Ibrahim Dursun

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.

Planar-integrated single-crystalline perovskite photodetectors

Hybrid perovskites are promising semiconductors for optoelectronic applications. However, they suffer from morphological disorder that limits their optoelectronic properties and, ultimately, device performance. Recently, perovskite single crystals have been shown to overcome this problem and exhibit impressive improvements: low trap density, low intrinsic carrier concentration, high mobility, and long diffusion length that outperform perovskite-based thin films. These characteristics make the material ideal for realizing photodetection that is simultaneously fast and sensitive; unfortunately, these macroscopic single crystals cannot be grown on a planar substrate, curtailing their potential for optoelectronic integration. Here we produce large-area planar-integrated films made up of large perovskite single crystals. These crystalline films exhibit mobility and diffusion length comparable with those of single crystals. Using this technique, we produced a high-performance light detector showing high gain (above 104 electrons per photon) and high gain-bandwidth product (above 108 Hz) relative to other perovskite-based optical sensors.

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.

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.

The recombination mechanisms leading to amplified spontaneous emission at the true-green wavelength in CH3NH3PbBr3 perovskites

We investigated the mechanisms of radiative recombination in a CH3NH3PbBr3 hybrid perovskite material using low-temperature, power-dependent (77 K), and temperature-dependent photoluminescence (PL) measurements. Two bound-excitonic radiative transitions related to grain size inhomogeneity were identified. Both transitions led to PL spectra broadening as a result of concurrent blue and red shifts of these excitonic peaks. The red-shifted bound-excitonic peak dominated at high PL excitation led to a true-green wavelength of 553 nm for CH3NH3PbBr3 powders that are encapsulated in polydimethylsiloxane. Amplified spontaneous emission was eventually achieved for an excitation threshold energy of approximately 350 μJ/cm2. Our results provide a platform for potential extension towards a true-green light-emitting device for solid-state lighting and display applications.

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.

Optical constants of CH 3 NH 3 PbBr 3 perovskite thin films measured by spectroscopic ellipsometry.

The lack of optical constants information for hybrid perovskite of CH₃NH₃PbBr₃ in thin films form can delay the progress of efficient LED or laser demonstration. Here, we report on the optical constants (complex refractive index and dielectric function) of CH₃NH₃PbBr₃ perovskite thin films using spectroscopic ellipsometry. Due to the existence of voids, the refractive index of the thin films is around 8% less than the single crystals counterpart. The energy bandgap is around 2.309 eV as obtained from photoluminescence and spectrophotometry spectra, and calculated from the SE analysis. The precise measurement of optical constants will be useful in designing optical devices using CH₃NH₃PbBr₃ thin films.

Enhanced Etching, Surface Damage Recovery, and Submicron Patterning of Hybrid Perovskites using a Chemically Gas-Assisted Focused-Ion Beam for Subwavelength Grating Photonic Applications

The high optical gain and absorption of organic-inorganic hybrid perovskites have attracted attention for photonic device applications. However, owing to the sensitivity of organic moieties to solvents and temperature, device processing is challenging, particularly for patterning. Here, we report the direct patterning of perovskites using chemically gas-assisted focused-ion beam (GAFIB) etching with XeF2 and I2 precursors. We demonstrate etching enhancement in addition to controllability and marginal surface damage compared to focused-ion beam (FIB) etching without precursors. Utilizing the GAFIB etching, we fabricated a uniform and periodic submicron perovskite subwavelength grating (SWG) absorber with broadband absorption and nanoscale precision. Our results demonstrate the use of FIB as a submicron patterning tool and a means of providing surface treatment (after FIB patterning to minimize optical loss) for perovskite photonic nanostructures. The SWG absorber can be patterned on perovskite solar cells to enhance the device efficiency through increasing light trapping and absorption.

Focused-ion beam patterning of organolead trihalide perovskite for subwavelength grating nanophotonic applications

The coherent amplified spontaneous emission and high photoluminescence quantum efficiency of organolead trihalide perovskite have led to research interest in this material for use in photonic devices. In this paper, the authors present a focused-ion beam patterning strategy for methylammonium lead tribromide (MAPbBr3) perovskite crystal for subwavelength grating nanophotonic applications. The essential parameters for milling, such as the number of scan passes, dwell time, ion dose, ion current, ion incident angle, and gas-assisted etching, were experimentally evaluated to determine the sputtering yield of the perovskite. Based on our patterning conditions, the authors observed that the sputtering yield ranged from 0.0302 to 0.0719 μm3/pC for the MAPbBr3 perovskite crystal. Using XeF2 for the focused-ion beam gas-assisted etching, the authors determined that the etching rate was reduced to between 0.40 and 0.97, depending on the ion dose, compared with milling with ions only. Using the optimized patterning...