Double-side 2D/3D heterojunctions for inverted perovskite solar cells.

Defects at the top and bottom interfaces of three-dimensional (3D) perovskite photoabsorbers diminish the performance and operational stability of perovskite solar cells owing to charge recombination, ion migration and electric-field inhomogeneities1-5. Here we demonstrate that long alkyl amine ligands can generate near-phase-pure 2D perovskites at the top and bottom 3D perovskite interfaces and effectively resolve these issues. At the rear-contact side, we find that the alkyl amine ligand strengthens the interactions with the substrate through acid-base reactions with the phosphonic acid group from the organic hole-transporting self-assembled monolayer molecule, thus regulating the 2D perovskite formation. With this, inverted perovskite solar cells with double-side 2D/3D heterojunctions achieved a power conversion efficiency of 25.6% (certified 25.0%), retaining 95% of their initial power conversion efficiency after 1,000 h of 1-sun illumination at 85 °C in air.

Controlled growth of perovskite layers with volatile alkylammonium chlorides.

Controlling the crystallinity and surface morphology of perovskite layers by methods such as solvent engineering1,2 and methylammonium chloride addition3-7 is an effective strategy for achieving high-efficiency perovskite solar cells. In particular, it is essential to deposit α-formamidinium lead iodide (FAPbI3) perovskite thin films with few defects due to their excellent crystallinity and large grain size. Here we report the controlled crystallization of perovskite thin films with the combination of alkylammonium chlorides (RACl) added to FAPbI3. The δ-phase to α-phase transition of FAPbI3 and the crystallization process and surface morphology of the perovskite thin films coated with RACl under various conditions were investigated through in situ grazing-incidence wide-angle X-ray diffraction and scanning electron microscopy. RACl added to the precursor solution was believed to be easily volatilized during coating and annealing owing to dissociation into RA0 and HCl with deprotonation of RA+ induced by RA⋯H+-Cl- binding to PbI2 in FAPbI3. Thus, the type and amount of RACl determined the δ-phase to α-phase transition rate, crystallinity, preferred orientation and surface morphology of the final α-FAPbI3. The resulting perovskite thin layers facilitated the fabrication of perovskite solar cells with a power-conversion efficiency of 26.08% (certified 25.73%) under standard illumination.

Unraveling the Influence of Solvent on Side Reactions between Formamidinium Lead Triiodide and Methylammonium Cations.

Formamidinium lead triiodide (FAPbI3) perovskite thin films are commonly deposited through a solution process, often incorporating a specific amount of methylammonium halide to stabilize the α-phase or enhance their crystallinity. The precursor solution for such coatings significantly influences the fabrication of perovskite solar cells (PSCs), involving time-dependent aging and byproduct formation. The chemical principle underlying this behavior is believed to be related to the deprotonation of methylamine cations (MA+) and subsequent chemical reactions with FA+ to generate N-methylformamidinium. Nevertheless, the role of the solvent in the side reactions between these organic cations remains unclear. This work systematically investigates the reaction reactivity in three protic solvents and three aprotic solvents. We uncover the hidden role of dimethylamine from the hydrolysis products of N,N-dimethylformamide, promoting the reaction between FA+ and MA+. Additionally, we elucidate the impact of environmental factors, such as water and oxygen, in stabilizing precursor solutions. This work establishes a basic concept and scientific direction for rationalizing high-efficiency, reproducible, and long-term-stable PSCs.

Deciphering Reaction Products in Formamidine-Based Perovskites with Methylammonium Chloride Additive.

The fabrication of formamidinium lead iodide (FAPbI3) perovskite solar cells (PSCs) involves the addition of methylammonium chloride (MACl) to promote low-temperature α-phase formation and grain growth. However, as the added MACl deprotonates and volatilizes into methylamine (MA0) and HCl for removal, MA0 can chemically interact with formamidinium (FA+), forming methyl formamidinium (MFA+) as a byproduct. Despite its significance, the chemical interactions among FAPbI3 perovskites, MACl additives, and their byproducts remain poorly understood. Our findings reveal that the FA+ and MA0 reaction primarily yields a mixture of cis/trans-N-methyl formamidinium iodide (MFAI) isomers, with cis-MFAI prevailing as the dominant species. Moreover, MFAI subsequently reacts with PbI2 to yield fully formed cis-MFAPbI3 2H-phase perovskite. We elucidated the effects of MFAI on the crystal growth, phase stability, and band gap of formamidine-based perovskites through the growth of single crystals. This research offers valuable insights into the role of these byproducts in influencing the efficiency and long-term stability of future PSCs.

Integrated System Built for Small-Molecule Semiconductors via High-Throughput Approaches.

High-throughput synthesis of solution-processable structurally variable small-molecule semiconductors is both an opportunity and a challenge. A large number of diverse molecules provide a possibility for quick material discovery and machine learning based on experimental data. However, the diversity of the molecular structure leads to the complexity of molecular properties, such as solubility, polarity, and crystallinity, which poses great challenges to solution processing and purification. Here, we first report an integrated system for the high-throughput synthesis, purification, and characterization of molecules with a large variety. Based on the principle "Like dissolves like," we combine theoretical calculations and a robotic platform to accelerate the purification of those molecules. With this platform, a material library containing 125 molecules and their optical-electronic properties was built within a timeframe of weeks. More importantly, the high repeatability of recrystallization we design is a reliable approach to further upgrading and industrial production.

Intrinsic Phase Stability and Inherent Bandgap of Formamidinium Lead Triiodide Perovskite Single Crystals.

Understanding the intrinsic phase stability and inherent band gap of formamidinium lead triiodide (FAPbI3 ) perovskites is crucial to further improve the performance of perovskite solar cells (PSCs). Herein, we explored the α- to δ-phase transition and band gap of FAPbI3 single crystals grown by an inverse temperature solubility method. We found that the residual γ-butyrolactone solvents in the inner empty space of the FAPbI3 single crystal accelerate the phase transition at kinetics. By adopting 2-methoxyethanol as the solvent, over 2000 h of stable α-FAPbI3 crystals could be acquired. This proves that although FAPbI3 is regarded as unstable at thermodynamics, it could own excellent kinetic stability without any doping or additives because of the slow solid to solid phase transition instead of the fast phase transition assisted by the solvents. Furthermore, we revealed that the bulk FAPbI3 single crystal with a size above 100 µm can have an inherent band gap of 1.41 eV. Thus, our work provides key scientific guidance for high-performance FAPbI3 -based PSCs.

Compositional engineering of perovskite materials for high-performance solar cells.

Of the many materials and methodologies aimed at producing low-cost, efficient photovoltaic cells, inorganic-organic lead halide perovskite materials appear particularly promising for next-generation solar devices owing to their high power conversion efficiency. The highest efficiencies reported for perovskite solar cells so far have been obtained mainly with methylammonium lead halide materials. Here we combine the promising-owing to its comparatively narrow bandgap-but relatively unstable formamidinium lead iodide (FAPbI3) with methylammonium lead bromide (MAPbBr3) as the light-harvesting unit in a bilayer solar-cell architecture. We investigated phase stability, morphology of the perovskite layer, hysteresis in current-voltage characteristics, and overall performance as a function of chemical composition. Our results show that incorporation of MAPbBr3 into FAPbI3 stabilizes the perovskite phase of FAPbI3 and improves the power conversion efficiency of the solar cell to more than 18 per cent under a standard illumination of 100 milliwatts per square centimetre. These findings further emphasize the versatility and performance potential of inorganic-organic lead halide perovskite materials for photovoltaic applications.

Unveiling the Relationship between the Perovskite Precursor Solution and the Resulting Device Performance.

For the fabrication of perovskite solar cells (PSCs) using a solution process, it is essential to understand the characteristics of the perovskite precursor solution to achieve high performance and reproducibility. The colloids (iodoplumbates) in the perovskite precursors under various conditions were investigated by UV-visible absorption, dynamic light scattering, photoluminescence, and total internal reflection fluorescence microscopy techniques. Their local structure was examined by in situ X-ray absorption fine structure studies. Perovskite thin films on a substrate with precursor solutions were characterized by transmission electron microscopy, X-ray diffraction analysis, space-charge-limited current, and Kelvin probe force microscopy. The colloidal properties of the perovskite precursor solutions were found to be directly correlated with the defect concentration and crystallinity of the perovskite film. This work provides guidelines for controlling perovskite films by varying the precursor solution, making it possible to use colloid-engineered lead halide perovskite layers to fabricate efficient PSCs.

Perovskite precursor solution chemistry: from fundamentals to photovoltaic applications.

Over the last several years, inorganic-organic hybrid perovskites have shown dramatic achievements in photovoltaic performance and device stability. Despite the significant progress in photovoltaic application, an in-depth understanding of the fundamentals of precursor solution chemistry is still lacking. In this review, the fundamental background knowledge of nucleation and crystal growth processes in solution including the LaMer model and Ostwald ripening process is described. This review article also highlights the recent progress in precursor-coordinating molecule interaction in solution along with the role of anti-solvent in the solvent engineering process to control nucleation and crystal growth. Moreover, chemical pathways from precursor solution to perovskite film formation are given. This represents identification of the intermediate phase induced by precursor-coordinating molecule interaction and responsible intermediate species for uniform and dense perovskite film formation. Further to the description of chemical phenomena in solution, the contemporary progress in chemical precursor composition is also provided to comprehend the current research approaches to further enhance photovoltaic performance and device stability. On the basis of the critical and comprehensive review, we provide some perspectives to further achieve high-performance perovskite solar cells with long-term device stability through precisely controlled nucleation and crystal growth in precursor solution.

Long-Term Chemical Aging of Hybrid Halide Perovskites.

Because the power conversion efficiency (PCE) of hybrid halide perovskite solar cells (PSCs) could exceed 24%, extensive research has been focused on improving their long-term stability for commercialization in the near future. In a previous study, we reported that the addition of a number of ionized iodide (triiodide: I3-) ions during perovskite film formation significantly improved the efficiency of PSCs by reducing deep-level defects in the perovskite layer. Understanding the relationship between the concentration of these defects and the long-term chemical aging of PSCs is important not only for obtaining fundamental insight into the perovskite materials but also for studying the long-term chemical stability of PSCs. Herein we aim to identify the origin of the natural decay in PCE during long-term chemical aging of PSCs in the dark based on formamidinium lead triiodide by comparing the performance of control and low-defect (LD) devices. After aging for 200 days, the change in the PCE of the LD devices (1.3%) was found to be half that of the control devices (2.6%). We investigated this difference using grazing incidence wide-angle X-ray scattering, deep-level transient spectroscopy, scanning photoelectron microscopy, and high-resolution photoemission spectroscopy. The addition of I3- was found to reduce the amounts of hydroxide and Ox in the halide perovskites (HPs), affecting the migration of defects and the structural transformation of the HPs.

Mixed Sulfur and Iodide-Based Lead-Free Perovskite Solar Cells.

The use of divalent chalcogenides and monovalent halides as anions in a perovskite structure allows the introduction of 3+ and 4+ charged cations in the place of the 2+ metal cations. Herein we report for the first time on the fabrication of solar cells exploiting methylammonium antimony sulfur diiodide (MASbSI2) perovskite structures, as light harvesters. The MASbSI2 was prepared by annealing under mild temperature conditions, via a sequential reaction between antimony trisulfide (Sb2S3), which is deposited by the chemical bath deposition (CBD) method, antimony triiodide (SbI3), and methylammonium iodide (MAI) onto a mesoporous TiO2 electrode, and then annealed at 150 °C in an argon atmosphere. The solar cells fabricated using MASbSI2 exhibited power conversion efficiencies (PCE) of 3.08%, under the standard illumination conditions of 100 mW/cm2.

Methodologies toward Highly Efficient Perovskite Solar Cells.

A perovskite solar cell (PSC) employing an organic-inorganic lead halide perovskite light harvester, seeded in 2009 with power conversion efficiency (PCE) of 3.8% and grown in 2011 with PCE of 6.5% in dye-sensitized solar cell structure, has received great attention since the breakthrough reports ≈10% efficient solid-state PCSs demonstrating 500 h stability. Developments of device layout and high-quality perovskite film eventually lead to a PCE over 22%. As of October 31, 2017, the highest PCE of 22.7% is listed in an efficiency chart provided by NREL. In this Review, the methodologies to obtain highly efficient PSCs are described in detail. In order to achieve a PCE of over 20% reproducibly, key technologies are disclosed from the viewpoint of precursor solution chemistry, processing for defect-free perovskite films, and passivation of grain boundaries. Understanding chemical species in precursor solution, crystal growth kinetics, light-matter interaction, and controlling defects is expected to give important insights into not only reproducible production of high PCE over 20% but also further enhancement of the PCE of PCSs.

Rational Strategies for Efficient Perovskite Solar Cells.

A long-standing dream in the large scale application of solar energy conversion is the fabrication of solar cells with high-efficiency and long-term stability at low cost. The realization of such practical goals depends on the architecture, process and key materials because solar cells are typically constructed from multilayer heterostructures of light harvesters, with electron and hole transporting layers as a major component. Recently, inorganic-organic hybrid lead halide perovskites have attracted significant attention as light absorbers for the fabrication of low-cost and high-efficiency solar cells via a solution process. This mainly stems from long-range ambipolar charge transport properties, low exciton binding energies, and suitable band gap tuning by managing the chemical composition. In our pioneering work, a new photovoltaic platform for efficient perovskite solar cells (PSCs) was proposed, which yielded a high power conversion efficiency (PCE) of 12%. The platform consisted of a pillared architecture of a three-dimensional nanocomposite of perovskites fully infiltrating mesoporous TiO2, resulting in the formation of continuous phases and perovskite domains overlaid with a polymeric hole conductor. Since then, the PCE of our PSCs has been rapidly increased from 3% to over 20% certified efficiency. The unprecedented increase in the PCE can be attributed to the effective integration of the advantageous attributes of the refined bicontinuous architecture, deposition process, and composition of perovskite materials. Specifically, the bicontinuous architectures used in the high efficiency comprise a layer of perovskite sandwiched between mesoporous metal-oxide layer, which is a very thinner than that of used in conventional dye-sensitized solar cells, and hole-conducting contact materials with a metal back contact. The mesoporous scaffold can affect the hysteresis under different scan direction in measurements of PSCs. The hysteresis also greatly depends on the cell architecture and perovskite composition. In this Account, we will describe what we do with major aspects including (1) the film morphology through the development of intermediate chemistry retarding the rapid reaction between methylammonium or formamidinium iodide and lead halide (PbI2) for improved perovskite film formation; (2) the phase stability and band gap tuning of the perovskite layer through the materials engineering; (3) the development of electron and hole transporting materials for carrier-selective contacting layers; and (4) the adoption of p-i-n and n-i-p architectures depending on the position of the electron or hole conducting layer in front of incident light. Finally, we will summarize the recent incredible achievements in PSCs, and finally provide challenges facing the future development and commercialization of PSCs.

Fabrication of Efficient Formamidinium Tin Iodide Perovskite Solar Cells through SnF2-Pyrazine Complex.

To fabricate efficient formamidinium tin iodide (FASnI3) perovskite solar cells (PSCs), it is essential to deposit uniform and dense perovskite layers and reduce Sn(4+) content. Here we used solvent-engineering and nonsolvent dripping process with SnF2 as an inhibitor of Sn(4+). However, excess SnF2 induces phase separation on the surface of the perovskite film. In this work, we report the homogeneous dispersion of SnF2 via the formation of the SnF2-pyrazine complex. Consequently, we fabricated FASnI3 PSCs with high reproducibility, achieving a high power conversion efficiency of 4.8%. Furthermore, the encapsulated device showed a stable performance for over 100 days, maintaining 98% of its initial efficiency.

Solvent engineering for high-performance inorganic-organic hybrid perovskite solar cells.

Organolead trihalide perovskite materials have been successfully used as light absorbers in efficient photovoltaic cells. Two different cell structures, based on mesoscopic metal oxides and planar heterojunctions have already demonstrated very impressive advances in performance. Here, we report a bilayer architecture comprising the key features of mesoscopic and planar structures obtained by a fully solution-based process. We used CH3NH3 Pb(I(1-x)Br(x))3 (x = 0.1-0.15) as the absorbing layer and poly(triarylamine) as a hole-transporting material. The use of a mixed solvent of γ-butyrolactone and dimethylsulphoxide (DMSO) followed by toluene drop-casting leads to extremely uniform and dense perovskite layers via a CH3NH3I-PbI2-DMSO intermediate phase, and enables the fabrication of remarkably improved solar cells with a certified power-conversion efficiency of 16.2% and no hysteresis. These results provide important progress towards the understanding of the role of solution-processing in the realization of low-cost and highly efficient perovskite solar cells.

CuSbS2 -sensitized inorganic-organic heterojunction solar cells fabricated using a metal-thiourea complex solution.

The device performance of sensitizer-architecture solar cells based on a CuSbS2 light sensitizer is presented. The device consists of F-doped SnO2 substrate/TiO2 blocking layer/mesoporous TiO2 /CuSbS2 /hole-transporting material/Au electrode. The CuSbS2 was deposited by repeated cycles of spin coating of a Cu-Sb-thiourea complex solution and thermal decomposition, followed by annealing in Ar at 500 °C. Poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)) (PCPDTBT) was used as the hole-transporting material. The best-performing cell exhibited a 3.1 % device efficiency, with a short-circuit current density of 21.5 mA cm(-2) , an open-circuit voltage of 304 mV, and a fill factor of 46.8 %.

o-Methoxy substituents in spiro-OMeTAD for efficient inorganic-organic hybrid perovskite solar cells.

Three spiro-OMeTAD derivatives have been synthesized and characterized by (1)H/(13)C NMR spectroscopy and mass spectrometry. The optical and electronic properties of the derivatives were modified by changing the positions of the two methoxy substituents in each of the quadrants, as monitored by UV-vis spectroscopy and cyclic voltammetry measurements. The derivatives were employed as hole-transporting materials (HTMs), and their performances were compared for the fabrication of mesoporous TiO2/CH3NH3PbI3/HTM/Au solar cells. Surprisingly, the cell performance was dependent on the positions of the OMe substituents. The derivative with o-OMe substituents showed highly improved performance by exhibiting a short-circuit current density of 21.2 mA/cm(2), an open-circuit voltage of 1.02 V, and a fill factor of 77.6% under 1 sun illumination (100 mW/cm(2)), which resulted in an overall power conversion efficiency (PCE) of 16.7%, compared to ~15% for conventional p-OMe substituents. The PCE of 16.7% is the highest value reported to date for perovskite-based solar cells with spiro-OMeTAD.

Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells.

Chemically tuned inorganic-organic hybrid materials, based on CH3NH3(═MA)Pb(I(1-x)Br(x))3 perovskites, have been studied using UV-vis absorption and X-ray diffraction patterns and applied to nanostructured solar cells. The band gap engineering brought about by the chemical management of MAPb(I(1-x)Br(x))3 perovskites can be controllably tuned to cover almost the entire visible spectrum, enabling the realization of colorful solar cells. We demonstrate highly efficient solar cells exhibiting 12.3% in a power conversion efficiency of under standard AM 1.5, for the most efficient device, as a result of tunable composition for the light harvester in conjunction with a mesoporous TiO2 film and a hole conducting polymer. We believe that the works highlighted in this paper represent one step toward the realization of low-cost, high-efficiency, and long-term stability with colorful solar cells.

Sb(2)Se(3) -sensitized inorganic-organic heterojunction solar cells fabricated using a single-source precursor.

The photovoltaic performance of Sb2 Se3 -sensitized heterojunction solar cells, which were fabricated by a simple deposition of Sb2 Se3 on mesoporous TiO2 by an approach that features multiple cycles of spin coating with a single-source precursor solution and thermal decomposition, is reported. Poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothioadiazole)] was used as the hole-transporting material. The most efficient cell exhibited a short-circuit current density of 22.3 mA cm(-2) , an open-circuit voltage of 304.5 mV, and a fill factor of 47.2 %, yielding a power conversion efficiency of 3.21 % under standard test conditions (irradiation of 1000 W m(-2) , air mass=1.5 G). The results of this study imply that the developed approach has a high potential as a simple and effective route for the fabrication of efficient and inexpensive solar cells.

Efficient inorganic-organic hybrid perovskite solar cells based on pyrene arylamine derivatives as hole-transporting materials.

A set of three N,N-di-p-methoxyphenylamine-substituted pyrene derivatives have successfully been synthesized and characterized by (1)H/(13)C NMR spectroscopy, mass spectrometry, and elemental analysis. The optical and electronic structures of the pyrene derivatives were adjusted by controlling the ratio of N,N-di-p-methoxyphenylamine to pyrene, and investigated by UV/vis spectroscopy and cyclic voltammetry. The pyrene derivatives were employed as hole-transporting materials (HTMs) in fabricating mesoporous TiO2/CH3NH3PbI3/HTMs/Au solar cells. The pyrene-based derivative Py-C exhibited a short-circuit current density of 20.2 mA/cm(2), an open-circuit voltage (Voc) of 0.886 V, and a fill factor of 69.4% under an illumination of 1 sun (100 mW/cm(2)), resulting in an overall power conversion efficiency of 12.4%. The performance is comparable to that of the well-studied spiro-OMeTAD, even though the Voc is slightly lower. Thus, this newly synthesized pyrene derivative holds promise as a HTM for highly efficient perovskite-based solar cells.