Bandgap-universal passivation enables stable perovskite solar cells with low photovoltage loss.

The efficiency and longevity of metal-halide perovskite solar cells are typically dictated by nonradiative defect-mediated charge recombination. In this work, we demonstrate a vapor-based amino-silane passivation that reduces photovoltage deficits to around 100 millivolts (>90% of the thermodynamic limit) in perovskite solar cells of bandgaps between 1.6 and 1.8 electron volts, which is crucial for tandem applications. A primary-, secondary-, or tertiary-amino-silane alone negatively or barely affected perovskite crystallinity and charge transport, but amino-silanes that incorporate primary and secondary amines yield up to a 60-fold increase in photoluminescence quantum yield and preserve long-range conduction. Amino-silane-treated devices retained 95% power conversion efficiency for more than 1500 hours under full-spectrum sunlight at 85°C and open-circuit conditions in ambient air with a relative humidity of 50 to 60%.

Correction to "A Templating Approach to Controlling the Growth of Coevaporated Halide Perovskites".

[This corrects the article DOI: 10.1021/acsenergylett.3c01368.].

A Templating Approach to Controlling the Growth of Coevaporated Halide Perovskites.

Metal halide perovskite semiconductors have shown significant potential for use in photovoltaic (PV) devices. While fabrication of perovskite thin films can be achieved through a variety of techniques, thermal vapor deposition is particularly promising, allowing for high-throughput fabrication. However, the ability to control the nucleation and growth of these materials, particularly at the charge-transport layer/perovskite interface, is critical to unlocking the full potential of vapor-deposited perovskite PV. In this study, we explore the use of a templating layer to control the growth of coevaporated perovskite films and find that such templating leads to highly oriented films with identical morphology, crystal structure, and optoelectronic properties independent of the underlying layers. Solar cells incorporating templated FA0.9Cs0.1PbI3-xClx show marked improvements with steady-state power conversion efficiency over 19.8%. Our findings provide a straightforward and reproducible method of controlling the charge-transport layer/coevaporated perovskite interface, further clearing the path toward large-scale fabrication of efficient PV devices.

Photovoltaic Performance of FAPbI3 Perovskite Is Hampered by Intrinsic Quantum Confinement.

Formamidinium lead trioiodide (FAPbI3) is a promising perovskite for single-junction solar cells. However, FAPbI3 is metastable at room temperature and can cause intrinsic quantum confinement effects apparent through a series of above-bandgap absorption peaks. Here, we explore three common solution-based film-fabrication methods, neat N,N-dimethylformamide (DMF)-dimethyl sulfoxide (DMSO) solvent, DMF-DMSO with methylammonium chloride, and a sequential deposition approach. The latter two offer enhanced nucleation and crystallization control and suppress such quantum confinement effects. We show that elimination of these absorption features yields increased power conversion efficiencies (PCEs) and short-circuit currents, suggesting that quantum confinement hinders charge extraction. A meta-analysis of literature reports, covering 244 articles and 825 photovoltaic devices incorporating FAPbI3 films corroborates our findings, indicating that PCEs rarely exceed a 20% threshold when such absorption features are present. Accordingly, ensuring the absence of these absorption features should be the first assessment when designing fabrication approaches for high-efficiency FAPbI3 solar cells.

Thermally Stable Perovskite Solar Cells by All-Vacuum Deposition.

Vacuum deposition is a solvent-free method suitable for growing thin films of metal halide perovskite (MHP) semiconductors. However, most reports of high-efficiency solar cells based on such vacuum-deposited MHP films incorporate solution-processed hole transport layers (HTLs), thereby complicating prospects of industrial upscaling and potentially affecting the overall device stability. In this work, we investigate organometallic copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) as alternative, low-cost, and durable HTLs in all-vacuum-deposited solvent-free formamidinium-cesium lead triodide [CH(NH2)2]0.83Cs0.17PbI3 (FACsPbI3) perovskite solar cells. We elucidate that the CuPc HTL, when employed in an "inverted" p-i-n solar cell configuration, attains a solar-to-electrical power conversion efficiency of up to 13.9%. Importantly, unencapsulated devices as large as 1 cm2 exhibited excellent long-term stability, demonstrating no observable degradation in efficiency after more than 5000 h in storage and 3700 h under 85 °C thermal stressing in N2 atmosphere.

Utilizing Nonpolar Organic Solvents for the Deposition of Metal-Halide Perovskite Films and the Realization of Organic Semiconductor/Perovskite Composite Photovoltaics.

Having captivated the research community with simple fabrication processes and staggering device efficiencies, perovskite-based optoelectronics are already on the way to commercialization. However, one potential obstacle to this commercialization is the almost exclusive use of toxic, highly coordinating, high boiling point solvents to make perovskite precursor inks. Herein, we demonstrate that nonpolar organic solvents, such as toluene, can be combined with butylamine to form an effective solvent for alkylammonium-based perovskites. Beyond providing broader solvent choice, our finding opens the possibility of blending perovskite inks with a wide range of previously incompatible materials, such as organic molecules, polymers, nanocrystals, and structure-directing agents. As a demonstration, using this solvent, we blend the perovskite ink with 6,6-phenyl-C-61-butyric acid methyl ester and show improved perovskite crystallization and device efficiencies. This processing route may enable a myriad of new possibilities for tuning the active layers in efficient photovoltaics, light-emitting diodes, and other semiconductor devices.

Improved Charge Balance in Green Perovskite Light-Emitting Diodes with Atomic-Layer-Deposited Al2O3.

Perovskite light-emitting diodes (LEDs) have experienced a rapid increase in efficiency over the last several years and are now regarded as promising low-cost devices for displays and communication systems. However, it is often challenging to employ ZnO, a well-studied electron transport material, in perovskite LEDs due to chemical instability at the ZnO/perovskite interface and charge injection imbalance caused by the relatively high conductivity of ZnO. In this work, we address these problems by depositing an ultrathin Al2O3 interlayer at the ZnO/perovskite interface, allowing the fabrication of green-emitting perovskite LEDs with a maximum luminance of 21 815 cd/m2. Using atomic layer deposition, we can precisely control the Al2O3 thickness and thus fine-tune the electron injection from ZnO, allowing us to enhance the efficiency and operational stability of our LEDs.

Crystalline Nature of Colloids in Methylammonium Lead Halide Perovskite Precursor Inks Revealed by Cryo-Electron Microscopy.

Metal halide perovskites have generated interest across many fields for the impressive optoelectronic properties achievable in films produced using facile solution-processing techniques. Previous research has revealed the colloidal nature of perovskite precursor inks and established a relationship between the colloid distribution and the film optoelectronic quality. Yet, the identity of colloids remains unknown, hindering our understanding of their role in perovskite crystallization. Here, we investigate precursor inks of the prototypical methylammonium lead triiodide perovskite using cryo-electron microscopy (cryo-EM) and show, for the first time, that the colloids are neither amorphous nor undissolved lead iodide, as previously speculated, but are a crystalline, non-perovskite material. We identify this as a perovskite precursor phase and discuss this as a potential means to understanding the role of chloride in processing. This work establishes cryo-EM as a viable technique to elucidate the nature of colloids in perovskite inks, a vital step toward a fundamental understanding of thin-film crystallization.

Facile Synthesis of Stable and Highly Luminescent Methylammonium Lead Halide Nanocrystals for Efficient Light Emitting Devices.

Metal halide perovskites are promising candidates for use in light emitting diodes (LEDs), due to their potential for color tunable and high luminescence efficiency. While recent advances in perovskite-based light emitting diodes have resulted in external quantum efficiencies exceeding 12.4% for the green emitters, and infrared emitters based on 3 D/2D mixed dimensional perovskites have exceeded 20%, the external quantum efficiencies of the red and blue emitters still lag behind. A critical issue to date is creating highly emissive and stable perovskite emitters with the desirable emission band gap to achieve full-color displays and white LEDs. Herein, we report the preparation and characterization of a highly luminescent and stable suspension of cubic-shaped methylammonium lead triiodide (CH3NH3PbI3) perovskite nanocrystals, where we synthesize the nanocrystals via a ligand-assisted reprecipitation technique, using an acetonitrile/methylamine compound solvent system to solvate the ions and toluene as the antisolvent to induce crystallization. Through tuning the ratio of the ligands, the ligand to toluene ratio, and the temperature of the toluene, we obtain a solution of CH3NH3PbI3 nanocrystals with a photoluminescence quantum yield exceeding 93% and tunable emission between 660 and 705 nm. We also achieved red emission at 635 nm by blending the nanocrystals with bromide salt and obtained perovskite-based light emitting diodes with maximum electroluminescent external quantum efficiency of 2.75%.

Mixed Lead-Tin Halide Perovskites for Efficient and Wavelength-Tunable Near-Infrared Light-Emitting Diodes.

Near-infrared (NIR) light-emitting diodes (LEDs), with emission wavelengths between 800 and 950 nm, are useful for various applications, e.g., night-vision devices, optical communication, and medical treatments. Yet, devices using thin film materials like organic semiconductors and lead based colloidal quantum dots face certain fundamental challenges that limit the improvement of external quantum efficiency (EQE), making the search of alternative NIR emitters important for the community. In this work, efficient NIR LEDs with tunable emission from 850 to 950 nm, using lead-tin (Pb-Sn) halide perovskite as emitters are demonstrated. The best performing device exhibits an EQE of 5.0% with a peak emission wavelength of 917 nm, a turn-on voltage of 1.65 V, and a radiance of 2.7 W Sr-1 m-2 when driven at 4.5 V. The emission spectra of mixed Pb-Sn perovskites are tuned either by changing the Pb:Sn ratio or by incorporating bromide, and notably exhibit no phase separation during device operation. The work demonstrates that mixed Pb-Sn perovskites are promising next generation NIR emitters.

Consolidation of the optoelectronic properties of CH3NH3PbBr3 perovskite single crystals.

Ultralow trap densities, exceptional optical and electronic properties have been reported for lead halide perovskites single crystals; however, ambiguities in basic properties, such as the band gap, and the electronic defect densities in the bulk and at the surface prevail. Here, we synthesize single crystals of methylammonium lead bromide (CH3NH3PbBr3), characterise the optical absorption and photoluminescence and show that the optical properties of single crystals are almost identical to those of polycrystalline thin films. We observe significantly longer lifetimes and show that carrier diffusion plays a substantial role in the photoluminescence decay. Contrary to many reports, we determine that the trap density in CH3NH3PbBr3 perovskite single crystals is 1015 cm-3, only one order of magnitude lower than in the thin films. Our enhanced understanding of optical properties and recombination processes elucidates ambiguities in earlier reports, and highlights the discrepancies in the estimation of trap densities from electronic and optical methods.Metal halide perovskites for optoelectronic devices have been extensively studied in two forms: single-crystals or polycrystalline thin films. Using spectroscopic approaches, Wenger et al. show that polycrystalline thin films possess similar optoelectronic properties to single crystals.

Crystallization Kinetics and Morphology Control of Formamidinium-Cesium Mixed-Cation Lead Mixed-Halide Perovskite via Tunability of the Colloidal Precursor Solution.

The meteoric rise of the field of perovskite solar cells has been fueled by the ease with which a wide range of high-quality materials can be fabricated via simple solution processing methods. However, to date, little effort has been devoted to understanding the precursor solutions, and the role of additives such as hydrohalic acids upon film crystallization and final optoelectronic quality. Here, a direct link between the colloids concentration present in the [HC(NH2 )2 ]0.83 Cs0.17 Pb(Br0.2 I0.8 )3 precursor solution and the nucleation and growth stages of the thin film formation is established. Using dynamic light scattering analysis, the dissolution of colloids over a time span triggered by the addition of hydrohalic acids is monitored. These colloids appear to provide nucleation sites for the perovskite crystallization, which critically impacts morphology, crystal quality, and optoelectronic properties. Via 2D X-ray diffraction, highly ordered and textured crystals for films prepared from solutions with lower colloidal concentrations are observed. This increase in material quality allows for a reduction in microstrain along with a twofold increase in charge-carrier mobilities leading to values exceeding 20 cm2 V-1 s-1 . Using a solution with an optimized colloidal concentration, devices that reach current-voltage measured power conversion efficiency of 18.8% and stabilized efficiency of 17.9% are fabricated.

Mechanism for rapid growth of organic-inorganic halide perovskite crystals.

Optoelectronic devices based on hybrid halide perovskites have shown remarkable progress to high performance. However, despite their apparent success, there remain many open questions about their intrinsic properties. Single crystals are often seen as the ideal platform for understanding the limits of crystalline materials, and recent reports of rapid, high-temperature crystallization of single crystals should enable a variety of studies. Here we explore the mechanism of this crystallization and find that it is due to reversible changes in the solution where breaking up of colloids, and a change in the solvent strength, leads to supersaturation and subsequent crystallization. We use this knowledge to demonstrate a broader range of processing parameters and show that these can lead to improved crystal quality. Our findings are therefore of central importance to enable the continued advancement of perovskite optoelectronics and to the improved reproducibility through a better understanding of factors influencing and controlling crystallization.

Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

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.

Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells.

Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce the oxidized I2 back into I(-), and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead.

Enhanced photoluminescence and solar cell performance via Lewis base passivation of organic-inorganic lead halide perovskites.

Organic-inorganic metal halide perovskites have recently emerged as a top contender to be used as an absorber material in highly efficient, low-cost photovoltaic devices. Solution-processed semiconductors tend to have a high density of defect states and exhibit a large degree of electronic disorder. Perovskites appear to go against this trend, and despite relatively little knowledge of the impact of electronic defects, certified solar-to-electrical power conversion efficiencies of up to 17.9% have been achieved. Here, through treatment of the crystal surfaces with the Lewis bases thiophene and pyridine, we demonstrate significantly reduced nonradiative electron-hole recombination within the CH(3)NH(3)PbI(3-x)Cl(x) perovskite, achieving photoluminescence lifetimes which are enhanced by nearly an order of magnitude, up to 2 µs. We propose that this is due to the electronic passivation of under-coordinated Pb atoms within the crystal. Through this method of Lewis base passivation, we achieve power conversion efficiencies for solution-processed planar heterojunction solar cells enhanced from 13% for the untreated solar cells to 15.3% and 16.5% for the thiophene and pyridine-treated solar cells, respectively.

Polystyrene templated porous titania wells for quantum dot heterojunction solar cells.

Polystyrene spheres are used to template TiO2 with a single layer of 300 nm wells which are infilled with PbS quantum dots to form a heterojunction solar cell. The porous well device has an efficiency of 5.7% while the simple planar junction is limited to 3.2%. Using a combination of optical absorption and photocurrent transient decay measurement we determined that the performance enhancement comes from a combination of enhanced optical absorption and increased carrier lifetime.

Lessons learned: from dye-sensitized solar cells to all-solid-state hybrid devices.

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.

Anomalous Hysteresis in Perovskite Solar Cells.

Perovskite solar cells have rapidly risen to the forefront of emerging photovoltaic technologies, exhibiting rapidly rising efficiencies. This is likely to continue to rise, but in the development of these solar cells there are unusual characteristics that have arisen, specifically an anomalous hysteresis in the current-voltage curves. We identify this phenomenon and show some examples of factors that make the hysteresis more or less extreme. We also demonstrate stabilized power output under working conditions and suggest that this is a useful parameter to present, alongside the current-voltage scan derived power conversion efficiency. We hypothesize three possible origins of the effect and discuss its implications on device efficiency and future research directions. Understanding and resolving the hysteresis is essential for further progress and is likely to lead to a further step improvement in performance.