2016 13th International Conference on Electrical Engineering, Computing Science and Automatic Control (CCE), Mexico, City. Mexico.
September 26-30, 2016.
Study Of Optoelectronics Properties Of Indium Tin
Oxide Films Fabricated By Sputtering In Oxygen
Atmosphere.
S. Vazquez1, A. Olivares1, I.Cosme*1,2, S. Mansurova1, A.Kosarev1, A. Itzmoyotl.
Instituto Nacional de Astrofsica, ptica y Electrnica1
Consejo Nacional de Ciencia y Tecnologa (CONACyT)-INAOE2
Puebla, Mxico, C.P. 72840
ismaelcb@inaoep.mx
Abstract Indium tin oxide (ITO) thin films were deposited
by magnetron sputtering with different oxygen flows rates
(%O2 = 1 % to 0 %). The films were deposited by RF
discharge in argon/oxygen atmosphere with a RF power W
= 150 W at substrate temperature T = 175 C and pressure P
= 6 mTorrs. Photoelectric parameters of fabricated ITO
films were characterized by four-point probe method and
transmittance measurements. It was found that reducing
oxygen concentration the sheet resistance decreases. For
samples fabricated in oxygen atmosphere the transmittance
reached values above 90 %. However, the sample with post-
deposition thermal treatment at T = 300 C in oxygen
atmosphere shows the best transmittance (95 %) and lowest
value of sheet resistance (Rs= 27 ohms-square). Finally, the
transparent conducting oxides were applied in hybrid
organic-inorganic photovoltaic structures. The best power
conversion efficiency in AM-1 sunlight = 2.13 % was
obtained for a structure with ITO fabricated at oxygen
concentration %O2 = 0.25 % in comparison with an
efficiency = 1.87 % obtained for a structure fabricated
with commercial ITO.
KeywordsTCO, ITO, sputtering.
I. INTRODUCTION
Transparent conducting oxide (TCO) thin films (such as
zinc oxide, tin oxide, indium tin oxide, cadmium oxide and
cadmium tin oxide, etc.) are widely used for a number of
important applications, such as transparent electrodes in
liquid crystal displays (LCD), organic light emitting diodes
(OLED), solar cells, plasma display panels, transparent heat
reflecting windows as well as surface heaters for cameras,
lenses, mirrors, car windows, gas sensors and ohmic
contacts for surface-emitting diodes [110]. Among the
TCO thin films, indium oxide doped with tin (ITO) is one of
the most attractive due to its unique electrical and optical
properties such as: good conductivity (about 104 1cm1)
and high transmittance ( 85%) in the visible region due to
its large bandgap of about 3.70 eV. As-grown ITO thin films
are usually highly degenerate n-type semiconductors due to
their large number of oxygen vacancies as well as
substitutional Sn dopants [1113]. It is well known, that
various fabrication conditions effects on properties of ITO-
based TCO such as: carrier concentration, crystallinity,
impurity levels and surface roughness of the grown films, as
a consequence producing different photoelectric
characteristics (resistivity and transparency).
A variety of the techniques, such as electron beam
evaporation [14], ion beam assisted deposition [15], pulsed
laser ablation [16, 17], ion implantation [18], and dc/RF
magnetron sputtering (DCMS/RFMS) [1921], are used for
the growth of ITO thin films. In the majority of reports, O2
is used as a reactive gas during growth and/or post-growth
annealing to decrease the resistivity of the films [11, 19, 22].
The aim of this work is to study of RFMS deposition
process and electronic properties of ITO films for obtaining
ITO films with low resistivity and high transmittance (with
the characteristics comparable with the commercially
produced substrates) within the visible spectrum range for
photovoltaic applications.
II. EXPERIMENTAL METHODS
A. Fabrication process
1) ITO films deposition: ITO films were deposited in
a magnetron sputtering system (ATC Orion Sputtering
System of AJA International Inc.). The deposition process is
accomplished by an RF discharge with a power W = 150 W,
at a temperature T = 175 C and pressure P = 6 mTorrs. Five
different samples have been fabricated, in each process
variations of oxygen concentration took place (the
specifications are showed in Table I). In the process called
V (Thermal 0), after deposition the sample was kept inside
the deposition chamber for thermal treatment at 300C in
oxygen atmosphere. The ITO films were deposited on top of
glass substrates (0.55 mm Corning Eagle XG) provided by
Precision Glass & Optics.
2) Hybryd photovoltaic p-i-n strucure fabrication:
Photovoltaic structures (Fig. 1) were fabricated on top of
glass substrates coated with ITO. The ITO films were etched
by hydrochloric acid to define the bottom electrode and
cleaned in ultrasound bath with acetone and isopropyl
alcohol, sequentially. Next, PEDOT:PSS blend mixtures
978-1-5090-3511-3/16/$31.00 2016 IEEE
were prepared from components purchased from "Ossila III. RESULTS AND DISCUSIONS
Ltd.".
A. Sheet resistance and optical transmittance
TABLE I. FABRICATION PARAMETERS In Fig. 2 the dependence of the ITO films sheet resistance as
Fabrication parameters a function of oxygen concentration is shown. It can be
Flow observed that when oxygen concentration is increased the
Sample
ID (sccm) Time
%O2 Thermal treatment
sheet resistance also increases. In the case of the sample
Ar+ (min) which undergoes the thermal treatment (Thermal 0) the
Ar
O2
resistance is the lowest obtained.
V(1.00) 9 1 25 1.00 -----
V(0.52) 9 0.5 25 0.52 -----
V(0.25) 19 0.5 25 0.25 -----
V(0) 9 ---- 25 0 -----
V(T0) 9 ------ 1 hour, 300C, 1sccsm,
25 0
1.5mTorrs

Prior to deposition, PEDOT:PSS mixture (1:6 weight ratio)

was filtered with a PVDF filter with pore sizes of 0.45 m. Fig.1 Cross sectional view of hybrid solar cell with ITO front electrode.
The PEDOT:PSS films with thickness of 45 nm were
obtained by spin coating at rotation speed of 2500 rpm in N2
ambient. The inorganic layers were deposited using a cluster
multi chamber PECVD system from "MVSystem Inc." with 4
10
RF discharge at frequency f = 13.56 MHz. The intrinsic Si:H

Resistance (ohm/square)
layer of 220 nm thickness was deposited from an 10%SiH4 +
90%H2 gas mixture at pressure P = 550 mTorr. The 20 nm
thick n-layers were deposited using 0.01%PH3 + 9.9%SiH4 + 3
10
90.09% H2 gas mixtures at pressure P = 550 mTorr. The
deposition temperature was fixed at Td = 160 C and power
at W = 3 Watt. The deposition of the top contacts was
performed by deposition of Ag electrod through a metal 2
shadow mask with an area of 0.09 cm2. The sequence of 10
deposition layers follows the structures showed in Fig. 1. Thermal 0 sample
B. Caracterization methods
0.0 0.2 0.4 0.6 0.8 1.0
Photoelectric parameters of fabricated ITO films were Oxygen concentration (%)
characterized by the following methods:
Fig.2 RS vs. O2 concentration for ITO films.
1) Four-point probe method: Sheet resistance Rs was
mesured using Keithley's Series 2400 Source Measure Unit
1.0
(SMU). A constant current IRS=45.32*10-6A passed through
outer probe and voltage VRS was measured though inner
probes. To obtain the sheet resistance the following 0.9
expression RS=(4.532*VRS)/IRS was used.
2) Transmittance measurements: An experimental setup 0.8
Transmittance

with a Triax320 monochromator, a Keithley 6517A

electrometer, a photodiode and a halogen lamp (in a
0.7
wavelengths range from 200 to 1230 nm) was used for the
transmission measurements. V(1.00%)
3) I(V) measurements: The current-voltage I(V) 0.6 V(0.52%)
characteristics of the photovoltaic devices were measured V(0.25%)
under constant with intensity Io = 100 mW/cm2 illumination V(0%)
0.5
V(Thermal 0%)
using a solar simulator Oriel 2A from Newport Corp
and electrometer Keithley 6517A.
0.4
200 400 600 800 1000 1200
Wavelength (nm)

Fig.3 Optical transmission spectra for ITO films.


As to the film transmittance, it can be observed in Fig. 3 that
despite the reduction of oxygen concentration from 1% to
0.25%, the transmittance does not vary significantly (keeps
about 90%). In the sample fabricated without oxygen,
transmittance is reduced about 20%. However, for the
sample without oxygen, but with thermal annealing the
transmission reaches 95 %. The summary of the
photoelectric characteristics of fabricated films are
presented in the Table II.
TABLE II. RESULTS
Results
Sample Average
Resistance
ID transmittance
(/)
(400-700nm)
V(1.00) 19K 0.90
V(0.52) 6.4K 0.91
V(0.25) 1.1K 0.90
V(0) 130 0.77
V(Thermal 0)
27.4 0.95
First, let us discuss possible impact of oxygen on ITOs
resistivity. The conductivity mechanism of the ITO films
has been attributed in literature to both substitutional tin and
oxygen vacancies [23]. These vacancies can be created
either during film growth or post-deposition annealing [26].
There are mainly two mechanisms by which oxygen content
may impact the conductivity: causing effect either on the
carriers mobility or on their concentration. It was reported
earlier [24] that increasing oxygen concentration would
result in an accumulation of excess oxygen, mainly at the
grain boundaries acting as trapping centers for free carriers.
This means, that the barrier scattering becomes the
dominant process since the barrier height increases strongly.
At the same time the density of free carriers is reduced as
they are partly localized at the trapping sites [25]. This
results in a decrease in the carrier mobility, and therefore a
corresponding fall in the film conductivity is observed. On
the other hand, Buchanan et al [26] have suggested that the
decrease in the conductivity in increased O2 partial pressure
is primarily due to a reduction in the carrier concentration
caused by the occupation of oxygen vacancies rather than
due to tin doping. A rapid increase in the ITO resistivity has
been consistently observed by Kellet et al [27, 28], they
have related this observation to ITO's wide oxygen
stoichiometry and its degeneracy (resulting in high
conductivity) when oxygen content is reduced.
Note, that our experimental results, namely the observed
increase on resistivity with growing oxygen concentration,
are consistent with the data presented in literature [23-25].
However, in order to distinguish, which of these two
mechanisms of conductivity decrease (diminishing mobility
and drop on carrier concentration) take place in our samples,
additional experimental study that involves measurements of
Hall mobility and carriers concentration should be
performed.
The underlying mechanisms which determine the effect of
oxygen on optical properties are complex and mainly
involve changes on electronic band structure (through e.g.
appearance of the additional bands [29, 30] and/or
variations on the dopants levels occupations, and, as a
consequence, variations of free carrier concentration) or
changes on materials structural properties or morphology.
With regard to the dependency of the transmission of ITO
films on the O2 concentration, there are contradictory
reports on literature. Fan et al [31] observed that the ITO
film transmittance increased rapidly with increasing oxygen
partial pressure exceeding 80% at a partial pressure of O2
0.003, then saturating around 90% for further increase. In
addition to increasing the transmission of the films, there is
also a shift of the intrinsic absorption edge to longer
wavelengths (i.e. lower photon energies) due to an increase
in O2. Study of RF sputtered ITO films by Ohhata et al
relates this phenomenon to a change in the carrier
concentration [30]. On the other hand, recent studies show
the opposite tendency: blue shift (larger optical gap) and
decreased transmittance with the increasing oxygen
concentration. Note that some opposite tendencies are also
observed in our experimental results: 1) there is blue shift of
the absorption edge when oxygen is incorporated in
fabrication process, however 2) when oxygen is
incorporated during post deposition annealing, there is red
shift of the absorption edge. On the other side, there is non-
monotonic increase on the optical transmission with the
oxygen concentration: transmittance is sharply increased
when incorporating oxygen, and then it is practically
independent on O2 content. Further studies are needed in
order to explain these results and to clarify the underlying
physics.
B. Performance of hybrid solar cells.
ITO films V(0.25) and V(thermal 0) as well as a
commercially available ITO called sample C1 (0.55mm
Eagle XG of Precision Glass & Optics with ITO coating),
were used to fabricate hybrid (organic-inorganic)
photovoltaic p-i-n structure. Fig. 4 shows the current-
voltage I(V) characteristics of these structures. One can see,
that device which uses commercial ITO films shows the
highest short circuit current JSC = 10.41 mA/cm2, while for
the p-i-n structure with the ITO films V(0.25) and V(thermal
0) the short circuit current density JSC values are rather
similar: JSC = 8.95 mA/cm2 and JSC = 8.15 mA/cm2
respectively. However the structure with ITO film V(0.25)
shows the highest open circuit voltage VOC = 0.645V and fill
factor FF = 0.37, and as a consequence the highest overall
power conversion efficiency (2.3 %). Table III presents the
summary of photovoltaic characteristics for the fabricated p-
i-n structures.
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