Organic-inorganic Perovskite Semiconductors Research Articles

Graphene-Templated Achiral Hybrid Perovskite for Circularly Polarized Light Sensing.

This study points out the importance of the templating effect in hybrid organic-inorganic perovskite semiconductors grown on graphene. By combining two achiral materials, we report the formation of a chiral composite heterostructure with electronic band splitting. The effect is observed through circularly polarized light emission and detection in a graphene/α-CH(NH2)2PbI3 perovskite composite, at ambient temperature and without a magnetic field. We exploit the spin-charge conversion by introducing an unbalanced spin population through polarized light that gives rise to a spin photoconductive effect rationalized by Rashba-type coupling. The prepared composite heterostructure exhibits a circularly polarized photoluminescence anisotropy gCPL of ∼0.35 at ∼2.54 × 103 W cm-2 confocal power density of 532 nm excitation. A carefully engineered interface between the graphene and the perovskite thin film enhances the Rashba field and generates the built-in electric field responsible for photocurrent, yielding a photoresponsivity of ∼105 A W-1 under ∼0.08 μW cm-2 fluence of visible light photons. The maximum photocurrent anisotropy factor gph is ∼0.51 under ∼0.16 μW cm-2 irradiance. The work sheds light on the photophysical properties of graphene/perovskite composite heterostructures, finding them to be a promising candidate for developing miniaturized spin-photonic devices.

Effect of Pd(II) uptake on high-temperature phase transitions in a hybrid organic-inorganic perovskite semiconductor.

Hybrid organic-inorganic perovskites (HOIPs) have been widely studied for their interesting functions and potential applications. Here, we report a novel sulfur-containing hybrid organic-inorganic perovskite based on a one-dimensional ABX3-type compound: [C3H7N2S]PbI3 ([C3H7N2S]+ is 2-amino-2-thiazolinium) (1). Compound 1 undergoes two high-temperature phase transitions at 363 K and 401 K, respectively, showing a band gap of 2.33 eV, and has a narrower band gap compared to other one-dimensional materials. Moreover, by introducing thioether groups into the organic component, 1 has the ability to uptake Pd(II) ions. Compared with previously reported low-temperature isostructural phase transition sulfur-containing hybrids, the molecular motion of 1 becomes more intense under the stimulation of high temperature, leading to changes in the space group during the two phase transitions (Pbca → Pmcn → Cmcm), which are no longer the previous isostructural phase transitions. Significant changes in the phase transition behavior and semiconductor properties before and after metal absorption make it possible to monitor the absorption process of metal ions. The study of the effect of Pd(II) uptake on phase transitions may be helpful to reveal the mechanism of phase transitions more deeply. This work will broaden the hybrid organic-inorganic ABX3-type semiconductor family and pave the way for the development of organic-inorganic hybrid-based multifunctional phase transition materials.

MaPBI3 and 2D hybrid organic-inorganic perovskite based microcavities employing periodic, aperiodic, and disordered photonic structures with light-induced tuning possibility

Inorganic-organic perovskites semiconductors are becoming increasingly interesting due to their remarkable optical properties, such as a high photoluminescence quantum yield and the possibility to show optical gain in a broad range of wavelengths. We have here simulated microcavities that embed MaPBI3 and 2D hybrid organic-inorganic perovskite semiconductors by sandwiching such active layers between periodic, aperiodic and disordered photonic structures. The complex refractive index dispersions of MaPBI3 and 2D hybrid organic-inorganic perovskite have been recently reported in literature. Thus, we have carefully considered the refractive index dispersion of all the materials employed, such as silicon dioxide, titanium dioxide, and the aforementioned perovskite layers. Moreover, by employing a photochromatic polymer, namely the diarylethene-based polyester pDTE, we have designed a microcavity with light-induced tuning of the cavity modes is possible.

Flexible Inkjet-Printed Triple Cation Perovskite X-ray Detectors.

Flexible direct conversion X-ray detectors enable a variety of novel applications in medicine, industry, and science. Hybrid organic-inorganic perovskite semiconductors containing elements of high atomic number combine an efficient X-ray absorption with excellent charge transport properties. Due to their additional cost-effective and low-temperature processability, perovskite semiconductors represent promising candidates to be used as active materials in flexible X-ray detectors. Inspired by the promising results recently reported on X-ray detectors that are based on either triple cation perovskites or inkjet-printed perovskite quantum dots, we here investigate flexible inkjet-printed triple cation perovskite X-ray detectors. The performance of the detectors is evaluated by the X-ray sensitivity, the dark current, and the X-ray stability. Exposed to 70 kVp X-ray radiation, reproducible and highly competitive X-ray sensitivities of up to 59.9 μC/(Gyaircm2) at low operating voltages of 0.1 V are achieved. Furthermore, a significant dark current reduction is demonstrated in our detectors by replacing spin-coated poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) with sputtered NiOx hole transport layers. Finally, stable operation of a flexible X-ray detector for a cumulative X-ray exposure of 4 Gyair is presented, and the applicability of our devices as X-ray imaging detectors is shown. The results of this study represent a proof of concept toward flexible direct conversion X-ray detectors realized by cost-effective and high-throughput digital inkjet printing.

NMR study of defect-induced magnetism in methylammonium lead iodide perovskite

In organic-inorganic perovskite semiconductor methylammonium lead iodide the occurrence of magnetism has been confirmed from magnetization and $^{1}\mathrm{H}$ nuclear magnetic resonance (NMR) measurements. From room temperature down to 4 K, the magnetization is a combination of weak ferromagnetism and paramagnetism. $^{1}\mathrm{H}$ NMR spectra at low temperatures also reveal two components, one with a small chemical shift characteristic of $^{1}\mathrm{H}$ resonance in nonmetals, and the other with a much larger shift of $\ensuremath{\sim}\ensuremath{-}100$ ppm that is ascribed to the ferromagnetism of the material. The analysis of NMR spectra as well as that of $^{1}\mathrm{H}$ spin-lattice relaxation rate ($1/{T}_{1}$) indicates that disorder produces an inhomogeneous distribution of magnetic moments that order ferromagnetically where they are dense enough and otherwise behave as random paramagnetic impurities. It is shown that magnetism arises from iodine and lead vacancies present in the orthorhombic and cubic crystal phases of the material.

Multifunctional atomic force probes for Mn2+ doped perovskite solar cells

Doping in organic–inorganic perovskite semiconductors is an effective method to tailor their optoelectronic properties. In this work, manganese-doped perovskite films with different Mn/Pb ratios ranging from 0% to 2% were systematically studied. The device performance of 0.2% Mn-doped devices was improved compared to that of a device without Mn. However, a further increase of the doping concentration induced a decrease in performance. Several characteristics (especially different scanning probe microscopy characteristics) reveal that an increased dopant concentration results in reduced crystallinity and a change in the film morphology and causes a deterioration in photovoltaic performance for higher dopant concentrations. In the best-performing samples (0.2%), a shift in the valence band level and band gap are found which are responsible for the increased open circuit voltage, while increased grain boundaries and lower surface charge density are responsible for a small reduction in the short circuit current. Thus, multifunctional scanning probe microscopy approaches, combined with different film characterization techniques, offer us effective tools to investigate the impact of doping in the perovskite materials and the corresponding device performance.

Simulation and design of folded perovskite x-ray detectors

A variety of medical, industrial, and scientific applications requires highly sensitive and cost-effective x-ray detectors for photon energies ranging from keV to MeV. Adapting the thickness of polycrystalline or single crystal conversion layers especially to high-energy applications increases the complexity of fabrication and potentially decreases the performance of conventional direct conversion x-ray detectors. To tackle the challenges with respect to the active layer thickness and to combine the superior performance of single crystal materials with the low-cost nature of polycrystalline conversion layers, we investigate thin film x-ray detector technologies based on a folded device architecture. Analytical models simulating the sensitivity and the detective quantum efficiency (DQE) are used to evaluate the performance of folded detectors based on polycrystalline organic-inorganic perovskite semiconductors in various layout configurations and for different photon energies. Simulations of folded perovskite devices show high sensitivities. The DQE analysis introduces additional noise related boundary conditions for the folding length. A comparison with conventional detectors based on state of the art conversion materials at different photon energies demonstrates the potential of the folded detector layout as simulated sensitivities are comparable to single crystal detectors.

Tunable Semiconductors: Control over Carrier States and Excitations in Layered Hybrid Organic-Inorganic Perovskites.

For a class of 2D hybrid organic-inorganic perovskite semiconductors based on π-conjugated organic cations, we predict quantitatively how varying the organic and inorganic component allows control over the nature, energy, and localization of carrier states in a quantum-well-like fashion. Our first-principles predictions, based on large-scale hybrid density-functional theory with spin-orbit coupling, show that the interface between the organic and inorganic parts within a single hybrid can be modulated systematically, enabling us to select between different type-I and type-II energy level alignments. Energy levels, recombination properties, and transport behavior of electrons and holes thus become tunable by choosing specific organic functionalizations and juxtaposing them with suitable inorganic components.

Room Temperature Coherently Coupled Exciton-Polaritons in Two-Dimensional Organic-Inorganic Perovskite.

Two-dimensional (2D) organic-inorganic perovskite semiconductors with natural multiquantum well structures and confined 2D excitons are intriguing for the study of strong exciton-photon coupling, due to their large exciton binding energy and oscillation strength. This strong coupling leads to a formation of the half-light half-matter bosonic quasiparticle called exciton-polariton, consisting of a linear superposition state between photonic and excitonic states. Here, we demonstrate room temperature strong coupling in exfoliated wavelength-tunable 2D organic-inorganic perovskite semiconductors embedded into a planar microcavity, exhibiting large energetic splitting-to-line width ratios (>34.2). Angular-dependent spectroscopy measurements reveal that hybridized polariton states act as an ultrafast and reversible energy oscillation, involving 2D perovskite exciton, cavity modes (CM), and Bragg modes of the distributed Bragg reflector. Meanwhile, sizable hybrid particles dominantly couple to the measured optical field through the CMs. Our findings advocate a considerable promise of 2D organic-inorganic perovskite to explore fundamental quantum phenomena such as Bose-Einstein condensation, superfluidity, and exciton-polariton networks.

Tightly bound indirect exciton in single-layer hybrid organic-inorganic perovskite semiconductor

We theoretically study the direct and indirect excitons (IXs) in a single-layer hybrid organic-inorganic perovskite (HOIP) semiconductor. Due to the 2D nature, the single-layer HOIP supports the large binding energy of IXs and direct excitons over a wide range of applied electric fields, which exceed the thermal energy of room temperature. Moreover, the ground-state IX has a lower energy than that of direct exciton, which will extend the coherence and relaxation time of IXs. This is beneficial to optoelectronic applications and excitonic information processing devices of IXs.

Solution-Processed Organic-Inorganic Perovskite Field-Effect Transistors with High Hole Mobilities.

A very high hole mobility of 15 cm2 V-1 s-1 along with negligible hysteresis are demonstrated in transistors with an organic-inorganic perovskite semiconductor. This high mobility results from the well-developed perovskite crystallites, improved conversion to perovskite, reduced hole trap density, and improved hole injection by employing a top-contact/top-gate structure with surface treatment and MoOx hole-injection layers.

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.

Exfoliation of self-assembled 2D organic-inorganic perovskite semiconductors

Ultra-thin flakes of 2D organic-inorganic perovskite (C6H9C2H4NH3)2PbI4 are produced using micromechanical exfoliation. Mono- and few-layer areas are identified using optical and atomic force microscopy, with an interlayer spacing of 1.6 nm. Refractive indices extracted from the optical spectra reveal a sample thickness dependence due to the charge transfer between organic and inorganic layers. These measurements demonstrate a clear difference in the exciton properties between “bulk” (>15 layers) and very thin (<8 layer) regions as a result of the structural rearrangement of organic molecules around the inorganic sheets.

Preparations and Characterizations of Luminescent Two Dimensional Organic-inorganic Perovskite Semiconductors

This article reviews the synthesis, structural and optical characterizations of some novel luminescent two dimensional organic-inorganic perovskite (2DOIP) semiconductors. These 2DOIP semiconductors show a self-assembled nano-layered structure, having the electronic structure of multi-quantum wells. 2DOIP thin layers and nanoparticles have been prepared through different methods. The structures of the 2DOIP semiconductors are characterized by atomic force microscopy and X-ray diffraction. The optical properties of the 2DOIP semiconductors are characterized from absorption and photoluminescence spectra measured at room and low temperatures. Influences of different components, in particular the organic parts, on the structural and optical properties of the 2DOIP semiconductors are discussed.