Stable α‐CsPbI3 Perovskite Nanowire Arrays with Preferential Crystallographic Orientation for Highly Sensitive Photodetectors

All‐inorganic metal‐halide perovskites CsPbX₃ (X = Cl, Br, I) exhibit higher stability than their organic–inorganic hybrid counterparts, but the thermodynamically instable perovskite α phase at room temperature of CsPbI₃ restricts the practical optoelectronic applications. Although the stabilization of α‐CsPbI₃ polycrystalline thin films is extensively studied, the creation of highly crystalline micro/nanostructures of α‐CsPbI₃ with large grain size and suppressed grain boundary remains challenging, which impedes the implementations of α‐CsPbI₃ for lateral devices, such as photoconductor‐type photodetectors. In this work, stable α‐CsPbI₃ perovskite nanowire arrays are demonstrated with large grain size, high crystallinity, regulated alignment, and position by controlling the dewetting dynamics of precursor solution on an asymmetric‐wettability topographical template. The correlation between the higher photoluminescence (PL) intensity and longer PL lifetime indicates the nanowires exhibit stable α phase and suppressed trap density. The preferential (100) orientation is characterized by discrete diffraction spots in grazing incidence wide‐angle scattering patterns, suggesting the long‐range crystallographic order of these nanowires. Based on these high‐quality nanowire arrays, highly sensitive photodetectors are realized with a responsivity of 1294 A W^?1 and long‐term stability with 90% performance retention after 30‐day ambient storage.     

Liquid Phase Exfoliated Indium Selenide Based Highly Sensitive Photodetectors

Layered semiconductors of the IIIA–VIA group have attracted considerable attention in (opto)electronic applications thanks to their atomically thin structures and their thickness‐dependent optical and electronic properties, which promise ultrafast response and high sensitivity. In particular, 2D indium selenide (InSe) has emerged as a promising candidate for the realization of thin‐film field effect transistors and phototransistors due to its high intrinsic mobility (>10² cm² V^?1 s^?1) and the direct optical transitions in an energy range suitable for visible and near‐infrared light detection. A key requirement for the exploitation of large‐scale (opto)electronic applications relies on the development of low‐cost and industrially relevant 2D material production processes, such as liquid phase exfoliation, combined with the availability of high‐throughput device fabrication methods. Here, a β polymorph of indium selenide (β‐InSe) is exfoliated in isopropanol and spray‐coated InSe‐based photodetectors are demonstrated, exhibiting high responsivity to visible light (maximum value of 274 A W^?1 under blue excitation 455 nm) and fast response time (15 ms). The devices show a gate‐dependent conduction with an n‐channel transistor behavior. Overall, this study establishes that liquid phase exfoliated β‐InSe is a valid candidate for printed high‐performance photodetectors, which is critical for the development of industrial‐scale 2D material‐based optoelectronic devices.     

Semitransparent,Flexible, and Self‐Powered Photodetectors Based on Ferroelectricity‐Assisted Perovskite Nanowire Arrays

Transparent and flexible photodetectors hold great promise in next‐generation portable and wearable optoelectronic devices. However, most of the previously reported devices need an external energy power source to drive its operation or require complex fabrication processes. Herein, designed is a semitransparent, flexible, and self‐powered photodetector based on the integrated ferroelectric poly(vinylidene‐fluoride‐trifluoroethylene) (P(VDF‐TrFE)) and perovskite nanowire arrays on the flexible polyethylene naphthalate substrate via a facile imprinting method. Through optimizing the treatment conditions, including polarization voltage, polarization time, and the concentration of P(VDF‐TrFE), the resulting device exhibits remarkable detectivity (7.3 × 10¹² Jones), fast response time (88/154 µs) at zero bias, as well as outstanding mechanical stability. The excellent performance is attributed to the efficient charge separation and transport originating from the highly oriented 1D transport pathway and the polarization‐induced internal electric field within P(VDF‐TrFE)/perovskite hybrid nanowire arrays.     

Ultrahigh‐Performance Flexible and Self‐Powered Photodetectors with Ferroelectric P(VDF‐TrFE)/Perovskite Bulk Heterojunction

Flexible and self‐powered perovskite photodetectors attract widespread research interests due to their potential applications in portable and wearable optoelectronic devices. However, the reported devices mainly adopt an independent layered structure with complex fabrication processes and high carrier recombination. Herein, an integrated ferroelectric poly(vinylidene‐fluoride‐trifluoroethylene) (P(VDF‐TrFE)) and perovskite bulk heterojunction film photodetector on the polyethylene naphthalate substrate is demonstrated. Under the optimum treatment conditions (the polarization voltage and time, and the concentration of P(VDF‐TrFE)), the photodetector exhibits a largely enhanced performance compared to the pristine perovskite device. The resulting device exhibits ultrahigh performance with a large detectivity (1.4 × 10¹³ Jones) and fast response time (92/193 µs) at the wavelength of 650 nm. The improved performance is attributed to the fact that the polarized P(VDF‐TrFE)/perovskite hybrid film provides a stronger built‐in electric field to facilitate the separation and transportation of photogenerated carriers. These findings provide a new route to design self‐powered photodetectors from the aspect of device structure and carrier transport.     

2D Nanomaterial Arrays for Electronics and Optoelectronics

Two‐dimensional (2D) materials, benefitting from their unique planar structure and various appealing electronic properties, have attracted much attention for novel electronic and optoelectronic applications. As a basis for practical devices, the study of micro/nano‐2D material arrays based on coupling effects and synergistic effects is critical to the functionalization and integration of 2D materials. Moreover, micro/nano‐2D material arrays are compatible with traditional complementary metal oxide semiconductor (CMOS) electronics, catering well to high‐integration, high‐sensitivity, and low‐cost sensing and imaging systems. This review presents some recent studies on 2D material arrays in sequence from their novel preparations to high‐integration applications as well as explorations on dimension tuning. A first focus is on various typical fabrication methods for 2D material arrays, including photolithography, 2D printing, seeded growth, van der Waals epitaxial growth, and self‐assembly. Then, the applications of 2D material arrays, such as field effect transistors, photodetectors, pressure sensors, as well as flexible electronic devices of photodetectors and strain sensors, are elaborately introduced. Furthermore, the recent burgeoning exploration of mixed‐dimensional heterostructure arrays including 0D/2D, 1D/2D, and 3D/2D is discussed. Ultimately, conclusions and an outlook based on the current developments in this promising field are presented.     

Inch‐Size Single Crystal of a Lead‐Free Organic–Inorganic Hybrid Perovskite for High‐Performance Photodetector

Large‐size crystals of organic–inorganic hybrid perovskites (e.g., CH₃NH₃PbX₃, X = Cl, Br, I) have gained wide attention since their spectacular progress on optoelectronic technologies. Although presenting brilliant semiconducting properties, a serious concern of the toxicity in these lead‐based hybrids has become a stumbling block that limits their wide‐scale applications. Exploring lead‐free hybrid perovskite is thus highly urgent for high‐performance optoelectronic devices. Here, a new lead‐free perovskite hybrid (TMHD)BiBr₅ (TMHD = N,N,N,N‐tetramethyl‐1,6‐hexanediammonium) is prepared from facile solution process. Emphatically, inch‐size high‐quality single crystals are successfully grown, the dimensions of which reach up to 32 × 24 × 12 mm³. Furthermore, the planar arrays of photodetectors based on bulk lead‐free (TMHD)BiBr₅ single crystals are first fabricated, which shows sizeable on/off current ratios (≈10³) and rapid response speed (τ_rise = 8.9 ms and τ_decay = 10.2 ms). The prominent device performance of (TMHD)BiBr₅ strongly underscores the lead‐free hybrid perovskite single crystals as promising material candidates for optoelectronic applications.     

White‐Light Emitting Diode Array of p+‐Si/Aligned n‐SnO2 Nanowires Heterojunctions

We report on the fabrication and optoelectronic properties of p‐n heterojunction arrays of p⁺‐type Si and aligned n‐type SnO₂ nanowires with high rectification ratios of >10⁴ at ±15 V. The electrical stability of the p‐n heterojunction devices was improved by coating the junction with poly(methylmethacrylate) to minimize the degradation of the interface layer at the junction. As a photodiode an enhanced UV photosensitivity higher than 10² was recorded under reverse bias. Using a large forward bias in the light‐emitting diode mode white light was emitted from the large‐scale heterojunction devices with at least three broad peaks in the visible range, which can be attributed to the interband transitions of the injected electrons or holes mediated by an interfacial SiO₂ layer with a contribution of trap‐level energies. These results indicate the high potential of Si/SnO₂ nanowires heterojunctions as optoelectronic devices with proper tuning of the recombination center at the junctions.     

Single‐Crystalline p‐Type Zn3As2 Nanowires for Field‐Effect Transistors and Visible‐Light Photodetectors on Rigid and Flexible Substrates

Zn₃As₂ is an important p‐type semiconductor with the merit of high effective mobility. The synthesis of single‐crystalline Zn₃As₂ nanowires (NWs) via a simple chemical vapor deposition method is reported. High‐performance single Zn₃As₂ NW field‐effect transistors (FETs) on rigid SiO₂/Si substrates and visible‐light photodetectors on rigid and flexible substrates are fabricated and studied. As‐fabricated single‐NW FETs exhibit typical p‐type transistor characteristics with the features of high mobility (305.5 cm² V^?1 s^?1) and a high I_on/I_off ratio (10⁵). Single‐NW photodetectors on SiO₂/Si substrate show good sensitivity to visible light. Using the contact printing process, large‐scale ordered Zn₃As₂ NW arrays are successfully assembled on SiO₂/Si substrate to prepare NW thin‐film transistors and photodetectors. The NW‐array photodetectors on rigid SiO₂/Si substrate and flexible PET substrate exhibit enhanced optoelectronic performance compared with the single‐NW devices. The results reveal that the p‐type Zn₃As₂ NWs have important applications in future electronic and optoelectronic devices.     

Ultrahigh Speed and Broadband Few‐Layer MoTe2/Si 2D–3D Heterojunction‐Based Photodiodes Fabricated by Pulsed Laser Deposition

2D transition metal dichalcogenides are promising candidates for high‐performance photodetectors. However, the relatively low response speed as well as the complex transfer process hinders their wide applications. Herein, for the first time, the fabrication of a few‐layer MoTe₂/Si 2D–3D vertical heterojunction for high‐speed and broadband photodiodes by a pulsed laser deposition technique is reported. Owing to the high junction quality, ultrathin MoTe₂ film thickness, and unique vertical n–n heterojunction structure, the photodiode exhibits excellent device performance in terms of a high responsivity of 0.19 A W^?1 and a large detectivity of 6.8 × 10¹³ Jones. The device is also capable of detecting a broadband light with wavelength spanning from 300 to 1800 nm. More importantly, the device possesses an ultrahigh response speed up to 150 ns with a 3‐dB electrical bandwidth approaching 0.12 GHz. This work paves the way toward the fabrication of novel 2D–3D heterojunctions for high‐performance, ultrafast photodetectors.     

Low‐Noise Multispectral Photodetectors Made from All Solution‐Processed Inorganic Semiconductors

Infrared, visible, and multispectral photodetectors are important components for sensing, security and electronics applications. Current fabrication of these devices is based on inorganic materials grown by epitaxial techniques which are not compatible with low‐cost large‐scale processing. Here, air‐stable multispectral solution‐processed inorganic double heterostructure photodetectors, using PbS quantum dots (QDs) as the photoactive layer, colloidal ZnO nanoparticles as the electron transport/hole blocking layer (ETL/HBL), and solution‐derived NiO as the hole transport/electron blocking layer (HTL/EBL) are reported. The resulting device has low dark current density of 20 nA cm^‐2 with a noise equivalent power (NEP) on the order of tens of picowatts across the detection spectra and a specific detectivity (D*) value of 1.2 × 10¹² cm Hz^1/2 W^‐1. These parameters are comparable to commercially available Si, Ge, and InGaAs photodetectors. The devices have a linear dynamic range (LDR) over 65 dB and a bandwidth over 35 kHz, which are sufficient for imaging applications. Finally, these solution‐processed inorganic devices have a long storage lifetime in air, even without encapsulation.     

Organic Single Crystal Patterning Method for Micrometric Photosensors

Light detection technologies are of interest due to their applications in energy conversion and optical communications. Single-crystal organic semiconductors, such as rubrene, present high detectivities and charge carrier mobility, making them attractive for light-sensing applications. Growth of high crystallinity organic crystals is achieved using vapor processes, forming crystals of arbitrary shapes and orientations and requiring posterior patterning processes. However, patterning the organic semiconductors using industry-standard microfabrication techniques is not straightforward, as these often cause irreversible damage to the crystals. Here the fabrication of patterned micrometric rubrene photosensors is demonstrated through a combination of photolithography and Reactive Ion Etching steps. Protective layers during microfabrication minimize degradation of optoelectronic properties of the organic single crystals during fabrication. Crystals undergoing the patterning process presented a survival rate of 39%. Photoresponse values of up to 41 mA W⁻¹ are obtained under illumination at 500 nm. This opens a route for the industrial-scale fabrication process of high-performance optoelectronic devices based on organic crystals semiconductors.     

Rapid 2D Patterning of High-Performance Perovskites Using Large Area Flexography

Solution processing of metal halide perovskites offers the potential for efficient, high-speed roll-based manufacturing of emerging optoelectronic devices such as lightweight photovoltaics and light emitting diodes at lower cost than achievable with incumbent technologies (e.g., Silicon). However, current perovskite fabrication methods are limited in their speed, uniformity, and patterning resolution, relying on subtractive postdeposition scribing for integration of modules and device arrays. Here, a method for flexographic printing of MA_0.6FA_0.4PbI₃ at 60 m min⁻¹, the fastest reported perovskite absorber deposition and the first report of inline drying integrated with roll-based printing, is presented. This process delivers high-resolution patterning (< 3 µm line edge roughness) and precise thickness control through rheological design of precursor inks, allowing scalably printed 50 µm features over large areas (140 cm²), while obviating damaging scribing steps. 2D scanning photoluminescence (PL) is applied to resolve correlations between ink leveling dynamics and optoelectronic quality. Integrating these highly uniform printed perovskite absorbers into n-i-p planar perovskite solar cells, photovoltaic conversion efficiency up to 20.4% (0.134 cm²), the highest performance yet reported for any roll-printed perovskite cells is achieved. This study, thus, establishes flexography as a scalable approach to deposit precisely-patterned high-quality perovskites extensible to applications in emitter and detector arrays.     

Fully Integrated Microscale Quasi‐2D Crystalline Molecular Field‐Effect Transistors

Monolithic integration of microscale organic field‐effect transistors (micro‐OFETs) is the only and inevitable path toward low‐cost large‐area electronics and displays. However, to date, such an ultimate technology has not yet evolved due to challenges in positioning and patterning highly crystalline microscale molecular layers as well as in developing micrometer scale integration schemes. In this work, by mastering the local growth of molecular semiconductors on pre‐defined terraces, single‐crystal quasi‐2D molecular layers tens of square micrometers in size are created in dense periodic arrays on a Si substrate. Nondestructive photolithographic processes are developed to pattern micro‐OFETs with mobilities up to 34.6 cm² V^?1 s^?1. This work demonstrates the feasibility to integrate arrays of short‐channel micro‐OFETs into electronic circuitry by highly parallel and size scalable fabrication technologies.     

Metal Halide Perovskite Arrays: From Construction to Optoelectronic Applications

Inorganic semiconductor arrays revolutionize many areas of electronics, optoelectronics with the properties of multifunctionality and large-scale integration. Metal halide perovskites are emerging as candidates for next-generation optoelectronic devices due to their excellent optoelectronic properties, ease of processing, and compatibility with flexible substrates. To date, a series of patterning technologies have been applied to perovskites to realize array configurations and nano/microstructured surfaces to further improve device performances. Herein, various construction methods for perovskite crystal or thin film arrays are summarized. The optoelectronic applications of the perovskite arrays are also discussed, in particular, for photodetectors, light-emitting diodes, lasers, and nanogratings.     

Synthesis of Large‐Area Atomically Thin BiOI Crystals with Highly Sensitive and Controllable Photodetection

Compared to the most studied 2D elements and binary compounds, ternary layered compounds with more adjustable physical and chemical properties have exhibited potential applications in electronic and optoelectronic devices. Here, 2D ternary layered BiOI crystals are synthesized first with a domain size up to 100 µm via space‐confined chemical vapor deposition. The photodetectors based on the as‐grown BiOI nanosheets demonstrate high sensitivity to 473 nm light. The I_on/I_off ratio and detectivity of BiOI photodetectors can reach up to 1 × 10⁵ and 8.2 × 10¹¹ Jones at 473 nm, respectively. Particularly, the contact and dark current of the photodetectors can be controlled by 254 nm ultraviolet light irradiation due to the introduction of oxygen vacancies. The facile synthesis of large‐area atomically thin BiOI and its controllable performance by ultraviolet light irradiation suggest that 2D BiOI crystal is a promising material for fundamental investigations and optoelectronic applications.     

ZnO Nanorod Arrays as Electron Injection Layers for Efficient Organic Light Emitting Diodes

Nanostructured oxide arrays have received significant attention as charge injection and collection electrodes in numerous optoelectronic devices. Zinc oxide (ZnO) nanorods have received particular interest owing to the ease of fabrication using scalable, solution processes with a high degree of control of rod dimension and density. Here, vertical ZnO nanorods as electron injection layers in organic light emitting diodes are implemented for display and lighting purposes. Implementing nanorods into devices with an emissive polymer, poly(9,9‐dioctyluorene‐alt‐benzothiadiazole) (F8BT) and poly(9,9‐di‐n‐octylfluorene‐alt‐N‐(4‐butylphenyl)dipheny‐lamine) (TFB) as an electron blocking layer, brightness and efficiencies up to 8602 cd m^?2 and 1.66 cd A^?1 are achieved. Simple solution processing methodologies combined with postdeposition thermal processing are highlighted to achieve complete wetting of the nanorod arrays with the emissive polymer. The introduction of TFB to minimize charge leakage and nonradiative exciton decay results in dramatic increases to device yields and provides an insight into the operating mechanism of these devices. It is demonstrated that the detected emission originates from within the polymer layers with no evidence of ZnO band edge or defect emission. The work represents a significant development for the ongoing implementation of ZnO nanorod arrays into efficient light emitting devices.     

Epitaxial Growth of Large‐Scale Orthorhombic CsPbBr3 Perovskite Thin Films with Anisotropic Photoresponse Property

Inorganic cesium lead halide perovskite (CsPbX₃, X = Cl, Br, I) is a promising material for developing novel electronic and optoelectronic devices. Despite the substantial progress that has been made in the development of large perovskite single crystals, the fabrication of high‐quality 2D perovskite single‐crystal films, especially perovskite with a low symmetry, still remains a challenge. Herein, large‐scale orthorhombic CsPbBr₃ single‐crystal thin films on zinc‐blende ZnSe crystals are synthesized via vapor‐phase epitaxy. Structural characterizations reveal a “CsPbBr₃(110)//ZnSe(100), CsPbBr₃[?110]//ZnSe[001] and CsPbBr₃[001]//ZnSe[010]” heteroepitaxial relationship between the covering CsPbBr₃ layer and the ZnSe growth substrate. It is exciting that the epitaxial film presents an in‐plane anisotropic absorption property from 350 to 535 nm and polarization‐dependent photoluminescence. Photodetectors based on the epitaxial film exhibit a high photoresponsivity of 200 A W^?1, a large on/off current ratio exceeding 10⁴, a fast photoresponse time of about 20 ms, and good repeatability at room temperature. Importantly, a strong polarization‐dependent photoresponse is also found on the device fabricated using the epitaxial CsPbBr₃ film, making the orthorhombic perovskite promising building blocks for optoelectronic devices featured with anisotropy.     

Synergistic Effect of Hybrid PbS Quantum Dots/2D‐WSe2 Toward High Performance and Broadband Phototransistors

The transitionmetal dichalcogenides‐based phototransistors have demonstrated high transport mobility but are limited to poor photoresponse, which greatly blocks their applications in optoelectronic fields. Here, light sensitive PbS colloidal quantum dots (QDs) combined with 2D WSe₂ to develop hybrid QDs/2D‐WSe₂ phototransistors for high performance and broadband photodetection are utilized. The device shows a responsivity up to 2 × 10⁵ A W^–1, which is orders of magnitude higher than the counterpart of individual material‐based devices. The detection spectra of hybrid devices can be extended to near infrared similar to QDs' response. The high performance of hybrid 0D‐2D phototransistor is ascribed to the synergistic function of photogating effect. PbS QDs can efficiently absorb the input illumination and 2D WSe₂ supports a transport expressway for injected photocarriers. The hybrid phototransistors obtain a specific detectivity over 10¹³ Jones in both ON and OFF state in contrast to the depleted working state (OFF) for other reported QDs/2D phototransistors. The present device construction strategy, photogating enhanced performance, and robust device working conditions contain high potential for future optoelectronic devices.     

Cover Picture: High Definition Digital Fabrication of Active Organic Devices by Molecular Jet Printing (Adv. Funct. Mater. 15/2007)

A new method for direct patterning of organic optoelectronic/electronic devices using a reconfigurable and scalable printing method is reported by Vladimir Bulovic and co‐workers on p. 2722. The printing technique is applied to the fabrication of high‐resolution printed organic light emitting devices (OLEDs) and organic field effect transistors (OFETs). Remarkably, the final print‐deposited films are evaporated onto the substrate (rather than solvent printed), giving high‐quality, solvent‐free, molecularly flat structures that match the performance of comparable high‐performance unpatterned films. We introduce a high resolution molecular jet (MoJet) printing technique for vacuum deposition of evaporated thin films and apply it to fabrication of 30 μm pixelated (800 ppi) molecular organic light emitting devices (OLEDs) based on aluminum tris(8‐hydroxyquinoline) (Alq₃) and fabrication of narrow channel (15 μm) organic field effect transistors (OFETs) with pentacene channel and silver contacts. Patterned printing of both organic and metal films is demonstrated, with the operating properties of MoJet‐printed OLEDs and OFETs shown to be comparable to the performance of devices fabricated by conventional evaporative deposition through a metal stencil. We show that the MoJet printing technique is reconfigurable for digital fabrication of arbitrary patterns with multiple material sets and high print accuracy (of better than 5 μm), and scalable to fabrication on large area substrates. Analogous to the concept of “drop‐on‐demand” in Inkjet printing technology, MoJet printing is a “flux‐on‐demand” process and we show it capable of fabricating multi‐layer stacked film structures, as needed for engineered organic devices.     

Highly Efficient Three Primary Color Organic Single‐Crystal Light‐Emitting Devices with Balanced Carrier Injection and Transport

Organic single crystals have a great potential in the field of organic optoelectronics because of their advantages of high carrier mobility and high thermal stability. However, the application of the organic single crystals in light‐emitting devices (OLEDs) has been limited by single‐layered structure with unbalanced carrier injection and transport. Here, fabrication of a multilayered‐structure crystal‐based OLED constitutes a major step toward balanced carrier injection and transport by introducing an anodic buffer layer and electron transport layer into the device structure. Three primary color single‐crystal‐based OLEDs based on the multilayered structure and molecular doping exhibit a maximum luminance and current efficiency of 820 cd cm^?2 and 0.9 cd A^?1, respectively, which are the highest performance to date for organic single‐crystal‐based OLEDs. This work paves the way toward high‐performance organic optoelectronic devices based on the organic single crystals.