The fields of photovoltaics, photodetection and light emission have seen tremendous activity in recent years with the advent of hybrid organic-inorganic perovskites. Yet, there have been far fewer reports of perovskite-based field-effect transistors. The lateral and interfacial transport requirements of transistors make them particularly vulnerable to surface contamination and defects rife in polycrystalline films and bulk single crystals. Here, we demonstrate a spatially-confined inverse temperature crystallization strategy which synthesizes micrometre-thin single crystals of methylammonium lead halide perovskites MAPbX3 (X = Cl, Br, I) with sub-nanometer surface roughness and very low surface contamination. These benefit the integration of MAPbX3 crystals into ambipolar transistors and yield record, room-temperature field-effect mobility up to 4.7 and 1.5 cm2 V−1 s−1 in p and n channel devices respectively, with 104 to 105 on-off ratio and low turn-on voltages. This work paves the way for integrating hybrid perovskite crystals into printed, flexible and transparent electronics.

Organolead trihalide perovskites have attracted significant attention for optoelectronic applications due to their excellent physical properties in the past decade. Generally, both grain boundaries in perovskite films and the device structure play key roles in determining the device performance, especially for horizontal‐structured device. Here, the first optimized vertical‐structured photodetector with the perovskite single crystal MAPbBr3 as the light absorber and graphene as the transport layer is shown. The hybrid device combines strong photoabsorption characteristics of perovskite and high carrier mobility of flexible graphene, exhibits excellent photoresponse performance with high photoresponsivity (≈1017.1 A W−1) and high photodetectivity (≈2.02 × 1013 Jones) in a low light intensity (0.66 mW cm−2) under the actuations of 3 V bias and laser irradiation at 532 nm. In particular, an ultrahigh photoconductive gain of ≈2.37 × 103 is attained because of fast charge transfer in the graphene and large recombination lifetime in the perovskite single crystal. The vertical architecture combining perovskite crystal with highly conductive graphene offers opportunities to fulfill the synergistic effect of perovskite and 2D materials, is thus promising for developing high‐performance electronic and optoelectronic devices.

Despite its extensive research in photovoltaics and light emitting diodes, the charge transport properties of all‐inorganic perovskite cesium lead bromide (CsPbBr3) remain elusive. Clarification of the intrinsic charge transport of this perovskite material is highly desirable, which will help to understand its working mechanism and fabricate high performance electronic devices. Here, it is demonstrated that the phototransistors based on CsPbBr3 microplates show anomalous ambipolar transport characteristics at room temperature. The hole mobility shows light dependence, while the electron mobility is identical under various light incidence. The hole mobility increases from 0.02 cm2 V−1 s−1 (in dark conditions) to 0.34 cm2 V−1 s−1 (50 mW cm−2); while the threshold voltage is shifted by 14 V when electron is the majority charge carrier. The anomalous transport behavior can be attributed to the photovoltaic and photoconductive effects. Moreover, the device shows photoresponsivity and detectivity up to 110 mA W−1 and 4.5 × 1013 Jones, respectively, under 532 nm laser illumination. This research unveils the charge transport mechanism of CsPbBr3 perovskite, provides more evidence and will thus contribute to the perovskite electronic and optoelectronic researches.