bias to almost 0.14 A/W at −5 V. In the
0 to −2 V range, responsivity increases almost quadrati-
cally, and in the later range slope of the R(V) curve, gradu-
ally decreases to reach saturation region. Responsivity of
the heterojunction is maximum for UV light due to strong
absorption of high energy photons by T ­ iO2 below its band
gap and then gradually decreases in chronological order for
simulated solar light, blue, green and red light. It can be
seen from the inset of Fig. 3, value of k and so also the
absorption coefficient α (=4π k/λ, where λ is the wavelength
of light) is almost zero in the range 400–1200 nm. Below
400 nm the absorption coefficient for ­TiO2 increases drasti-
cally. The responsivity value ~0.14 A/W at −5 V is compa-
rable to those of commercially available UV detectors which
are in the range 0.1–0.2 A/W [24]. In addition to the high
responsivity of photodiode in the UV range, absorption of
photons in the visible and infrared range by Si can also con-
tribute to the generation of photocurrent. This is the reason
for the observation of photogenerated current under illu-
mination with different colors of light like blue, green and
red. It was previously reported that ­TiO2 based photodiode
shows higher order of responsivity ~1–3 A/W in the UV
region. However, Si based p–n junction photodiode or p–i–n
photodiode have the responsivity in the range ~0.5–0.6 A/W.
Generally, Si based photodiode shows poor responsivity for
higher energy photons because of their shallow penetration
depth in Si. But in the visible and infrared region, respon-
sivity of Si photodiode increases considerably. In our case,
higher value of responsivity with simulated solar light is
mainly due to the absorption of photons by ­TiO2 in the UV
range 300–400 nm exceeding its band gap. To explore the
possibility of fabrication of solar cell using n-TiO2/p-Si, we
have studied the J–V curve under illumination with simu-
lated solar light in the fourth quadrant as shown in Fig. 9 to
calculate the solar cell efficiency (n) from the equation [25]:
J V
Pout J V
n= = M M = FF SC OC , (9)
Pin Pin Pin
where, Pout, Pin, VOC, JSC, FF, JM and VM are the maximum
power in the load, input power, open circuit voltage, short
circuit current, fill factor, current at the maximum output
power and voltage at the maximum output power, respec-
tively. Values of these parameters with different thicknesses
have been tabulated in Table 2. It can be seen from the table
that both the fill factor and efficiency of solar cell decrease
significantly with the increment of T­ iO2 thickness of the het-
erojunction. The reason behind this is the same as the incre-
ment of series resistance, sheet resistance and deterioration
of optical reflectance. Now, it is important to study the EQE
together with the absorption spectra or optical density of
the photo-active materials with respect to the wavelength of
the incident light [26–29]. The EQE of the best sample (S2)
has been plotted together with the absorbance of T ­ iO2, Si
and n-TiO2 (55 nm)/p-Si heterostructure is shown in Fig. 10.
It shows that the device has maximum optical absorbance
~90% in the wavelength region >500 nm. Here, it is to be
noted that the major part of the emission energy of the solar
spectrum is in the range 400–700 nm. From Fig. 10, it is

13

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J Mater Sci: Mater Electron (2017) 28:18075–18084 18083

25 100 holes from n-TiO2 to p-Si. But due to low potential energy
barrier, electrons will move easily from p-Si to n-TiO2. So,
80 electrons would have the major contribution for photogen-
20 erated current.
Adsorption of oxygen molecules on the surface of T ­ iO2

Absorbance (%)
EQE 60
EQE (%)

Si/TiO2 (55 nm) thin film leads to the adsorption sites by trapping electrons
15
TiO2 from the conduction band of T ­ iO2. Under illumination pho-
Pristine Si 40
togenerated electron–hole pairs are created in n-TiO2/p-Si
10 heterojunction. Holes from the photogenerated electron–hole
20 pairs would be trapped by oxygen ions and unpaired elec-
trons will flow under the influence of built-in and applied
5 0 electric field. Desorption of surface ions by trapping of holes
400 500 600 700 800
Wavelength (nm) will reduce the thickness of the depletion region.
Under illumination with any kind of light photodiodes
Fig. 10  EQE spectrum of the sample S2 together with the absorb- operate in photoconductive mode where as solar cells in
ance of the device and the photo-active materials photovoltaic mode. In the photoconductive mode photodi-
odes are generally operated under reverse biased condition
with an applied voltage. In case of a solar cell, it operates
observed that the absorbance of Si in 450–800 nm wave- under unbiased condition. Under illumination in case of
length range is very high while T­ iO2 has almost zero absorb- both the devices, initially electron–hole pairs are generated
ance in this region. Hence, increment of EQE of sample S2 mainly in the depletion region. In case of solar cells, these
with heterostructure n-TiO2/p-Si in the region 450–800 nm photogenerated electron–hole pairs are then separated solely
should be attributed to Si. by the in-built electric field, whereas, in case of photodi-
The energy band diagram of n-TiO2/p-Si heterostructure ode, in addition to in-built electric field an external volt-
is constructed in accordance with Anderson’s model [6, 30] age is applied under reverse biased condition to drift the
under equilibrium at zero bias in dark and under illumina- electron and hole pairs with high speed. For photodiodes,
tion with light as shown in Fig. 11a and b, respectively. beside responsivity and sensitivity, response time or speed
In this band
( diagram, band gap values of n-TiO2 Eg,TiO2 is also another important parameter. In the present ­TiO2/
( )

and p-Si Eg,Si are taken as 3.20 and 1.12 eV, respec- Si heterostructure system, T ­ iO2 is a wide band gap semi-
)

tively. Electron affinities are taken as χ(TiO2) = 4.10 eV
[30] and χ(Si) = 4.05 eV [8], respectively. Conduction
band offset (ΔE c) and valence band offset (ΔEv) can
be calculated as ΔE c = χ(TiO 2) − χ(Si) = 0.05 eV and
ΔEv = Eg,TiO2 − Eg,Si + ΔEc = 2.13 eV, respectively. It shows
that the valence band offset is much higher than the conduc-
tion band offset. Therefore, it would be difficult to inject
conductor with band gap ~3.2 eV which corresponds to
~380 nm. It can also be seen from the reflection spectrum
(Fig. 3) as well as from the extinction coefficient (in the inset
of Fig. 3) that it strongly absorbs light below the band gap
(hν > 3.2 eV), i.e., 380 nm. Hence, photocurrent generated
in the UV region of solar spectrum <400 nm is from the
contribution of the absorption of UV light by ­TiO2. This

Fig. 11  Schematic energy-band (a) n-TiO2 p-Si

(b) n-TiO2 Electric field p-Si
diagram of n-TiO2/p-Si hetero-
junction diode under a dark and Φo Evac Evac
Φo
b illumination of light using Evac Evac
Anderson’s model. Here, ­Evac is
χ (Si) χ (Si)
the vacuum level, E­ c is the bot-
electron drift
tom of the conduction band, ­Ev χ (TiO2) χ (TiO2)
is the top of the valance band, Ec Ec
­EF is the Fermi level, ­Eg is the
ΔEc=0.05eV Eg,Si ΔEc=0.05eV Eg,Si
band gap and χ is the electron Ec Ec
EF EF
affinity Ev Ev
Eg,TiO2 Eg,TiO2
hν

ΔEv=2.13eV
ΔEv=2.13eV
Ev Ev

hole drift

13

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18084
result can also be correlated with the fact that under reverse
bias condition, depletion region is expected to be extended
in the full region of n-TiO2 (thickness 55–201 nm) which is
much less than the absorption length of UV photons. But
the major portion of the solar spectrum lies in the visible or
near infrared region with photon energies, hν, greater than
the band gap of Si but less than the band gap of T ­ iO2. There-
fore, under solar illumination of light, UV portion of light
would be absorbed by ­TiO2, and visible, near infrared part
by Si, thereby creating electron hole pairs contributing to the
generation of photocurrent under reverse biased condition.
As the strong electric field is created in the depletion region,
the photogenerated electron–hole pairs created in this region
would be separated by the built in electric field as well as
the applied electric field under reverse bias. Due to the band
structure of Si and T ­ iO2 electrons move from Si towards
­TiO2 and are collected by Al electrode, where as holes move
towards Si and get collected by Ag electrode. Electrons gen-
erated outside the depletion region would diffuse towards the
depletion region and then be drifted away by the in-built and
applied electric field. So, the photocurrent density depends
on several factors like the average number of photogenerated
electron–hole pair, their average drift velocities and their
diffusion lengths such that they can easily reach the in-built
electric field region to be separated away.
4 Conclusion
In conclusion, we have deposited T ­ iO2 thin films of different
thicknesses on p type Si substrates using PLD technique. All
the films show good crystallinity attributing to the anatase
phase of T­ iO2. An effort has been made to correlate the elec-
trical properties of the thin films along with optical prop-
erties like reflection. Study of the I–V characteristic curve
under illumination with solar simulated light, UV light and
laser lights of wavelengths 405, 532 and 670 nm reveals that
the responsivity of the photodiode as well as the efficiency
of solar photovoltaic cell improves significantly with the
decrease of thickness of T ­ iO2. This may be attributed to the
increase of series and sheet resistance of the n-TiO2/p-Si het-
erostructure and deterioration of antireflection property due
to the increment in the thickness of the deposited ­TiO2 film.
Further research is required before n-TiO2/p-Si heterostruc-
ture can replace Si based solar cells as the ideal candidates.
Acknowledgements The authors would like to thank Vamsi K.
Komarala from Indian Institute of Technology Delhi (IIT Delhi), India,
for providing EQE measurement Facility at IIT Delhi. A. Dewasi would
also like to acknowledge IIT Roorkee and Ministry of Human Resource
Development (MHRD), Government of India, for providing research
assistantship.
13
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J Mater Sci: Mater Electron (2017) 28:18075–18084
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