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Solar Energy Materials & Solar Cells 133 (2015) 156162

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Solar Energy Materials & Solar Cells


journal homepage: www.elsevier.com/locate/solmat

Modulated surface textured glass as substrate for high efciency


microcrystalline silicon solar cells
Guangtao Yang n, Ren A.C.M.M. van Swaaij, Hairen Tan, Olindo Isabella, Miro Zeman
Laboratory of Photovoltaic Material and Device, Delft University of Technology, P.O. Box 5031, Delft 2600 GA, The Netherlands

art ic l e i nf o a b s t r a c t

Article history: In this paper, we investigate three different procedures for making modulated surface textures (MST) on
Received 30 July 2014 glass substrates and show the application of these substrates to microcrystalline silicon solar cells. MST
Received in revised form substrates have broader surface angle distribution (AD) than a single textured glass substrate and this
30 October 2014
distribution peaks at higher angles. Therefore, (i) the haze in reection of MST substrates covered with
Accepted 5 November 2014
an Ag layer is over 99% in the wavelength range above 350 nm, which is higher than in the case of a
single textured glass substrate; (ii) more reected light is scattered into higher angles, resulting in a
Keywords: broader reective angular intensity distribution (AID) in air. These properties lead to a higher Jsc for n-i-p
Modulated surface textures microcrystalline silicon solar cells deposited on the MST substrates compared to cells deposited on single
Glass texturing
textured glass substrate. A solar cell deposited on a MST glass substrate with smoother peaks shows the
Light trapping
highest electrical performance (Voc  FF value), because of a lower density of defective regions. The best
Thin-lm silicon solar cells
cell achieved in this work has an active-area efciency of 10.49%, with a Voc of 0.532 V, a Jsc of 26.36 mA/cm2,
and a FF of 74.8% for a 3-m thick absorber layer.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction combines different textures in order to scatter light within a broad


wavelength range efciently in both multi- and single-junction solar
Effective light management technology is essential to enhance cells [1214]. A MST substrate can be prepared by a stack of layers of
the photo-generated current density by trapping the light into the the same [15,16] or different materials [3,13] with a broad range in
solar cell for achieving high efcient thin-lm microcrystalline feature sizes (lateral and vertical). Compared to single textures, the
silicon (c-Si:H) based solar cells. Texturing the surface is a common MST gives a high level of light scattering because of the super-
approach for this purpose. Surface textured transparent conductive position of different scattering mechanisms caused by the combina-
oxide (TCO) layers, e.g. SnO2:F, ZnO:Al, and ZnO:B [16], are often tion of different feature sizes on one individual interface.
used as substrates to increase the light path within the absorber Besides the optical performance, the electrical performance of
layer for enhancing the light absorption in the solar cell. For solar- c-Si:H solar cells is even more sensitive to the substrate mor-
cell application a compromise must be found between the electrical phology [17,18]. A steep V-shaped textured substrate induces a
and optical properties of these TCO layers on one hand, and the high micro-void density in the mc-Si:H intrinsic layer, which will
etching behaviour or the as grown surface morphology of TCO layers act as recombination centres and deteriorate the solar-cell perfor-
in order to achieve an optimum textured substrate on the other mance, especially the open-circuit voltage (Voc) and ll factor (FF)
hand. Recently, some research groups have developed technologies [19,20]. Recently, some research groups reported that by carefully
for the texturing of glass for solar-cell application [79]. However, controlling the features of the substrate they can obtain a textured
when using these textured surfaces as substrates for micromorph surface with high haze factor without reduction of the cell Voc and
solar cells, it proves to be difcult to provide efcient light trapping FF [21]. Some groups have also reported high effciency single
for both the top and bottom cell at the same time. Therefore the junction mc-Si:H solar cells with very high short-circuit current
concept of modulated surface textures (MST) has been developed density, Jsc, of over 30 mA/cm2 [22]. In our group, micro-textured
[10,11] and used for micromorph solar cells [12]. An MST substrate glass with large features was developed, and the solar cells
deposited subsequently on this glass showed a high Voc and FF
even for thick absorber layers [14,23]. Although such micro-
n textures can maintain high Voc and FF in solar cells, it is still
Corresponding author.
E-mail address: G.Yang@tudelft.nl (G. Yang). challenging to obtain efcient light trapping comparable to

http://dx.doi.org/10.1016/j.solmat.2014.11.013
0927-0248/& 2014 Elsevier B.V. All rights reserved.
G. Yang et al. / Solar Energy Materials & Solar Cells 133 (2015) 156162 157

commonly used nano-textures. In this study, we propose MST's in reference. The inuence of the surface morphology of the textured
which smooth and smaller features are added onto the micro- substrates on the mc-Si:H solar-cell performance is also discussed.
textures, with the aim to enhance the light trapping while keeping
the high Voc and FF in c-Si:H solar cells.
For the work presented in this paper we made MST substrates 2. Experimental
based on textured glass or a wet etched ZnO:Al coating layer on top
of the single textured glass substrate. The surface morphology of 2.1. Preparation and characterization of MST glass substrates
the MST substrates is presented. Then 250-nm thick Ag is evapo-
rated onto the rough surface of the substrate to form the back In this subsection we will discuss the methods that we have used to
reector (BR). In order to study the effect of the substrate morphol- make the MST structures. The MST structures were fabricated in a two-
ogy on the solar-cell performance, we deposit n-i-p single junction step process. First we describe the ITO Induced Texturing (IIT) process
c-Si:H substrate type solar cells on the rough surface of these BRs. that we used to make textured surfaces with larger features. Subse-
This implies that the light enters the solar cell via the silicon layers quently, three different methods were used to implement smaller
and not via the glass side of the solar cells. The optical properties of features onto the previously obtained larger features. These three
the obtained BRs and the performance of the substrate n-i-p mc-Si:H processes are on glass: (i) Aluminium Induced Texture (AIT), (ii) wet
solar cells are presented with single textured glass substrate as etching of ZnO:Al coating layer (EAZO), and (iii) ZnO:Al Induced Texture

Fig. 1. AFM scan of (a) IIT textured glass, (b) MST-AIT textured glass, (c) MST-EAZO textured substrate, (d) MST-ZIT textured glass; (e) arbitrary surface cross-section and
(f) Surface AngleDistribution (AD) of textured substrates.
158 G. Yang et al. / Solar Energy Materials & Solar Cells 133 (2015) 156162

(ZIT). Then a 250-nm thick Ag layer is evaporated onto the rough 2.1.5. Preparation of MST substrates
surface of these MST substrates to form the BRs for the following optical First, the IIT process is used to texture the glass to obtain a
measurements and deposition of substrate n-i-p mc-Si:H solar cell. rough surface with large features. Second, in order to obtain the
In order to get the MST substrate surface morphology para- smaller features that are embedded in the larger features, three
meters, e.g. the root mean square roughness (RMS), the textured different processes (AIT, EAZO and ZIT) are carried out on the
substrates are studied by an atomic force microscope (AFM, NT- rough glass surface obtained by IIT process. After the second
MDT). The optical properties of the 250-nm Ag coated BRs (i.e., processing procedure an MST is obtained. The AFM scan of MST
total reection, haze in reection, and angular intensity distribu- glass obtained by an AIT process following the IIT process on glass
tion (AIDair) of reected light) are measured in air using an (MST-AIT) is shown in Fig. 1(b), by an EAZO process following the
integrating sphere and the Angular Resolved Transmittance/ IIT process is shown in Fig. 1(c), and by a ZIT process following the
Reectance Analyzer in a PerkinElmer Lambda 950 spectrophot- IIT process is shown in Fig. 1(d).
ometer. Experimental details of the measurements can be found
elsewhere [24,25].
2.2. Preparation and characterization of solar cells

2.1.1. ITO Induced Textures (IIT) On IIT and MST substrates, we have deposited c-Si:H single
Corning Eagle XG glass covered with 200-nm thick In2O3:Sn junction substrate n-i-p solar cells in order to study the effect of the
(ITO) sacricial layer is wet etched with H2O2 and HF to achieve a substrate morphology on the solar-cell performance. The structure of
textured surface. The ITO layer is deposited with a magnetron the solar cells is as follows: textured substrate/Ag/n-SiOx:H/i-c-Si:H/
sputtering system at a substrate temperature of 115 1C, a sputter- p-SiOx:H/In2O3:Sn (ITO)/metal grid. The n-SiOx:H layer used here has
ing pressure of 2.6 mbar, a target-to-substrate distance of 110 mm, a similar reective index (2.3, in the wavelength range from
and a power density of 0.9 W/cm2. More detailed information on 400 nm to 1100 nm) compared to that for ZnO layer (2.0, in the
this process is published elsewhere [13,14]. The typical horizontal wavelength range from 400 nm to 1100 nm). It was shown before
feature size obtained with such IIT method is 15 m in average, as that the reectance for ZnO:Al/Ag BR and SiOx:H/Ag BR congura-
is shown in atomic force microscopy (AFM) picture in Fig. 1(a). tions is similar [27], which implies that the plasmonic absorption
losses are similar for these two BR congurations. Our experimental
results showed that the Voc of the solar cells on ZnO:Al/Ag BR is
2.1.2. Aluminium Induced Textures (AIT) slightly lower (not shown here) and therefore we did not use a ZnO:
AIT (Aluminium Induced Texturing) texturing of glass was Al layer between Ag and n-SiOx:H layer. The structure of the n-i-p c-
developed by Aberle et al. [9]. In this process 200-nm thick Si:H solar cells is schematically shown in Fig. 2. All the silicon layers
aluminium (Al) is evaporated on a glass substrate. Then this are deposited in a multi-chamber PECVD system: n-SiOx:H (50 nm)
structure is annealed at 600 1C in vacuum (at a background and p-SiOx:H (20 nm) layers are deposited with rf-PECVD, while the
pressure of 10  7 mbar) for 3 h before etching with HNO3 and HF. intrinsic c-Si:H layer is deposited with VHF-PECVD at 40.68 MHz
The feature size of textured glass obtained by the AIT technique with SiH4 and H2 as precursor gases [14]. The deposition rate is 6.7 /s
can be tuned by changing the Al thickness, annealing temperature, and the i-layer thickness varies from 2.0 m to 3.0 m. Then a 75-nm
and annealing duration. The obtained feature size in this work is thick ITO layer is sputtered, onto which a metallic grid (Ag-100 nm/Cr-
23 m. 30 nm/Al-300 nm) is evaporated to form the solar-cell device with an
area of 0.25 cm2. Before the measurements, the solar cells were
annealed for 2 h at 170 1C.
2.1.3. ZnO Induced Textures (ZIT) The Voc and FF of the solar cells are determined from JV
A 300-nm thick ZnO:Al (AZO) sacricial layer is sputtered on measurements under 100 mW/cm2 illumination (PASAN). The results
glass and followed by etching with HNO3 and HF to obtain a reported in this paper are the average from the 10 best performing
textured surface. ZnO:Al lm is sputtered using a magnetron cells out of 24 cells on one substrate stripe. The Jsc is calculated from
sputtering system at substrate temperature of 200 1C, a pressure the external quantum efciency (EQE) measured with an in-house
of 2.5 mbar, and a sputtering plasma power density of 1.25 W/cm2, built setup under short-circuit condition in the wavelength range
and using 2 wt% Al2O3 doped ceramic ZnO:Al as target. The from 300 nm to 1100 nm using the AM1.5G spectrum [28]. In this
etchant ratio of [HNO3] (68%):[HF] (40%) is 8:1. The obtained way the overestimation of the Jsc due to the lateral current collection
feature size can be tuned by varying the ZnO:Al layer thickness, and inaccuracy in dening the active area of the solar cells in JV
ZnO:Al layer crystal properties (by adjusting the sputtering con- measurements is excluded [29].
ditions), and the etchant composition. Details on how to prepare
ZIT textured glass is published elsewhere [23]. The feature size
obtained in this work is 2 m on average.

2.1.4. Etched ZnO:Al Textures (EAZO)


ZnO:Al lms (AZO) are sputtered on glass using a magnetron
sputtering system with 2 wt% Al2O3 doped ceramic ZnO:Al target
at a substrate temperature of 225 1C, the pressure used in this case
is 2.5 mbar and the power density is 1.67 W/cm2. The thickness
before etching is 1500 nm. 0.5% HCl is used to etch ZnO:Al to
achieve a textured surface. More details on AZO etching have also
been published elsewhere [26]. The obtained surface feature size
can be controlled by tuning the crystal properties of AZO (espe-
cially the substrate temperature during sputtering), and the Fig. 2. Schematic representation of the n-i-p structured microcrystalline silicon
etchant concentration. The crater-like features obtained in this solar cells deposited on (a) IIT glass substrate and (b) modulated surface textured
work have a size of 1.52 m. (MST) substrate.
G. Yang et al. / Solar Energy Materials & Solar Cells 133 (2015) 156162 159

3. Results

3.1. Morphology and optical properties of textured substrates

AFM scans of the IIT glass together with three different MST
substrates fabricated are shown in Fig. 1. Compared to IIT glass, the
RMS MST-AIT and MST-EAZO are higher, but MST-ZIT becomes less
rough after the ZIT process giving a smaller RMS. This difference is
mainly due to the difference in texturing mechanisms:

(i) The MST-AIT morphology is achieved with a spatially non-


uniform redox reaction between the SiOx (the main composi-
tion of glass) and Al during the annealing step [9]. The
following wet-etching step is only used to remove the reac-
tion products (Al2O3 and Si).
(ii) MST-EAZO morphology is achieved by adding an additional
wet-etched ZnO:Al layer on the IIT glass. Interestingly, the
thickness of sputtered and subsequently etched ZnO:Al layer
varies from the ridge to the valley of the craters of IIT glass
with the thickest part at the crater valley. This can be seen
from the cross-section SEM image of the solar cell deposited
on MST-EAZO substrate (see positions A and B in Fig. 6(b)).
(iii) During the ZIT etching step, glass near the crater ridge is
Fig. 3. (a) Diffused reectance and (b) haze in reection for textured substrates
exposed to the etchants rst because of a thinner ZnO:Al covered with a 250-nm thick Ag layer.
sacricial layer there (see position A, Fig. 6(b)). As a result the
sharp glass peaks are smoothened during the etching of
thicker ZnO:Al at the valley of the craters. In this way a
smaller RMS is obtained for MST-ZIT substrates after the ZIT
process.

The difference in surface morphology of the MST structures can


be clearly seen in Fig. 1(e) showing an arbitrary surface cross-
section of the textured substrates. The IIT and MST-AIT textured
glasses have very sharp peaks, while peaks for MST-ZIT textured
glass are smoother. As will be discussed later, we think that this
smoothened surface is particularly suitable for microcrystalline
silicon deposition [30]. Because of the smoother peaks, the angle
distribution (AD) for MST-ZIT peaks at a lower angle (13.01)
Fig. 4. The angular intensity distribution (AIDair) in reection of textured sub-
compared to MST-AIT (19.41) and MST-EAZO (15.51), but still peaks
strates, normalized at 51, measured using incident light with a wavelength of
at higher angle compared to IIT glass (8.11), as shown in Fig. 1(f). 800 nm. For reference the normalized AIDair of a Lambertian reector is plotted
Note that the surface angle distribution obtained by AFM as as well.
presented in Fig. 1(f) represents the steepness distribution of the
U-type crater surfaces. It is not comparable to the opening angle of
a V-shaped textured substrate as discussed by Sever et al. [31]. 3.2. Solar-cell performance
They showed that the opening angle of a V-shape texture is closely
related to the growth of defective regions in c-Si:H layers Table 1 shows the external parameters of n-i-p solar cells
deposited on it. deposited on these single and modulated textured substrates with
In Fig. 3 the diffused reectance and the haze in reection are 2.0-m or 3.0-m thick c-Si:H intrinsic layers. Solar cells depos-
shown for these four BRs, textured substrates covered with a 250- ited on MST textured glass have a higher Jsc than cells deposited on
nm thick Ag layer on their rough surface. All MST substrates IIT glass. The increase in Jsc for MST cells compared to IIT cell with
present a very high diffused reectance of over 95%, as shown in 3 m thick i-layers is listed in Table 1. It is also reected in the EQE
Fig. 3(a). Compared to the other textured substrates, MST-EAZO for solar cells with 3.0-m thick i-layer shown in Fig. 5, where all
shows a relatively low diffused reectance in the shorter wave- solar cells deposited on MST substrates show a higher red
length region, because of the plasmonic absorption of nano-rough response compared to the cell on IIT glass substrate. This increase
Ag surface on the etched ZnO:Al [32]. From Fig. 3(b) we can see is mainly due to the fact that these substrates scatter more light in
that all MST substrates have higher reective haze than the IIT the red part of the solar spectrum with more light scattering into
glass substrate, although IIT glass shows also a very high reective higher angles, as shown in Figs. 3 and 4. The highest increase in Jsc
haze of over 96% in the studied wavelength range. This result is observed for the MST-EAZO cell compared to MST-AIT and MST-
indicates that more light is scattered by the MST substrates. In ZIT cells. This additional increase compared to the other two cells
Fig. 4 the reective AIDair of these BRs is plotted. From this gure, is attributed to its relatively rougher front surface than the others,
we can see that the reective AIDair of the MST BRs is higher than which originates from the deep V-shaped craters of the wet etched
in case of IIT glass. This means that more light is scattered into AZO layer compared to the shallower U-shaped craters after the
higher angles for MST substrates, which is benecial for light AIT or ZIT process on glass. Therefore, this morphology induces
trapping into the solar cells. For reference the reective AIDair for a more scattering at the front side of the cell and leads to a larger
Lambertian reector is also shown in Fig. 4. current density gain for the MSTEAZO cell.
160 G. Yang et al. / Solar Energy Materials & Solar Cells 133 (2015) 156162

Table 1
Performance of solar cells deposited on textured substrates. The standard deviation (SD) for each solar cell parameter calculated from the 10 best performing cells on each
substrate is similar: SD (Voc) E 0.003 V, SD (FF) E0.004, SD (Jsc) E0.42 mA/cm2, SD (Eff.)E 0.13%, SD (Voc   FF) E0.005 (V).

Substrate Thickness (m) Voc (V) FF (-) Jsc (mA/cm2) Eff. (%) Voc  FF (V)

IIT 2.0 0.525 0.740 23.52 9.14 0.389


MST-AIT 2.0 0.530 0.723 25.90 10.1%a 9.92 8.5%b 0.383
MST-EAZO 2.0 0.517 0.732 25.65 9.1%a 9.71 6.2%b 0.378
MST-ZIT 2.0 0.546 0.745 25.61 8.9%a 10.41 13.9%b 0.407
IIT 3.0 0.529 0.724 25.40 9.73 0.383  1.5%c
MST-AIT 3.0 0.532 0.726 26.31 3.4%a 10.17 4.5%b 0.386 0.7%c
MST-EAZO 3.0 0.496 0.691 27.40 7.8%a 9.40  3.4%b 0.343  9.3%c
MST-ZIT 3.0 0.532 0.748 26.36 3.7%a 10.49 7.8%b 0.398  2.2%c

a
The variation of Jsc for solar cells deposited on MST substrates compared to the solar cell deposited on IIT substrate.
b
The variation of the efciency for solar cells deposited on MST substrates compared to IIT substrate.
c
The variation of Voc  FF products when the solar cell i-layer thickness is increased from 2 m to 3 m.

Fig. 5. External quantum efciency (EQE) for solar cells with 3.0-m thick c-Si:H
i-layer deposited on different textured substrates.

Also shown in Table 1 is the electrical performance (Voc  FF


product) of the solar cells. The effect of increasing the i-layer
thickness from 2 m to 3 m on the Voc  FF product is displayed
in this table. For all solar cells a drop in this product is observed,
except for the MST-AIT cell, which shows a small increase when
increasing the cell thickness to 3 m. Compared to the other cells,
the MST-EAZO cell shows the largest decrease in electrical perfor-
mance, which is due to defective regions induced by the deep
V-shaped craters (see Fig. 6). For this reason, even though the MST-
EAZO cell has the highest Jsc, its efciency is still lower than that of
Fig. 6. Cross sectional scanning electron microscope (SEM) images for (a) a MST-
the other solar cells because of its poorer Voc and FF as listed in ZIT solar cell, and (b) a MST-EAZO solar cell.
Table 1 (3-m thick solar cells). From Table 1 it is clear that the
highest Voc  FF product is obtained for the solar cell deposited on
the MST-ZIT substrate, which indicates this solar cell has the most quantum efciency from the visible region to the near-infrared
optimal electrical properties. As discussed in Section 3.1, this high region [20].
Voc  FF product is a good indication that the MST-ZIT substrate is The quality of the c-Si:H deposition is also supported by a
more suitable for high quality c-Si:H deposition. The efciency for scanning electron microscope (SEM) images for cells on MST-ZIT
MST-ZIT cell with 3-m thick i-layer is 10.49%, which is 7.8% higher and MST-EAZO substrates with 3-m thick i-layer, shown in Fig. 6.
than the IIT cell, as it is listed in Table 1. From the SEM image of the cell deposited on MST-ZIT substrate,
From Table 1 we see that the Jsc increase of solar cells deposited shown in Fig. 6(a), we can clearly see the smoothened peaks of
on MST-AIT and MST-ZIT substrates compared to the IIT substrate etched glass substrate in contrast to MST-EAZO substrate shown in
is larger for an intrinsic layer thickness of 2 m than of 3 m. This the SEM image in Fig. 6(b). The small features of the MST-ZIT glass
observation can be explained by taking into account the feature resulting from the ZIT process has a U-type shape, compared to the
size of the textured substrates when increasing the absorber layer V-type craters from the wet-etched ZnO:Al surface. A U-type
thickness [21]. If the cell thickness exceeds a certain value, the Jsc shape substrate induces less defective regions in c-Si:H lm
increase will be constrained because of the attening of solar-cell [33]. As shown in Fig. 6(a) and (a1), the c-Si:H layer deposited
surface. For the MST-EAZO cells we found that the Jsc increase on the MST-ZIT substrate is nearly free of defective regions in the
compared to the IIT cell is only slightly smaller when increasing silicon layer. For the cell deposited on the MST-EAZO substrate,
the thickness from 2 to 3 m. We ascribe this observation to the shown in Fig. 6(b), many defective regions appear in the beginning
fact that the front surface is still quite rough after deposition of (in the valley, see Fig. 6(b1)) or during the deposition (in the upper
3 m-thick silicon layers, as can be seen from Fig. 6. This rougher half of the material, see Fig. 6(b2)) of the c-Si:H layer, which
front surface enhances light absorption and thus the external ultimately will induce recombination centres and shunt paths, and
G. Yang et al. / Solar Energy Materials & Solar Cells 133 (2015) 156162 161

n from 1.5 to 2 indicates an increase in the bulk recombination.


Then we can attribute the Voc loss observed in this work for MST-
EAZO cells to bulk recombination, which we ascribe to the highly
defective intrinsic layer.

4. Conclusion

In this paper, we reported three ways to make modulated


surface textures (MST) for c-Si:H solar-cell application. We
compared their surface morphology, optical properties, and their
effect on the solar-cell performance. All MST substrates show
higher reective haze and broader reective angular intensity
distribution (AIDair) than the single textured substrate. Therefore a
higher red response in the EQE curves for solar cells deposited on
MST substrates is observed. We also found that solar cells on MST
glass substrate made from ZnO induced textures (ZIT) process has
a nearly defective-region free bulk c-Si:H layer and gives the
highest electrical performance. The highest solar cell active area
Fig. 7. Dark current-voltage (JV) curves measured at 40 1C for solar cells with efciency achieved in this work is 10.49%.
i-layer thickness of 3.0 m deposited on different textured glass substrates. Two
curves with ideality factor of n 2 and n 1.5 are also shown (dashed line).

Acknowledgement
reduce the solar-cell electrical performance, resulting in a lower
Voc and FF. These ndings are in agreement with results reported The authors thank Martijn Tijssen and Stefaan Heirman for
by other groups [21,30,34]. The increase in the density of defective their technical support, DoYun Kim for the useful discussion. G.
regions for the cell deposited on the MSTEAZO substrate is also Yang thanks the China Scholarship Council for the nancial
one of the main reasons for the rapid drop of the Voc  FF product, support.
by 9.3%, when the i-layer thickness increases from 2 m to 3 m
(see Table 1).
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