Hybrid Organic–Inorganic Perovskite Photodetectors

Hybrid organic–inorganic perovskite materials garner enormous attention for a wide range of optoelectronic devices. Due to their attractive optical and electrical properties including high optical absorption coefficient, high carrier mobility, and long carrier diffusion length, perovskites have opened up a great opportunity for high performance photodetectors. This review aims to give a comprehensive summary of the significant results on perovskite‐based photodetectors, focusing on the relationship among the perovskite structures, device configurations, and photodetecting performances. An introduction of recent progress in various perovskite structure‐based photodetectors is provided. The emphasis is placed on the correlation between the perovskite structure and the device performance. Next, recent developments of bandgap‐tunable perovskite and hybrid photodetectors built from perovskite heterostructures are highlighted. Then, effective approaches to enhance the stability of perovskite photodetector are presented, followed by the introduction of flexible and self‐powered perovskite photodetectors. Finally, a summary of the previous results is given, and the major challenges that need to be addressed in the future are outlined. A comprehensive summary of the research status on perovskite photodetectors is hoped to push forward the development of this field.     

High‐Performance Flexible Photodetectors based on High‐Quality Perovskite Thin Films by a Vapor–Solution Method

Organometal halide perovskites are new light‐harvesting materials for lightweight and flexible optoelectronic devices due to their excellent optoelectronic properties and low‐temperature process capability. However, the preparation of high‐quality perovskite films on flexible substrates has still been a great challenge to date. Here, a novel vapor–solution method is developed to achieve uniform and pinhole‐free organometal halide perovskite films on flexible indium tin oxide/poly(ethylene terephthalate) substrates. Based on the as‐prepared high‐quality perovskite thin films, high‐performance flexible photodetectors (PDs) are constructed, which display a nR value of 81 A W^?1 at a low working voltage of 1 V, three orders higher than that of previously reported flexible perovskite thin‐film PDs. In addition, these flexible PDs exhibit excellent flexural stability and durability under various bending situations with their optoelectronic performance well retained. This breakthrough on the growth of high‐quality perovskite thin films opens up a new avenue to develop high‐performance flexible optoelectronic devices.     

Revealing Electrical-Poling-Induced Polarization Potential in Hybrid Perovskite Photodetectors

Despite recent rapid advances in metal halide perovskites for use in optoelectronics, the fundamental understanding of the electrical-poling-induced ion migration, accounting for many unusual attributes and thus performance in perovskite-based devices, remain comparatively elusive. Herein, the electrical-poling-promoted polarization potential is reported for rendering hybrid organic–inorganic perovskite photodetectors with high photocurrent and fast response time, displaying a tenfold enhancement in the photocurrent and a twofold decrease in the response time after an external electric field poling. First, a robust meniscus-assisted solution-printing strategy is employed to facilitate the oriented perovskite crystals over a large area. Subsequently, the electrical poling invokes the ion migration within perovskite crystals, thus inducing a polarization potential, as substantiated by the surface potential change assessed by Kelvin probe force microscopy. Such electrical-poling-induced polarization potential is responsible for the markedly enhanced photocurrent and largely shortened response time. This work presents new insights into the electrical-poling-triggered ion migration and, in turn, polarization potential as well as into the implication of the latter for optoelectronic devices with greater performance. As such, the utilization of ion-migration-produced polarization potential may represent an important endeavor toward a wide range of high-performance perovskite-based photodetectors, solar cells, transistors, scintillators, etc.     

Perovskite Granular Wire Photodetectors with Ultrahigh Photodetectivity

Control over the morphology and crystallinity of metal halide perovskite materials is of key importance to enable high-performance optoelectronics. Here, a simple yet effective template-free self-assembly synthesis of perovskite granular wires with ultrahigh photodetectivity (3.17 × 10¹⁵ Jones) is reported. The 1D self-assembly of perovskite grains is driven by differences in the surface interaction energies of the granular facets. The superb photodetecting performance originates from extremely low dark current engendered by energetic barriers featuring unique band-edge modulation along the long axis of wire. Flexible photodetector arrays, fabricated by selectively placing perovskite granular wires onto pre-patterned electrode arrays on a transparent polymer substrate, show independently addressable photonic signal mapping with remarkably high detectivity, photoconductive gain, and responsivity. The “self-assembled nanograin engineering” strategy developed in this study provides a viable method for the development of high-performance perovskite photodetectors and can be extended to other integrated optoelectronic systems.     

Atomic‐Layer Deposition‐Assisted Double‐Side Interfacial Engineering for High‐Performance Flexible and Stable CsPbBr3 Perovskite Photodetectors toward Visible Light Communication Applications

Self‐powered photodetectors (PDs) based on inorganic metal halide perovskites are regarded as promising alternatives for the next generation of photodetectors. However, uncontrollable film growth and sluggish charge extraction at interfaces directly limit the sensitivity and response speed of perovskite‐based photodetectors. Herein, by assistance of an atomic layer deposition (ALD) technique, CsPbBr₃ perovskite thin films with preferred orientation and enlarged grain size are obtained on predeposited interfacial modification layers. Thanks to improved film quality and double side interfacial engineering, the optimized CsPbBr₃ (Al₂O₃/CsPbBr₃/TiO₂, ACT) perovskite PDs exhibit outstanding performance with ultralow dark current of 10^?11 A, high detectivity of 1.88 × 10¹³ Jones and broad linear dynamic range (LDR) of 172.7 dB. Significantly, excellent long‐term environmental stability (ambient conditions >100 d) and flexibility stability (>3000 cycles) are also achieved. The remarkable performance is credited to the synergistic effects of high carrier conductivity and collection efficiency, which is assisted by ALD modification layers. Finally, the ACT PDs are successfully integrated into a visible light communication system as a light receiver on transmitting texts, showing a bit rate as high as 100 kbps. These results open the window of high performance all‐inorganic halide perovskite photodetectors and extends to rational applications for optical communication.     

Thermal Management Enables Bright and Stable Perovskite Light-Emitting Diodes

The performance of lead-halide perovskite light-emitting diodes (LEDs) has increased rapidly in recent years. However, most reports feature devices operated at relatively small current densities (<500 mA cm⁻²) with moderate radiance (<400 W sr⁻¹ m⁻²). Here, Joule heating and inefficient thermal dissipation are shown to be major obstacles toward high radiance and long lifetime. Several thermal management strategies are proposed in this work, such as doping charge-transport layers, optimizing device geometry, and attaching heat spreaders and sinks. Combining these strategies, high-performance perovskite LEDs are demonstrated with maximum radiance of 2555 W sr⁻¹ m⁻², peak external quantum efficiency (EQE) of 17%, considerably reduced EQE roll-off (EQE > 10% to current densities as high as 2000 mA cm⁻²), and tenfold increase in operational lifetime (when driven at 100 mA cm⁻²). Furthermore, with proper thermal management, a maximum current density of 2.5 kA cm⁻² and an EQE of ≈1% at 1 kA cm⁻² are shown using electrical pulses, which represents an important milestone toward electrically driven perovskite lasers.     

Highly Oriented Thin Films of 2D Ruddlesden‐Popper Hybrid Perovskite toward Superfast Response Photodetectors

2D hybrid perovskites have shown great promise in the photodetection field, due to their intriguing attributes stemming from unique structural architectures. However, the great majority of detectors based on this 2D system possess a relatively low response speed (≈ms), making it extremely urgent to develop new candidates for superfast photodetection. Here, a new organic–inorganic hybrid perovskite, (PA)₂(FA)Pb₂I₇ (EFA, where PA is n‐pentylaminium and FA is formamidine), which features the 2D Ruddlesden–Popper type perovskite framework that is composed of the corner‐sharing PbI₆ octahedra is reported. Significantly, photodetectors fabricated on highly oriented thin films, which exhibit a perfect orientation parallel to 2D inorganic perovskite layers, exhibit a superfast response time up to ≈2.54 ns. To the best of the knowledge, this figure‐of‐merit catches up with that of the top‐ranking commercial materials, and sets a new record for 2D hybrid perovskite photodetectors. Moreover, extremely high photodetectivity (≈1.73 × 10¹⁴ Jones, under an incident power intensity of ≈46 µW cm^?2), considerable switching ratios (>10³), and low dark current (≈10 pA) are also achieved in the detector, indicating its great potential for high‐efficiency photodetection. These results shed light on the possibilities to explore new 2D candidates for assembling future high‐performance optoelectronic devices.     

Nested Inverse Opal Perovskite toward Superior Flexible and Self-Powered Photodetection Performance

Flexible and self-powered perovskite photodetectors have attracted tremendous research interests due to their applications in wearable and portable devices. However, the conventional planar structured photodetectors are always accompanied with limited device performance and undesired mechanical stability. Herein, a nested inverse opal (NIO) structured perovskite photodetector via a facile template-assisted spin-coating method is reported. The coupling effect of enhanced light capture, increased carrier transport, and improved perovskite film quality enables NIO device to exhibit superior photoresponse performance. The NIO photodetector exhibits a high responsivity of 473 mA W⁻¹ and detectivity up to 1.35 × 10¹³ Jones at 720 nm without external bias. The NIO structure can efficiently release mechanical stress during the bending process and the photocurrent has no degradation even after 500 cycles of bending. Moreover, the unencapsulated NIO device can operate for over 16 d under ambient conditions, presenting a significantly enhanced environmental stability compared to the planar device. This work demonstrates that deliberate structural design is an effective avenue for constructing self-powered, flexible, and stable optoelectronic devices.     

Highly Efficient and Ultrasensitive Large‐Area Flexible Photodetector Based on Perovskite Nanowires

Hybrid organic–inorganic perovskites have shown exceptional semiconducting properties and microstructural versatility for inexpensive, solution‐processable photovoltaic and optoelectronic devices. In this work, an all‐solution‐based technique in ambient environment for highly sensitive and high‐speed flexible photodetectors using high crystal quality perovskite nanowires grown on Kapton substrate is presented. At 10 V, the optimized photodetector exhibits a responsivity as high as 0.62 A W^?1, a maximum specific detectivity of 7.3 × 10¹² cm Hz^1/2 W^?1, and a rise time of 227.2 µs. It also shows remarkable photocurrent stability even beyond 5000 bending cycles. Moreover, a deposition of poly(methyl methacrylate) (PMMA) as a protective layer on the perovskite yields significantly better stability under ambient air operation: the PMMA‐protected devices are stable for over 30 days. This work demonstrates a cost‐effective fabrication technique for high‐performance flexible photodetectors and opens opportunities for research advancements in broadband and large‐scale flexible perovskite‐based optoelectronic devices.     

Improving All‐Inorganic Perovskite Photodetectors by Preferred Orientation and Plasmonic Effect

All‐inorganic perovskites have high carrier mobility, long carrier diffusion length, excellent visible light absorption, and well overlapping with localized surface plasmon resonance (LSPR) of noble metal nanocrystals (NCs). The high‐performance photodetectors can be constructed by means of the intrinsic outstanding photoelectric properties, especially plasma coupling. Here, for the first time, inorganic perovskite photodetectors are demonstrated with synergetic effect of preferred‐orientation film and plasmonic with both high performance and solution process virtues, evidenced by 238% plasmonic enhancement factor and 10⁶ on/off ratio. The CsPbBr₃ and Au NC inks are assembled into high‐quality films by centrifugal‐casting and spin‐coating, respectively, which lead to the low cost and solution‐processed photodetectors. The remarkable near‐field enhancement effect induced by the coupling between Au LSPR and CsPbBr₃ photogenerated carriers is revealed by finite‐difference time‐domain simulations. The photodetector exhibits a light on/off ratio of more than 10⁶ under 532 nm laser illumination of 4.65 mW cm^?2. The photocurrent increases from 0.67 to 2.77 μA with centrifugal‐casting. Moreover, the photocurrent rises from 245.6 to 831.1 μA with Au NCs plasma enhancement, leading to an enhancement factor of 238%, which is the most optimal report among the LSPR‐enhanced photodetectors, to the best of our knowledge. The results of this study suggest that all‐inorganic perovskites are promising semiconductors for high‐performance solution‐processed photodetectors, which can be further enhanced by Au plasmonic effect, and hence have huge potentials in optical communication, safety monitoring, and biological sensing.     

Fast-Response,Highly Air-Stable,and Water-Resistant Organic Photodetectors Based on a Single-Crystal Pt Complex

Organic semiconductors demonstrate several advantages over conventional inorganic materials for novel electronic and optoelectronic applications, including molecularly tunable properties, flexibility, low-cost, and facile device integration. However, before organic semiconductors can be used for the next-generation devices, such as ultrafast photodetectors (PDs), it is necessary to develop new materials that feature both high mobility and ambient stability. Toward this goal, a highly stable PD based on the organic single crystal [PtBr₂(5,5′-bis(CF₃CH₂OCH₂)-2,2′-bpy)] (or “Pt complex (1o)”) is demonstrated as the active semiconductor channel—a material that features a lamellar molecular structure and high-quality, intraligand charge transfer. Benefitting from its unique crystal structure, the Pt-complex (1o) device exhibits a field-effect mobility of ≈0.45 cm² V⁻¹ s⁻¹ without loss of significant performance under ambient conditions even after 40 days without encapsulation, as well as immersion in distilled water for a period of 24 h. Furthermore, the device features a maximum photoresponsivity of 1 × 10³ A W⁻¹, a detectivity of 1.1 × 10¹² cm Hz^1/2 W⁻¹, and a record fast response/recovery time of 80/90 µs, which has never been previously achieved in other organic PDs. These findings strongly support and promote the use of the single-crystal Pt complex (1o) in next-generation organic optoelectronic devices.     

Low‐Noise and Large‐Linear‐Dynamic‐Range Photodetectors Based on Hybrid‐Perovskite Thin‐Single‐Crystals

Organic–inorganic halide perovskites are promising photodetector materials due to their strong absorption, large carrier mobility, and easily tunable bandgap. Up to now, perovskite photodetectors are mainly based on polycrystalline thin films, which have some undesired properties such as large defective grain boundaries hindering the further improvement of the detector performance. Here, perovskite thin‐single‐crystal (TSC) photodetectors are fabricated with a vertical p–i–n structure. Due to the absence of grain‐boundaries, the trap densities of TSCs are 10–100 folds lower than that of polycrystalline thin films. The photodetectors based on CH₃NH₃PbBr₃ and CH₃NH₃PbI₃ TSCs show low noise of 1–2 fA Hz^?1/2, yielding a high specific detectivity of 1.5 × 10¹³ cm Hz^1/2 W^?1. The absence of grain boundaries reduces charge recombination and enables a linear response under strong light, superior to polycrystalline photodetectors. The CH₃NH₃PbBr₃ photodetectors show a linear response to green light from 0.35 pW cm^?2 to 2.1 W cm^?2, corresponding to a linear dynamic range of 256 dB.     

A Review on Organic–Inorganic Halide Perovskite Photodetectors: Device Engineering and Fundamental Physics

The last eight years (2009–2017) have seen an explosive growth of interest in organic–inorganic halide perovskites in the research communities of photovoltaics and light‐emitting diodes. In addition, recent advancements have demonstrated that this type of perovskite has a great potential in the technology of light‐signal detection with a comparable performance to commercially available crystalline Si and III–V photodetectors. The contemporary growth of state‐of‐the‐art multifunctional perovskites in the field of light‐signal detection has benefited from its outstanding intrinsic optoelectronic properties, including photoinduced polarization, high drift mobilities, and effective charge collection, which are excellent for this application. Photoactive perovskite semiconductors combine effective light absorption, allowing detection of a wide range of electromagnetic waves from ultraviolet and visible, to the near‐infrared region, with low‐cost solution processability and good photon yield. This class of semiconductor might empower breakthrough photodetector technology in the field of imaging, optical communications, and biomedical sensing. Therefore, here, the focus is specifically on the critical understanding of materials synthesis, design, and engineering for the next‐stage development of perovskite photodetectors and highlighting the current challenges in the field, which need to be further studied in the future.     

Dual‐Phase CsPbBr3–CsPb2Br5 Perovskite Thin Films via Vapor Deposition for High‐Performance Rigid and Flexible Photodetectors

Inorganic perovskites with special semiconducting properties and structures have attracted great attention and are regarded as next generation candidates for optoelectronic devices. Herein, using a physical vapor deposition process with a controlled excess of PbBr₂, dual‐phase all‐inorganic perovskite composite CsPbBr₃–CsPb₂Br₅ thin films are prepared as light‐harvesting layers and incorporated in a photodetector (PD). The PD has a high responsivity and detectivity of 0.375 A W^?1 and 10¹¹ Jones, respectively, and a fast response time (from 10% to 90% of the maximum photocurrent) of ≈280 µs/640 µs. The device also shows an excellent stability in air for more than 65 d without encapsulation. Tetragonal CsPb₂Br₅ provides satisfactory passivation to reduce the recombination of the charge carriers, and with its lower free energy, it enhances the stability of the inorganic perovskite devices. Remarkably, the same inorganic perovskite photodetector is also highly flexible and exhibits an exceptional bending performance (>1000 cycles). These results highlight the great potential of dual‐phase inorganic perovskite films in the development of optoelectronic devices, especially for flexible device applications.     

Ultrahigh‐Performance Self‐Powered Flexible Double‐Twisted Fibrous Broadband Perovskite Photodetector

Self‐powered flexible photodetectors without an external power source can meet the demands of next‐generation portable and wearable nanodevices; however, the performance is far from satisfactory becuase of the limited match of flexible substrates and light‐sensitive materials with proper energy levels. Herein, a novel self‐powered flexible fiber‐shaped photodetector based on double‐twisted perovskite–TiO₂–carbon fiber and CuO–Cu₂O–Cu wire is designed and fabricated. The device shows an ultrahigh detectivity of 2.15 × 10¹³ Jones under the illumination of 800 nm light at zero bias. CuO–Cu₂O electron block bilayer extends response range of perovskite from 850 to 1050 nm and suppresses dark current down to 10^?11 A. The fast response speed of less than 200 ms is nearly invariable after dozens of cycles of bending at the extremely 90 bending angle, demonstrating excellent flexibility and bending stability. These parameters are comparable and even better than reported flexible and even rigid photodetectors. The present results suggest a promising strategy to design photodetectors with integrated function of self‐power, flexibility, and broadband response.