J. Chem. Eng. Chem. Res.

Journal of
Vol. 1, No. 3, 2014, pp. 179-184 Chemical Engineering
Received: June 5, 2014; Published: September 25, 2014 and Chemistry Research

Effect of -diketonates Aluminum Films on Solar Cells

Parameters

Khrypko Sergii and Kidalov Valery

Sciences Institute Nanotechnologies, Berdyansk State Pedagogical University, Berdyansk 71100, Ukraine

Corresponding author: Khrypko Sergii ([email protected])

Abstract: The experimental results of a research of the solar cells parameters covered with InxSnyOz and InxAlyOz films, obtained by
dispersion of alcoholic solutions of three-chloride Indium and acetyl acetonate of aluminum were represented. The spectral
dependencies of reflection factor and open circuit voltage with the different film covered solar cells were obtained. The conditions
for the production of porous silicon and thin metal oxide films were obtained. The properties of anti reflective coatings were
represented. It has been shown influence of combination many layers covering films consisting of porous silicon and metal oxide on
the parameters solar cells. It has been shown that the use of such coating increases the efficiency of solar cells to 15.8%.

Key words: Silicon, anodization, porous, films, β-diketonates.

1. Introduction The width of a forbidden zone of these materials

was about 3.0-3.65 eV. Therefore, these materials are
The silicon is one of the base semiconductors of transparent for a greater part of a solar radiation.
modern semiconductor solar power engineering. One Their factor of refraction is in limits of 1.6-2.1 and
of perspective directions of researches connected with they can be used together with many semiconductors.
a raise of effectiveness of transformation solar energy Anti reflecting cover can reduce factor of a reflection
in an electrical energy, is the development of the for given wave length almost up to zero. For deriving
photoelectric converters on structures of the zero reflection in the interval of wave lengths
semiconductor-insulator-semiconductor (SIS) [1, 2]. solar radiation, may be use multilayer anti reflecting
Such solar cells differ by high effectiveness of cover.
photoelectric transformation, simplicity of a Except the materials listed above, a film of porous
construction and process engineering, small power silicon, that have an index of refraction of the order
consumption. However, here there is a series, of the 1.95 ± 0.05, can be used as anti reflecting cover.
physical and engineering tasks, solution which will be Obtained by vacuum evaporation of SiO coatings
successful and in many respects will depend of the use coincide reflection efficiency, with a coating of porous
of the researched solar cells in semiconductor silicon. Coating of Porous Silicon reduces optical
engineering. losses in the silicon from 37% to 8%. Due to a high
With the purpose raise the requirements on of porosity of cover it is necessary to expect
efficiency and the of maximum diminution of losses magnification of a current of a short-circuit, open
on a reflection in the field of spectral sensitivity of the circuit voltage and efficiency of the photoelectric
solar element with use films SnO2, In2O3, InxSnyOz, converters. Application Β-diketonates of aluminum
ZnO etc. [3-7] films in conjunction with porous silicon will reduce
180 Effect of -diketonates Aluminum Films on Solar Cells Parameters

the reflection of solar radiation and increase the 500-1500 Ǻ.

parameters of solar cells. The solar cells were produced by sequential
The purpose of work is the research of a structure covering of a porous silicon film and film InxSnyOz on
and electro-physical performances of film covers for a surface of silicon specimens. The contacts were
different conditions of their manufacture and influence created by vacuum evaporation of In-Cu-Cr film. The
of these performances to basic parameters of the radiation power on a surface was 100 mWt/cm2, and
photoelectric converters. active area of the solar element was 8.82 cm2.
The surface resistance of InxSnyOz films, their
2. Experimental spectral dependencies, and influence of film
parameters on current-voltage plot of the solar cells
The research were fulfilled on slices of the silicon
were investigated.
which has been brought up on a Czochralski method
To reduce magnitude of oxide metal cover surface
[8], p-type conductivity, boron doped with a resistivity
resistance one can use β-diketonates, for example
of 0.5 Ohm·cm and n+-type conductivity, antimony
acetil acetonate of aluminium Al(AA)3. Al(AA)3 was
doped with a resistivity of 0.01 Ohm·cm. The porous
obtained from a solution of AlCl3·6H2O, is rectified
silicon films were created by anode handling of a front
by zone method and had such crystal and chemical
face of silicon HF-electrolyte. The density of an anode
characteristics: coordination of an metal ion –
current varied from 1.0 to 30 mA/cm2. The time of
octahedron; space group – P21/c; syngony –
anode handling did not exceed 10 minutes. Intensity
monocline; parameters of a lattice – a = 14.16Ǻ, b =
of illumination for anode handling of n-type
7.48Ǻ, c=16.43Ǻ, β = 98°. The InxAlyOz films were
conductivity specimens was made 20 mWt/cm2 [8-11].
obtained by thermal decomposition on the heated
For security of uniform of an anodization on reverse
surface of silicon (up to 470 °C) substrate in inert gas
side or silicon specimens were evaporated films of
stream with adding of an oxidizer.
aluminum (98% Al + 2% Si), which then were
annealed at the temperature of 575 °C. The 3. Result and Discussion
micro-contour of a porous silicon film surface was
3.1 Properties of Porous Silicon Films
investigated with optical and electronic microscopy.
The thickness of porous silicon films was determined The dependencies of a thickness of porous silicon
by an oblique grind method. The density of porous films from time of anode handling in 15% a solution
silicon was calculated: HF for slices n+-type are represented on Fig. 1. This
ρporous = ρSi – ΔP /S • hporous (1) figure shows that the thickness of a porous silicon film
3
where ρSi = 2.33 gramme/cm -density of will increase linearly with magnification of the anode
mono-crystalline silicon; ΔP-alteration of a sample handling process duration. The plot slope is increased
weight after anode handling (gramme); S-surface area with growth of a density of the anode current. Also the
of a silicon slice subjected to anode handling (cm2); growth rate of porous silicon films will increase
hporous-thickness of a porous silicon film (cm). linearly in indicated interval and makes for plot 1-4.3
The InxSnyOz films were formed on a front face of nm/s, plot 2-4.2 nm/s, plot 3-19.0 nm/s, plot 4-21.6
silicon specimens by pulverization of nm/s.
InCl3:SnCl4(5H2O): H2O:CH3CH2OH alcoholic Fig. 2 shows the dependencies of a thickness of the
solution in a weight relation 34:1:150:150. The porous silicon films obtained on samples of silicon of
temperature of specimens was 430 °C. The thickness a p-type with a resistivity 0.5 Ohm·cm from times of
of covers depends on time of covering and was anode handling in the concentrated HF (49%). For
 Effect of -diketonates Aluminum Films on Solar Cells Parameters 181

anode handling of n- and p- type silicon differs due to

difference in concentration of mobile positive charge
carriers.
As in acceptor, doped silicon holes are the basic
charge carriers and their concentration in a considered
case is sufficient for a reaction:
Si + 2HF + 2e+ → SiF + H2 ↑
running, so the basic influence on the anodization
Fig. 1 Dependence of thickness of a film porous silicon
from time of anodic processing in 15% a solution fluoride renders the mechanism of F ions delivery. In donor,
of an acid and density of an anodic current (mA/cm2). doped silicon the holes concentration is small;
Specific resistance samples of a n+-type-0.01 Ohm·cm. therefore, the exterior stimulating factor is necessary
for anodization running.
Fig. 3 shows the experimental dependencies of a
volumetric density of porous silicon obtained by
handling n+- specimens in 15% HF solution, from a
density of anode current.
The figure shows that the increasing of thickness of
a porous silicon film causes describing of material
density, which characterizes the structure of the
Fig. 2 Dependence of thickness of a film porous silicon material: Thus, there is possibility to operate by
from time of anodic processing in 49% a solution fluoride structure of porous silicon with changing conditions of
of an acid and density of an anodic current (mA/cm2). anode handling.
Specific resistance samples of a p-type-0.5 Ohm·cm.
The study of porous silicon structure shows, that the
these conditions of handling the growth rate of a magnification of a current density causes the
porous silicon film makes for plot 1-2.2 nm/s, plot increasing of the amorphous phase part in material.
2-10.8 nm/s, plot 3-15.0 nm/s, plot 4-18.3 nm/s, plot The REM establishes analysis of a surface with
5-21.4 nm/s. various volumetric densities, that there are reflexes,
The linearity of a dependence of a porous silicon which correspond to crystallographic planes for
film thickness from time of an anodization testifies the samples with curves one, two and tree on Fig. 3.
constant growth rate of a film with constant density of However, on the REM data there are no Kikuchi
anode current. lines that generally appear for monocrystalline silicon.
The observed magnification of growth rate is A dependence of a volumetric density of p-type
connected with increasing of a density of anode porous silicon from thickness of layer and the
current with magnification of the dissolved silicon densities of anode current are represented on Fig. 4.
amount in accordance with magnification of an The figure shows, that in a researched range of current
amount of solution ions that participates in a current. densities and thicknesses the volumetric density vanes
The process of formation of porous silicon is unsignificantly, that testifies to homogeneity of the
determined mainly by two factors: by delivery of F process of dissolution of silicon. The pores diameter
ions in reaction zone with formation of SiF2 and for investigated samples was 40-210Ǻ, and number of
presence of a positive sign charge carriers, in surface pores  4·108-8·109 cm2. The size of pores will
layer of the silicon anode. Therefore, a process of increase with magnification of a current density, time
182 Effect of -diketonates Aluminum Films on Solar Cells Parameters

of anode handling and thickness of a porous silicon 3.2 Properties of films InxSnyOz , InxAlyOz
film.
Fig. 6 shows the dependence of the turn InxSnyOz
The number of pores is maximum for pores with
surface resistance from percentage SnCl4(5H2O) in a
40-80Ǻ diameter. The further magnification of a
solution. The least magnitude of a surface resistance
diameter of pores happens not only due to dissolution
has the samples with an In2O3 film. Increasing of a
of silicon on the pores walls, but also at the expense of
SnCl4(5H2O) content causes the rise of surface
secondary effect of join small-sized, close located
resistance from 20 up to 600 Ohm/cm2. It may be
pores (Fig. 5).
explained, apparently, by substituting of In atoms by
small amounts of tin, that representing itself as the
donors. However, with SnCl4(5H2O) content
increasing the content of SnO2 phase in InxSnyOz film
structure grows, that reduces the charge carriers
concentration and material conductivity.
The surface resistance of a InxAlyOz film decreases
and makes 7-10 Ohm/cm2 (Fig. 6, curve 2).
On the surface of silicon, substrate for normal
Fig. 3 Dependence of volumetric density of porous conditions of an environment the film atmospheric
n+-type silicon from density of anode current for different SiOx grows. Strictly speaking, in this case on the
thickness of films (mkm):1-1.0; 2-2.0; 3-4.0; 4-6.0; 5-8.0.
surface of silicon the structure InxSnyOz/SiOx/Si is
created.
Preoxidizing handling included growth of oxide by
a thickness 5000Ǻ (T=900 °C in a damp atmosphere).
Then that oxide was etching and the silicon slices
were washed in a boiling solution
(H2O2:NH4OH:H2O=1:1:4) and deionic water with
consequent drying. After daily endurance in air, the
thickness of natural oxide was 14Ǻ, and after
Fig. 4. Dependence of volumetric density of porous p-type endurance within 4 day  43Ǻ. The structures
silicon from density of anode current for different thickness InxSnyOz/SiOx after daily endurance in air had a
of films (mkm): 1-1.0; 2-2.0; 3-4.0; 4-6.0; 5-8.0. surface resistance of 65 Ohm/cm2, and after endurance

Fig. 6 Dependence of InxSnyOz films surface resistance

from SnCl4(5H2O) contents in solution (1) and InxAlyOz
films surface resistance from Al(AA)3 contents in gas phase
Fig. 5 Morphology porous p-type silicon. (2).
 Effect of -diketonates Aluminum Films on Solar Cells Parameters 183

during 4 day-140 Ohm/cm2. Annealing of structures in These data show, that optimum pairs for silicon of
air at the temperature of 200 °C within 10 minutes p-type are In2O3, InxSnyOz, ZnO, CdO. For silicon of
reduced the surface resistance from 65 Ohm/cm2 till n-type optimum cover forming a barrier is SnO2.
75-80 Ohm/cm2 and from 140 Ohm/cm2 up to 170 The spectral characteristics of photoelectric
Ohm/cm2. The annealing time about 20 minutes converters with structures InxSnyOz/SiOx/nSi,
promoted further growth of a surface resistance. InxSnyOz/SiOx/porousSi/nSi, InxAlyO/SiOx/porousSi/
Cyclical annealing of InxSnyOz/Si structure in nSi arc submitted on Fig. 7.
hydrogen and argon at the temperature of 550 °C The best spectral performances have
promoted a drop of InxSnyOz film surface resistance InxSnyOz/SiOx/porousSi/nSi, InxAlyO/SiOx/porousSi/
from 20 Ohm/cm2 up to 7-8 Ohm/cm2, and film nSi structures. In addition, the curve (2) shifts more in
InxAlyOz  from 10 Ohm/cm2 up to 3-4 Ohm/cm2. long wavelength area of a spectrum, and curve (3)-in
During the annealing there is the restoring of oxide short wave.
and release of metal atoms, therefore the surface
resistance decreases.

3.3 Performances of the Photoelectric Converters

It must be matched such condition for high

effectiveness of the photo-electric converters with
semiconductor-dielectric-semiconductor structures:
the width of a forbidden zone (Eg) of cover, that
Fig. 7 The spectral characteristics of photoelectric
forms a potential barrier, should be ≥ 3.0 eV and this converters with structure: 1-InxSnyOz/SiOx/nSi;
semiconductor should be degenerate. In case of a base 2-InxSnyOz/SiOx/porousSi/nSi; 3-InxAlyO/SiOx/porousSi/nSi.
semiconductor of p-type, work function (A) of
semiconductor cover, forming a barrier, and value
electron affility of a base semiconductor (χs) should
satisfy to a relation A < (χs). In case of a base
semiconductor of n-type the validity of a relation A >
χs + Eg is necessary. The mismatch of lattice constants
should be minimum. In a Table 1 some data on a
relation between A, χs and Eg for some semiconductor
covers forming on silicon a potential barrier are Fig. 8 Current-voltage characteristics of photoelectric
converters with structure: 1-InxSnyOz/SiOx/nSi;
represented.
2-InxSnyOz/SiOx/porousSi/nSi; 3-InxAlyO/SiOx/porousSi/nSi;
Table 1 Parameters of semiconductors forming potential 4-InxSnyOz/SiOx/porousSi/pSi.
barrier with silicon.
Table 2 The characteristics of photoelectric converters.
Parameters
Semiconductor Eg χs A- χs χs+Eg-A Characteristics
A (eV) Structure
(eV) (eV) (eV) (eV) Jsc, mA/cm2 Uoc, mV FF η, %
Si 1.12 - 4.05 - - InxSnyOz/SiOx/porousSi/
41 550 0.74 15.8
In2O3 3.00 4.30-4.45 - 0.25-0.40 0.85-0.70 pSi
SnO2 3.50 4.60-4.90 - 0.55-0.85 0.55-0.25 InxSnyOz/SiOx/nSi 37 510 0.57 12.5
InxSnyOz/SiOx/porousSi/
InxSnyOz 3.65 4.10-4.60 - 0.05-0.55 1.05-0.55 38 530 0.61 14.3
nSi
ZnO 3.20 4.20-4.57 - 0.15-0.52 0.95-0.58 InxAlyO/SiOx/porousSi/
CdO 2.70 4.47 - 0.42 0.68 40 515 0.63 14.6
nSi
184 Effect of -diketonates Aluminum Films on Solar Cells Parameters

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