Sensitive and Stable Tin–Lead Hybrid Perovskite Photodetectors Enabled by Double‐Sided Surface Passivation for Infrared Upconversion Detection

Tin(Sn)‐based perovskite is currently considered one of the most promising materials due to extending the absorption spectrum and reducing the use of lead (Pb). However, Sn²⁺ is easily oxidized to Sn⁴⁺ in atmosphere, causing more defects and degradation of perovskite materials. Herein, double‐sided interface engineering is proposed, that is, Sn‐Pb perovskite films are sandwiched between the phenethylammonium iodide (PEAI) in both the bottom and top sides. The larger organic cations of PEA+ are arranged into a perovskite surface lattice to form a 2D capping layer, which can effectively prevent the water and oxygen to destroy bulk perovskite. Meanwhile, the PEA+ can also passivate defects of iodide anions at the bottom of perovskite films, which is always present but rarely considered previously. Compared to one sided passivation, Sn‐Pb hybrid perovskite photodetectors contribute a significant enhancement of performance and stability, yielding a broadband response of 300–1050 nm, a low dark current density of 1.25 × 10^–3 mA cm^–2 at –0.1 V, fast response speed of 35 ns, and stability beyond 240 h. Furthermore, the Sn‐Pb broadband photodetectors are integrated in an infrared up‐conversion system, converting near‐infrared light into visible light. It is believed that a double‐sided passivation method can provide new strategies to achieving high‐performance perovskite photodetectors.     

Flexible Quasi-2D Perovskite/IGZO Phototransistors for Ultrasensitive and Broadband Photodetection

Organic–inorganic hybrid perovskites (PVKs) have recently emerged as attractive materials for photodetectors. However, the poor stability and low electrical conductivity still restrict their practical utilization. Owing to the quantum-well feature of two-dimensional (2D) Ruddlesden–Popper PVKs (2D PVKs), a promising quasi-2D PVK/indium gallium zinc oxide (IGZO) heterostructure phototransistor can be designed. By using a simple ligand-exchange spin-coating method, quasi-2D PVK fabricated on flexible substrates exhibits a desirable type-II energy band alignment, which facilitates effective spatial separation of photoexcited carriers. The device exhibits excellent photoresponsivity values of >10⁵ A W⁻¹ at 457 nm, and broadband photoresponse (457–1064 nm). By operating the device in the depletion regime, the specific detectivity is found to be 5.1 × 10¹⁶ Jones, which is the record high value among all PVK-based photodetectors reported to date. Due to the resistive hopping barrier in the quasi-2D PVK, the device can also work as an optoelectronic memory for near-infrared information storage. More importantly, the easy manufacturing process is highly beneficial, enabling large-scale and uniform quasi-2D PVK/IGZO hybrid films for detector arrays with outstanding ambient and operation stabilities. All these findings demonstrate the device architecture here provides a rational avenue to the design of next-generation flexible photodetectors with unprecedented sensitivity.     

Perovskite/Organic Bulk‐Heterojunction Integrated Ultrasensitive Broadband Photodetectors with High Near‐Infrared External Quantum Efficiency over 70%

Ultraviolet‐visible‐near infrared (UV‐Vis‐NIR) broadband detection is important for image sensing, communication, and environmental monitoring, yet remains as a challenge in achieving high external quantum efficiency (EQE) in the broad spectrum range. Herein, sensitive broadband integrated photodetectors (PDs) with high EQE levels are reported. The organic bulk‐heterojunction (OBHJ) layer, based on a NIR sensitive organic acceptor, is employed to extend the response spectrum of the perovskite PDs. A key strategy of introducing dual electron transport materials respectively for Vis and NIR regions into the active layer of integrated PDs is applied. Further combined with the proper energy level alignment and reasonable distribution of PC₆₁BM in the active layer, the extraction and transport of photo induced charges in between perovskite and OBHJ is promoted efficiently. The integrated PD with the optimized structure exhibits an EQE mostly beyond 70% in the Vis–NIR region, which is the highest value among the ever reported solution‐processable broadband PDs. The highest responsivity is 0.444 and 0.518 A W^?1 in the Vis and NIR region, respectively. The specific detectivity is beyond 10¹⁰ Jones in the range from 340 to 940 nm, enabling the device to detect weak signals in the UV to NIR broad region.     

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.     

Molecular Synergistic Passivation for Efficient Perovskite Solar Cells and Self-Powered Photodetectors

The interface between the perovskite and electron-transporting material is often treated for defect passivation to improve the photovoltaic performance of devices. A facile 4-Acetamidobenzoic acid (containing an acetamido, a carboxyl, and a benzene ring)-based molecular synergistic passivation (MSP) strategy is developed here to engineer the SnO_x/perovskite interface, in which dense SnO_x are prepared using an E-beam evaporation technology while the perovskite is deposited with vacuum flash evaporation deposition method. MSP engineering can synergistically passivate defects at the SnO_x/perovskite interface by coordinating with Sn⁴⁺ and Pb²⁺ with functional group  CO in the acetamido and carboxyl. The optimized solar cell devices can achieve the highest efficiency of 22.51% based on E-Beam deposited SnO_x and 23.29% based on solution-processed SnO₂, respectively, accompanied by excellent stability exceeding 3000 h. Further, the self-powered photodetectors exhibit a remarkably low dark current of 5.22 × 10⁻⁹ A cm⁻², a response of 0.53 A W⁻¹ at zero bias, a detection limit of 1.3 × 10¹³ Jones, and a linear dynamic range up to 80.4 dB. This work proposes a molecular synergistic passivation strategy to enhance the efficiency and responsivity of solar cells and self-powered photodetectors.     

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.     

Highly Sensitive,Fast Response Perovskite Photodetectors Demonstrated in Weak Light Detection Circuit and Visible Light Communication System

Organic–inorganic hybrid perovskite (OIHP) photodetectors have presented unprecedented device performance mainly owing to outstanding material properties. However, the solution‐processed OIHP polycrystalline thin films with defective surface and grain boundaries always impair the key parameter of photodetectors. Herein, a nonfullerene passivation layer exhibits more efficient passivation for OIHP materials to dramatically reduce the trap density of state, yielding a dark current as low as 2.6 × 10^?8 A cm^?2 under ?0.1 V. In addition, the strong absorption in near‐infrared (NIR) region of nonfullerene/C₆₀ heterojunction broadens the detectable range to over 900 nm by effective charge transport, ultimately leading to a specific detectivity of 1.45 × 10¹² and 7.37 × 10¹¹ cm Hz^1/2 W^?1 at 650 and 820 nm, respectively. Encouragingly, the response speed of 27 ns is obtained at 0.6 mm² of device area by removing constrain from the resistance–capacitance constant. Moreover, the prominent practical application of the photodetector is demonstrated in a weak light detection circuit and a visible light communication system. It is believed that the OIHP photodetectors with high sensitivity, NIR photoresponse, and ultrafast speed would pave the way to commercial applications.     

Broadband Light Absorption and Efficient Charge Separation Using a Light Scattering Layer with Mixed Cavities for High‐Performance Perovskite Photovoltaic Cells with Stability

CH₃NH₃PbI₃ is one of the promising light sensitizers for perovskite photovoltaic cells, but a thick layer is required to enhance light absorption in the long‐wavelength regime ranging from PbI₂ absorption edge (500 nm) to its optical band‐gap edge (780 nm) in visible light. Meanwhile, the thick perovskite layer suppresses visible‐light absorption in the short wavelengths below 500 nm and charge extraction capability of electron–hole pairs produced upon light absorption. Herein, we find that a new light scattering layer with the mixed cavities of sizes in 100 and 200 nm between transparent fluorine‐doped tin oxide and mesoporous titanium dioxide electron transport layer enables full absorption of short‐wavelength photons (λ < 500 nm) to the perovskite along with enhanced absorption of long‐wavelength photons (500 nm < λ < 780 nm). Moreover, the light‐driven electric field is proven to allow efficient charge extraction upon light absorption, thereby leading to the increased photocurrent density as well as the fill factor prompted by the slow recombination rate. Additionally, the photocurrent density of the cell with a light scattering layer of mixed cavities is stabilized due to suppressed charge accumulation. Consequently, this work provides a new route to realize broadband light harvesting of visible light for high‐performance perovskite photovoltaic cells.     

Sensitive and Stable 2D Perovskite Single-Crystal X-ray Detectors Enabled by a Supramolecular Anchor

Perovskite X-ray detectors have been demonstrated to be sensitive to soft X-rays (<80 keV) for potential medical imaging applications. However, developing X-ray detectors that are stable and sensitive to hard X-rays (80 to 120 keV) for practical medical imaging is highly desired. Here, a sensitive 2D fluorophenethylammonium lead iodide ((F-PEA)₂PbI₄) perovskite single-crystal hard-X-ray detector from low-cost solution processes is reported. Dipole interaction of organic ions promotes the ordering of benzene rings as well as the supramolecular electrostatic interaction between electron-deficient F atoms with neighbor benzene rings. Supramolecular interactions serve as a supramolecular anchor to stabilize and tune the electronic properties of single crystals. The 2D (F-PEA)₂PbI₄ perovskite single crystal exhibits an intrinsic property with record bulk resistivity of 1.36 × 10¹² Ω cm, which brings a low device noise for hard X-ray detection. Meanwhile, the ion-migration phenomenon is effectively suppressed, even under the large applied bias of 200 V, by blocking the ion migration paths after anchoring. Consequently, the (F-PEA)₂PbI₄ single crystal detector yields a sensitivity of 3402 μC Gy⁻¹air cm⁻² to 120 keV_p hard X-rays with lowest detectable X-ray dose rate of 23 nGy_air s⁻¹, outperforming the dominating CsI scintillator of commercial digital radiography systems by acquiring clear X-ray images under much lower dose rate. In addition, the detector shows high operation stability under extremely high-flux X-ray irradiation.     

Metal‐Halide Perovskites for Gate Dielectrics in Field‐Effect Transistors and Photodetectors Enabled by PMMA Lift‐Off Process

Metal‐halide perovskites have emerged as promising materials for optoelectronics applications, such as photovoltaics, light‐emitting diodes, and photodetectors due to their excellent photoconversion efficiencies. However, their instability in aqueous solutions and most organic solvents has complicated their micropatterning procedures, which are needed for dense device integration, for example, in displays or cameras. In this work, a lift‐off process based on poly(methyl methacrylate) and deep ultraviolet lithography on flexible plastic foils is presented. This technique comprises simultaneous patterning of the metal‐halide perovskite with a top electrode, which results in microscale vertical device architectures with high spatial resolution and alignment properties. Hence, thin‐film transistors (TFTs) with methyl‐ammonium lead iodide (MAPbI₃) gate dielectrics are demonstrated for the first time. The giant dielectric constant of MAPbI₃ (>1000) leads to excellent low‐voltage TFT switching capabilities with subthreshold swings ≈80 mV decade^?1 over ≈5 orders of drain current magnitude. Furthermore, vertically stacked low‐power Au‐MAPbI₃‐Au photodetectors with close‐to‐ideal linear response (R² = 0.9997) are created. The mechanical stability down to a tensile radius of 6 mm is demonstrated for the TFTs and photodetectors, simultaneously realized on the same flexible plastic substrate. These results open the way for flexible low‐power integrated (opto‐)electronic systems based on metal‐halide perovskites.