Project -1

Title
FABRICATION AND CHARACTERISATION OF p-type
porous Si/ ZnO HETEROJUNCTION SOLAR CELL
Introduction:
Solar energy is a very large inexhaustible source of energy. Sunlight is an
abundant energy resource freely available to everyone as the amount of
solar energy reaching the surface of the earth is 1.7 x 105 TW and a
practical terrestrial global solar potential value is estimated to be about
600 TW, which is many thousands of times larger than the present
consumption rate of earth from all commercial energy resources. Thus in
principle, solar energy could supply all the present and future energy
needs of the world on a continuing basis. It is the most promising
unconventional energy source and is economical and environmentally
clean.
The spectrum of the solar light that reaches the earth is influenced by
absorption of radiation in the earth’s atmosphere and therefore by the
path length of the photons through the atmosphere. Fig. 1.1.

Figure 1.1: Solar irradiance

Solar cells are elements that convert solar energy into electrical energy
Has been attracting attention as the most promising new and renewable

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energy technology. High price competitiveness due to high price
compared to other energy sources Next-generation solar cells need to be
developed. Since discovery of the first solar cell in mid-nineteenth century,
several individuals including Albert Einstein (Stark-Einstein Law) and
groups have contributed to understanding the underlying mechanism of
light induced carrier generation/excitation. The first practical solar cell was
demonstrated by Bell Laboratories in 1954 using a diffused Si p-n junction
having efficiency around 6% [1]. The table 1.1 shows the efficiencies of
different types of research-cells [2].

Table 1.1 best research solar cell efficiencies [2]

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Solar cell theory :
Basics of solar cells Solar cells are semiconductor devices that convert
sunlight into direct current electricity. Si-solar cells typically comprise of a
thin wafer consisting of an ultra-thin layer of phosphorus-doped (n-type)
silicon on top of a thicker layer of boron-doped (p-type) silicon. An
electrical field is created near the top surface of the cell where these two
materials are in contact, called the p-n junction. The p side contains holes
as majority charge carriers, while n side contains electrons as majority
charge carriers. In the region near the junction an electric field is formed.
The electrons and holes, which are generated through light absorption in
the bulk of Si, diffuse to this junction, where they are directed by the
electric field towards the respective electrodes (as shown in Fig. 1.2). The
amount of current or power generated from a solar cell along with some
other characteristics are presented in next sections.[3]

Figure 1.2: A schematic depiction of p-n junction Si solar cell.

Basically, photovoltaic conversion occurs through three separate
processes;
1. The absorption of light to create electron-hole pair in the appropriate
semiconductor.
2. Collection and separation of these carriers by internal field.
3. Distribution to an external load.
To obtain higher output voltage, individual solar cells are frequently
cascaded in series and / or parallel combinations.
The most basic parameters of solar cells are the power conversion
efficiency (PCE) usually measured under simulated AM1.5 G (1 Sun)

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standard conditions, and the spectral dependent external quantum
efficiency (EQE), which is also called as incident photon to current
collected efficiency (IPCE).
The current density-voltage measurements of solar cells are usually
performed under illumination of intensity 100 mW/cm2 . A typical I-V curve
is shown in Fig. 1.3.

Solar cell parameters :

1- Short-circuit current (Isc): The short-circuit current is the cell
photocurrent measured at zero voltage. In general, it is presented in
the form of the short circuit current density (Jsc) defined as the ratio
of the short circuit photocurrent to the active cell area.
2- Open-circuit voltage (Voc): The open-circuit voltage (Voc) is the cell
voltage measured when current within the cell is equal to zero.
Maximum open circuit voltage is limited to difference in Fermi levels
on p and n sides and may only be obtained at very high incident
radiation intensity.
3- Fill Factor (FF): The fill factor (FF) is defined as the ratio of the
maximum power output (Pmax) to the product of short circuit
photocurrent and open circuit voltage, which is defined as:

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where Imax and Vmax represent the current and voltage corresponding
to the maximal power point, respectively.
4- Power conversion efficiency: The energy conversion efficiency is
defined as the ratio of Pmax to the incident radiation power (Pin)
illuminated on the solar cell surface.

As η is a function of Isc, Voc and FF, improvement of the solar cell

performance is achieved by optimization of all the three parameters. η is
also dependent on the incident irradiation power Pin, a white light intensity
of 5, 20 mW/cm2 was used in some of solar cell measurements.
5- Incident photon to current conversion efficiency: The IPCE is
measured by illuminating the solar cell with monochromatic light
with the power Pin and recording the short circuit current Isc at
different wavelengths λ. Thus, the IPCE can be calculated as
follows:

The equivalent circuit diagram (ECD) of a solar cell can be drawn as

shown in Fig.1.4.

Figure 1.4: Equivalent circuit diagram of a solar cell.

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 In the 1980s, the photovoltaic conversion efficiency reached 20%
due to the rapid development of monocrystalline silicon solar cell
manufacturing technology, as the solar power was introduced in earnest
for electric power in the face of energy crisis such as oil shock in the late
1970s. In the ultra-high-efficiency structure using the silicon substrate, the
efficiency is 25.6% [4]. In addition to solar cell using silicon, a structure
capable of implementing solar cells in a thin film form on a glass substrate,
a metal substrate or a plastic substrate has been introduced, and a variety
of solar absorbing layers such as CuInGaSe2 (CIGS), CdTe, organic, dye-
Materials have been developed.
In recent years, this structure has been introduced to maximize the use of
the solar spectrum, achieving an efficiency of more than 40.6%. The
results of the study were published [5].

The p-n junction solar cell using single crystal Si has recently shown a
light efficiency exceeding about 20%, but it has a disadvantage that it is
expensive because a complicated structure is required to constitute such
a high efficiency solar cell. Therefore, solar cells with a structure of
semiconductor-insulator-semiconductor (SIS) or metal-insulator-
semiconductor MIS) solar cells as a low-cost solar cell which can lower
the price even if the light efficiency is a little lower, In this SIS solar cell,
the efficiency of the ITO / n-Si solar cell is about 15%, which is expected
to be practically used.
The advantages of hetero p-n junction solar cell are the liberty to choose
material, layer thickness, dopant concentrations, inherent surface
passivation, and low temperature approach [6,7]. The most standard type
of heterojunction solar cell uses hydrogenated amorphous silicon (a-Si:H)
to create a-Si:H(n,p)/c-Si(p,n) structure. The fundamental challenge in this
and other heterojunction solar cells is to avoid recombination due to
interface states which is mostly addressed by inserting a buffer layer. The
key to the success of heterojunction solar cells lies in separation of highly
recombination-active contacts from the crystalline semiconductor surface
by the insertion of a passivating semiconductor film with a wider bandgap
[8]. For heterojunction solar cell, a-Si:H is an ideal candidate as a buffer
layer because its bandgap is wider than that of c-Si and it can be n- or p-

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doped relatively easily enabling the fabrication of electronic heterojunction
for solar cell.

Compound semiconductor and their alloys are of considerable interest in

the field of electronic and optoelectrical device. ZnO film is receiving
increased attention for various microelectronic applications. It has
potential uses in photo detectors, solar cells and light emitting diodes [9].
ZnO is a II-VI compound semiconductor with a wide direct band of 3.3 ev
(at room temperature) and has a hexagonal quartzite structure with cell
parameters of a = 0.325 nm, c = 0.5206 nm [10]. Zinc oxide has emerged
as one of the most important window materials due to its large bandgap
and used in photovoltaic especially in large area solar cells[11]. The high
production cost of the conventional solar cells require the search for
cheaper methods suitable for solar energy conversion. ZnO thin film have
been prepared by wide variety of techniques such as sputtering,
evaporation, chemical vapor deposition (CVD) and spray pyrolsis [12].

In this study design solar cell structure to achieve the Reduction of

optical losses in crystalline silicon solar cells which is the one of the most
important issues of silicon photovoltaics. Nano p-type Porous Si layers as
a textured Si substrates with ZnO layer as a n type semiconductor will
investigated with the aim of improving the optical losses of the solar cells
because an anti-reflection coating (ARC) and a surface passivation can
be obtained simultaneously in one process.
The porous Si layers were formed by electrochemical etching in HF
solutions. After that, the properties of porous Si in terms of morphology,
structure and reflectance are summarized. The structure of porous Si
layers will investigated with FESEM. The formation of the stocks a
nanoporous Si layer /ZnO will lower the reflectance for the wavelength
region from 500 to 900 nm. Another study for surface modification allows
the Si solar cell characteristics to be improved will use the CO2 laser light
for annealing which give more quality of the ZnO layer and give more
improvement for solar cell efficiency.

Problem statement
Statement of the problem The p-n junction solar cell studied by many
researchers. The initial studies showed good conversion efficiency and
fill factor (FF). To improve the conversion efficiency of this
heterojunction structure ZnO as n-type semiconductor materials and p-
type porous silicon as the absorber and p-type layer, It is a good idea
to study the growing parameters of the ZnO using chemical bath and
annealing the structure by Laser and conventional furnace and

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 compare the result for both methods. The solar cell when exposed to
different annealing conditions, this will contribute immensely both as
fundamental work as well as technological point of view.

Research objectives
The objectives of this research
1- Nano P-type porous silicon fabrication using electrochemical
etching method.
2- Nano-porous structure optimization by using different
parameters such as etching current and time.
3- Investigation the structural, optical and electrical properties of
the of the p-type porous silicon.
4- Study the ZnO growing films using chemical bath deposition on
porous silicon substrate.
5- Study the quality of the structure after annealing by CO2 Laser
in different watts and normal annealing using furnace in
different temperatures and compare the results.
6- Solar cell fabrication and testing before improvement and after.
.

Scope of research
It have been recently proved that the performance of the solar cell can be
enhanced by developing new semiconductor absorber, counter
electrodes and electro-hole transporters which should offer new
opportunities. A surface treatment is also important to be a powerful
parameter to provide a reduction in the recombination and to control band
alignment. By using laser treatment some characteristic of the quality of
the film have shown the ability to reduce the recombination, and give
better conversion.

Significant of research
The significant of this research give alternative easy way to improve the
solar cell efficiency by using laser technology to improve the performance
of any kind of semiconductor that using for solar cell device. This will
contribute immensely both as fundamental work as well as technological
point of view.

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Materials and methods
Essentially a solar cell consists of a p-n junction of the same material
(homo-junction) or two different materials (hetero-junction). The p-type
material is the absorber of the incident solar radiation and the n-type
material serves as a window to provide the junction field. The output
voltage of the photovoltaic cell is decided by the band gap of the p -type
material.
In our research methodology will divided to two parts:
1- P-type Porous silicon formation methodology :
Materials for the porous silicon fabrication:
P-type silicon (1 0 0) – Pt wire -HF and Ethanol -Teflon cavity – DC
power supply 30V-3A.

Nano-Porous Silicon Fabrication

The electrochemically etched area for all samples has been of (1cm2 ).The

porous silicon was etched in (ethanol /HF) mixture (1/1). Ethanol will add

to the (HF) solution in order to improve the wettability of the acid and to

allow for the F ions diffusion into pores [13]. The sample has been

mounted in cavity from Teflon cell .The electrical circuit was completed by

putting platinum electrode as a cathode in parallel way to achieve the

homogeneous (P-type Si) layers. The Si wafer acts as the anode and the

platinum is the cathode. The value of the utilized current density for (EC)

etching process has been of (0.5-10 mA/cm2 ). Digital multi meter will

contacted with silicon and the other side with power supply. The

methodology flowchart shown in figure 1.5.

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Figure 1.5 flowchart of p-type nano-porous fabrication process

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 2- Synthesis ZnO nanorods on p-type porous silicon substrate
using CBD method
Material using for chemical bath deposition :

1- Zinc nitrate hexahydrate [Zn(NO3)2·6H2O]

2- hexamethylenetetramine (C6H12N4)

3- DI Water

Chemical bath methodology

For chemical bath method firstly we should deposited ZnO seed

layer on the prepared p-type porous silicon substrates, a radio-

frequency magnetron sputtering system was used with ZnO

target 99.999% purity. The sputtering power and argon pressure

were fixed at 150 W and 15 mTorr, respectively. A 150 nm ZnO

seed layer deposited on the PS substrates.

An aqueous

solution of hexamethylenetetramine (C6H12N4)and zinc

nitrate hexahydrate [Zn(NO3)2·6H2O] will prepared for growing

the ZnO nanorods by CBD. About 0.050 M/L of C6H12N4 and an

equal molar concentration of Zn(NO3)2·6H2O were separately

dissolved in DI water. The two solutions were combined in a

beaker, and the prepared substrate was vertically immersed in

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the aqueous solution. To study the influence of growth duration,

the beaker will placed in an oven for various durations (4, 6, 10,

and 20 h) at 95 °C to grow ZnO nanorods. After nanorods ZnO

growing the Samples will be expose to annealing using furnace

(300, 400, and 500 0C) for 4 hours and Another group of samples

treated by CW CO2 Laser (10, 20, and 30 watt) for 30 sec. The

chemical bath deposition process shown in figure 1.6.

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Figure 1.5 flowchart of ZnO nanorods chemical bath deposition process

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 Time line/gantt chart
Task JA FA MA AP MA JU JU AU SE OC NO DE
N B R R Y N L G P T V C
Literature review
Silicon
preparation
And cavity deign
and fabrication
Porous silicon
experiment,
changing current
and time
Samples
characterization
and optimization
Optimized
samples focus
on optimum
current and time
Chemical bath
process, RF for
seed layer , CBD
different time
and
concentrations
Nanrods ZnO
Characterization
s
Annealing the
samples using
furnace and
Laser
Characterization
after annealing
Optimum
samples using
for solar cell
fabrication by
electrodes
deposition
Testing the solar
cell and analysis
the results
Thesis writing

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