Ternary two‐dimensional (2D) semiconductors with controllable wide bandgap, high ultraviolet (UV) absorption coefficient, and critical tuning freedom degree of stoichiometry variation have a great application prospect for UV detection. However, as‐reported ternary 2D semiconductors often possess a bandgap below 3.0 eV, which must be further enlarged to achieve comprehensively improved UV, especially deep‐UV (DUV), detection capacity. Herein, sub‐one‐unit‐cell 2D monolayer BiOBr nanoflakes (≈0.57 nm) with a large size of 70 µm are synthesized for high‐performance DUV detection due to the large bandgap of 3.69 eV. Phototransistors based on the 2D ultrathin BiOBr nanoflakes deliver remarkable DUV detection performance including ultrahigh photoresponsivity (Rλ, 12739.13 A W−1), ultrahigh external quantum efficiency (EQE, 6.46 × 106%), and excellent detectivity (D*, 8.37 × 1012 Jones) at 245 nm with a gate voltage (Vg) of 35 V attributed to the photogating effects. The ultrafast response (τrise = 102 µs) can be achieved by utilizing photoconduction effects at Vg of −40 V. The combination of photocurrent generation mechanisms for BiOBr‐based phototransistors controlled by Vg can pave a way for designing novel 2D optoelectronic materials to achieve optimal device performance.

The ultrabroadband spectrum detection from ultraviolet (UV) to long‐wavelength infrared (LWIR) is promising for diversified optoelectronic applications of imaging, sensing, and communication. However, the current LWIR‐detecting devices suffer from low photoresponsivity, high cost, and cryogenic environment. Herein, a high‐performance ultrabroadband photodetector is demonstrated with detecting range from UV to LWIR based on air‐stable nonlayered ultrathin Fe3O4 nanosheets synthesized via a space‐confined chemical vapor deposition (CVD) method. Ultrahigh photoresponsivity (R) of 561.2 A W−1, external quantum efficiency (EQE) of 6.6 × 103%, and detectivity (D*) of 7.42 × 108 Jones are achieved at the wavelength of 10.6 µm. The multimechanism synergistic effect of photoconductive effect and bolometric effect demonstrates the high sensitivity for light with any light intensities. The outstanding device performance and complementary mixing photoresponse mechanisms open up new potential applications of nonlayered 2D materials for future infrared optoelectronic devices.

2D planar structures of nonlayered wide‐bandgap semiconductors enable distinguished electronic properties, desirable short wavelength emission, and facile construction of 2D heterojunction without lattice match. However, the growth of ultrathin 2D nonlayered materials is limited by their strong covalent bonded nature. Herein, the synthesis of ultrathin 2D nonlayered CuBr nanosheets with a thickness of about 0.91 nm and an edge size of 45 µm via a controllable self‐confined chemical vapor deposition method is described. The enhanced spin‐triplet exciton (Zf, 2.98 eV) luminescence and polarization‐enhanced second‐harmonic generation based on the 2D CuBr flakes demonstrate the potential of short‐wavelength luminescent applications. Solar‐blind and self‐driven ultraviolet (UV) photodetectors based on the as‐synthesized 2D CuBr flakes exhibit a high photoresponsivity of 3.17 A W−1, an external quantum efficiency of 1126%, and a detectivity (D*) of 1.4 × 1011 Jones, accompanied by a fast rise time of 32 ms and a decay time of 48 ms. The unique nonlayered structure and novel optical properties of the 2D CuBr flakes, together with their controllable growth, make them a highly promising candidate for future applications in short‐wavelength light‐emitting devices, nonlinear optical devices, and UV photodetectors.