Disentangling Thermal from Electronic Contributions in the Spectral Response of Photoexcited Perovskite Materials.

Disentangling electronic and thermal effects in photoexcited perovskite materials is crucial for photovoltaic and optoelectronic applications but remains a challenge due to their intertwined nature in both the time and energy domains. In this study, we employed temperature-dependent variable-angle spectroscopic ellipsometry, density functional theory calculations, and broadband transient absorption spectroscopy spanning the visible to mid-to-deep-ultraviolet (UV) ranges on MAPbBr3 thin films. The use of deep-UV detection opens a new spectral window that enables the exploration of high-energy excitations at various symmetry points within the Brillouin zone, facilitating an understanding of the ultrafast responses of the UV bands and the underlying mechanisms governing them. Our investigation reveals that the photoinduced spectral features remarkably resemble those generated by pure lattice heating, and we disentangle the relative thermal and electronic contributions and their evolutions at different delay times using combinations of decay-associated spectra and temperature-induced differential absorption. The results demonstrate that the photoinduced transients possess a significant thermal origin and cannot be attributed solely to electronic effects. Following photoexcitation, as carriers (electrons and holes) transfer their energy to the lattice, the thermal contribution increases from ∼15% at 1 ps to ∼55% at 500 ps and subsequently decreases to ∼35-50% at 1 ns. These findings elucidate the intricate energy exchange between charge carriers and the lattice in photoexcited perovskite materials and provide insights into the limited utilization efficiency of photogenerated charge carriers.

Suppressing phase disproportionation in quasi-2D perovskite light-emitting diodes.

Electroluminescence efficiencies and stabilities of quasi-two-dimensional halide perovskites are restricted by the formation of multiple-quantum-well structures with broad and uncontrollable phase distributions. Here, we report a ligand design strategy to substantially suppress diffusion-limited phase disproportionation, thereby enabling better phase control. We demonstrate that extending the π-conjugation length and increasing the cross-sectional area of the ligand enables perovskite thin films with dramatically suppressed ion transport, narrowed phase distributions, reduced defect densities, and enhanced radiative recombination efficiencies. Consequently, we achieved efficient and stable deep-red light-emitting diodes with a peak external quantum efficiency of 26.3% (average 22.9% among 70 devices and cross-checked) and a half-life of ~220 and 2.8 h under a constant current density of 0.1 and 12 mA/cm2, respectively. Our devices also exhibit wide wavelength tunability and improved spectral and phase stability compared with existing perovskite light-emitting diodes. These discoveries provide critical insights into the molecular design and crystallization kinetics of low-dimensional perovskite semiconductors for light-emitting devices.

Lead-Free Organic-Perovskite Hybrid Quantum Wells for Highly Stable Light-Emitting Diodes.

Two-dimensional perovskites that could be regarded as natural organic-inorganic hybrid quantum wells (HQWs) are promising for light-emitting diode (LED) applications. High photoluminescence quantum efficiencies (approaching 80%) and extremely narrow emission bandwidth (less than 20 nm) have been demonstrated in their single crystals; however, a reliable electrically driven LED device has not been realized owing to inefficient charge injection and extremely poor stability. Furthermore, the use of toxic lead raises concerns. Here, we report Sn(II)-based organic-perovskite HQWs employing molecularly tailored organic semiconducting barrier layers for efficient and stable LEDs. Utilizing femtosecond transient absorption spectroscopy, we demonstrate the energy transfer from organic barrier to inorganic perovskite emitter occurs faster than the intramolecular charge transfer in the organic layer. Consequently, this process allows efficient conversion of lower-energy emission associated with the organic layer into higher-energy emission from the perovskite layer. This greatly broadened the candidate pool for the organic layer. Incorporating a bulky small bandgap organic barrier in the HQW, charge transport is enhanced and ion migration is greatly suppressed. We demonstrate a HQW-LED device with pure red emission, a maximum luminance of 3466 cd m-2, a peak external quantum efficiency up to 3.33%, and an operational stability of over 150 h, which are significantly better than previously reported lead-free perovskite LEDs.

High-Performance Perovskite-Based Light-Emitting Diodes from the Conversion of Amorphous Spin-Coated Lead Bromide with Phenethylamine Doping.

Large-grained and well-oriented methylammonium lead tribromide (MAPbBr3) perovskite was formed from the conversion of amorphous lead bromide (PbBr2) doped with phenethylamine (PEA). The addition of PEA ions (with an optimized molar ratio of 0.008%) to the PbBr2 solution assisted the formation of a smooth PEA-doped PbBr2 layer by spin-coating. Then, the PEA-doped PbBr2 thin film would convert into large-grained and well-oriented MAPbBr3 with the help of a solid-vapor reaction under a vaporized methylammonium bromide (MABr) and choline chloride (CC) atmosphere. Furthermore, both PEA and CC would passivate the defects of perovskite to improve the crystal quality of perovskite. By applying this perovskite layer in perovskite light-emitting diodes (PeLEDs), the maximum luminance and current efficiency of PeLEDs could reach 20,869 cd/m2 and 3.99 cd/A, respectively; these values are approximately five and three times larger than those of PeLEDs without PEA. The perovskite converted from spin-coated PbBr2 with a PEA dopant remarkably improved the luminance and current efficiency of its PeLEDs.

Lead-Free Antimony-Based Light-Emitting Diodes through the Vapor-Anion-Exchange Method.

Hybrid lead halide perovskites continue to attract interest for use in optoelectronic devices such as solar cells and light-emitting diodes. Although challenging, the replacement of toxic lead in these systems is an active field of research. Recently, the use of trivalent metal cations (Bi3+ and Sb3+) that form defect perovskites A3B2X9 has received great attention for the development of solar cells, but their light-emissive properties have not previously been studied. Herein, an all-inorganic antimony-based two-dimensional perovskite, Cs3Sb2I9, was synthesized using the solution process. Vapor-anion-exchange method was employed to change the structural composition from Cs3Sb2I9 to Cs3Sb2Br9 or Cs3Sb2Cl9 by treating CsI/SbI3 spin-coated films with SbBr3 or SbCl3, respectively. This novel method facilitates the fabrication of Cs3Sb2Br9 or Cs3Sb2Cl9 through solution processing without the need of using poorly soluble precursors (e.g., CsCl and CsBr). We go on to demonstrate electroluminescence from a device employing Cs3Sb2I9 emitter sandwiched between ITO/PEDOT:PSS and TPBi/LiF/Al as the hole and electron injection electrodes, respectively. A visible-infrared radiance of 0.012 W·Sr-1·m-2 was measured at 6 V when Cs3Sb2I9 was the active emitter layer. These proof-of-principle devices suggest a viable path toward low-dimensional, lead-free A3B2X9 perovskite optoelectronics.

Surfactant-Enriched ZnO Surface via Sol-Gel Process for the Efficient Inverted Polymer Solar Cell.

In this study, we demonstrate that the top surface is enriched by surfactants, tetraoctylammonium bromide, and cetylpyridinium bromide (CPB), in the sol-gel ZnO, being evidenced by the Br depth profile of electron spectroscopy for chemical analysis data. X-ray photoelectron spectroscopy results showed the formation of Zn-Br bonding due to the oxygen defects occupied by Br at the surfactant-enriched ZnO surface. The surfactant-enriched ZnO surface possessed a smoother surface and more hydrophobicity than the pristine ZnO from the experimental results of atomic force microscopy and contact angle, respectively. On the basis of ultraviolet photoelectron spectroscopy data, the work function slightly reduced due to the dipole built-up by the electrostatic force between Br- and N+ to enhance the electron extraction ability. The improved properties benefited the power conversion efficiency (PCE) of bulk-heterojunction polymer solar cells (PSCs) by spin-coating the active layer on the surfactant-enriched ZnO surface. The inverted PSCs with the surfactant-enriched ZnO surface showed the highest PCE of 9.55% for the CPB case, in comparison with the pristine ZnO surface (8.08% PCE). This study discloses that turning the ZnO surface is easily achieved by the addition of surfactants with different molecular structures in the sol-gel ZnO for high performance polymer solar cells.

Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low-Pressure Vapor-Assisted Solution Process.

The fabrication of multidimensional organometallic halide perovskite via a low-pressure vapor-assisted solution process is demonstrated for the first time. Phenyl ethyl-ammonium iodide (PEAI)-doped lead iodide (PbI2 ) is first spin-coated onto the substrate and subsequently reacts with methyl-ammonium iodide (MAI) vapor in a low-pressure heating oven. The doping ratio of PEAI in MAI-vapor-treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV-vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI2 ratio, which suggests the coexistence of low-dimensional perovskite (PEA2 MAn-1 Pbn I3n+1 ) with various values of n after vapor reaction. The dimensionality of the as-fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI2 ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI-containing perovskite grain is presumably formed around the MAPbI3 perovskite grain to benefit MAPbI3 grain growth. The device employing perovskite with PEAI/PbI2 = 0.05 achieves a champion power conversion efficiency of 19.10% with an open-circuit voltage of 1.08 V, a current density of 21.91 mA cm-2 , and a remarkable fill factor of 80.36%.

Enhancement of Inverted Polymer Solar Cells Performances Using Cetyltrimethylammonium-Bromide Modified ZnO.

In this study, the performance and stability of inverted bulk heterojunction (BHJ) polymer solar cells (PSCs) is enhanced by doping zinc oxide (ZnO) with 0-6 wt % cetyltrimethylammonium bromide (CTAB) in the sol-gel ZnO precursor solution. The power conversion efficiency (PCE) of the optimized 3 wt % CTAB-doped ZnO PSCs was increased by 9.07%, compared to a PCE of 7.31% for the pristine ZnO device. The 0-6 wt % CTAB-doped ZnO surface roughness was reduced from 2.6 to 1 nm and the number of surface defects decreased. The X-ray photoelectron spectroscopy binding energies of Zn 2p3/2 (1021.92 eV) and 2p1/2 (1044.99 eV) shifted to 1022.83 and 1045.88 eV, respectively, which is related to strong chemical bonding via bromide ions (Br-) that occupy oxygen vacancies in the ZnO lattice, improving the PCE of PSCs. The concentration of CTAB in ZnO significantly affected the work function of PSC devices; however, excessive CTAB increased the work function of the ZnO layer, resulting from the aggregation of CTAB molecules. In addition, after a 120-hour stability test in the atmosphere with 40% relative humidity, the inverted device based on CTAB-doped ZnO retained 92% of its original PCE and that based on pristine ZnO retained 68% of its original PCE. The obtained results demonstrate that the addition of CTAB into ZnO can dramatically influence the optical, electrical, and morphological properties of ZnO, enhancing the performance and stability of BHJ PSCs.

Roller-Induced Bundling of Long Silver Nanowire Networks for Strong Interfacial Adhesion, Highly Flexible, Transparent Conductive Electrodes.

Silver nanowires (AgNWs) have been the most promising electrode materials for fabrication of flexible transparent touch panel, displays and many other electronics because of their excellent electrical properties, cost effectiveness, synthesis scalability, and suitability for mass production. Although a few literature reports have described the use of short Ag NWs in fabrication of randomly oriented Ag NW network-based electrode, their electrical conductivities are still far lower than that of Ag films. So far, no any literature report was able to provide any simple solution to fabrication of large-area and mass-manufactural ability to address the issues, such as, conductivity, transparency, electrical current withstand, bending stability, and interfacial adhesion. In the current work, we provide a simple solution to conquer the above-mentioned challenges, and report the development of long Ag NW bundle network electrodes on large area PET films that were coated, aligned, and bundled quickly and simply using a steel roller. Our developed AgNWs-bundle networks had superior performance in optoelectronic properties (sheet resistance 5.8 Ω sq-1; optical transmittance 89% at 550 nm wavelength), electrical current withstand up to 500 mA, and bending stability over 5000 bending cycles, and strong interfacial adhesion.

Robust and Recyclable Substrate Template with an Ultrathin Nanoporous Counter Electrode for Organic-Hole-Conductor-Free Monolithic Perovskite Solar Cells.

A robust and recyclable monolithic substrate applying all-inorganic metal-oxide selective contact with a nanoporous (np) Au:NiOx counter electrode is successfully demonstrated for efficient perovskite solar cells, of which the perovskite active layer is deposited in the final step for device fabrication. Through annealing of the Ni/Au bilayer, the nanoporous NiO/Au electrode is formed in virtue of interconnected Au network embedded in oxidized Ni. By optimizing the annealing parameters and tuning the mesoscopic layer thickness (mp-TiO2 and mp-Al2O3), a decent power conversion efficiency (PCE) of 10.25% is delivered. With mp-TiO2/mp-Al2O3/np-Au:NiOx as a template, the original perovskite solar cell with 8.52% PCE can be rejuvenated by rinsing off the perovskite material with dimethylformamide and refilling with newly deposited perovskite. A renewed device using the recycled substrate once and twice, respectively, achieved a PCE of 8.17 and 7.72% that are comparable to original performance. This demonstrates that the novel device architecture is possible to recycle the expensive transparent conducting glass substrates together with all the electrode constituents. Deposition of stable multicomponent perovskite materials in the template also achieves an efficiency of 8.54%, which shows its versatility for various perovskite materials. The application of such a novel NiO/Au nanoporous electrode has promising potential for commercializing cost-effective, large scale, and robust perovskite solar cells.

NiOx Electrode Interlayer and CH3 NH2 /CH3 NH3 PbBr3 Interface Treatment to Markedly Advance Hybrid Perovskite-Based Light-Emitting Diodes.

The performance of hybrid perovskite-based light-emitting diodes (LEDs) is markedly enhanced by the application of a NiOx electrode interlayer and moderate methylamine treatment. A hybrid perovskite-based LED exhibits a peak luminous efficiency of 15.9 cd A-1 biased at 8.5 V, 407.65 mA cm-2 , and 65 300 cd m-2 , showing a distinctive impact for future applications.

Low-Pressure Vapor-Assisted Solution Process for Thiocyanate-Based Pseudohalide Perovskite Solar Cells.

In this report, we fabricated thiocyanate-based perovskite solar cells with low-pressure vapor-assisted solution process (LP-VASP) method. Photovoltaic performances are evaluated with detailed materials characterizations. Scanning electron microscopy images show that SCN-based perovskite films fabricated using LP-VASP have long-range uniform morphology and large grain sizes up to 1 µm. The XRD and Raman spectra were employed to observe the characteristic peaks for both SCN-based and pure CH3 NH3 PbI3 perovskite. We observed that the Pb(SCN)2 film transformed to PbI2 before the formation of perovskite film. X-ray photoemission spectra (XPS) show that only a small amount of S remained in the film. Using LP-VASP method, we fabricated SCN-based perovskite solar cells and achieved a power conversion efficiency of 12.72 %. It is worth noting that the price of Pb(SCN)2 is only 4 % of PbI2 . These results demonstrate that pseudo-halide perovskites are promising materials for fabricating low-cost perovskite solar cells.

Ultrafast Dynamics of Hole Injection and Recombination in Organometal Halide Perovskite Using Nickel Oxide as p-Type Contact Electrode.

There is a mounting effort to use nickel oxide (NiO) as p-type selective electrode for organometal halide perovskite-based solar cells. Recently, an overall power conversion efficiency using this hole acceptor has reached 18%. However, ultrafast spectroscopic investigations on the mechanism of charge injection as well as recombination dynamics have yet to be studied and understood. Using time-resolved terahertz spectroscopy, we show that hole transfer is complete on the subpicosecond time scale, driven by the favorable band alignment between the valence bands of perovskite and NiO nanoparticles (NiO(np)). Recombination time between holes injected into NiO(np) and mobile electrons in the perovskite material is shown to be hundreds of picoseconds to a few nanoseconds. Because of the low conductivity of NiO(np), holes are pinned at the interface, and it is electrons that determine the recombination rate. This recombination competes with charge collection and therefore must be minimized. Doping NiO to promote higher mobility of holes is desirable in order to prevent back recombination.

Oxidized Ni/Au Transparent Electrode in Efficient CH3 NH3 PbI3 Perovskite/Fullerene Planar Heterojunction Hybrid Solar Cells.

UNLABELLED: The successful application of a Ni/Au transparent electrode for fabricating efficient perovskite-based solar cells is demonstrated. Through interdiffusion of the Ni/Au bilayer, Au forms an interconnected metallic network structure as the transparent electrode. Ni diffuses to the bilayer surface and oxidizes into NiOx becoming an appropriate electrode interlayer. These ITO- and PEDOT: PSS-free devices have potential applications in the design of future cost-effective, low-weight, and stable solar cells.

Improved air stability of perovskite solar cells via solution-processed metal oxide transport layers.

Lead halide perovskite solar cells have recently attracted tremendous attention because of their excellent photovoltaic efficiencies. However, the poor stability of both the perovskite material and the charge transport layers has so far prevented the fabrication of devices that can withstand sustained operation under normal conditions. Here, we report a solution-processed lead halide perovskite solar cell that has p-type NiO(x) and n-type ZnO nanoparticles as hole and electron transport layers, respectively, and shows improved stability against water and oxygen degradation when compared with devices with organic charge transport layers. Our cells have a p-i-n structure (glass/indium tin oxide/NiO(x)/perovskite/ZnO/Al), in which the ZnO layer isolates the perovskite and Al layers, thus preventing degradation. After 60 days storage in air at room temperature, our all-metal-oxide devices retain about 90% of their original efficiency, unlike control devices made with organic transport layers, which undergo a complete degradation after just 5 days. The initial power conversion efficiency of our devices is 14.6 ± 1.5%, with an uncertified maximum value of 16.1%.

Recent Advances in the Inverted Planar Structure of Perovskite Solar Cells.

Inorganic-organic hybrid perovskite solar cells research could be traced back to 2009, and initially showed 3.8% efficiency. After 6 years of efforts, the efficiency has been pushed to 20.1%. The pace of development was much faster than that of any type of solar cell technology. In addition to high efficiency, the device fabrication is a low-cost solution process. Due to these advantages, a large number of scientists have been immersed into this promising area. In the past 6 years, much of the research on perovskite solar cells has been focused on planar and mesoporous device structures employing an n-type TiO2 layer as the bottom electron transport layer. These architectures have achieved champion device efficiencies. However, they still possess unwanted features. Mesoporous structures require a high temperature (>450 °C) sintering process for the TiO2 scaffold, which will increase the cost and also not be compatible with flexible substrates. While the planar structures based on TiO2 (regular structure) usually suffer from a large degree of J-V hysteresis. Recently, another emerging structure, referred to as an "inverted" planar device structure (i.e., p-i-n), uses p-type and n-type materials as bottom and top charge transport layers, respectively. This structure derived from organic solar cells, and the charge transport layers used in organic photovoltaics were successfully transferred into perovskite solar cells. The p-i-n structure of perovskite solar cells has shown efficiencies as high as 18%, lower temperature processing, flexibility, and, furthermore, negligible J-V hysteresis effects. In this Account, we will provide a comprehensive comparison of the mesoporous and planar structures, and also the regular and inverted of planar structures. Later, we will focus the discussion on the development of the inverted planar structure of perovskite solar cells, including film growth, band alignment, stability, and hysteresis. In the film growth part, several methods for obtaining high quality perovskite films are reviewed. In the interface engineering parts, the effect of hole transport layer on subsequent perovskite film growth and their interface band alignment, and also the effect of electron transport layers on charge transport and interface contact will be discussed. As concerns stability, the role of charge transport layers especially the top electron transport layer in the devices stability will be concluded. In the hysteresis part, possible reasons for hysteresis free in inverted planar structure are provided. At the end of this Account, future development and possible solutions to the remaining challenges facing the commercialization of perovskite solar cells are discussed.

Synthesis and Evaluation of Self-Assembled Azido Monolayer as a Novel Dielectric Layer for Fabricating Pentacene-Based Organic Thin Film Transistors.

Self-assembled 3-azidopropyltriethoxysilane monolayer (SAM) is used as a dielectric layer to modify the interface between the silicon dioxide wafer and the pentacene semiconductor layer in an organic thin film transistor (OTFT), Au/pentacene/3-azidopropyltriethoxysilane/SiO2/Si. Compared to the commonly used alkyl siliane C18 dielectric, 3-azidopropyltriethoxysilane which possesses stable formal charges is far more effective in increasing the ON/OFF ratio of OTFT device with an improvement of nearly three orders of magnitude. Analysis and measurements reported in this paper have illustrated for the first time the improvement of OTFT performance by a SAM compound with stable formal charges.

Functional p-Type, Polymerized Organic Electrode Interlayer in CH3NH3PbI3 Perovskite/Fullerene Planar Heterojunction Hybrid Solar Cells.

Thermal curing of the styrene-functionalized 9,9-diarylfluorene-based triaryldiamine monomer (VB-DAAF) forms an ideal p-type organic electrode interlayer capable of resisting solvation of the polar precursor solution in fabricating methylammonium lead iodide (CH3NH3PbI3) perovskite/fullerene (C60) planar heterojunction hybrid solar cells. The polymerized VB-DAAF film exhibits a good energy level alignment with the valence-band-edge level of the CH3NH3PbI3 perovskite to facilitate the transport of holes. The large energy barrier to the conduction-band-edge level of the CH3NH3PbI3 perovskite effectively blocks electrons from reaching the positive electrode and reduces the photon energy loss due to recombination. The best-performing cell with the configuration of glass/indium-tin oxide/polymerized VB-DAAF/CH3NH3PbI3 perovskite/C60/bathocuproine/aluminum is free of a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PEDOT: PSS) layer to achieve an open-circuit voltage (VOC) = 1.02 V, a short-circuit current (JSC) = 18.92 mA/cm(2), and a fill factor (FF) = 0.78, corresponding to a power conversion efficiency (PCE) of 15.17% under standard 1 sun AM 1.5G simulated solar irradiation. The performance is much superior to the device applying the PEDOT: PSS interlayer with photovoltaic parameters of VOC = 0.85 V, JSC = 16.37 mA/cm(2), and FF = 0.74, corresponding to a PCE of 10.27%. Additionally, we had applied a UV-assisted process to polymerize the VB-DAAF film at relatively lower temperature and fabricate decent perovskite-based solar cells on the flexible substrate for real applications.

Novel spiro-based hole transporting materials for efficient perovskite solar cells.

Three spiro-acridine-fluorene based hole transporting materials (HTMs), namely CW3, CW4 and CW5, are employed in the fabrication of organic-inorganic hybrid perovskite solar cells. The corresponding mesoscopic TiO2/CH3NH3PbI3/HTM devices are investigated and compared with that made with commercial spiro-OMeTAD. The best conversion efficiency of 16.56% is achieved for CW4 in the presence of tBp and Li-TFSI as additives and without a cobalt dopant. The performances of CW4 are further examined in terms of conductivity, mobility, morphology, and stability to show its potential as an alternative HTM.

Low-temperature sputtered nickel oxide compact thin film as effective electron blocking layer for mesoscopic NiO/CH3NH3PbI3 perovskite heterojunction solar cells.

We introduce the use of low temperature sputtered NiOx thin film, which substitutes the PEDOT-PSS and solution-processed NiOx as an effective electron blocking layer for mesoscopic NiO/CH3NH3PbI3 perovskite solar cells. The influences of film thickness and oxygen doping on the photovoltaic performances are scrutinized. The cell efficiency has been improved from 9.51 to 10.7% for devices using NiOx fabricated under pure argon atmosphere. With adequate doping under 10% oxygen flow ratio, we achieved power conversion efficiency of 11.6%. The procedure is large area scalable and has the advantage for cost-effective perovskite-based photovoltaics.