Review of Solar Silicon Recycling

York R. Smith and Pamela Bogust

Abstract Photovoltaic (PV) modules are becoming an ever increasingly larger part
of our energy portfolio. As more and more PV modules are installed and come
on-line, management of end-of-life (EOL) modules becomes an important issue.
Currently, management of overburden EOL PV modules is not an issue, but is
anticipated to be by 2030. Recovery and recycling of valuable metals in PV
modules presents several environmental and economic advantages. In this brief
review, we will describe processes for refurbishing and recycling of PV silicon.
These processes involve some combination of mechanical, thermal, and chemical
processing, all of which all have their oPV) modules have become wn respective
challenges. Also, projections of PV module material streams are also highlighted.

Keywords Photovoltaic
Silicon
Recycling

Introduction

Photovoltaic (PV) modules have become a significant contributor to our current

global power production in a short amount of time, with a production of only 40
GW in 2010 up to 227 GW in 2015 [1–3]. The growth rate of power production
from PV’s was 74% from 2006–2011 and 42% from 2010–2015, a significantly
higher growth rate than any other renewable energy [2, 3]. The amount of power
supplied by PV modules is expected to keep growing with an estimated cumulative
installed capacity of 4,512 GW by 2050 [2, 3]. This dramatic increase in use of PV
modules in a short time and the long life of PV modules (25–30 years) will result in
a dramatic influx of PV module waste around 2030 [1, 4–6].

Y. R. Smith (&)
P. Bogust

Metallurgical Engineering Department, University of Utah,
Salt Lake City, UT, USA
e-mail: york.smith@utah.edu
P. Bogust
e-mail: u1128127@utah.edu

© The Minerals, Metals & Materials Society 2018 463

Z. Sun et al. (eds.), Energy Technology 2018, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-319-72362-4_42
464 Y. R. Smith and P. Bogust

Currently, most EOL PV modules are being disposed of in landfills [4–6].

However, PV modules contain hazardous metals such as Pb and Cd, and leaching of
these chemicals into water supplies from landfills would be harmful to the envi-
ronment [6, 7]. The sale of some PV modules containing Cd are prohibited in China
because of the high toxicity [7]. Recycling of PV modules can be even costlier then
proper waste disposal, even in the case of hazardous waste disposal which,
depending on the module type and applicable laws/regulations, may be required
[4, 5, 7, 8]. Common recycling processes currently available focus on recycling the
largest percent mass, and not on recovering valuable or hazardous materials [4, 5, 9].
This increases the environmental impact of PV use, making PV use less attractive [4, 5].
The cost of recycling is expected to decrease as the technology continues to develop,
however [4, 5]. Disposal in landfills and as hazardous waste is expected to increase
discouraging landfill use and encouraging recycling [4, 5].
The recycling of metals from PV modules would not only reduce the amount of
waste but also preserve our limited supply of natural resources and reduce the
amount of energy consumed to obtain and refine these resources [5, 6, 10]. There
are currently studies investigating the need to recycle PV modules from an eco-
nomic and environmental stand point. Many of these studies discuss the cost of
recycling versus the cost of waste disposal [7, 8]. The low levels of valuable
materials in the PV modules makes recycling currently not economical for crys-
talline Si modules and CdTe, while CIGS can be recycled for a profit [4, 8].
Commonly discussed alongside the economics of recycling is the responsibility of
recycling. Studies of other electronic recycling regulations are compared to the PV
market in an attempt to increase recycling of PV modules while not harming the PV
market or detracting from PV use [4, 7].

Recoverable Materials and Projections

In crystalline Si modules, a p-n junction is installed on the front surface of the Si wafer
and then coated with an anti-reflective layer [6]. An Al contact and a grid of Ag is
screen printed on the back and front of the wafer, respectively to create cells [1, 11–
13]. The cells are then connected by electrodes to make a module [6]. Ethylene vinyl
acetate (EVA) is used to adhered the cells to the front glass and back sheet, commonly
made of polyethylene terephthalate [14]. An aluminum frame is sometimes added to
the modules for structural strength [14]. The general construction of a crystalline
Si PV cell can be seen in Fig. 1. The crystalline Si wafers used in these modules
accounts for about 4% of the panel by weight but the manufacturing of the high-purity
Si wafer accounts for about 65% of the cost of the crystalline Si modules [6, 15, 16].
There are several common types of PV modules currently used; Copper indium
gallium (Cu(InxGa1–x)Se2 (CIGS)), CdTe, monocrystalline Si and polycrystalline
Si. CIGS make up about 4% of the current market and are expected to make up
about 6.4% of the market by 2030 [1]. CdTe modules currently make up about 5%
of the market and are expected decline to about to about 4.7% of the market by
Review of Solar Silicon Recycling 465

Fig. 1 Components of a crystalline Si PV cell

2030 [1]. About 92% of modules in use today are crystalline Si modules and they
are projected to continue to dominate the market with 82% of market in 2020
[1, 6, 15]. Amorphous Si PV modules have recently been phased out due to their
low efficiency and they contain the least value in metals and are therefore not
considered in this analysis [1, 7].
Waste projections of PV modules were reported by International Energy Agency
and International Renewable Energy Agency [1]. The production of each module
type as well as the composition of the different modules was used for projections of
waste categorized by material. The recovery rates of each material are from past
reported studies, as seen in Table 1. A projection of the amount of valuable metals
was estimated using the percentage of each metal by weight in each panel type and
the amount of each panel manufactured as well as the expected recycling date of the
panels, seen in Fig. 2. By mass, Si represents the second largest recoverable metal
from PV modules.

Current Recycling Methods

In order to make recycling of PV modules economical, the cost of recycling must be

reduced and the recovery of the valuable materials increased. A single recycling
processes that could recycle all common types of PV modules would reduce the
466 Y. R. Smith and P. Bogust

Table 1 The weight percentage of the materials in each module type and their respective recovery
rates
Component Crystalline Si modules CIGS modules CdTe modules Recovery rate
Weight [%} Weight [%} Weight [%}
Glass 71 88 96 0.9
Silcon 4 0 0 0.9
Aluminum 13 7 0 0.9
EVA 9 4 3 0
Copper 0.1 0.1 0.02 0.95
Silver 0.1 0 0 0.95
Indium 0 0.28 0 0.85
Gallium 0 0.1 0 0.85
Selenium 0 0.52 0 0.85
Nickel 0 0 0.1 0.85
Zinc 0 0 0.1 0.85
Tin 0 0 0.1 0.85
CdTe 0 0 0.12 0.85
Sources [1, 10–13, 17–20]

Fig. 2 The cumulative possible recovery of each metal from PV modules by year
Review of Solar Silicon Recycling 467

costs of recycling [18, 21]. A recycling method that can allow for disposal of
different PV module types is available, but this method does not recover the PV cell
material. In this method, the frame and glass are manually removed for recycling
and then the PV material is disposed of [4]. This method requires fewer treatments
for recycling and reduces the amount of material to be disposed of in a landfill
dramatically, making it a cheap waste treatment method [4]. While, this method
allows for the processing of different PV module types, it does not extract the
valuable or hazardous metals form the module [4].

Recycling Methods of Crystalline Si Modules

There are a few different focuses in current research on recycling and reuse of
crystalline Si modules. These focuses are the reuse of PV cells and of Si wafers
(remanufacturing), and the recovery and recycling of Si, Ag, and/or the largest
percent of the panel [12]. A recent review by Tao and Yu [20] examines three types
of recycling pathways from the perspectives of close-loop life cycle, which are
manufacturing waste recycling, disposed module re-manufacturing, and recycling.
In order to reuse the PV cell or wafer they must not be damaged, if they are
damaged they can be recycled and used as raw material [22]. The Si wafers used in
crystalline Si modules are manufactured by melting Si and then solidifying it using
a variety of techniques, such as Czochralski or directional solidification, to produce
ingots [16, 20, 23]. The ingots are sliced using a multi-wire saw with an abrasive of
ethylene glycol and silicon carbide to create the wafers [20, 24]. More than 40% of
the Si ingot is lost in the slurry waste in the processes of manufacturing the wafer
[16, 20, 23]. The loss of Si in manufacturing of the wafer as well as, the energy
consumed in manufacturing processes makes the reuse of wafers desirable [20].
However, in the processes of etching the wafer to remove the p-n junctions part of
the Si is lost leaving a thinner wafer [6, 24]. As much as 38% of the Si is lost in the
etching processes performed by Wang et al. [24].
First Solar Inc. has developed a process for recovering crystalline Si cells, where
the modules are lightly heated to remove the backing [4]. Then a thermal pyrolysis
treatment is performed on the cells to decompose the EVA [4]. This leaves the
crystalline Si cells to be recovered and reused [4]. The cells need to be intact to be
reused and these reused cells have a slightly lower efficiency then new cells [4].
A recent study on the reuse of recovered Si wafers from crystalline Si modules
was performed by Klugmann-Radziemska et al. [15]. The first step in recovering
the Si wafer was heating the PV module in a SiO2 bed. This process allowed for the
separation of the cell from the PV module. The top Ag layer is first removed using
aq.HNO3 at 40 °C and then the Ag is recovered from the waste acid by electrolysis.
The Al layer is removed next using KOH at 80 °C. The AR coating and p-n
junction are removed last using a mixture of HNO3, HF, CH3COOH and Br2 at
temperatures ranging from 70 to 80 °C dependent on module type. The intact
recovered Si wafers are then rinsed with deionized water and laser cut in
468 Y. R. Smith and P. Bogust

preparation to be reused for a new PV cell. In order to create a new cell, the wafer
was texturized by etching with KOH and isopropyl alcohol for 30 min at 80 °C
followed by HF for monocrystalline wafers and HF + HNO3 + H2O at 25 °C for
polycrystalline. The wafers are then rinsed with deionized water again, before the
p-n junction is formed. The p-n junction is formed through the process of diffusion
with the liquid donor source, POCl3, from 825 to 900 °C. The wafers are then
covered by a phosphorus-silicate glass while a donor-doping layer is applied to the
sides and edges. This is followed by chemical etching using HF + HNO3 + H2O to
remove the parasitic junction. The wafer is then immersed in HF for 2 min to
remove the phosphorus-silicate glaze. The wafer is then subject to a surface pas-
sivation process and then coated with a layer of SiO2 by thermal oxidation. The
electrical contacts are then printed on the wafer and annealed. These new cells had
efficiencies of 12.7 and 15% without the AR layer. It was recognized that that the
chemicals used in the etching process are toxic, reactive, and if released could be
hazardous [15].
Another recent study to recover the Si wafer was performed by Shin et al. [25].
The modules were heated to 480 °C at a rate of 15 °C/min, separating the PV cells
from the module. The unbroken wafers are then collected and immersed in HNO3
then, KOH at 80 °C removing the Ag and Al. An etching paste containing phos-
phoric acid is then applied to the wafers and then the wafer are annealed with the
applied paste. The wafers are then dipped in KOH, removing the top layer of the
wafer and dissolving the AR coating. The new solar cells are then fabricated using
the cleaned Si wafer, by first dipping the wafer in KOH to texturize the wafer. The
n-doped layer is formed by thermal treatment with liquid source, POCl3.
Phosphosilicate glass is then removed using an HF solution. The AR coating is
applied to the wafer by plasma-enhanced chemical vapor. This is followed by
screen printing of the Al and Ag metal contacts to the wafer with an annealing
step. Mini modules were then made using Pb free solder, 60SN-38Bi-2Ag, lami-
nated using glass, EVA, and Tedlar. The modules had power conversion efficien-
cies of 15.0–16.0% compared to the initial module efficiencies of 16.5–17.0%. This
process demonstrates that the Si wafer could be recovered without the use of
harmful surfactants and the cell could be manufactured without the use of Pb [25].
Research on recovery of Si particles from crystalline Si modules was performed
by Kang et al. [6]. The first step in the recycling processes was determining an
organic solvent that would cause dissolution and swelling of the EVA resin. The
module was immersed in toluene for 2 days at 90 °C, resulting in swollen and
dissolved EVA that was separate from the tempered glass. The swollen EVA
remained attached to the PV cell. The PV cell and EVA was heated to 600 °C and
held there for 1 h under a flow of argon gas. This resulted in the complete removal
of the EVA, but the metal electrodes, anti-reflective coating and the p-n junction
layers remained on the PV cell. The PV cell particles were then put in a chemical
etching solution made of HF, HNO3, H2SO4, CH3 COOH, distilled water and a
surfactant of CMPMO- 2 for 20 min [6]. The metal impurities were oxidized,
reduced and dissolved in the etching fluid, leaving Si of purity 99.999%. The
recovery of the high purity Si was 86% using this method. In both recycling
Review of Solar Silicon Recycling 469

methods performed by Kang et al. and Shin et al., the metals removed from the PV
cell are not recovered while, Klugmann-Radziemska recovers Ag and not the Al
from the etching processes [6, 13, 15].

Conclusion

Studies show that recycling technologies for EOL PV modules are explored and
some are commercially available, although challenges still remain in process
efficiency/continuous processing, reduction in process complexity, energy
requirements, and use of chemicals. Environmental benefits and economic viability
are also important to the establishment of feasible PV recycling systems, thereby
improving the sustainability of PV. Studies suggest that EOL module recycling can
have significant positive impacts on reducing environmental loads, required
chemicals, scarce resources and energy for new modules are reduced. However,
economic motivation to recycle is currently not favorable. The realization of PV
recycling will depend on developing innovative processes and technologies capable
of handling and separating large throughputs of PV material.

Acknowledgements Authors would like to acknowledge support provided by the U.S.

Department of Energy, Office of Science, Energy Efficiency Renewable Energy, Sunshot Initiative.
This publication was developed under an appointment to the Energy Efficiency and Renewable
Energy (EERE) Research Participation Program, administered for the U.S. Department of Energy
(DOE) by the Oak Ridge Institute for Science and Education (ORISE). ORISE is managed by
ORAU under DOE contract number DESC0014664. This document has not been formally
reviewed by DOE. The views and conclusions contained in this document are those of the authors
and should not be interpreted as necessarily representing the official policies, either expressed or
implied, of DOE, or ORAU/ORISE. DOE and ORAU/ORISE do not endorse any products or
commercial services mentioned in this publication.

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