Controllable Growth of High-Quality Inorganic Perovskite Microplate Arrays for Functional Optoelectronics

Inorganic perovskite single crystals have emerged as promising vapor-phase processable structures for optoelectronic devices. However, because of material lattice mismatch and uncontrolled nucleation, vapor-phase methods have been restricted to random distribution of single crystals that are difficult to perform for integrated device arrays. Herein, an effective strategy to control the vapor-phase growth of high-quality cesium lead bromide perovskite (CsPbBr₃) microplate arrays with uniform morphology as well as controlled location and size is reported. By introducing perovskite seeds on substrates, intractable lattice mismatches and random nucleation barriers are surpassed, and the epitaxial growth of perovskite crystals is accurately controlled. It is further demonstrated that CsPbBr₃ microplate arrays can be monolithically integrated on substrates for the fabrication of high-performance lasers and photodetectors. This strategy provides a facile approach to fabricate high-quality CsPbBr₃ microplates with controllable size and location, which offers new opportunities for the scalable production of integrated optoelectronic devices.     

Metal-Organic Framework Materials in Perovskite Solar Cells: Recent Advancements and Perspectives

Organic–inorganic hybrid perovskite solar cells (PSCs) are among the most promising candidates for the next generation of photovoltaic devices because of the significant increase in their power conversion efficiency (PCE) from less than 10% to 25.7% in past decade. The metal-organic framework (MOF) materials owing to their unique properties, such as large specific surface area, abundant binding sites, adjustable nanostructures, and synergistic effects, are used as additives or functional layers to enhance the device performance and long-term stability of PSCs. This review focuses on the recent advancements in the applications of MOFs as/in different functional layers of PSCs. The photovoltaic performance, impact, and advantages of MOF materials integrated into the perovskite absorber, electron transport layer, hole transport layer, and interfacial layer are reviewed. In addition, the applicability of MOFs to mitigate leakage of Pb²⁺ from halide perovskites and corresponding devices is discussed. This review concludes with the perspectives on further research directions for employing MOFs in PSCs.     

2D organic single crystals: Synthesis,novel physics,high-performance optoelectronic devices and integration

In the last decade, two-dimensional organic single crystals (2D OSCs), defined as a class of ultrathin crystals with atomic or molecular level thickness and micrometer-scale-lateral dimension, has emerged as a rising star due to ultrathin feature, high crystallinity, low-structure symmetry, larger material library, diverse processing technique and excellent flexibility, etc. Due to these advantages, 2D OSCs offer exciting application prospects for flexible electronics, optoelectronics, sensing, energy harvesting, biology and medicine, etc. However, it is still challenging to synthesize large-area highly crystalline 2D OSCs as well as investigate their intrinsic properties and structure–property relationships. Herein, we first treat the growth techniques of 2D OSCs carefully and then discuss their novel physics and optoelectronic properties at the 2D limit. A significant effort has been made in evaluating the latest advances in high-performance devices applying 2D OSCs and corresponding heterostructures. In terms of practical applications, their integrations and device arrays are discussed. Furthermore, we point out several important research directions of 2D OSCs and corresponding heterostructures. Finally, the state-of-the-art challenges and future opportunities that include the investigation and application of 2D OSCs have been presented, which will provoke more researchers to come into this field.     

Precise Patterning of Organic Semiconductor Crystals for Integrated Device Applications

Development of high‐performance organic electronic and optoelectronic devices relies on high‐quality semiconducting crystals that have outstanding charge transport properties and long exciton diffusion length and lifetime. To achieve integrated device applications, it is a prerequisite to precisely locate the organic semiconductor crystals (OSCCs) to form a specifically patterned structure. Well‐patterned OSCCs can not only reduce leakage current and cross‐talk between neighboring devices, but also facilely integrate with other device elements and their corresponding interconnects. In this Review, general strategies for the patterning of OSCCs are summarized, and the advantages and limitations of different patterning methods are discussed. Discussion is focused on an advanced strategy for the high‐resolution and wafer‐scale patterning of OSCC by a surface microstructure‐assisted patterning method. Furthermore, the recent progress on OSCC pattern‐based integrated circuities is highlighted. Finally, the research challenges and directions of this young field are also presented.     

High‐Performance As‐Cast Nonfullerene Polymer Solar Cells with Thicker Active Layer and Large Area Exceeding 11% Power Conversion Efficiency

In this work, a nonfullerene polymer solar cell (PSC) based on a wide bandgap polymer donor PM6 containing fluorinated thienyl benzodithiophene (BDT‐2F) unit and a narrow bandgap small molecule acceptor 2,2′‐((2Z,2′Z)‐((4,4,9,9‐tetrahexyl‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl)bis(methanylylidene))bis(3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile (IDIC) is developed. In addition to matched energy levels and complementary absorption spectrum with IDIC, PM6 possesses high crystallinity and strong π–π stacking alignment, which are favorable to charge carrier transport and hence suppress recombination in devices. As a result, the PM6:IDIC‐based PSCs without extra treatments show an outstanding power conversion efficiency (PCE) of 11.9%, which is the record value for the as‐cast PSC devices reported in the literature to date. Moreover, the device performances are insensitive to the active layer thickness (≈95–255 nm) and device area (0.20–0.81 cm²) with PCEs of over 11%. Besides, the PM6:IDIC‐based flexible PSCs with a large device area of 1.25 cm² exhibit a high PCE of 6.54%. These results indicate that the PM6:IDIC blend is a promising candidate for future roll‐to‐roll mass manufacturing and practical application of highly efficient PSCs.     

Thermally Stable MAPbI3 Perovskite Solar Cells with Efficiency of 19.19% and Area over 1 cm2 achieved by Additive Engineering

Solution‐processed perovskite (PSC) solar cells have achieved extremely high power conversion efficiencies (PCEs) over 20%, but practical application of this photovoltaic technology requires further advancements on both long‐term stability and large‐area device demonstration. Here, an additive‐engineering strategy is developed to realize a facile and convenient fabrication method of large‐area uniform perovskite films composed of large crystal size and low density of defects. The high crystalline quality of the perovskite is found to simultaneously enhance the PCE and the durability of PSCs. By using the simple and widely used methylammonium lead iodide (MAPbI₃), a certified PCE of 19.19% is achieved for devices with an aperture area of 1.025 cm², and the high‐performing devices can sustain over 80% of the initial PCE after 500 h of thermal aging at 85 °C, which are among the best results of MAPbI₃‐based PSCs so far.     

Graphdiyne and its Assembly Architectures: Synthesis,Functionalization, and Applications

Graphdiyne (GDY), a novel one‐atom‐thick carbon allotrope that features assembled layers of sp‐ and sp²‐hybridized carbon atoms, has attracted great interest from both science and industry due to its unique and fascinating structural, physical, and chemical properties. GDY‐based materials with different morphologies, such as nanowires, nanotube arrays, nanosheets, and ordered stripe arrays, have been applied in various areas such as catalysis, solar cells, energy storage, and optoelectronic devices. After an introduction to the fundamental properties of GDY, recent advances in the fabrication of GDY‐based nanostructures and their applications, and corresponding mechanisms, are covered, and future critical perspectives are also discussed.     

Tuning Solute‐Redistribution Dynamics for Scalable Fabrication of Colloidal Quantum‐Dot Optoelectronics

Solution‐processed colloidal quantum dots (CQDs) are attractive materials for the realization of low‐cost and efficient optoelectronic devices. Although impressive CQD‐solar‐cell performance has been achieved, the fabrication of CQD films is still limited to laboratory‐scale small areas because of the complicated deposition of CQD inks. Large‐area, uniform deposition of lead sulfide (PbS) CQD inks is successfully realized for photovoltaic device applications by engineering the solute redistribution of CQD droplets. It is shown experimentally and theoretically that the solute‐redistribution dynamics of CQD droplets are highly dependent on the movement of the contact line and on the evaporation kinetics of the solvent. By lowering the friction constant of the contact line and increasing the evaporation rate of the droplets, a uniform deposition of CQD ink in length and width over large areas is realized. By utilizing a spray‐coating process, large‐area (up to 100 cm²) CQD films are fabricated with 3–7% thickness variation on various substrates including glass, indium tin oxide glass, and polyethylene terephthalate. Furthermore, scalable fabrication of CQD solar cells is demonstrated with 100 cm² CQD films which exhibits a notably high efficiency of 8.10%.     

General Spatial Confinement Recrystallization Method for Rapid Preparation of Thickness-Controllable and Uniform Organic Semiconductor Single Crystals

Organic semiconductor single crystals (OSSCs) are ideal materials for studying the intrinsic properties of organic semiconductors (OSCs) and constructing high-performance organic field-effect transistors (OFETs). However, there is no general method to rapidly prepare thickness-controllable and uniform single crystals for various OSCs. Here, inspired by the recrystallization (a spontaneous morphological instability phenomenon) of polycrystalline films, a spatial confinement recrystallization (SCR) method is developed to rapidly (even at several second timescales) grow thickness-controllable and uniform OSSCs in a well-controlled way by applying longitudinal pressure to tailor the growth direction of grains in OSCs polycrystalline films. The relationship between growth parameters including the growth time, temperature, longitudinal pressure, and thickness is comprehensively investigated. Remarkably, this method is applicable for various OSCs including insoluble and soluble small molecules and polymers, and can realize the high-quality crystal array growth. The corresponding 50 dinaphtho[2,3-b:2″,3″-f]thieno[3,2-b]thiophene (DNTT) single crystals coplanar OFETs prepared by the same batch have the mobility of 4.1 ± 0.4 cm² V⁻¹ s⁻¹, showing excellent uniformity. The overall performance of the method is superior to the reported methods in term of growth rate, generality, thickness controllability, and uniformity, indicating its broad application prospects in organic electronic and optoelectronic devices.     

Thermodynamically Stable Synthesis of Large‐Scale and Highly Crystalline Transition Metal Dichalcogenide Monolayers and their Unipolar n–n Heterojunction Devices

Transition metal dichalcogenide (TMDC) monolayers are considered to be potential materials for atomically thin electronics due to their unique electronic and optical properties. However, large‐area and uniform growth of TMDC monolayers with large grain sizes is still a considerable challenge. This report presents a simple but effective approach for large‐scale and highly crystalline molybdenum disulfide monolayers using a solution‐processed precursor deposition. The low supersaturation level, triggered by the evaporation of an extremely thin precursor layer, reduces the nucleation density dramatically under a thermodynamically stable environment, yielding uniform and clean monolayer films and large crystal sizes up to 500 µm. As a result, the photoluminescence exhibits only a small full‐width‐half‐maximum of 48 meV, comparable to that of exfoliated and suspended monolayer crystals. It is confirmed that this growth procedure can be extended to the synthesis of other TMDC monolayers, and robust MoS₂/WS₂ heterojunction devices are easily prepared using this synthetic procedure due to the large‐sized crystals. The heterojunction device shows a fast response time (≈45 ms) and a significantly high photoresponsivity (≈40 AW^?1) because of the built‐in potential and the majority‐carrier transport at the n–n junction. These findings indicate an efficient pathway for the fabrication of high‐performance 2D optoelectronic devices.     

Suppressing Defects-Induced Nonradiative Recombination for Efficient Perovskite Solar Cells through Green Antisolvent Engineering

Organic–inorganic hybrid perovskites have attracted considerable attention due to their superior optoelectronic properties. Traditional one-step solution-processed perovskites often suffer from defects-induced nonradiative recombination, which significantly hinders the improvement of device performance. Herein, treatment with green antisolvents for achieving high-quality perovskite films is reported. Compared to defects-filled ones, perovskite films by antisolvent treatment using methylamine bromide (MABr) in ethanol (MABr-Eth) not only enhances the resultant perovskite crystallinity with large grain size, but also passivates the surface defects. In this case, the engineering of MABr-Eth-treated perovskites suppressing defects-induced nonradiative recombination in perovskite solar cells (PSCs) is demonstrated. As a result, the fabricated inverted planar heterojunction device of ITO/PTAA/Cs_0.15FA_0.85PbI₃/PC₆₁BM/Phen-NADPO/Ag exhibits the best power conversion efficiency of 21.53%. Furthermore, the corresponding PSCs possess a better storage and light-soaking stability.     

TiO2纳米碗阵列作为电子传输层构筑高效率彩色钙钛矿太阳能电池（英文）

钙钛矿太阳能电池的飞速发展及其在构筑一体化和可穿戴器件中的应用前景激发了人们对于彩色钙钛矿太阳能电池的浓厚兴趣,但如何将可见光宽波段吸收且具有高吸光系数的钙钛矿材料构筑成高性能的彩色太阳能电池仍是一个挑战.本文利用TiO2纳米碗阵列作为结构化的电子传输层,并在纳米碗内均匀填充一层CH3NH3PbI3钙钛矿薄膜,成功制备了具有鲜艳结构色的钙钛矿@TiO2纳米碗阵列薄膜,其结构色具有显著的角度依赖特征.通过路易斯酸碱加合物法制备得到基于醋酸铅的新型晶态中间体薄膜,使得高质量的CH3NH3PbI3钙钛矿薄膜能够在纳米碗内均匀填充.利用该钙钛矿@TiO2纳米碗薄膜可以制备出具有鲜艳结构色的平面异质结钙钛矿太阳能电池,其最高光电转化效率可以达到16.94%,平均效率达到15.47%,均高于现已报道的彩色钙钛矿太阳能电池的转化效率.     

Embedded Nickel-Mesh Transparent Electrodes for Highly Efficient and Mechanically Stable Flexible Perovskite Photovoltaics: Toward a Portable Mobile Energy Source

The rapid development of Internet of Things mobile terminals has accelerated the market's demand for portable mobile power supplies and flexible wearable devices. Here, an embedded metal-mesh transparent conductive electrode (TCE) is prepared on poly(ethylene terephthalate) (PET) using a novel selective electrodeposition process combined with inverted film-processing methods. This embedded nickel (Ni)-mesh flexible TCE shows excellent photoelectric performance (sheet resistance of ≈0.2–0.5 Ω sq⁻¹ at high transmittance of ≈85–87%) and mechanical durability. The PET/Ni-mesh/polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS PH1000) hybrid electrode is used as a transparent electrode for perovskite solar cells (PSCs), which exhibit excellent electric properties and remarkable environmental and mechanical stability. A power conversion efficiency of 17.3% is obtained, which is the highest efficiency for a PSC based on flexible transparent metal electrodes to date. For perovskite crystals that require harsh growth conditions, their mechanical stability and environmental stability on flexible transparent embedded metal substrates are studied and improved. The resulting flexible device retains 76% of the original efficiency after 2000 bending cycles. The results of this work provide a step improvement in flexible PSCs.     

Effect of the substrate on the properties of ZnO-MgO thin films grown by atmospheric pressure metal-organic chemical vapor deposition

The ZnO-MgO alloys possess attractive properties for possible applications in optoelectronic and display devices; however, the optical properties are strongly dependent on the deposition parameters. In this work, the effect of the glassy and metallic substrates on the structural, morphological and optical properties of ZnO-MgO thin films using atmospheric pressure metal-organic chemical vapor deposition was investigated at relatively low deposition temperature, 500 °C. Magnesium and zinc acetylacetonates were used as the metal-organic source. X-ray diffraction experiments provided evidence that the kind of substrates cause a deviation of c-axis lattice constant due to the constitution of a oxide mixture (ZnO and MgO) in combination with different intermetallic compounds(Mg₂Zn₁₁ and Mg₄Zn₇) in the growth films. The substitutional and interstitial sites of Mg²⁺ instead of Zn²⁺ ions in the lattice are the most probable mechanism to form intermetallic compounds. The optical parameters as well as thickness of the films were calculated by Spectroscopic Ellipsometry using the classical dispersion model based on the sum of the single and double Lorentz and Drude oscillators in combination with Kato-Adachi equations, as well as X-ray reflectivity.     

Bifacial Contact Junction Engineering for High‐Performance Perovskite Solar Cells with Efficiency Exceeding 21%

Ordered 1D metal oxide structure is desirable in thin film solar cells owing to its excellent charge collection capability. However, the electron transfer in 1D electron transporting layer (ETL)‐based devices is still limited to a submicrometer‐long pathway that is vertical to the substrate. Here, an innovative closely packed rutile TiO₂ nanowire (CRTNW) network parallel to the facet of fluorine‐doped tin oxide (FTO) substrate is reported, which can serve as a 1D nanoscale electron transport pathway for efficient perovskite solar cells (PSCs). The PSC constructed using newly prepared CRTNW ETL achieves an impressive power conversion efficiency of 21.10%, which can be attributed to the facilitated electron extraction induced by the favorable junctions formed at FTO/ETL and ETL/perovskite interfaces and also the suppressed charge recombination originating from improved perovskite morphology with large grains, flat surface, and good surface coverage. The bifacial contact junctions engineering also enables large‐area device fabrication. The PSC with 1 cm² aperture yields an efficiency of 19.50% under one sun illumination. This work highlights the significance of controlling the orientation and packing density of the ordered 1D oxide nanostructured thin films for highly efficient optoelectronic devices in a large‐scale manner.     

Chemical Patterning of High‐Mobility Semiconducting 2D Bi2O2Se Crystals for Integrated Optoelectronic Devices

Patterning of high‐mobility 2D semiconducting materials with unique layered structures and superb electronic properties offers great potential for batch fabrication and integration of next‐generation electronic and optoelectronic devices. Here, a facile approach is used to achieve accurate patterning of 2D high‐mobility semiconducting Bi₂O₂Se crystals using dilute H₂O₂ and protonic mixture acid as efficient etchants. The 2D Bi₂O₂Se crystal after chemical etching maintains a high Hall mobility of over 200 cm² V^?1 s^?1 at room temperature. Centimeter‐scale well‐ordered arrays of 2D Bi₂O₂Se with tailorable configurations are readily obtained. Furthermore, integrated photodetectors based on 2D Bi₂O₂Se arrays are fabricated, exhibiting excellent air stability and high photoresponsivity of ≈2000 A W^?1 at 532 nm. These results are one step towards the practical application of ultrathin 2D integrated digital and optoelectronic circuits.     

Organic UV-Sensitive Phototransistors Based on Distriphenylamineethynylpyrene Derivatives with Ultra-High Detectivity Approaching 1018

Organic photodetectors with UV-sensitivity are of great potential for various optoelectronic applications. Integration of high charge carrier mobility, long exciton diffusion length as well as unique UV-sensitivity for active materials is crucial for construction of UV-sensitive devices with high performance, however, very few organic semiconductors can integrate these properties simultaneously. Herein, two novel organic semiconductors containing large steric hindrance triphenylamine groups, 1,6-distriphenylamineethynylpyrene (1,6-DTEP) and 2,7-distriphenylamineethynylpyrene (2,7-DTEP) are designed and synthesized. It demonstrates that the single crystals of both 1,6-DTEP and 2,7-DTEP exhibit superior integrated optoelectronic properties of high charge carrier mobility, unique UV absorption, high photoluminescence quantum yields as well as small exciton binding energies. Organic phototransistors constructed using 1,6-DTEP and 2,7-DTEP single crystals show ultrasensitive performance with ultra-high photoresponsivity of 2.86 × 10⁶ and 1.04 × 10⁵ A W⁻¹, detectivity (D*) of above 1.49 × 10¹⁸ and 5.28 × 10¹⁶ Jones under 370 nm light illumination, respectively. It indicates the great potential of 1,6-DTEP and 2,7-DTEP-based phototransistors for organic UV-photodetector applications and also provides a new design strategy to develop series of better performance UV photoelectric organic materials for related research in organic optoelectronics.     

In Situ Formation of Compact PbI2 Shell Boosts the Efficiency and Thermostability of Perovskite Solar Cells

Judicious tailoring of a robust interlayer is central to maintain the durable operation of optoelectronic devices. In this paper, an ultrathin, compact, and uniform PbI₂ shell on the surface of perovskite via the method of ZnI₂ aided in situ transformation is produced. The resultant PbI₂ interlayer can prolong the excited‐state lifetime of perovskite and attenuate the recombination kinetics of separated charges, leading to an improvement of power conversion efficiency up to 22.5% for perovskite solar cells (PSCs) at the AM 1.5G conditions. Moreover, the PSC with PbI₂ interlayer exhibits an enhanced thermostability, retaining 87% of initial efficiency after aging at 60 °C for 1000 h.     

Donor:Acceptor Janus Nanoparticle-Based Films as Photoactive Layers: Control of Assembly and Impact on Performance of Devices

Water-processable organic semiconductor nanoparticles (NPs) are considered promising materials for the next-generation of optoelectronic applications due to their controlled size, internal structure, and environmentally friendly processing. Reasonably, the controllable assembly of donor:acceptor (D:A) NPs on large areas, quality, and packing density of deposited films, as well as layer morphology, will influence the effectiveness of charge transfer at an interface and the final performance of designed optoelectronic devices.This work represents an easy and effective approach for designing self-assembled monolayers of D:A NPs. In this self-assembly procedure, the NP arrays are prepared on a large scale (2 × 2 cm²) at the air/water interface with controlled packing density and morphology. Due to the unique structure of individual D:A Janus particles and their assembled arrays, the Janus nanoparticle (JNP)-based device exhibits an 80% improvement of electron mobility and more balanced charge extraction compared to the conventional core–shell NP-based device. An outstanding performance of polymer solar cells with over 5% efficiency is achieved after post-annealing treatment of assembled arrays, representing one of the best results for NP-based organic photovoltaics. Ultimately, this work provides a new protocol for processing water-processable organic semiconductor colloids and future optoelectronic fabrication.     

Designed Growth of Large-Size 2D Single Crystals

In the “post-Moore's Law” era, new materials are highly expected to bring next revolutionary technologies in electronics and optoelectronics, wherein 2D materials are considered as very promising candidates beyond bulk materials due to their superiorities of atomic thickness, excellent properties, full components, and the compatibility with the processing technologies of traditional complementary metal-oxide semiconductors, enabling great potential in fabrication of logic, storage, optoelectronic, and photonic 2D devices with better performances than state-of-the-art ones. Toward the massive applications of highly integrated 2D devices, large-size 2D single crystals are a prerequisite for the ultimate quality of materials and extreme uniformity of properties. However, at present, it is still very challenging to grow all 2D single crystals into the wafer scale. Therefore, a systematic understanding for controlled growth of various 2D single crystals needs to be further established. Here, four key aspects are reviewed, i.e., nucleation control, growth promotion, surface engineering, and phase control, which are expected to be controllable at different periods during the growth. In addition, the perspectives on designed growth and potential applications are discussed for showing the bright future of these advanced material systems of 2D single crystals.