Graphene Interface Engineering for Perovskite Solar Modules: 12.6% Power Conversion Efficiency over 50 cm2 Active Area - General Graphene Corp
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Letter
http://pubs.acs.org/journal/aelccp
Graphene Interface Engineering for Perovskite
Solar Modules: 12.6% Power Conversion
Efficiency over 50 cm2 Active Area
Antonio Agresti,§ Sara Pescetelli,§ Alessandro L. Palma,§ Antonio E. Del Rio Castillo,‡
Dimitrios Konios,∥ George Kakavelakis,∥ Stefano Razza,§ Lucio Cinà,§ Emmanuel Kymakis,∥
Francesco Bonaccorso,*,‡ and Aldo Di Carlo*,§
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
§
C.H.O.S.E. (Centre for Hybrid and Organic Solar Energy), Department of Electronic Engineering, University of Rome Tor Vergata,
via del Politecnico 1, 00133 Rome, Italy
‡
Istituto Italiano di Tecnologia, Graphene Labs, Via Morego 30, 16163 Genova, Italy
∥
Center of Materials Technology and Photonics & Electrical Engineering Department School of Applied Technology, Technological
Downloaded via DURHAM UNIV on July 25, 2018 at 06:23:25 (UTC).
Educational Institute (T.E.I) of Crete Heraklion, 71 004 Crete, Greece
*
S Supporting Information
ABSTRACT: Interfaces between perovskite solar cell (PSC) layer
components play a pivotal role in obtaining high-performance
premium cells and large-area modules. Graphene and related two-
dimensional materials (GRMs) can be used to “on-demand” tune
the interface properties of PSCs. We successfully used GRMs to
realize large-area (active area 50.6 cm2) perovskite-based solar
modules (PSMs), achieving a record high power conversion
efficiency of 12.6%. We on-demand modulated the photoelectrode
charge dynamic by doping the mesoporous TiO2 (mTiO2) layer
with graphene flakes. Moreover, we exploited lithium-neutralized
graphene oxide flakes as interlayer at the mTiO2/perovskite
interface to improve charge injection. Notably, prolonged aging
tests have shown the long-term stability for both small- and large-
area devices using graphene-doped mTiO2. Furthermore, the possibility of producing and processing GRMs in the form of
inks opens a promising route for further scale-up and stabilization of the PSM, the gateway for the commercialization of
this technology.
in spin-coating the perovskite layer by using a mixture of γ-
T he recent development of perovskite solar cell (PSC)
technology gave rise to an unprecedented power
conversion efficiency (PCE) improvement from η =
3.8%1 up to 22.1%2 in less than 7 years. The demonstrated PCE
values make the PSC technology competitive with second-
butyrolactone (GBL) and dimethyl sulfoxide (DMSO) as the
main solvents, followed by a toluene or chlorobenzene (used as
antisolvents) treatments during the spinning process.15−18
However, although uniform and pinhole-free perovskite layers
generation thin-film photovoltaics such as copper indium are produced, this approach is hardly scalable to large and
gallium selenide (CIGS) or cadmium telluride (CdTe).3 The module size substrates because of the difficulty in uniformly
PSC success is strictly linked with the remarkable efforts made depositing by spin coating the antisolvent on large-area
to improve the device’s structure, to fine control the growth
substrates. To overcome such limitations, several alternative
and the morphology of the active perovskite layer, and to
techniques for the perovskite deposition have been proposed,19
engineer the interfaces between the cell’s constituent layers.4−10
The PCE record of PSCs11 has been achieved with the with the solution-process methods being the most promising
archetypal mesoscopic device configuration using n-type ones, e.g., enabling cost-effective20,21 roll-to-roll production.22
mesoporous TiO2 (mTiO2) layer as electron transport layer In particular, the one-step deposition allows a pinhole-free
(ETL).12,13 For this structure,11 a mixture of formamidinium perovskite deposition directly on compact TiO2 layer (cTiO2),
and methylammonium as the monovalent cations with the
addition of inorganic cesium has been used to grow perovskite Received: December 9, 2016
crystals, with the layer morphology finely controlled by Accepted: December 27, 2016
exploiting a solvent-engineering technique.14 The latter consists Published: December 27, 2016
© 2016 American Chemical Society 279 DOI: 10.1021/acsenergylett.6b00672
ACS Energy Lett. 2017, 2, 279−287
ACS Energy Letters Letter
Figure 1. Structures of small-area PSCs: (a) PSC-A with the reference mesoscopic structure FTO/cTiO2/mTiO2/perovskite/spiro-OMeTAD/
Au, (b) PSC-B with GO-Li as interlayer between perovskite and mTiO2, (c) PSC-C using graphene-doped mTiO2 layer, and (d) combined
PSC-D structure FTO/cTiO2/G+mTiO2/GO-Li/perovskite/spiro-OMeTAD/Au.
in the so-called planar configuration, leading to the most treatment of the mTiO2 layer prior to the perovskite
efficient fabrication procedure (i.e., PCE approaching 18%).23 deposition32,50 and/or TiO2 doping,51,52 (ii) the use of different
However, planar PSCs usually suffer from large current−voltage TiO2 nanostructures53−55 and heterostructures,56 and (iii) the
(I−V) hysteresis phenomena.24−26 The insertion of a mTiO2 modification of energy levels by the addition of interface
scaffold25 combined with a two-step perovskite deposition,27 layers.57−59 Moreover, the potential to tune the perovskite/
with the deposition of PbI2 layer prior to dipping the substrate mTiO2 interface60 allows the reduction of the I−V curve
in a methylammonium iodide (MAI)−2-propanol (IPA) hysteresis,61 while at the same time improving the charge
solution,28−30 reduces the I−V hysteresis.25 In fact, the collection at the PE.32
presence of mesoporous metal oxide scaffolds such as Al2O331 Graphene and related two-dimensional (2D) materials
or TiO232 aids the perovskite crystal formation, hindering short (GRMs) are emerging as the paradigm shift of interface
circuit between photo (PE) and counter (CE) electrodes.25,33 engineering to boost both photovoltaic performance19,62,63 and
The two-step procedure is the preferred perovskite deposition stability of PSCs.58,64 In fact, owing to their 2D nature and the
method for large-area mesoscopic PSCs and perovskite-based large variety of 2D crystals possessing complementary (opto)-
solar modules (PSMs), ensuring a deeper perovskite infiltration electronic properties,65 which can be on-demand tuned by
into the mTiO2 scaffolds compared to the single-step process.34 chemical functionalization and edge modification,66 GRMs can
This determines a fine control of the morphology of the be considered ideal materials for PSC interface engineering.
perovskite capping layer over interpenetrated TiO2/perovskite The first experiments have demonstrated the use of graphene
substrate, which is beneficial for improving the perovskite film oxide (GO) or reduced graphene oxide (RGO) as dopants in
uniformity,35 boosting the performance of the final devices.27 transport layers67−69 and as interlayers between perovskite and
Despite the remarkable PCE value achieved by using transporting layers70,71 with the aim of improving the charge
mesoscopic PSCs,36−38 record efficiency (22.1%)11 is yet far collection mechanism at the electrodes.72,73 Moreover, GRM-
from the predicted efficiency limit (∼31%).39 Notably, losses based inks can be produced by cheap and high-yield
due to interfacial recombination40 negatively affect the charge manufacturing processes using nontoxic solvents such as
injection at perovskite/transporting layer interface. Similarly, ethanol (EtOH) or IPA.74−76 This allows the integration of
poor charge transport in electron (ETL)41 and hole (HTL)42,43 GRMs in an in-line production process for large-area perovskite
transporting layers severely limits charge collection at the devices and modules, with the aim of reducing performance
electrodes. These phenomena lead to a reduction of both losses experienced by PSC scale-up.77,78 In fact, the scale-up
device short-circuit current (ISC) and fill factor (FF),44−46 thus process amplifies typical problems79 undergone in perovskite
reducing the PCE. Among the recently identified recombina- films deposition such as nanoscale pinholes,80 crystal grain
tion mechanisms for methylammonium lead triiodide (MAPI) boundaries,81 and perovskite film roughness,82 which can
based PSCs,47 those involving TiO2/MAPI and MAPI/hole severely affect the film quality and consequently the module
transport material (HTM) interfaces play a crucial role in PCE.23,83−87 The aforementioned problems have so far limited
limiting the PCE.40 In particular, (i) interfacial electron transfer the maximum delivered power (MDP) of PSMs. The record
from the MAPI conduction band (CB) to the HTM and/or to PSM efficiency, i.e., PCE = 14.9%, has been achieved for an
TiO2 surface states47 and (ii) interfacial electron transfer from active area of 4 cm2 with a MDP of 58 mW;88,89 when the
TiO2 CB to the HTM and/or to MAPI need to be active area is increased to 60 cm2, the PCE reduces to 8.7%,14
prevented.48,49 A fine-tuning of interface and interlayer with a MDP of 552 mW.
properties is mandatory to enhance the charge transport and In this work, we demonstrate that GRMs can indeed be the
extraction at the mTiO2/MAPI interface by (i) chemical key elements for an efficient strategy of PSC scale-up.
280 DOI: 10.1021/acsenergylett.6b00672
ACS Energy Lett. 2017, 2, 279−287
ACS Energy Letters Letter
Figure 2. Photovoltaic parameters measured at 1 SUN and relative standard deviation on 12 PSCs (open-circuit voltage, VOC; short-circuit
current density, JSC; fill factor, FF; and PCE reported in panels a, b, c, and d, respectively), for the four investigated PSCs.
Graphene interface engineering (GIE) is proposed as an with respect to the PSC-A, mainly due to an increase of the
effective way to boost PCE of both PSCs and PSMs by limiting short-circuit current density (JSC), see Figure 2. In particular,
the charge losses occurring at the perovskite/mTiO2 interface, the insertion of GO-Li, as interlayer between perovskite and
improving at the same time the stability. In particular, lithium- mTiO2 (PSC-B), leads to a significant improvement of the
neutralized graphene oxide (GO-Li) flakes have been average JSC values (+18%), while a 4.3% loss in the averaged
introduced as interlayer at the mTiO2/perovskite interface72 open-circuit voltage (VOC) is observed. We do hypothesize that
with the aim of improving the charge injection from the the VOC reduction is linked with the presence of the GO-Li,
perovskite to the mTiO2, while graphene flakes have been which induces a downward displacement of the TiO 2
dispersed into the mTiO2 layer58 to speed up the charge conduction band (CB) with a consequent reduction of
dynamic at the PE.58 This allowed us to realize a GRMs-based VOC72,94 (see Figure 2a). With respect to the use of graphene
PSC module having a PCE of 12.6% on an over 50 cm2 active flakes, the GO-Li insertion within the mesoporous layer
area and a MDP of 638 mW at 1 SUN illumination conditions. resulted in an increased JSC (+9.6%) compared to that of the
Small-Area Cells. Small-area solar cells (0.1 cm2) are realized PSC-A (Figure 2b). Contrary to the GO-Li case, the graphene
to assess the influence of GIE on PSCs with respect to the flakes addition does not lead to a reduction in the VOC value.
reference device (Figure 1a). We exploit graphene flakes and Finally, the type D structure shows an overall PCE improve-
GO-Li produced by solution processing;75,90 see the Support- ment of about 7% with respect to the reference one, which is
ing Information for both technical details and morphological linked with an increase of 7% of the JSC value, retaining, at the
characterization. In addition, Raman characterization91−93 of same time, satisfying VOC values when compared to that of the
graphene-based mesoscopic substrates is provided in Figure S3. PSC-A. We point out that the reduction of the PCE standard
By using the standard two-step production procedure detailed deviation achieved in the case of PSC-D is highly desirable for
in the Supporting Information, the small-area reference PSCs large-area PSCs, where local inhomogeneity of the active layer
(indicated in the following as PSC-A) have shown an averaged can affect the device’s PCE.34,95
PCE of 13.5% calculated on 12 cells. In addition, 3 PSC sets are To gain a deeper understanding of the effect of GIE on the
realized by using the GIE strategy. In particular, in sample B PSCs performance, electro-optical characterizations and tran-
(PSC-B), a GO-Li interlayer is spin coated onto the mTiO2 sient measurements are carried out on encapsulated PSCs (see
layer before the perovskite deposition (Figure 1b), while in the Supporting Information for details). The increase in JSC for
sample C (PSC-C), see Figure 1c, graphene ink is dispersed PSC-B and PSC-C (see Figure 2b), with respect to PSC-A, is
into the mTiO2 paste to form the graphene-doped cell scaffold confirmed by the incident photon-to-current conversion
(G+mTiO2); see the Supporting Information for experimental efficiency (IPCE) spectra and by the extracted integrated JSC
details and Raman characterization (Figure S3). Finally, in values reported in Figure S5a. In particular, the GO-Li
device D (PSC-D), the GO-Li interlayer is deposited onto the interlayer enhances the IPCE in the spectral range between
G+mTiO2 scaffold (Figure 1d), realizing a combined structure. 400 and 600 nm, with respect to the PSC-A,72 up to a
The different PSC configurations are reported in Figure 1 (see maximum of +7% at 440 nm (see Figure S5b). An IPCE
Figure S4 for the corresponding energy band diagram), while increase of 8.6% is observed at ∼760 nm. The long-wavelength
the statistical photovoltaic parameters measured for each set of IPCE rise with respect to reference PSC is more significant for
PSCs are reported in Figure 2. PSC having the G+mTiO2 scaffold (PSC-B), see Figure S5b.
The GRM-based PSCs (i.e., PSC-B, PSC-C, and PSC-D) This phenomenon could be linked with two different processes,
show higher PCEs (+14.8%, +13.6%, and +6.1%, respectively) i.e., (i) efficient electron injection from perovskite to mTiO2
281 DOI: 10.1021/acsenergylett.6b00672
ACS Energy Lett. 2017, 2, 279−287
ACS Energy Letters Letter
Figure 3. (a) JSC and (b) normalized VOC rise profile acquired by retaining the tested devices in open-circuit conditions, in the dark, and by
suddenly (t = 0) switching on the light at 1 SUN irradiation conditions.
and/or (ii) increased charge transport and collection at the PE. have been used in dye-sensitized solar cell (DSC) technology
To get an insight into the physical mechanism responsible for and recently adopted also for PSCs.99,100 The VOC rise test is
the IPCE increase, discriminating the charge injection process carried out by taking the device from steady-state operating
from transport and collection phenomena, we carried out conditions under dark at open circuit, switching on the light
transient measurements. We recorded JSC (Figure 3a) and VOC source, and monitoring the subsequent rise in photovoltage.101
(Figure S6a) over 3 decades of incident optical power (i.e., The concentration of the photoinjected electrons in the TiO2
from 0.002 to 2 SUN) by using a white LED (see the film primarily determines the photovoltage transient profile.
Supporting Information for details). Moreover, the buildup of electrons is in competition with the
The JSC vs Pinc plots of Figure 3a show linear trends for all the electron recombination processes, which is detrimental for the
investigated PSCs, an indication of energy level matching (see device performance. As reported in Figure 3b, both PSC-B and
Figure S4) of the device component layers. In fact, a nonlinear PSC-D show faster VOC rise profile, which can be associated
trend of JSC versus light intensity is linked with the existence of with a better charge injection at the perovskite/mTiO2
energy barriers within the device, negatively affecting the charge interface, with respect to the reference one. This result is
extraction process.96 Moreover, a nonlinear shape is indicative correlated to the increase of JSC vs Pinc slope already reported in
of geminate recombination mechanism involving the hole− Figure 3a. Remarkably, PSC-C and PSC-D have shown the
electron exciton and/or space charge limitation at the fastest dynamic due to the presence of graphene flakes within
heterojunction associated with unbalanced electron and hole the mTiO2 layer. Thus, the obtained PCE values reported in
mobilities.97 For our PSCs, both the insertion of graphene into Figure 2d (i.e., PCE = 16.4% for top PCE using G+mTiO2
the mTiO2 layer (PSC-C) and the GO-Li interlayer between layer) are linked with optimized charge injection processes.
perovskite and mTiO2 (PSC-B) led to an improvement of the The influence of GIE on the stability of the PSCs is assessed
electron injection at the perovskite/TiO2 interface, as by both prolonged illumination at maximum power point
confirmed by the increase of JSC vs Pinc slope,96 i.e., up to (MPP) and shelf life tests at open-circuit conditions (see
18.4% (Figure 3a), with respect to that of the reference PSC-A. Figure.S6 and Figure.S7).
In fact, for PSC-B the slope of the linear fitting is 224 mA/W, Among the tested PSCs, the PSC-C and PSC-D retain ∼88%
for PSC-C 217 mA/W, and for PSC-D 225 mA/W, while for of the initial PCE after 16 h of endurance test, showing longer
the reference PSC-A a value of only 190 mA/W is obtained. lifetime with respect to the one obtained by the other types of
The optimization of charge extraction has been experimentally PSCs. Stationary and transient electro-optical analyses, reported
demonstrated recently for both graphene flakes/perovskite58 in Figures S6 and S8, show that PSC-C and PSC-D have a
and GO-Li/perovskite72 interfaces. In particular, Volonakis and moderated PE degradation with respect to PSC-A, suggesting a
Giustino98 predicted, by means of first-principles calculations reduced occurrence of trap sites and charge recombination
on graphene−CH3NH3PbI3 interfaces, that pristine graphene paths following the light soaking test. In contrast, the GO-Li
suppresses the octahedral tilt in the first perovskite monolayer, interlayer dramatically affects the device’s long-term stability
leading to a nanoscale ferroelectric distortion with a permanent because of a significant reduction of the JSC (−84% after 16.5 h
polarization. This interfacial ferroelectricity drives electron of light soaking test at 1 SUN). Lithium atoms degrade the
extraction from the perovskite, hindering electron−hole perovskite layer,69,102−104 thus compromising the perovskite/
recombination,98 a phenomenon that could explain the electron GO-Li/mTiO2 interface and, consequently, the electron
injection mechanism at the perovskite/graphene-doped mTiO2 injection process. Notably, the combined use of graphene in
interface experimentally demonstrated in this work. Addition- mTiO2 and GO-Li interlayer results in a considerably improved
ally, the energy level matching between GO-Li and the mTiO2 stability with respect to the PSC-B, especially for what concerns
layer together with TiO2 trap passivation72 facilitate electron light stress at MPP. In fact, PSC-D (Figure S6d, curve D)
injection in PSCs with a GO-Li interlayer. A detailed study of retains more than 70% of the initial PCE after 16 h of
the VOC dependence on Pinc (see Figure S6a) further confirms prolonged 1 SUN stress test.
that neither graphene flakes nor GO-Li introduce trap states in Large-Area Modules. To test the effectiveness of our proposed
PSCs. GIE approach, we developed large-area modules, fabricated on
To investigate the influence of the GRM on the electron a 10 × 10 cm2 substrate area, consisting of eight series-
injection and collection at the PE of the devices, we tested the connected PSCs (active area 6.32 cm2), with an overall active
dynamic performance under pulsed light conditions with area of 50.56 cm2. The module aperture ratio, i.e., the ratio
transient photovoltage (TPV) measurements.99 TPV tests between the active area and the aperture area, is approximately
282 DOI: 10.1021/acsenergylett.6b00672
ACS Energy Lett. 2017, 2, 279−287
ACS Energy Letters Letter
73% (see the schematic representation of module layout +mTiO2 and GO-Li interlayer in PSM-D results in the most
reported in Figure S10). efficient PSM, i.e., exceeding by 9% the PCE of the reference
The I−V characteristics of the as-produced PSMs are one. The as-obtained PCE values are linked with the increase of
reported in Figure 4b for each tested device structures named FF (+8.8%), still maintaining a VOC of 8.57 V. Differently from
the results obtained with PSCs, the PSM-D has shown the best
PCE performance (Table 1), confirming the crucial role of GIE
in retaining high PCE uniformity passing from small-area, i.e.,
ACS Energy Letters Letter
Figure 5. Normalized (a) VOC, (b) ISC, (c) FF, and (d) PCE trends vs time extracted by 1 SUN I−V characteristics, periodically acquired
during the shelf life test (ISOS-D-1) for the four PSMs.
and GO-Li interlayer has a T80 lifetime 3 times greater than the
reference one. Moreover, the exploitation of GIE resulted in
■ ACKNOWLEDGMENTS
This project has received funding from the European Union’s
prolonged shelf life stability for PSM that retained more than Horizon 2020 research and innovation programme under grant
90% of the initial PCE after 1630 h when G+mTiO2 is used as agreement No. 696656 − GrapheneCore1.
■
scaffold.
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