Advanced Materials - 2023 - Game - Direct Integration of Perovskite Solar Cells with Carbon Fiber Substrates

RESEARCH ARTICLE
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Direct Integration of Perovskite Solar Cells with Carbon

Fiber Substrates
Onkar S. Game, Timothy Thornber, Fernando Cepero-Mejías, Luis C. Infante-Ortega,
Mustafa Togay, Elena J. Cassella, Rachel C. Kilbride, Robert H. Gordon, Nic Mullin,
Rachael C. Greenhalgh, Patrick J. M. Isherwood, J. Michael Walls, J. Patrick A. Fairclough,
and David G. Lidzey*
single-junction devices (25.7%) now ap-

Integrating photovoltaic devices onto the surface of carbon-fiber-reinforced proaching that of top-performing silicon so-
polymer substrates should create materials with high mechanical strength lar cells.[1] The outstanding optoelectronic
that are also able to generate electrical power. Such devices are anticipated to properties, high lab-scale efficiencies, and
find ready applications as structural, energy-harvesting systems in both the facile, low-cost solution processability make
perovskite PV an ideal system for integra-
automotive and aeronautical sectors. Here, the fabrication of triple-cation
tion with novel substrate materials that have
perovskite n–i–p solar cells onto the surface of planarized thermal processing limitations.[2] This al-
carbon-fiber-reinforced polymer substrates is demonstrated, with devices lows perovskite solar cells (PSCs) to be de-
utilizing a transparent top ITO contact. These devices also contain a posited onto flexible polymer substrates,
“wrinkled” SiO2 interlayer placed between the device and substrate that with other work demonstrating devices that
are transparent or have high performance
alleviates thermally induced cracking of the bottom ITO layer. Devices are
under diffuse or low light conditions.[3,4]
found to have a maximum stabilized power conversion efficiency of 14.5% These advantages may allow PSCs to oper-
and a specific power (power per weight) of 21.4 W g−1 (without ate in niche applications where crystalline
encapsulation), making them highly suitable for mobile power applications. silicon is poorly suited. Indeed, PSCs have
been integrated with a variety of materials,
including transparent polymers—namely
poly(ethylene terephthalate)[5] (PET) and poly(ethylene
1. Introduction naphthalate)[3] (PEN), metal foils such as titanium[6,7] and
copper, [8] titanium[9] and steel, [10] metal wires[11,12] and fibers;
[13,14]
Organic–inorganic hybrid perovskite materials have generated and even paper. [15,16] For readers interested in fiber based
substantial interest within the photovoltaic (PV) research com- PSCs, we highlight a recent review.[17] Such integration of PSCs
munity, with the record power conversion efficiency (PCE) of with novel substrate materials opens a broad range of possible
O. S. Game[+] , T. Thornber, E. J. Cassella, R. C. Kilbride[++] , R. H. Gordon, F. Cepero-Mejías, J. P. A. Fairclough

N. Mullin, D. G. Lidzey Department of Mechanical Engineering
Department of Physics & Astronomy University of Sheffield
University of Sheffield Sir Frederick Mappin Building, Mappin Street, Sheffield S1 3JD, UK
Hicks Building, Hounsfield Road, Sheffield S3 7RH, UK L. C. Infante-Ortega, M. Togay, R. C. Greenhalgh, P. J. M. Isherwood,
E-mail: d.g.lidzey@sheffield.ac.uk J. M. Walls
CREST
Wolfson School of Mechanical
The ORCID identification number(s) for the author(s) of this article Electrical and Manufacturing Engineering
can be found under https://doi.org/10.1002/adma.202209950 Loughborough University
Loughborough, Leicestershire LE11 3TU, UK
[+] Present address:Department of Physics, Indian Institute of Technology
(IIT) – Indore, Khandwa Road, Simrol, Indore, Madhya Pradesh 453552,
India
[++] Present address: Department of Chemistry, University of Sheffield,
Dainton Building, Brook Hill, Sheffield S3 7HF, UK
© 2023 The Authors. Advanced Materials published by Wiley-VCH
GmbH. This is an open access article under the terms of the Creative
Commons Attribution License, which permits use, distribution and
reproduction in any medium, provided the original work is properly cited.
DOI: 10.1002/adma.202209950
Adv. Mater. 2024, 36, 2209950 2209950 (1 of 9) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH
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applications ranging from portable or wearable consumer tations and finite fixed wingspans.[30] Indeed, it has been demon-
electronics to power sources for the “internet of things”.[18–20] strated that by integrating solar cells over curved surfaces, devices
One particular emerging application of PSC-based technolo- can be realized having a power output exceeding that of planar
gies is in decentralized solar power generation, where high cells occupying an equivalent area.[31,32] We note, however, that
power-per-weight (or specific power) is critical. This is most im- CFRP composites often have a high level of surface roughness
portant in the automotive and aerospace industries, building- that is much greater than the polished glass surfaces on which
integrated PV and military applications. Previous work by PSCs are most often deposited, and planarizing such surfaces is
Kaltenbrunner et al. demonstrated that the specific power of expected to be a key challenge.
PSCs outperforms that of all other PV materials while rivalling In this paper, we directly fabricate n–i–p architecture
those of other power generation technologies.[21] Here, ultra- “triple-cation” (TC) based PSCs (ITO/SnO2 /TC-perovskite/spiro-
lightweight, 3 μm-thick PSCs were fabricated on a PET foil, with OMeTAD/Au (0.8 nm)/ITO) in substrate configuration onto
devices having a PCE of 12% and a specific power of up to epoxy-planarized CFRP composite substrates, with devices illu-
23 W g−1 . Such devices were shown to be capable of powering minated through a transparent top indium tin oxide (ITO) con-
a direct-current motor for a model aeroplane when connected to tact. A key challenge we address is the preparation of the CFRP
an 8 × 8 PSC array. Kang et al. have also created flexible PSCs surface. We show that the roughness of such a surface can be
having a specific power of 29.4 W g−1 with devices being light substantially reduced to a root-mean-squared (RMS) roughness
enough to rest on the surface of soap bubbles.[22] More recently, of 29 nm by using a commercial epoxy-based mesh material.
Wu et al. have demonstrated ultrathin PSCs fabricated on pary- However, the differing thermal expansion coefficients of the ITO
lene substrates using a flip-over transfer technique, with devices charge-extracting layer and the CFRP substrate leads to severe
demonstrated to have a PCE of up to 20.2% with a record specific cracking during the thermal annealing necessary to process the
power of 30.3 W g−1 .[23] TC-perovskite. We show that this problem can be overcome via
The application of PSCs for portable power applications there- the use of an intermediate “wrinkled” SiO2 film placed between
fore represents an extremely attractive prospect, with one pos- the ITO and the CFRP surface, which prevents cracking of the
sible application route being the lamination of flexible PSC de- ITO during annealing. Using this approach, we realize devices
vices onto curved surfaces such as the envelope of a dirigible, the having PCEs up to 14.4% and stabilized PCEs of 14.5%. The use
fuselage of an aircraft or the monocoque of an automobile.[21] of Au (0.8 nm)/ITO as a transparent top contact results in devices
We believe, however, that this approach has some drawbacks. In having promising stability, with control (glass-substrate) PSCs
particular, the weight of the substrate and associated adhesives having dark-storage lifetimes in excess of 1 month.
is expected to reduce the specific power of the resultant device,
with the potential delamination of the device from the surface 2. Results
of interest representing a possible failure mechanism. Further-
more, while it is possible to “wrap” a 2D flexible PV device over a 2.1. Preparation of the CFRP Substrate
surface that curves in one direction (e.g., a cylinder), it is not pos-
sible to wrap a flexible device over a complex surface that curves Samples were fabricated from unidirectional XC130 “pre-preg”
in two directions (e.g., a sphere); a limitation that restricts the (Easy Composites Ltd, Stoke on Trent, UK). This material is typi-
surfaces over which such an approach can be applied.[24] Indeed, cal of those used in the automotive and aerospace industries and
PSC devices fabricated on flexible substrates can also have a lim- was selected due to its high carbon fiber-content and strength af-
ited bend-radius;[25] a feature that could limit the curvature of the ter curing. XC130 is composed of unidirectional carbon fiber pre-
surface on which they can be fixed. Finally, we note that the per- impregnated with a bisphenol-A-based epoxy resin. A cleaned,
formance metrics of flexible PSCs currently lag behind those of scratch free, smooth glass substrate was prepared with a release
rigid cells with such devices prone to mechanical fracture due to film and three XC130 20 × 20 cm sheets. A breather fabric was
repeated flexing.[26] then placed on top of the CFRP pre-preg sheets and the assem-
An alternate approach to utilizing PSCs for mobile power ap- bly placed inside an air-tight bag before a vacuum was applied.
plications that we explore here involves directly coating such de- The pre-preg-glass assembly was then placed inside an autoclave
vices onto a surface of choice. Here, a key material of interest for that was pressurized to 6 bar and heated at a rate of 2 °C min−1 to
mobile power applications are carbon-fiber-reinforced polymer 100 °C. The assembly was then held at 100 °C for 4 h to cure. Pres-
(CFRP) composites. These materials are widely used in the au- sure and temperature were then slowly reduced at 0.2 bar min−1
tomotive (e.g., high-performance race cars) and aerospace (e.g., and 2 °C min−1 to return the assembly to atmospheric conditions.
aircraft fuselages) industries as they combine high strength and The resultant sample had a thickness of 0.9 mm and an areal
elastic modulus compared to metallic materials or other struc- mass of 1050 g m−2 . To prepare samples for device fabrication,
tural polymers.[27,28] Here, the combination of PSCs with CFRP the 20 × 20 cm sheets were waterjet cut (ProtoMax) into 19 ×
composites creates materials having a unique balance of high 15 mm sections.
power-per-weight and high strength-per-weight, realizing a class Figure 1a shows an image of a CFRP substrate, with Figure 1b
of structural materials that also act as a power source. Criti- showing a surface topograph of its surface recorded using a Dek-
cally, the ability to process PSCs from solution using techniques tak surface profilometer system. It was found, as expected, that
such as spray coating allows them to be deposited over curved such surfaces were relatively rough with an RMS roughness of
surfaces.[29] PSC devices on CFRP composites could be readily 35 nm over a 2 × 2 mm area, and peak height features of up to
employed in unmanned aerial vehicles (UAVs) and high-altitude 1.2 μm; values likely problematic for the direct integration of PSC
pseudo-satellites (HAPSs), where there are stringent weight limi- devices. Here, a series of carbon fibers can be seen that are close
Figure 1. a,c) Photographs of unplanarized (a) and planarized (C) CFRP composite substrates. b,d) Corresponding surface topography maps of unpla-
narized (b) and planarized (CFRP composite substrates.
to the surface and are not entirely encapsulated by the epoxy ma- 2.2. Deposition of the ITO Bottom Contact
trix. Such carbon fibers render the CFRP electrically conductive,
with a resistance of 20 Ω typically measured between points 1 cm PSC device fabrication proceeded with an ITO bottom contact de-
apart on the surface. While such conductivity could be potentially position onto the planarized CFRP. To ensure an effective, strong
helpful for future applications, here it was found to generate elec- bond was formed between the ITO and the CFRP, the surface was
trical pathways that resulted in short-circuited devices. To over- first treated using a commercially available primer layer (Plasti-
come such issues, the surface was coated by a planarization layer coat Plastic Primer) that was spray-cast onto the CFRP surface.
that both reduced the roughness of the CFRP and rendered its ITO was then deposited onto the primed planarization layer via
surface electrically insulating. RF sputtering at a deposition power of 155 W from a 4" diam-
The planarization layer was based on an XA120 epoxy-resin ad- eter ITO target in a vacuum chamber through which argon gas
hesive film (Easy Composites) that is generally utilized to bond flowed at 7 SCCM. In all cases, ITO films were not heated dur-
honeycomb aluminium, Nomex or foam structures to composite ing or after their deposition. The bottom ITO films deposited on
parts. This material was placed on the surface of the CFRP next to the CFRP substrate had a typical thickness of 200 nm and sheet
the glass mould surface. XA120 was used due to its excellent ad- resistance of 20 Ω/□. The transmission of a typical ITO film de-
hesion to the XC130 CFRP and its ability to reduce surface rough- posited on glass is shown in Figure 2a, where the film has an
ness substantially. Figure 1c shows an image of a CFRP substrate optical transmission of 86.1% at 480 nm. While it is not pos-
with an XA120 epoxy laminate that was obtained by cutting indi- sible to directly measure the optical transmission of ITO films
vidual substrates via a waterjet cutter, with a surface topograph deposited onto CFRP substrates (as they are completely opaque),
of the same surface shown in Figure 1d. The planarization layer we have characterized their optical properties by measuring their
was found to reduce the RMS surface roughness to 29 nm over 2 angular-dependent optical reflectivity. Typical reflectivity data for
× 2 mm, with maximum peak heights being ≈400 nm. This com- ITO films deposited by sputtering on both glass and CFRP sub-
pares with a typical RMS roughness of 13 nm for a quartz-coated strates is shown in Figure S1 (Supporting Information). Here, we
glass substrate over a similar length scale. A honeycomb motif find that the optical-reflectivity of the ITO deposited on each type
having a height of ≈350 nm can be seen in the topography map. of substrate is very similar, with any differences likely resulting
This structure originates from the supporting mesh within the from the underlying CFRP/ITO interface.
epoxy planarization layer. As the core-mesh structure has a low Atomic force microscopy (AFM) measurements (see
aspect ratio, we found that subsequent coatings formed a com- Figure S2, Supporting Information) indicated that the ITO
pletely conformal layer over the surface that made them suitable deposited onto the CFRP/primer surface was relatively smooth,
substrates for device fabrication. having an RMS roughness of 15 nm over a length scale of
Figure 2. a) Optical transmission (T) (black) and reflectance (R) (red) for the bottom ITO electrode when fabricated on glass. b) Photograph of an
ITO-coated CFRP-planarized substrate heated to 100 °C in the absence of the crack-preventing SiO2 layer. Here, cracks (marked by white arrows) in the
ITO layer can be clearly seen. c) AFM image of the surface of a CFRP-planarized substrate upon which SiO2 has been deposited via e-beam evaporation.
d) Photograph of an ITO coated CFRP-planarized substrate incorporating the crack-prevention layer, with the whole structure subsequently heated to
100 °C. Note that cracks are visible near the edges of the ITO, but these are completely arrested at the SiO2 boundary (marked by yellow dotted lines).
10 × 10 μm. Despite this promising finding, we found that substrates have previously been shown to improve the ductil-
such multilayer structures were highly unstable when thermally ity of a brittle poly(selenophene-alt-3,6-dithophene-2-yl-2,5-bis-
annealed at the temperatures typically used to process materials (2-octyldodecyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione) thin
used in perovskite solar cells. Indeed, significant surface crack- film via a stress-reduction mechanism.[35] In our experiments,
ing became evident after an ITO covered CFRP substrate had the crack-prevention layer was based on a 150 nm-thick layer of
been heated to 100 °C and then cooled to room temperature (see SiO2 deposited via e-beam evaporation onto the primed CFRP
Figure 2b). This resulted in the failure of all devices fabricated substrate. As seen in the AFM image shown in Figure 2c, this
onto such CFRP surfaces, as the cracks generated electrical layer has a densely wrinkled structure, with such wrinkles hav-
short circuits between the ITO and the PSC top contact. We ing lateral dimensions of up to 2.5 μm with a height of up to
suspect that the cracking of the ITO resulted from the fact that 450 nm. The wrinkled structure is created by the combination
the coefficient of thermal expansion (CTE) of ITO is an order of of thermal radiation that is generated by the e-beam source as
magnitude lower than that measured (see Table S1, Supporting it heats the SiO2 target and the kinetic energy of the evaporated
Information) for our planarized CFRP (being 7.2 × 10−6 K−1 and material. We suspect that this process provides sufficient energy
7.9 × 10−5 K−1 respectively).[33] As a result of this mismatch, the to cause localized heating of the primer layer and planarization
difference in expansion between the substrate and ITO during epoxy to cause it to partially soften and expand during the SiO2
thermal annealing resulted in the generation and long-range deposition. On cooling, these layers contract, causing the dense,
propagation of cracks in the ITO. Such cracks apparently do not non-compressible SiO2 layer to adopt a highly crenulated struc-
“heal” when the substrate is cooled; we suspect that internal ture, as has been demonstrated by depositing metallic films using
tensile stress in the ITO film causes the edges of the cracks to an e-beam on poly(dimethylsiloxane) (PDMS).[36]
curl away from the surface. An ITO layer was then deposited onto the wrinkled SiO2 layer
To alleviate this issue, we have incorporated a “crack- via RF sputtering, forming a near conformal coating. Our ex-
prevention” layer between the ITO contact and the planarized periments demonstrate that such “wrinkled” structures do not
CFRP. This approach was inspired by previous work in which form when ITO is directly deposited on the surface of the pla-
ITO was deposited by DC sputtering onto an optically curable narized CFRP as the sputtering process does not appear to gen-
epoxy that underwent “wrinkling” and increased both the opti- erate sufficient heat to soften the surface layer (see Figure S2,
cal reflectance and flexibility of the ITO film.[34] We note that Supporting Information). AFM measurements (see Figure S3,
similar wrinkled poly(vinylidene fluoride-hexafluoropropylene) Supporting Information) indicate the surface roughness of the
wrinkled ITO is rougher than that of ITO deposited on a polished of 0.45%, as calculated via finite element analysis. Beyond this
glass surface (RMS roughness being 27 and 12 nm, respectively, point, the samples without the SiO2 layer underwent a dramatic
over a scan area of 5 × 5 μm). We believe that such wrinkles are increase in resistance as a function of deflection. However, the
not sufficient to cause device failure—indeed, similar structures samples incorporating the SiO2 layer underwent a more mod-
have been used to enhance light management in thin-film optical est, linear increase in resistance (see Figure S11, Supporting In-
devices by—for example—preventing optical waveguiding in or- formation). We suspect that the crack-prevention layer reduces
ganic light emitting diodes and improving light outcoupling.[37] damage to the ITO at any given strain due to improved adhesion
Importantly the ITO layer is strongly bonded to the wrinkled as a result of higher surface roughness that provides a good key
SiO2 ; this has been confirmed by sticking and then removing an for the ITO. We note that during these tests, the force required to
adhesive tape to the surface, performing a so-called “peel test”. achieve a strain of 0.45% was calculated to be in excess of 100 N;
Here it was found that the removal of the adhesive tape did not this force is well beyond that which soda-lime glass substrates of
remove or delaminate the ITO layer, indicating that it is strongly the same thickness would undergo complete failure.[38,39]
attached to the SiO2 surface.
We have found that such a wrinkled structure effectively “pro-
tects” the ITO during subsequent thermal annealing and cooling 2.3. Device Fabrication and Testing
processes. Figure 2d shows an image of a SiO2 –ITO layer on pla-
narized CFRP that has been thermally annealed at 100 °C before We have used the structures described above as the substrates
being allowed to cool. Here it can be seen that the ITO remains for PSC devices. A typical device stack is shown schemati-
uncracked, making it a suitable substrate for PSC device depo- cally in Figure 3a. Devices were fabricated on planarized CFRP
sition. Indeed, we find that if a surface is partially coated using substrates together with control devices on standard ITO/glass
such a “protective” silica layer, then cracks form in the ITO in substrates. In all cases, devices utilized an electron extraction
the unprotected regions upon heating and cooling, however such layer based on a colloidal SnO2 nanoparticle dispersion that
cracks do not propagate into the protected region (see Figure S4, was spin-cast onto the ITO and then thermally annealed at
Supporting Information). 100 °C for 30 min before being treated via exposure to a UV-
To explore the crack prevention mechanism, we first recorded generated ozone source for 20 min. Following this, a spin-
the CTE of the surface of CFRP substrates both with and with- cast TC-perovskite was deposited onto the SnO2 layer from
out the SiO2 layer (see Tables S1 and S2 for raw data, Figures S5 a DMF/DMSO solution and then quenched during the spin-
and S6 for experimental set up, Supporting Information for exact coating cycle using a chlorobenzene antisolvent to initiate nu-
methodology). Here, measurements were made along and across cleation of the perovskite grains. Following a thermal anneal at
the unidirectional carbon fiber axis, as any expansion could rea- 100 °C for 20 min, a perovskite film was formed, having an op-
sonably be assumed to be anisotropic. We found that the CTE tical bandgap of 1.61 eV, or 770 nm (see Figure S12, Support-
for samples without the SiO2 interlayer measured along and ing Information). Following this, a hole-extraction layer of doped
across the fiber axis were <1.0 × 10−6 and 7.9 × 10−5 K−1 , respec- spiro-OMeTAD was spin-cast onto the perovskite surface. Full ex-
tively. On addition of the SiO2 layer, the CTE of the surface layer perimental details of materials and processing techniques can be
was largely unchanged, indicating that the wrinkled layer does found in previous publications and Supporting Information.[40,41]
not modify the degree to which the surface layer expands when Importantly, as the CFRP substrate is completely opaque, it
heated. Notably, however, the significant anisotropy measured in was necessary to design the device such that light could enter
the CTE explains our observation that cracks in the ITO only de- the device through a transparent top contact. This was achieved
velop parallel to the fiber axis, as can be seen in Figure 2b. We by sputter coating a film of ITO onto the top spiro-OMeTAD.
have also characterized the surface structure of CFRP substrates This was done via a two-step deposition process[42] in which a
with and without the wrinkled-SiO2 and ITO layers as a function 30 nm-thick ITO “buffer” layer was first sputtered at 40 W, fol-
of temperature up to 150 °C. Here, we identify only fairly small lowed by the deposition at 200 W of a thicker (80 nm) “bulk” layer.
changes in the roughness of the wrinkled surface as a function The use of a buffer layer deposited at a lower magnetron power
of temperature (see Figures S7 and S8, Supporting Information). was found to reduce damage to the spiro-OMeTAD hole-transport
We conclude therefore that such wrinkled layers most likely pre- layer due to reduced exposure to the magnetron plasma. The two-
vent cracking by: 1) creating a roughened surface to which ITO step deposition process used 10 SCCM of argon for both stages,
bonds very securely and 2) by preventing the long-range propa- creating a film with a sheet resistance of 42 Ω/□ and an opti-
gation of cracks. cal transmission of 91.2% at 529 nm (see Figure 3b). The ITO
For completeness, we have also investigated the degree to contact was deposited through a shadow mask, creating a series
which the wrinkled layer confers additional mechanical protec- of pixels, each having an active area of 6 mm2 . To further pro-
tion to the ITO. Here, we carried out 4-point bend tests on ITO- tect the spiro-OMeTAD hole-transport layer, we found that it was
covered CFRP-planarized substrates (having dimensions 100 × necessary to insert a thin (0.8 nm) gold film (deposited by ther-
25 mm) either with or without a wrinkled SiO2 protection layer. mal evaporation) between the ITO and the spiro-OMeTAD hole-
Details of the experimental set up are shown in Figures S9 and transport layer. Without this layer, we found that the device JV
S10 (Supporting Information). During these bending tests, the curves typically had an "s-shape", indicating an inefficient extrac-
ITO resistance was measured as a function of roll displacement. tion of carriers (see Figure S13, Supporting Information). Here,
Here, we found that ITO resistance remained constant until the we suspect that the plasma utilized during the ITO sputter de-
center rolls were displaced by ≈3.5 mm. This level of bend cor- position partially degraded the surface of the spiro-OMeTAD and
responded to an apex displacement of ≈4.6 mm, and a strain reduced its ability to conduct charge, with the thin gold layer both
Figure 3. a) Schematic of our typical device structure, with an arrow to indicate direction of illumination. b) Optical transmission (T) (black) and
reflectance (R) (red) of the top ITO electrode when deposited on glass. c) Photograph of PSC devices on CFRP composite. Note that the light-gray
material visible on each device pixel and the bus bar is silver loaded paste that was used to improve electrical contact to the device. d) Box-plot summary
of key device performance metrics derived from reverse JV sweeps of control devices fabricated on glass together with those on CFRP.
acting as a protection layer by attenuating the passage of ionizing substrates. Here, we find that the mean average device efficiency
species into the spiro-OMeTAD and also enhancing charge ex- was ≈12.5%, with the performance of the control devices closely
traction from the spiro-OMeTAD into the ITO. Finally, to improve matching that of the devices fabricated on CFRP. We attribute the
device efficiency, an anti-reflection layer consisting of 100 nm of relatively low PCE of the control devices on a glass substrate to the
LiF was deposited onto the ITO surface via thermal evaporation. fact that they are illuminated through the top of the device, with
Figure 3c shows an image of a fully fabricated device on a light passing through ITO, gold (0.8 nm) and spiro-OMeTAD lay-
CFRP substrate. Electrical contact was made to each device using ers before reaching the active perovskite layer. This results in
a semiconductor probe station, with efficiency measurements significant parasitic absorption by the UV/blue absorbing spiro-
performed through an aperture mask (area 2.385 mm2 ) placed OMeTAD layer (bandgap of 2.70–2.98 eV[43,44] ). This is in contrast
onto the surface of the substrate (see Figure S14, Supporting In- to a typical n–i–p stack that is illuminated through its substrate.
formation). Figure 3d shows box plots of the key device metrics In such devices, it is only necessary for light to pass through a thin
(PCE, JSC , VOC and FF), with data recorded from 8 independent (30 nm), wide-bandgap (3.6–4.2 eV[40] ) SnO2 layer before absorp-
devices containing 16 pixels in total. Here, it can be seen that we tion by the perovskite, with the SnO2 layer resulting in negligi-
record a mean average device PCE of 12.0% with a typical de- ble optical losses. To confirm that our glass control devices were
vice yield of ≈40%. We attribute the relatively low device yield fully optimized, we first recorded JV curves in which devices were
to the fact that the ITO/CFRP surface is rougher than commer- instead illuminated through the glass substrate. Here, we deter-
cially available ITO coated glass substrates. Such roughness can mined PCE values of up to 16.2%; a result that confirms the effect
result in device failure through the generation of electrical short- of parasitic absorption within the spiro-OMeTAD (see Figure S15,
circuits. We believe that further optimization of the CFRP fab- Supporting Information). We then fabricated identical control de-
rication and planarization processes will lead to surfaces having vices in which the top Au (0.8 nm)/ITO layer was replaced by a
reduced roughness and thus improved device yield. conventional thick (80 nm) Au electrode. Devices were then illu-
Figure 3d also shows device performance metrics for a series minated through the bottom ITO/SnO2 contact. Figure S15 (Sup-
of control devices fabricated onto an ITO/glass substrate. Here, porting Information) plots typical JV curves, where it can be seen
the device stack is identical to that shown in Figure 3a except for that best performing devices had a PCE of 20.2%; a value com-
the CFRP substrate (i.e., incorporating a transparent ITO top con- mensurate with this n–i–p device architecture. We therefore con-
tact). For the sake of fair comparison, control devices were illu- clude that the reduced efficiency of devices fabricated on CFRP
minated through the top ITO contact using an aperture mask in substrates results from optical absorption in the spiro-OMeTAD
a similar way to that used to study devices on the opaque CFRP layer and the lack of a back-reflector to recycle light not absorbed
Figure 4. a) JV data for the champion CFRP-based device, with metrics derived from the reverse sweep. b) Details the stabilized power output of the
same device held at close to the maximum power point voltage for 60 s. c) EQE spectrum of a typical CFRP-based device. d) Stabilized power output of
glass control devices as a function of storage time in air.
in the perovskite on its first optical pass, together with a relatively the promising stability to the TC perovskite formulation[46] to-
higher sheet resistance of the ITO top contact in comparison with gether with the use of an ITO top contact. We note that other
that of a thick gold electrode. approaches to the development of semi-transparent top-contact
For completeness, Figure 4a plots a JV curve under AM1.5 ir- electrodes based on ultrathin metallic films typically suffer from
radiation of the champion CFRP device. Here, the device had a reduced stability resulting from oxidation or reactions with I-
JSC of 18.91 mA cm−2 , a VOC of 1.06 V, an FF of 71.7% and a ions that diffuse out of the perovskite.[47–49] Such reactions do not
PCE of 14.35%. A stabilized power output of 14.5% was recorded occur with transparent conductive oxide materials such as ITO,
for this device when held under illumination near the maximum with our selection of materials, therefore, conferring a high de-
power point voltage, as shown in Figure 4b. Figure 4c shows a gree of intrinsic stability to the device. Indeed, our preliminary
typical external quantum efficiency (EQE) spectrum of a device findings also suggest that devices fabricated onto CFRP can show
on a CFRP substrate. Here we extract an integrated JSC value of a promising level of dark-storage stability (see Figure S17, Sup-
18.3 mA cm−2 ; a value in agreement with the short circuit cur- porting Information).
rent determined from the solar simulator measurements. Note
that due to parasitic absorption by the spiro-OMeTAD HTL, we 3. Discussion
see a drop-off in the EQE response between 300–400 nm. The ef-
fect of the spiro-OMeTAD absorption is illustrated in Figure S16 We have demonstrated the integration of PSC devices onto
(Supporting Information), where we plot an EQE measurement planarized carbon fiber substrates, with devices having a
of a glass control device illuminated through the glass substrate. similar PCE to control devices fabricated on conventional
Here, a UV/blue EQE response is evident as the incident light no glass substrates. Although we have used spin-coating to de-
longer passes through a spiro-OMeTAD layer. posit the solution-processable device layers (np-SnO2 electron-
We have also made a preliminarily assessment of the op- transport layer, TC perovskite precursor, and spiro-OMeTAD
erational stability of the Au(0.8 nm)/ITO top electrodes using hole-transport layer), we note that such layers can be deposited
dark-storage tests, with unencapsulated devices fabricated on via spray-coating, allowing devices to be created over complex,
glass/ITO electrodes stored in 30% RH air as per ISOS-D-1 curved substrates.[29]
requirements.[45] Here, such devices were illuminated through Our devices are fabricated directly onto a surface that could
the top electrode during testing, with such measurements pro- have a significant second function—e.g., acting as the wing of
viding some measure of the stability of this transparent contact. an aircraft or the roof of a car. To estimate the specific power
As shown in Figure 4d, we find that devices retain 85% of their of our devices, we simply consider the masses of the layers that
peak efficiency during a period of over 35 days. Here, we ascribe we have deposited. In our calculation of the areal mass of each
layer, we use its known thicknesses and reported density (see compares favorably with control devices fabricated onto conven-
Table S3, Supporting Information, for exact methodology). Us- tional ITO/glass substrates. The devices realized had a specific
ing this approach, we find the mass per unit area of our com- power (power per mass) of 21.4 W g−1 (an estimate that ignores
plete PSC devices to be ≈6.78 g m−2 , indicating a specific power the mass of the CFRP substrate), with the practical application of
of ≈21.4 W g−1 . This value compares favorably with a-Si cells[50] this technology requiring the development of ultralow mass en-
that have a maximum reported specific power of 8.31 W g−1 but capsulation layers. The substrates utilized combine high strength
is, however smaller than the specific power of PSC devices fab- and low mass, making them directly applicable as structural ma-
ricated onto ultrathin flexible PEN (29.4 W g−1 )[22] or ultrathin terials that can simultaneously generate electrical power. We ex-
flexible parylene-C (30.3 W g−1 ).[23] We note however that the fab- pect further work (including device deposition by spray-coating,
rication of PSC devices onto ultrathin substrates will also require device scale-up, modularization and encapsulation) to create sys-
an adhesive layer to attach them to a surface of interest, thereby tems having direct employment in mobile power applications,
reducing their effective specific power. Furthermore, as such de- including UAVs, HAPSs, and electric vehicles.
vices are illuminated through the substrate, the application of ad-
hesives might damage the semiconductor layers, necessitating
the use of a back encapsulant layer, with this layer also reducing Supporting Information
effective specific power. Finally, as noted above, wrapping of com-
plex shapes via lamination is likely to introduce unwanted pleats Supporting Information is available from the Wiley Online Library or from
the author.
into the PSC device.[24]
We note that our estimate of specific power ignores the mass of
any encapsulation material, with encapsulation being critical for
“real-world” applications. Typically, we encapsulate regular de- Acknowledgements
vices using a glass coverslip and a UV-cured epoxy; however, this O.S.G., T.T. and F.C-M. contributed equally to this work. This work was
would account for over 98% of the total device mass and would funded by the Engineering and Physical Sciences Research Council (EP-
reduce device specific power to just 0.4 W g−1 . To enhance the SRC) grant EP/S009213/1 (The Integration of Photovoltaic Devices with
specific power of our devices, it will clearly be necessary to de- Carbon-Fiber Composites). E.J.C. thanks the EPSRC for a PhD studentship
velop ultralow mass encapsulation layers, with such layers likely from grant EP/L01551X/1 (Centre for Doctoral Training in New and Sus-
being deposited via a combination of vapor deposition and spray- tainable PV). R.H.G thanks the EPSRC for a PhD studentship from grant
EP/T012455/1 (Molecular Photonic Breadboards). T.T. thanks the Univer-
coating, allowing them to also cover curved surfaces. If we as- sity of Sheffield for the provision of a PhD studentship.
sume the thickness of the encapsulation layers could be reduced
to ≈3 μm (e.g., composed of an evaporated metal oxide), then we
might expect a specific power of ≈5.4 W g−1 . If devices were in-
stead encapsulated using a 1 μm-thick solution-processed poly- Conflict of Interest
meric film (such as polyurethane),[21] then we estimate a specific D.G.L. is a co-director of the company Ossila Ltd. which retails materials
power of ≈18.2 W g−1 should be possible. We note that our de- and equipment used in perovskite photovoltaic device research and devel-
vices are designed to be rigid rather than flexible; therefore, any opment.
polymeric material used would not require a great deal of flexibil-
ity. This would allow the utilization of materials having a higher
crosslink density and thus superior oxygen and moisture barrier Data Availability Statement
properties.[51] Such devices would clearly represent an important
The data that support the findings of this study are available from the cor-
step toward the development of practical power sources for mo-
responding author upon reasonable request.
bile automotive and aerospace applications.
4. Conclusion Keywords
We have outlined an approach to the direct integration of PSCs carbon-fiber-reinforced polymers, integrated photovoltaics, perovskite so-
with a planarized CFRP composite substrate. We show that the lar cells, specific power, structural photovoltaics
successful integration of devices onto the surface of the CFRP
necessitates the planarization of the substrate, together with the Received: October 27, 2022
use of a crack-prevention layer that is formed from a “wrinkled” Revised: March 7, 2023
SiO2 film that is formed onto the surface of the planarization Published online: May 17, 2023
layer. This wrinkled structure is created by partially softening the
surface of the primer and planarization layer as a result of the
thermal energy provided by the e-beam deposition process. This
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Advanced Materials - 2023 - Game - Direct Integration of Perovskite Solar Cells with Carbon Fiber Substrates

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RESEARCH ARTICLE

Direct Integration of Perovskite Solar Cells with Carbon

single-junction devices (25.7%) now ap-

O. S. Game[+] , T. Thornber, E. J. Cassella, R. C. Kilbride[++] , R. H. Gordon, F. Cepero-Mejías, J. P. A. Fairclough

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