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Summary Multijunction all-perovskite solar cells offer a route toward efficiencies of III-V materials at low cost by combining the advantages of low thermalization loss in multijunction architectures with the beneficial properties of perovskites—namely, low processing cost, high-throughput fabrication, and compatibility with flexible substrates. However, there are two main challenges for enabling high-efficiency tandems: (1) design of a recombination layer to efficiently combine two perovskite subcells while also preventing bottom cell damage during top cell processing and (2) achieving high open-circuit voltage of the wide-gap subcell. Herein, we overcome both of these challenges. First, we demonstrate a nucleation layer consisting of an ultra-thin polymer with nucleophilic hydroxyl and amine functional groups for nucleating a conformal, low-conductivity aluminum zinc oxide layer by atomic layer deposition (ALD). This method enables ALD-grown recombination layers that reduce shunting as well as solvent degradation from solution processing on top of existing perovskite active layers. Next, we demonstrate a band-gap tuning strategy based on A-site cations of mismatched size (dimethylammonium and cesium) to enable a 1.7 eV perovskite with high, stable voltages. By combining these advances, we fabricate two-terminal all-perovskite tandem solar cells with 23.1% power conversion efficiency on rigid substrates and 21.3% on flexible plastic substrates.

This review article examines the current state of understanding in how metal halide perovskite solar cells can degrade when exposed to moisture, oxygen, heat, light, mechanical stress, and reverse bias. It also highlights strategies for improving stability, such as tuning the composition of the perovskite, introducing hydrophobic coatings, replacing metal electrodes with carbon or transparent conducting oxides, and packaging. The article concludes with recommendations on how accelerated testing should be performed to rapidly develop solar cells that are both extraordinarily efficient and stable.

Metal halide perovskite semiconductors possess excellent optoelectronic properties, allowing them to reach high solar cell performances. They have tunable bandgaps and can be rapidly and cheaply deposited from low-cost precursors, making them ideal candidate materials for tandem solar cells, either by using perovskites as the wide-bandgap top cell paired with low-bandgap silicon or copper indium diselenide bottom cells or by using both wide- and small-bandgap perovskite semiconductors to make all-perovskite tandem solar cells. This Review highlights the unique potential of perovskite tandem solar cells to reach solar-to-electricity conversion efficiencies far above those of single-junction solar cells at low costs. We discuss the recent developments in perovskite-based tandem fabrication, and detail directions for future research to take this technology beyond the proof-of-concept stage. Perovskites, with their wide bandgap range, are good partners for both commercial and novel photovoltaic technologies in multijunction solar cells. Here, McGehee and co-workers review recent material and device developments and highlight future challenges and opportunities for perovskite-based tandems.

Metal-contact-induced degradation and escape of volatile species from perovskite solar cells necessitate excellent diffusion barrier layers. We show that metal-induced degradation limits thermal stability in several perovskite chemistries with Au, Cu, and Ag gridlines even when the metal is separated from the perovskite by a layer of indium tin oxide (ITO). Channels in a sputtered ITO layer that align with perovskite grain boundaries are pathways for metal and halide diffusion into or out of the perovskite. Planarizing the perovskite morphology with a spin-cast organic charge-transport layer results in a subsequently deposited ITO layer that is uniform and impermeable. We show that it is critical to seal the edges of the active layers to prevent escape of volatile species. We demonstrate 1000 h thermal stability at 85 °C in CH3NH3PbI3 solar cells with complete-coverage silver contacts. Our barrier layer design enables long-term thermal stability of perovskite solar cells, a critical step to commercialization.

Metal halide perovskites are attractive candidates for the wide band gap absorber in tandem solar cells. While their band gap can be tuned by partial halide substitution, mixed halide perovskites often have lower open-circuit voltage than would be expected and experience photoinduced trap formation caused by halide segregation. We investigate solar cell performance and photostability across a compositional space of formamidinium (FA) and cesium (Cs) at the A-site at various halide compositions and show that using more Cs at the A-site rather than more Br at the X-site to raise band gap is more ideal as it improves both VOC and photostability. We develop band gap maps and design criteria for the selection of perovskite compositions within the CsxFA1–xPb(BryI1–y)3, space. With this, we identify perovskites with tandem-relevant band gaps of 1.68 and 1.75 eV that demonstrate high device efficiencies of 17.4 and 16.3%, respectively, and significantly improved photostability compared to that of the higher Br-co...

Perovskite solar cells (PSCs) are highly promising, but they are mechanically fragile, composed of layers with mismatches in thermal expansion coefficients, and known to decompose in the presence of heat and moisture. Here we show the development of a glass–glass encapsulation methodology for PSCs that enables them to pass the industry standard IEC 61646 damp heat and thermal cycling tests. It is important to select a thermally stable perovskite composition to withstand the encapsulation process at 150 °C and design a cell that minimizes metal diffusion. Moreover, the package needs an edge seal to effectively prevent moisture ingress and an inert encapsulant with an appropriate elastic modulus to hold the package together while allowing for compliance during temperature fluctuations. Our work demonstrates that industrially relevant encapsulation techniques have the potential to enable the commercial viability of PSCs.

Tin-lead perovskites have low band gaps (1.2 eV – 1.4 eV) that offer complementary absorption spectra to mixed halide perovskites with band gaps in the range of 1.6 eV – 1.85 eV. In combination, tin-lead and mixed halide perovskites can be used to make efficient all-perovskite tandem solar cells. While these can achieve high efficiency, they are hampered by the unproven longterm stability of tin-containing perovskites. We make the first demonstration of tin-lead perovskite solar cells that pass benchmark 1000-hour tests of stability under stressors of heat, light, and atmospheric exposure. We identify that mixed tin-lead perovskites oxidise by a different chemical pathway, one that is much less favourable, than the oxidation pathway followed by pure tin perovskites, making them significantly more stable. Fortuitously, mixed tin-lead perovskites also have band gaps that are close to ideal for the rear cell of an all-perovskite monolithic two-junction tandem. Beyond selecting the composition of the perovskite to be one that has inherently suppressed tendency to oxidise, we also fabricate a novel heterojunction-based architecture that eliminates the commonly used acidic PEDOT:PSS layer, which leads to enhanced stability. By packaging the resulting solar cell in a glass-on-glass package with a pliable low-elastic-modulus polyolefin encapsulant and a butyl rubber edge seal, we also demonstrate that the low band gap perovskite solar cell that passes the IEC damp heat test for thin film solar cells – a milestone that demonstrates the removal of a significant impediment to the commercialization of high efficiency perovskite tandem solar cells.

Metal-halide perovskites are promising solution-processable semiconductors for efficient solar cells and show unexpectedly high diffusion ranges of photogenerated charges. Here, we study charge extraction and recombination in metal-halide perovskite back-contact devices, which provide a powerful experimental platform to resolve electron- or hole-only transport phenomena. We prepare thin films of perovskite semiconductors over laterally-separated electron- and hole-selective materials of SnO¬2 and NiOx, respectively. Upon illumination, electrons (holes) generated over SnO¬2 (NiOx) rapidly transfer to the buried collection electrode, leaving holes (electrons) to diffuse laterally as majority carriers in the perovskite layer. Under these conditions, we find recombination is strongly suppressed. Resulting surface recombination velocities are below 2 cm s-1, an order of magnitude lower than in the presence of both carrier types, and approaching values of high-quality silicon. We find diffusion lengths of electrons and holes exceed 12 µm in our horizontal polycrystalline device, an order of magnitude higher than reported in vertically stacked architectures. We fabricate back-contact solar cells with short-circuit currents as high as 18.4 mA cm-2, reaching 70% external quantum efficiency.

We demonstrate four-and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA(0.75)Cs(0.25)Sn(0.5)Pb(0.5)I(3), that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA(0.83)Cs(0.17)Pb(I0.5Br0.5)(3) material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with > 1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable "all-perovskite" thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs. We thank M. T. Horantner for performing the Shockley-Queisser calculation. The research leading to these results has received funding from the Graphene Flagship (Horizon 2020 grant no. 696656 - GrapheneCore1), the Leverhulme Trust (grant RL-2012-001), the UK Engineering and Physical Sciences Research Council (grant EP/J009857/1 and EP/M020517/1), and the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement nos. 239578 (ALIGN) and 604032 (MESO). T.L. is funded by a Marie Sklodowska Curie International Fellowship under grant agreement H2O2IF-GA-2015-659225. A.B. is financed by IMEC (Leuven) in the framework of a joint Ph.D. program with Hasselt University. B.C. is a postdoctoral research fellow of the Research Fund Flanders (FWO). We also acknowledge the U.S. Office of Naval Research for support. We acknowledge the use of the University of Oxford Advanced Research Computing (ARC) facility (http://dx.doi.org/10.5281/zenodo.22558) and the ARCHER UK National Super-computing Service under the "AMSEC" Leadership project. We thank the Global Climate and Energy Project (GCEP) at Stanford University. All data pertaining to the conclusions of this work can be found in the main paper and the supplementary materials.

Hole-transport material optimization is an important step toward maximizing the efficiency of perovskite solar cells. Here, we investigate the role of one hole-transport material property, the ionization potential, on the performance of perovskite solar cells. We employ a device architecture that allows us to systematically tune the ionization potential while avoiding any impact to other device parameters, and we find that for a wide range of ionization potentials the photovoltaic performance is minimally affected. This finding relaxes the requirement for the development of hole-transport materials with particular ionization potentials, allowing for the optimization of hole-transport materials that can improve performance in differing ways such as through increased stability or decreased parasitic absorption.

Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance.

Despite rapid developments in both photovoltaic and light-emitting device performance, the understanding of the optoelectronic properties of hybrid lead halide perovskites is still incomplete. In particular, the polarizability of the material, the presence of molecular dipoles, and their influence on the dynamics of the photoexcitations remain an open issue to be clarified. Here, we investigate the effect of an applied external electric field on the photoexcited species of CH3NH3PbI3 thin films, both at room temperature and at low temperature, by monitoring the photoluminescence (PL) yield and PL decays. At room temperature we find evidence for electric-field-induced reduction of radiative bimolecular carrier recombination together with motion of charged defects that affects the nonradiative decay rate of the photoexcited species. At low temperature (190 K), we observe a field-induced enhancement of radiative free carrier recombination rates that lasts even after the removal of the field. We assign this to field-induced alignment of the molecular dipoles, which reduces the vibrational freedom of the lattice and the associated local screening and hence results in a stronger electron-hole interaction.

Metal halide perovskites are promising candidates for the wide band gap top cell in tandem solar cells. By introducing a tin oxide buffer layer via atomic layer deposition, we have improved the efficiency of monolithic, two-terminal, perovskite/silicon tandems to 23.6% by combining an infraredtuned silicon heterojunction bottom cell with the more stable cesium formamidinium lead halide perovskite. We show that further improvements to current and voltage can be made by introducing a PDMS scattering layer to reduce front surface reflection and using compositional engineering to simultaneously increase bandgap and Voc, while mitigating voltage losses arising from photo-induced halide segregation.

Tin-lead halide perovskites show promise as low- band gap absorbers to enable efficient all-perovskite tandem solar cells. While they have reached high efficiencies in single junction and in tandem solar cells, tin-containing perovskites face unique challenges- such as a tendency to degrade by oxidation of tin and sometimes very short carrier lifetimes that limit diffusion lengths. We map oxidation stability and important optoelectronic properties- band gap, carrier lifetime, and solar cell performance - across a wide range of compositions varying the A-site cation and the tin:lead ratio at the B-site. We identify mechanisms by which composition tunes the band gap in ways distinct from what has been reported for pure lead-based perovskites. We show that alloying tin with lead changes the mechanism by which tin is oxidized to a pathway that is relatively unfavourable. This significantly stabilizes the perovskite toward oxidation. Using a low band gap perovskite absorber, we demonstrate a 17.8% efficient single junction solar cell. Further, by employing a sputtered ITO top electrode, we demonstrate continuous operation of a solar cell in air with only a small drop in efficiency that is reversible upon storage in the dark This work creates a set of guiding principles to intelligently choose the best compositions for making efficient and stable solar cells based on tin-containing low band gap perovskites.

We report the fabrication of monolithic all-perovskite tandem solar cells with a stabilized power conversion efficiency of 19.1% and demonstrate improved thermal, atmospheric, and operational stability of the tin–lead perovskite (FA0.75Cs0.25Sn0.5Pb0.5I3) used as the low gap absorber. To achieve a high matched current density in the two-terminal tandem, we develop a route to fabricate uniform and thick tin–lead perovskites that enable the two-terminal tandem to attain external quantum efficiencies >80% in the near infrared. By post-processing the as-deposited tin–lead perovskite films with methylammonium chloride vapor, we increase grain sizes to over a micron and boost solar cell open circuit voltage and fill factor. Tin–lead perovskite solar cells made by this method exhibit the most stable operation at maximum power under simulated sunlight of any reported small bandgap perovskite solar cell to date. We show that an unencapsulated tin–lead perovskite solar cell maintains its full performance after 150 hours at 85C in air, which is substantially better than has been observed previously. This work identifies strategies for attaining highly efficient all-perovskite tandem solar cells while maintaining thermal and operational stability.

Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood and neither has the impact of moisture on the physical properties of resultant films. Herein, we carry out a comprehensive and well-controlled study of the effect of moisture exposure on methylammonium lead halide perovskite film formation and properties. We find that films formed in higher humidity atmospheres have a less continuous morphology but significantly improved photoluminescence, and that film formation is faster. In photovoltaic devices, we find that exposure to moisture, either in the precursor solution or in the atmosphere during formation, results in significantly improved open-circuit voltages and hence overall device performance. We then find that by post-treating dry films with moisture exposure, we can enhance photovoltaic performance and photoluminescence in a similar way. The enhanced photoluminescence and open-circuit voltage imply that the material quality is improved in films that have been exposed to moisture. We determine that this improvement stems from a reduction in trap density in the films, which we postulate to be due to the partial solvation of the methylammonium component and "self-healing" of the perovskite lattice. This work highlights the importance of controlled moisture exposure when fabricating high-performance perovskite devices and provides guidelines for the optimum environment for fabrication. Moreover, we note that often an unintentional water exposure is likely responsible for the high performance of solar cells produced in some laboratories, whereas careful synthesis and fabrication in a dry environment will lead to lower-performing devices.

In dye-sensitized solar cells (DSSCs) photogenerated positive charges are normally considered to be carried away from the dyes by a separate phase of hole-transporting material (HTM). We show that there can also be significant transport within the dye monolayer itself before the hole reaches the HTM. We quantify the fraction of dye regeneration in solid-state DSSCs that can be attributed to this process. By using cyclic voltammetry and transient anisotropy spectroscopy, we demonstrate that the rate of interdye hole transport is prevented both on micrometer and nanometer length scales by reducing the dye loading on the TiO2 surface. The dye regeneration yield is quantified for films with high and low dye loadings (with and without hole percolation in the dye monolayer) infiltrated with varying levels of HTM. Interdye hole transport can account for >50% of the overall dye regeneration with low HTM pore filling. This is reduced to about 5% when the infiltration of the HTM in the pores is optimized in 2 μm th...

Organic-inorganic halide perovskite solar cells have recently emerged as high-performance photovoltaic devices with low cost, promising for affordable large-scale energy production, with laboratory cells already exceeding 20% power conversion efficiency (PCE). To date, a relatively expensive organic hole-conducting molecule with low conductivity, namely spiro-OMeTAD (2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine) 9,9'- spirobifluorene), is employed widely to achieve highly efficient perovskite solar cells. Here, we report that by replacing spiro-OMeTAD with much cheaper and highly conductive poly(3,4-ethylenedioxythiophene) (PEDOT) we can achieve PCE of up to 14.5%, with PEDOT cast from a toluene based ink. However, the stabilized power output of the PEDOT-based devices is only 6.6%, in comparison to 9.4% for the spiro-OMeTAD-based cells. We deduce that accelerated recombination is the cause for this lower stabilized power output and postulate that reduced levels of p-doping are required to match the stabilized performance of Spiro-OMeTAD. The entirely of the materials employed in the perovskite solar cell are now available at commodity scale and extremely inexpensive.

Metal halide perovskite semiconductors offer rapid, low-cost deposition of solar cell active layers with a wide range of band gaps, making them ideal candidates for multijunction solar cells. Here, we combine optical and electrical models using experimental inputs to evaluate the feasible performances of all-perovskite double-junction (2PJ), triple-junction (3PJ), and perovskite-perovskite-silicon triple-junction (2PSJ) solar cells. Using parameters and design constraints from the current state-of-the-art generation of perovskite solar cells, we find that 2PJs can feasibly approach 32% power conversion efficiency, 3PJs can reach 33%, and 2PSJs can surpass 35%. We also outline pathways to improve light harvesting and demonstrate that it is possible to raise the performances to 34%, 37%, and 39% for the three architectures. Additionally, we discuss important future directions of research. Finally, we perform energy yield modeling to demonstrate that the multijunction solar cells should not suffer from reduced operational performances due to discrepancies between the AM1.5G and real-world spectrum over the course of a year.

Tin and lead iodide perovskite semiconductors of the composition AMX3, where M is a metal and X is a halide, are leading candidates for high efficiency low cost tandem photovoltaics, in part because they have band gaps that can be tuned over a wide range by compositional substitution. We experimentally identify two competing mechanisms through which the A-site cation influences the band gap of 3D metal halide perovskites. Using a smaller A-site cation can distort the perovskite lattice in two distinct ways: by tilting the MX6 octahedra, or by simply contracting the lattice isotropically. The former effect tends to raise the band gap, while the latter tends to decrease it. Lead iodide perovskites show an increase in band gap upon partial substitution of the larger formamidinium with the smaller cesium, due to octahedral tilting. Perovskites based on tin, which is slightly smaller than lead, show the opposite trend – they show no octahedral tilting upon Cs-substitution, but only a contraction of the lattice, leading to progressive reduction of the band gap. We outline a strategy to systematically tune the band gap and valence and conduction band positions of metal halide perovskites through control of the cation composition. Using this strategy, we demonstrate solar cells that harvest light in the infrared up to 1040 nm, reaching a stabilized power conversion efficiency of 17.8%, showing promise for improvements of the bottom cell of all-perovskite tandem solar cells. The mechanisms of cation-based band gap tuning we describe are broadly applicable to 3D metal halide perovskites, and will be useful in further development of perovskite semiconductors for optoelectronic applications. We thank Kevin A. Bush and Kyle Frohna for productive and stimulating conversations, Adam H. Slavney and David A. Hanifi for insightful comments on the manuscript, and Caleb C. Boyd for assistance with solar cell fabrication. This research was supported by the Office of Naval Research, U.S. Department of Defense. Use of the Stanford Synchrotron Radiation Light-source, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. T.L. is funded by a Marie Sklodowska Curie International Fellowship under grant agreement H2O2IF-GA-2015-659225. A.G. is supported by NSF GRFP (DGE-1147470). B.C. is a postdoctoral research fellow of the Research Fund Flanders (FWO). A.B. is a Ph.D. fellow of FWO.

Solution-processable metal halide perovskites show immense promise for use in photovoltaics and other optoelectronic applications. The ability to tune their bandgap by alloying various halide anions (for example, in CH3NH3Pb(I1-x Br-x)(3), 0 < x < 1) is however hampered by the reversible photoinduced formation of sub-bandgap emissive states. We find that ion segregation takes place via halide defects, resulting in iodide-rich low-bandgap regions close to the illuminated surface of the film. This segregation may be driven by the strong gradient in carrier generation rate through the thickness of these strongly absorbing materials. Once returned to the dark, entropically driven intermixing of halides returns the system to a homogeneous condition. We present approaches to suppress this process by controlling either the internal light distribution or the defect density within the film. These results are relevant to stability in both single- and mixed-halide perovskites, leading the way toward tunable and stable perovskite thin films for photovoltaic and light-emitting applications.

Solution-processed organometal trihalide perovskite solar cells are attracting increasing interest, leading to high performances over 15% in thin film architectures. Here, we probe the presence of sub gap states in both solid and mesosuperstructured perovskite films and determine that they strongly influence the photoconductivity response and splitting of the quasi-Fermi levels in films and solar cells. We find that while the planar perovskite films are superior to the mesosuperstructured films in terms of charge carrier mobility (in excess of 20 cm(2) V(-1) s(-1)) and emissivity, the planar heterojunction solar cells are limited in photovoltage by the presence of sub gap states and low intrinsic doping densities.

The ability to process amorphous or polycrystalline solar cells at low temperature (

Unrestricted Travel in Solar Cells In the past 2 years, organolead halide perovskites have emerged as a promising class of light-harvesting media in experimental solar cells, but the physical basis for their efficiency has been unclear (see the Perspective by Hodes ). Two studies now show, using a variety of time-resolved absorption and emission spectroscopic techniques, that these materials manifest relatively long diffusion paths for charge carriers energized by light absorption. Xing et al. (p. 344 ) independently assessed (negative) electron and (positive) hole diffusion lengths and found them well-matched to one another to the ~100-nanometer optical absorption depth. Stranks et al. (p. 341 ) uncovered a 10-fold greater diffusion length in a chloride-doped material, which correlates with the material's particularly efficient overall performance. Both studies highlight effective carrier diffusion as a fruitful parameter for further optimization.

Transient mobility spectroscopy (TMS) is presented as a new tool to probe the charge carrier mobility of commonly employed organic and inorganic semiconductors over the relevant range of charge densities. The charge density dependence of the mobility of semiconductors used in hybrid and organic photovoltaics gives new insights into charge transport phenomena in solid state dye sensitized solar cells. Copyright © 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim.

One of the greatest attributes of metal halide perovskite solar cells is their surprisingly low loss in potential between bandgap and open-circuit voltage, despite the fact that they suffer from a non-negligible density of sub gap defect states. Here, we use a combination of transient and steady state photocurrent and absorption spectroscopy to show that CH3NH3PbI3 films exhibit a broad distribution of electron traps. We show that the trapped electrons recombine with free holes unexpectedly slowly, on microsecond time scales, relaxing the limit on obtainable open-circuit voltage (VOC) under trap-mediated recombination conditions. We find that the observed VOCs in such perovskite solar cells can only be rationalized by considering the slow trap mediated recombination mechanism identified in this work. Our results suggest that existing processing routes may be good enough to enable open circuit voltages approaching 1.3 V in ideal devices with perfect contacts.

The active layers of perovskite solar cells are also structural layers and are central to ensuring that the structural integrity of the device is maintained over its operational lifetime. Our work evaluating the fracture energies of conventional and inverted solution-processed MAPbI3 perovskite solar cells has revealed that the MAPbI3 perovskite exhibits a fracture resistance of only ∼0.5 J/m2, while solar cells containing fullerene electron transport layers fracture at even lower values, below ∼0.25 J/m2. To address this weakness, a novel styrene-functionalized fullerene derivative, MPMIC60, has been developed as a replacement for the fragile PC61BM and C60 transport layers. MPMIC60 can be transformed into a solvent-resistant material through curing at 250 °C. As-deposited films of MPMIC60 exhibit a marked 10-fold enhancement in fracture resistance over PC61BM and a 14-fold enhancement over C60. Conventional-geometry perovskite solar cells utilizing cured films of MPMIC60 showed a significant, 205% impro...

The field of solution-processed photovoltaic cells is currently in its second spring. The dye-sensitized solar cell is a widely studied and longstanding candidate for future energy generation. Recently, inorganic absorber-based devices have reached new record efficiencies, with the benefits of all-solid-state devices. In this rapidly changing environment, this review sheds light on recent developments in all-solid-state solar cells in terms of electrode architecture, alternative sensitizers, and hole-transporting materials. These concepts are of general applicability to many next-generation device platforms. The field of solution-processed photovoltaic cells is currently in its second spring, with solid-state devices incorporating novel inorganic absorbers reaching record efficiencies. This review sheds light on recent developments in all-solid-state solar cells in terms of electrode architecture, alternative sensitizers, and hole-transporting materials: concepts applicable to many next-generation device platforms. © 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim.

High-efficiency perovskite solar cells typically employ an organic–inorganic metal halide perovskite material as light absorber and charge transporter, sandwiched between a p-type electron-blocking organic hole-transporting layer and an n-type hole-blocking electron collection titania compact layer. Some device configurations also include a thin mesoporous layer of TiO2 or Al2O3 which is infiltrated and capped with the perovskite absorber. Herein, we demonstrate that it is possible to fabricate planar and mesoporous perovskite solar cells devoid of an electron selective hole-blocking titania compact layer, which momentarily exhibit power conversion efficiencies (PCEs) of over 13%. This performance is however not sustained and is related to the previously observed anomalous hysteresis in perovskite solar cells. The “compact layer-free” meso-superstructured perovskite devices yield a stabilised PCE of only 2.7% while the compact layer-free planar heterojunction devices display no measurable steady state power output when devoid of an electron selective contact. In contrast, devices including the titania compact layer exhibit stabilised efficiency close to that derived from the current voltage measurements. We propose that under forward bias the perovskite diode becomes polarised, providing a beneficial field, allowing accumulation of positive and negative space charge near the contacts, which enables more efficient charge extraction. This provides the required built-in potential and selective charge extraction at each contact to temporarily enable efficient operation of the perovskite solar cells even in the absence of charge selective n- and p-type contact layers. The polarisation of the material is consistent with long range migration and accumulation of ionic species within the perovskite to the regions near the contacts. When the external field is reduced under working conditions, the ions can slowly diffuse away from the contacts redistributing throughout the film, reducing the field asymmetry and the effectiveness of the operation of the solar cells. We note that in light of recent publications showing high efficiency in devices devoid of charge selective contacts, this work reaffirms the absolute necessity to measure and report the stabilised power output under load when characterizing perovskite solar cells.

We present the synthesis and device characterization of new hole transport materials (HTMs) for application in solid-state dye-sensitized solar cells (ssDSSCs). In addition to possessing electrical properties well suited for ssDSSCs, these new HTMs have low glass transition temperatures, low melting points, and high solubility, which make them promising candidates for increased pore filling into mesoporous titania films. Using standard device fabrication methods and Z907 as the sensitizing dye, power conversion efficiencies (PCE) of 2.94% in 2-μm-thick cells were achieved, rivaling the PCE obtained by control devices using the state-of-the-art HTM spiro-OMeTAD. In 6-μm-thick cells, the device performance is shown to be higher than that obtained using spiro-OMeTAD, making these new HTMs promising for preparing high-efficiency ssDSSCs.

Mesoporous single crystals (MSCs) of TiO2 are promising materials for more efficient dye sensitized solar cells and other energy conversion or storage devices, since they combine high surface area with large crystalline domain size. In this work, we investigate the charge transport properties of TiO2 MSCs after annealing them within a confining template at temperatures from 500 to 850 C. We observe that higher anneal temperatures do not change the crystal phase, as in nanocrystalline TiO 2, but do influence the MSC absorption spectrum in a manner consistent with the signature of increased oxygen-vacancy defects. By comparing MSC film conductivity in vacuum and in air, we infer that these anneal-induced defects increase the background charge density in TiO2. Subsequently, we measure higher effective mobility in annealed MSCs using transient mobility spectroscopy (TMS), consistent with higher anneal temperatures filling sub-bandgap trap states by n-doping TiO2. Finally, we measure faster charge transport rates in solid-state dye sensitized solar cells as well as increased open-circuit voltages at low light intensity with increasing MSC anneal temperature. This study leverages the fixed geometry and crystal phase of MSCs under thermal treatment to identify and isolate the doping effect of annealing at high temperature, previously inaccessible for mesoporous anatase TiO2. The results offer insight into the influence of doping on charge transport in TiO2-based solar cells and the tunability of MSCs for use in enhancing device performance. © 2013 American Chemical Society.

A new low-temperature synthetic method of growing semiconductor mesoporous single crystals of titanium dioxide is described; the resulting films have much higher conductivities and electron mobilities than nanocrystalline titanium dioxide. Mesoporous semiconductors and ceramics have large surface areas that can be exploited in high-performance solar cells, as photocatalysts and in batteries. This paper describes a low-temperature (below 150 °C) general synthetic method of growing micrometre-sized semiconductor mesoporous single crystals of a form of titanium dioxide (TiO2) known as anatase, based on seeded nucleation and growth inside a mesoporous template immersed in a dilute reaction solution. The authors demonstrate that both isolated crystals and ensembles incorporated into films exhibit dramatically higher conductivities and electron mobilities than nanocrystalline TiO2. Dye-sensitized solar cells made from these materials demonstrate 7.3% efficiency, the highest value so far reported using low-temperature processing. The synthesis method should be generally applicable to other functional ceramics and semiconductors. Mesoporous ceramics and semiconductors enable low-cost solar power, solar fuel, (photo)catalyst and electrical energy storage technologies1. State-of-the-art, printable high-surface-area electrodes are fabricated from thermally sintered pre-formed nanocrystals2,3,4,5. Mesoporosity provides the desired highly accessible surfaces but many applications also demand long-range electronic connectivity and structural coherence6. A mesoporous single-crystal (MSC) semiconductor can meet both criteria. Here we demonstrate a general synthetic method of growing semiconductor MSCs of anatase TiO2 based on seeded nucleation and growth inside a mesoporous template immersed in a dilute reaction solution. We show that both isolated MSCs and ensembles incorporated into films have substantially higher conductivities and electron mobilities than does nanocrystalline TiO2. Conventional nanocrystals, unlike MSCs, require in-film thermal sintering to reinforce electronic contact between particles, thus increasing fabrication cost, limiting the use of flexible substrates and precluding, for instance, multijunction solar cell processing. Using MSC films processed entirely below 150 °C, we have fabricated all-solid-state, low-temperature sensitized solar cells that have 7.3 per cent efficiency, the highest efficiency yet reported. These high-surface-area anatase single crystals will find application in many different technologies, and this generic synthetic strategy extends the possibility of mesoporous single-crystal growth to a range of functional ceramics and semiconductors.

Thermal and environmental stability of metal halide perovskite solar cells remains a major barrier to their commercialization. The industry standard transparent electrode, ITO, has good optoelectronic properties and high stability. We introduce a robust buffer layer by solution-processing AZO nanoparticles, enabling a sputtered amorphous ITO layer without damaging the underlying device. We make both semitransparent cells (12.3%) and mechanically stacked tandems (12.3% + 5.7% = 18.0%) using monocrystalline-silicon solar cells as the bottom cell. We operate the inverted-architecture, semitransparent perovskite solar cell without additional sealing in ambient atmosphere under one-sun equivalent visible illumination and measure a Ts0 lifetime of 124 hours at 100°C.

Styrene functionalized fullerene derivatives have been designed for use as electron-selective contacts in perovskite solar cells. Unlike films of PC 61 BM and C 60 fullerene, films of these styrene-functionalized fullerenes (SFFs) can be transformed into a solvent resistant material through thermal curing. Conventional-geometry perovskite solar cells utilizing cured and uncured thin films of SFFs on titania were fabricated and tested for PCE and fracture resistance, and compared to cells employing C 60 . These cells displayed significant improvements in the fracture resistance (> 200 %) while exhibiting only a 7% drop in PCE (13.8 % vs 14.8 % PCE), with larger V OC and J SC values in comparison to the C 60 control cell. Inverted cells fabricated with SFFs displayed an even greater increase in fracture resistance (> 400 %) with only a 6 % reduction in PCE (12.3 % vs 13.1 %) in comparison to those utilizing PC 61 BM.

A semiconductor that can be processed on a large scale with a bandgap around 1.8 eV could enable the manufacture of highly-efficient low cost double-junction solar cells. Solution-processable organic-inorganic halide perovskites have recently generated considerable excitement as absorbers in single-junction solar cells, and while it is possible to tune the bandgap of (CH 3 NH 3 )Pb(Br x I 1−x ) 3 between 2.3 and 1.6 eV by controlling the halide concentration, optical instability due to photo-induced phase segregation limits the voltage that can be extracted from compositions with appropriate bandgaps for tandem applications. Moreover, these materials have been shown to suffer from thermal degradation at temperatures within the processing and operational window. By replacing the volatile methylammonium cation with cesium, it is possible to synthesize a mixed halide absorber material with improved optical and thermal stability, a stabilized photoconversion efficiency of 6.5%, and a bandgap of 1.9 eV.

A sputtered oxide layer enabled by a solution-processed oxide nanoparticle buffer layer to protect underlying layers is used to make semi-transparent perovskite solar cells. Single-junction semi-transparent cells are 12.3% efficient, and mechanically stacked tandems on silicon solar cells are 18.0% efficient. The semi-transparent perovskite solar cell has a T 80 lifetime of 124 h when operated at the maximum power point at 100 °C without additional sealing in ambient atmosphere under visible illumination.

A semiconductor that can be processed on a large scale with a bandgap around 1.8 eV could enable the manufacture of highly efficient low cost double-junction solar cells on crystalline Si. Solution-processable organic-inorganic halide perovskites have recently generated considerable excitement as absorbers in single-junction solar cells, and though it is possible to tune the bandgap of (CH3NH3)Pb(BrxI1-x)3 between 2.3 and 1.6 eV by controlling the halide concentration, optical instability due to photoinduced phase segregation limits the voltage that can be extracted from compositions with appropriate bandgaps for tandem applications. Moreover, these materials have been shown to suffer from thermal degradation at temperatures within the processing and operational window. By replacing the volatile methylammonium cation with cesium, it is possible to synthesize a mixed halide absorber material with improved optical and thermal stability, a stabilized photoconversion efficiency of 6.5%, and a bandgap of 1.9 eV.

Here, we report the use of polymer-wrapped carbon nanotubes as a means to enhance charge extraction through undoped spiro-OMeTAD. With this approach a good solar cell performance is achieved without the implementation of conventional doping methods. We demonstrate that a stratified two-layer architecture of sequentially deposited layers of carbon nanotubes and spiro-OMeTAD, outperforms a conventional blend of the hole-conductor and the carbon nanotubes. We also provide insights into the mechanism of the rapid hole extraction observed in the two-layer approach.

Emerging from the field of dye-sensitized solar cells, organometal halide perovskite-based solar cells have recently attracted considerable attention. In these devices, the perovskite light absorbers can also be used as charge transporting materials, changing the requirements for efficient device architectures. The perovskite deposition can vary from merely sensitizing the TiO2 electron transporting scaffold as an endowment of small nanoparticles, to completely filling the pores where it acts as both light absorber and hole transporting material in one. By decreasing the TiO 2 scaffold layer thickness, we change the solar cell architecture from perovskite-sensitized to completely perovskite-filled. We find that the latter case leads to improvements in device performance because higher electron densities can be sustained in the TiO2, improving electron transport rates and photovoltage. Importantly, the primary recombination pathway between the TiO2 and the hole transporting material is blocked by the perovskite itself. This understanding helps to rationalize the high voltages attainable on mesoporous TiO2-based perovskite solar cells. © 2014 American Chemical Society.

The study of the photophysical properties of organic-metallic lead halide perovskites, which demonstrate excellent photovoltaic performance in devices with electron- and hole-accepting layers, helps to understand their charge photogeneration and recombination mechanism and unravels their potential for other optoelectronic applications. We report surprisingly high photoluminescence (PL) quantum efficiencies, up to 70%, in these solution-processed crystalline films. We find that photoexcitation in the pristine CH3NH3PbI3-xClx perovskite results in free charge carrier formation within 1 ps and that these free charge carriers undergo bimolecular recombination on time scales of 10s to 100s of ns. To exemplify the high luminescence yield of the CH3NH3PbI3-xClx perovskite, we construct and demonstrate the operation of an optically pumped vertical cavity laser comprising a layer of perovskite between a dielectric mirror and evaporated gold top mirrors. These long carrier lifetimes together with exceptionally high luminescence yield are unprecedented in such simply prepared inorganic semiconductors, and we note that these properties are ideally suited for photovoltaic diode operation.

Organic-inorganic halide perovskite solar cells have recently emerged as high performance photovoltaic devices with low cost, promising for affordable large-scale energy production. The power conversion efficiency (PCE) from solar energy to electricity in solid state photovoltaic devices has risen from 10% to over 20% within two years of development. To date, a relatively expensive organic hole-conducting molecule with low conductivity, namely Spiro-OMeTAD (2,2′,7,7′-tetrakis (N,N-di-p-methoxyphenyl-amine) 9,9′- Spirobifluorene), is employed widely to achieve highly efficient perovskite solar cells. Here, we report two low cost candidates to replace spiro-OMeTAD for perovskite solar cells, Poly(3,4-ethylenedioxythiophene) (PEDOT) and copper thiocyanate (CuSCN). Stabilized power conversion efficiency of 6.6% and 9.1% can be obtained when the new materials are used as the hole-conductor respectively, comparing to 9.6% for device using Spiro-OMeTAD.

Dye-sensitized TiO2 can be used as the active layer of solar-cell devices without an additional hole-transporting material. In this architecture, holes are transported through the dye monolayer.

This work is concerned with the modeling of perovskite based hybrid solar cells formed by sandwiching a slab of organic lead halide perovskite (CH3NH3PbI3-xCIx) photo-absorber between (n-type) acceptor and (p-type) donor materials -typically titanium dioxide and spiro. A model for the electrical behavior of these cells is formulated based on drift-diffusion equations for the motion of the charge carriers and Poisson's equation for the electric potential. It is closed by (i) internal interface conditions accounting for charge recombination/generation and jumps in charge carrier densities arising from differences in the electron affinity/ionization potential between the materials and (ii) ohmic boundary conditions on the contacts. The model is analyzed by using a combination of asymptotic and numerical techniques. This leads to an approximate - yet highly accurate - expression for the current-voltage relationship as a function of the solar induced photo-current. In addition, we show that this approximate current-voltage relation can be interpreted as an equivalent circuit model consisting of three diodes, a resistor, and a current source. For sufficiently small biases the device's behavior is diodic and the current is limited by the recombination at the internal interfaces, whereas for sufficiently large biases the device acts like a resistor and the current is dictated by the ohmic dissipation in the acceptor and donor. The results of the model are also compared to experimental current-voltage curves, and good agreement is shown.

The ability to process amorphous or polycrystalline solar cells at low temperature (