Fabrication technologies and processes for Solar

Cells: Etching
Juan Esteban Villegas Delgado*
Department of Microsystems Engineering, Masdar Institute of Science and Technology, P.O. Box 24224,
Masdar City, Abu Dhabi, UAE
*
jvillegasdelgado@masdar.ac.ae

Abstract: Etching is the technique used for the removal of material in

micro processing. It has many different techniques that vary in
complexity, from simple surface scratching to complex focused ion
beam (FIB) material removal. This report discusses some of the etching
techniques employed in the manufacturing processes of solar cells,
through our experimental application on the fabrication of the PIN aSi
solar cell.
©2017, Masdar Institute of Science and Technology

References and links

1 Verhagen, E., Deleglise, S., Weis, S., Schliesser, A., and Kippenberg, T.J.: ‘Quantum-coherent coupling
of a mechanical oscillator to an optical cavity mode’, Nature, 2012, 482, (7383), pp. 63-67
2 http://www.as.utexas.edu/astronomy/research/people/jaffe/micro_si_diff.html, accessed 20th march 2017
3 Huang, C.J., Su, Y.K., and Wu, S.L.: ‘The effect of solvent on the etching of ITO electrode’, Materials
Chemistry and Physics, 2004, 84, (1), pp. 146-150

1. Introduction
After the deposition and patterning of the layer of photoresist, we have an organic mask
that protects specific areas of our solar cell. This mask allows us to selectively etched away
specific regions in the wafer. Such mask are most commonly made with organic
photoresists, but they could as well be made of metals or dielectrics (hardmasks).
The first parameter to consider for to the design of the etch process is the selectivity.
We need to ensure to etch only those materials that we want, and specially avoid the
unintentional removal of the mask. To some extent we will always etch away all materials
in our substrate, each one at different ratios in every process, therefore such rates are to be
considered during the previous steps.
During this fabrication step, the PIN aSi solar cell is to be separated into different
individual cells. The array of cells desired will grant us the possibility to study different
design characteristics in the cell, including area effects and different configurations of
fingers and busbars in the electrode. Two different etching steps are necessary for the
removal of the indium tin oxide (ITO) layer and the underplayed Silicon, hereinunder we
will discuss the processes used for each.

2. Wet etching

2.1. Overview
Wet etching refers to the process in which material is removed through the chemical
reaction between the substrate and precursors in liquid form. It is the most common form
of etching thanks to its low cost and the low requirement of complex systems for its
implementation. This comes with the backdrop that process variables are harder to control,
and in general the process is more keen to change as its relation with its surroundings
change. A characteristic feature of wet etched materials is the isotropy of the process; as
the reaction takes places in all directions, the process is specifically suited for fabrication
of complex microstructures such as cantilevers or suspended donut resonators (Figure 1
a). Additionally, the different reactivity of crystalline materials per their orientation allows
the anisotropic wet etch of tailored structures ((Figure 1 b).

Figure 1. a) SEM image of an etched SiO2 donut [1], b) Anisotropic etch of silicon grooves [2]

2.2. Etching of ITO

We use the recipe of Aqua Regia for the etching of ITO. Aqua Regia is comprised of Nitric
Acid (𝐻𝑁𝑂3 ), Hydrochloric Acid (𝐻𝐶𝑙) and water. The stochiometric ratio is 1 part of
nitric acid, 10 parts of hydrochloric acid and 10 parts of water. To start we will prepare
the base as 250ml of water, 250ml of hydrochloric acid is added afterwards and finally 25
ml of nitric acid. Is very important that the acid is dissolved into the more basic substance
and not the other way around, otherwise the high volume of acid will rapidly react with
the first droplets of water and the solution heats up it can potentially evaporate the water
which will spill out.
The solution of Aqua Regia will start to decompose by the reaction between its
components. After some time, the solution will still be acid but will not be an efficient
etcher, that is why it is normally mixed right before its intended usage. The etching
reaction of the process is [3]:

𝐼𝑛2 𝑂3 + 2𝐻𝐶𝑙 → 2𝐼𝑛𝐶𝑙 + 𝐻2𝑂 + 𝑂2 (∆𝐻)

𝐼𝑛2 𝑂3 + 12𝐻𝑁𝑂3 → 2𝐼𝑛(𝑁𝑂3 )3 + 6𝑁𝑂2 + 6𝐻2 𝑂
When the solution is ready, the wafer is completely submerged on the Aqua Regia;
after 2:30 minutes on exposure all ITO is successfully removed. Immediately after
finishing the substrate etching, it is rinsed in a second beaker with DI water, this will stop
the reactions on the surface off the wafer dissolving any remaining acid on the substrate.

3. Dry etching

3.1. Overview
After etching away the unprotected areas of the ITO we can continue to the etch of the
Silicon layers. For this process, we use dry etching. Dry etching of substrates can include
plasma assisted or non-plasma methods. Non-plasma methods utilize the chemical
reaction between a gaseous precursor (normally fluorine gases) and the substrate, the
reaction is controlled through temperature and the input volume of gases and in general
the process can be either mass transport or surface reaction dominated. The main
advantage of non-plasma methods is the lack of plasma triggering equipment, which lower
the equipment price significantly.
 Plasma triggered methods can be either physical or chemical. Physical process consists
on the sputtering of ions onto the substrate, physically removing atoms as the ions are
bombarded into the surface. Chemical processes use the chemical reaction of the ionized
gases in the chamber to take atoms from the substrate surface as new molecules are
formed. Between dry plasma chemical etching process, two can be specifically
highlighted, reactive ion etching (RIE) and deep reactive ion etching (DRIE). For RIE a
Bias is introduced to give directionality to the flow of reactive ions while DRIE is a
sequenced process that both etch and protects the etched walls (Bosch process) to have a
very directional etching.

3.2. RIE etching

The setup for the RIE etching consist on a set of two parallel plates that create a DC electric
field within them, and a secondary -high frequency power source (ICP). The inductively
coupled plasma (ICP) source will create a high density of ions and electrons in the plasma,
whereas the first power source will provide directionality to the ions that will precipitate
on the wafer and react with its surface. This configuration will give comparatively high
etching rates while having a good directionality in the process (anisotropy). Masdar’s setup
for the etching of Silicon substrates use gases like Silicon Hexafluoride (SF6),
tetrafluoromethane (𝐶𝐹4 ) and fluoromethane (𝐶𝐻𝐹3 ).
The reaction of 𝑆𝐹6 depends on the pressure in the chamber. At low pressures the high
concentration of SFx atoms will sputter the substrate surface, whereas at high pressure,
the increased density of ions will enable a larger chain reaction in the plasma, thus
resulting in a larger concentration of free Fluorine atoms, these will react with the substrate
creating new 𝑆𝐹4 molecules.
For the chlorine based reactions, CF4 (as an inert gas - Freon 14) is used to etch Silicon.
As it flows through the plasma, it cedes a Fluorine atom per the following reactions:

𝐶𝐹4 + 𝑒 − → 𝐶𝐹3+ + 𝐹 + 2𝑒 −
𝐶𝐹4 + 𝑒 − → 𝐶𝐹3 + 𝐹 + 𝑒 −
The free Fluorine atoms will react afterwards with the wafer creating 𝑆𝐹4, that will
flow out from the reaction chamber. A similar process is present in the 𝐶𝐻𝐹3 reaction,
both ions of HF and free F are created in the plasma, these will etch the oxide in the
substrate

𝑆𝑖𝑂2 + 4 𝐻𝐹 → 𝑆𝑖𝐹4 + 2 𝐻2𝑂

Any exposed Silicon will be etched as well by the free Fluorine in the plasma, with a
selectivity ratio of 10:1 (this is the etching rate of the Silicon will be 10 time lower than
that of the oxide). Our etching process is set per the following parameters:

Gas Input 𝑆𝐹4 5 sccm

𝐴r 70 sccm
Power BIAS 100 W
ICP 40 W
Pressure 20 mTorr
Table 1. RIE process parameters

Note that the plasma enables a mass transport controlled reaction, this enhances the
controllability of the reaction but for large work areas the total reaction load will tend to
decrease the etching rate as the total available precursors are reacting with a larger surface
(macro loading). A similar effect causes a higher etching rate close to the edges of the
wafer.
At the end of the process we etched away 800 nm (80 nm of ITO + 720 nm of Silicon),
this corresponds to all the cell layers plus a small part of the bottom substrate. These results
are good as the intention was to isolate the cells between them, and we got a fully isolated
set of cells, nevertheless surface charges on the sides of the cell ay present a limitation for
the cells themselves. The final cut section of the cell is as presented in the figure.

Figure 2. Cross section of the fully etched solar cell

3.3. Plasma Ashing

After its hard baking and being exposed to the high energy of the DRIE, the photoresist
used to define the features that were to be protected is hardened and is no longer affected
by normal solvents. Stronger methods for the removal of the resist are required, these could
be the usage stronger solvents, e.g. 1-Methyl-2-pyrrolidon, Dimethyl sulfoxide, KOH or
NaOH alkaline solutions or amine solvents. Highly crosslinked photoresist will however
need an oxygen combustion or ashing.
Ashing is a plasma assisted process carried to remove the remaining photoresist on top
of the substrate. At low pressure (200 mTorr) plasma is induced using a 100W RF electric
field as oxygen is pumped into the chamber. The process is carried for 20 minutes.
Plasma ashing is carried normally using monatomic Oxygen or Fluorine as reactive
species. It can be classified between stripping, a high temperature ashing to remove large
volumes of photoresist, and “descum”, used to remove residual resist in small features.
Modern plasma ashing systems will create the plasma in a different area than on the
process chamber, this prevents free radicals created in the plasma to react with the
substrate, which would damage it.

Figure 3. Plasma asher at Masdar Institute, image courtesy of Omar Albadwawi

4. Conclusions
Two etching processes were carried out in the PIN aSi solar cell. First through Aqua Regia
wet etched the unprotected ITO was etched away, and later the Silicon layer were etched
using RIE. Note that the isotropic etch of ITO caused and under cut on the silicon, as
material was removed under the protective layer of photoresist. This is visible in the Figure
4, the top layer of photoresist is already ashed away and we can note that the Silicon
(greenish color in the image) and the ITO (darker color in the image) have a different
geometry. An under-etch larger than 40um was measured for the feature in the figure.
The cell is now ready for the deposition of the metal contacts on its surface.

Figure 4. Optical microscope image of etched features, courtesy of Omar Albadwawi