2D materials exhibit superior properties in electronic and optoelectronic fields. The wide demand for high‐performance optoelectronic devices promotes the exploration of diversified 2D materials. Recently, 2D covalent organic frameworks (COFs) have emerged as next‐generation layered materials with predesigned π‐electronic skeletons and highly ordered topological structures, which are promising for tailoring their optoelectronic properties. However, COFs are usually produced as solid powders due to anisotropic growth, making them unreliable to integrate into devices. Here, by selecting tetraphenylethylene monomers with photoelectric activity, elaborately designed photosensitive 2D‐COFs with highly ordered donor‐acceptor topologies are in situ synthesized on graphene, ultimately forming COF‐graphene heterostructures. Ultrasensitive photodetectors are successfully fabricated with the COFETBC–TAPT‐graphene heterostructure and exhibited an excellent overall performance with a photoresponsivity of ≈3.2 × 107 A W−1 at 473 nm and a time response of ≈1.14 ms. Moreover, due to the high surface area and the polarity selectivity of COFs, the photosensing properties of the photodetectors can be reversibly regulated by specific target molecules. The research provides new strategies for building advanced functional devices with programmable material structures and diversified regulation methods, paving the way for a generation of high‐performance applications in optoelectronics and many other fields.

Planar optical elements that can manipulate the multidimensional physical parameters of light efficiently and compactly are highly sought after in modern optics and nanophotonics. In recent years, the geometric phase, induced by the photonic spin–orbit interaction, has attracted extensive attention for planar optics due to its powerful beam shaping capability. The geometric phase can usually be generated via inhomogeneous anisotropic materials, among which liquid crystals (LCs) have been a focus. Their pronounced optical properties and controllable and stimuli‐responsive self‐assembly behavior introduce new possibilities for LCs beyond traditional panel displays. Recent advances in LC‐mediated geometric phase planar optics are briefly reviewed. First, several recently developed photopatterning techniques are presented, enabling the accurate fabrication of complicated LC microstructures. Subsequently, nematic LC‐based transmissive planar optical elements and chiral LC‐based broadband reflective elements are reviewed systematically. Versatile functionalities are revealed, from conventional beam steering and focusing, to advanced structuring. Combining the geometric phase with structured LC materials offers a satisfactory platform for planar optics with desired functionalities and drastically extends exceptional applications of ordered soft matter. Some prospects on this rapidly advancing field are also provided.

Uniform and patterned orientation of a crystallographic direction of ordered materials is of fundamental significance and of great interest for electronic and photonic applications. However, such orientation control is generally complicated and challenging with regard to inorganic and organic crystalline materials due to the occurrence of uncontrollable dislocations or defects. Achieving uniform lattice orientation in frustrated liquid-crystalline phases, like cubic blue phases, is a formidable task. Taming and tailoring the ordering of such soft, cubic lattices along predetermined or desired directions, and even imparting a prescribed pattern on lattice orientation, are more challenging, due to the entropy-domination attribute of soft matter. Herein, we disclose a facile way to realize designed micropatterning of a crystallographic direction of a soft, cubic liquid-crystal superstructure, exhibiting an alternate uniform and random orientation of the lattice crystallographic direction enabled by a photoalignment technique. Because of the rewritable trait of the photoalignment film, the pattern can be erased and rewritten on-demand by light. Such an oriented soft lattice sensitively responds to various external stimuli such as temperature, electric field, and light irradiation. Furthermore, advanced reflective photonic applications are achieved based on the patterned crystallographic orientation of the cubic blue phase, soft lattice.