Erkki Alarousu

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals

Large-crystal perovskite films The performance of organic-inorganic hybrid perovskite planar solar cells has steadily improved. One outstanding issue is that grain boundaries and defects in polycrystalline films degrade their output. Now, two studies report the growth of millimeter-scale single crystals. Nie et al. grew continuous, pinhole-free, thin iodochloride films with a hot-casting technique and report device efficiencies of 18%. Shi et al. used antisolvent vapor-assisted crystallization to grow millimeter-scale bromide and iodide cubic crystals with charge-carrier diffusion lengths exceeding 10 mm. Science, this issue p. 522, p. 519 Solution processing techniques enable the growth of high-quality, large-area perovskite crystals for solar cells. The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3 (MA = CH3NH3+; X = Br– or I–) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3 single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics. We observed exceptionally low trap-state densities on the order of 109 to 1010 per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization

Single crystals of methylammonium lead trihalide perovskites (MAPbX3; MA=CH3NH3+, X=Br− or I−) have shown remarkably low trap density and charge transport properties; however, growth of such high-quality semiconductors is a time-consuming process. Here we present a rapid crystal growth process to obtain MAPbX3 single crystals, an order of magnitude faster than previous reports. The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures. The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters. Despite the rapidity of the method, the grown crystals exhibit transport properties and trap densities comparable to the highest quality MAPbX3 reported to date. The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.

CH3NH3PbCl3 Single Crystals: Inverse Temperature Crystallization and Visible-Blind UV-Photodetector

Single crystals of hybrid perovskites have shown remarkably improved physical properties compared to their polycrystalline film counterparts, underscoring their importance in the further development of advanced semiconductor devices. Here we present a new method of growing sizable CH3NH3PbCl3 single crystals based on the retrograde solubility behavior of hybrid perovskites. We show, for the first time, the energy band structure, charge recombination, and transport properties of CH3NH3PbCl3 single crystals. These crystals exhibit trap-state density, charge carrier concentration, mobility, and diffusion length comparable with the best quality crystals of methylammonium lead iodide or bromide perovskites reported so far. The high quality of the crystal along with its suitable optical band gap enabled us to build an efficient visible-blind UV-photodetector, demonstrating its potential in optoelectronic applications.

Air-Stable Surface-Passivated Perovskite Quantum Dots for Ultra-Robust, Single- and Two-Photon-Induced Amplified Spontaneous Emission

We demonstrate ultra-air- and photostable CsPbBr3 quantum dots (QDs) by using an inorganic-organic hybrid ion pair as the capping ligand. This passivation approach to perovskite QDs yields high photoluminescence quantum yield with unprecedented operational stability in ambient conditions (60 ± 5% lab humidity) and high pump fluences, thus overcoming one of the greatest challenges impeding the development of perovskite-based applications. Due to the robustness of passivated perovskite QDs, we were able to induce ultrastable amplified spontaneous emission (ASE) in solution processed QD films not only through one photon but also through two-photon absorption processes. The latter has not been observed before in the family of perovskite materials. More importantly, passivated perovskite QD films showed remarkable photostability under continuous pulsed laser excitation in ambient conditions for at least 34 h (corresponds to 1.2 × 10(8) laser shots), substantially exceeding the stability of other colloidal QD systems in which ASE has been observed.

Solution-Grown Monocrystalline Hybrid Perovskite Films for Hole-Transporter-Free Solar Cells.

High-quality perovskite monocrystalline films are successfully grown through cavitation-triggered asymmetric crystallization. These films enable a simple cell structure, ITO/CH3 NH3 PbBr3 /Au, with near 100% internal quantum efficiency, promising power conversion efficiencies (PCEs) >5%, and superior stability for prototype cells. Furthermore, the monocrystalline devices using a hole-transporter-free structure yield PCEs ≈6.5%, the highest among other similar-structured CH3 NH3 PbBr3 solar cells to date.

Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals

Controllable doping of semiconductors is a fundamental technological requirement for electronic and optoelectronic devices. As intrinsic semiconductors, hybrid perovskites have so far been a phenomenal success in photovoltaics. The inability to dope these materials heterovalently (or aliovalently) has greatly limited their wider utilizations in electronics. Here we show an efficient in situ chemical route that achieves the controlled incorporation of trivalent cations (Bi(3+), Au(3+), or In(3+)) by exploiting the retrograde solubility behavior of perovskites. We term the new method dopant incorporation in the retrograde regime. We achieve Bi(3+) incorporation that leads to bandgap tuning (∼300 meV), 10(4) fold enhancement in electrical conductivity, and a change in the sign of majority charge carriers from positive to negative. This work demonstrates the successful incorporation of dopants into perovskite crystals while preserving the host lattice structure, opening new avenues to tailor the electronic and optoelectronic properties of this rapidly emerging class of solution-processed semiconductors.

Perovskite Photodetectors Operating in Both Narrowband and Broadband Regimes.

Photodetectors are designed, which operate in the broadband regime upon bottom illumination (from the indium tin oxide (ITO) side) and in the narrowband regime upon top illumination (from the air/perovskite side). The narrowband photodetectors show high external quantum efficiency of above 104 %. The operational spectrum of the photodetectors can also be tuned by adjusting the halide composition in the active material.

Quantum Confinement-Tunable Ultrafast Charge Transfer at the PbS Quantum Dot and Phenyl-C_(61)-butyric Acid Methyl Ester Interface

Quantum dot (QD) solar cells have emerged as promising low-cost alternatives to existing photovoltaic technologies. Here, we investigate charge transfer and separation at PbS QDs and phenyl-C61-butyric acid methyl ester (PCBM) interfaces using a combination of femtosecond broadband transient absorption (TA) spectroscopy and steady-state photoluminescence quenching measurements. We analyzed ultrafast electron injection and charge separation at PbS QD/PCBM interfaces for four different QD sizes and as a function of PCBM concentration. The results reveal that the energy band alignment, tuned by the quantum size effect, is the key element for efficient electron injection and charge separation processes. More specifically, the steady-state and time-resolved data demonstrate that only small-sized PbS QDs with a bandgap larger than 1 eV can transfer electrons to PCBM upon light absorption. We show that these trends result from the formation of a type-II interface band alignment, as a consequence of the size distribution of the QDs. Transient absorption data indicate that electron injection from photoexcited PbS QDs to PCBM occurs within our temporal resolution of 120 fs for QDs with bandgaps that achieve type-II alignment, while virtually all signals observed in smaller bandgap QD samples result from large bandgap outliers in the size distribution. Taken together, our results clearly demonstrate that charge transfer rates at QD interfaces can be tuned by several orders of magnitude by engineering the QD size distribution. The work presented here will advance both the design and the understanding of QD interfaces for solar energy conversion.

Fast Crystallization and Improved Stability of Perovskite Solar Cells with Zn2SnO4 Electron Transporting Layer: Interface Matters

Here we report that mesoporous ternary oxide Zn2SnO4 can significantly promotes the crystallization of hybrid perovskite layers and serves as an efficient electron transporting material in perovskite solar cells. Such devices exhibit an energy conversion efficiency of 13.34%, which is even higher than that achieved with the commonly used TiO2 in the similar experimental conditions (9.1%). Simple one-step spin coating of CH3NH3PbI3-xClx on Zn2SnO4 is found to lead to rapidly crystallized bilayer perovskite structure without any solvent engineering. Furthermore, ultrafast transient absorption measurement reveals efficient charge transfer at the Zn2SnO4/perovskite interface. Most importantly, solar cells with Zn2SnO4 as the electron-transporting material exhibit negligible electrical hysteresis and exceptionally high stability without encapsulation for over one month. Besides underscoring Zn2SnO4 as a highly promising electron transporting material for perovskite solar cells, our results demonstrate the significant role of interfaces on improving the perovskite crystallization and photovoltaic performance.

Zero-Dimensional Cs4PbBr6 Perovskite Nanocrystals

Perovskite nanocrystals (NCs) have become leading candidates for solution-processed optoelectronics applications. While substantial work has been published on 3-D perovskite phases, the NC form of the zero-dimensional (0-D) phase of this promising class of materials remains elusive. Here we report the synthesis of a new class of colloidal semiconductor NCs based on Cs4PbBr6, the 0-D perovskite, enabled through the design of a novel low-temperature reverse microemulsion method with 85% reaction yield. These 0-D perovskite NCs exhibit high photoluminescence quantum yield (PLQY) in the colloidal form (PLQY: 65%), and, more importantly, in the form of thin film (PLQY: 54%). Notably, the latter is among the highest values reported so far for perovskite NCs in the solid form. Our work brings the 0-D phase of perovskite into the realm of colloidal NCs with appealingly high PLQY in the film form, which paves the way for their practical application in real devices.