Rhombohedral-stacked transition-metal dichalcogenides (3R-TMDs), which are distinct from their hexagonal counterparts, exhibit higher carrier mobility, sliding ferroelectricity, and coherently enhanced nonlinear optical responses. However, surface epitaxial growth of large multilayer 3R-TMD single crystals is difficult. We report an interfacial epitaxy methodology for their growth of several compositions, including molybdenum disulfide (MoS ₂ ), molybdenum diselenide, tungsten disulfide, tungsten diselenide, niobium disulfide, niobium diselenide, and molybdenum sulfoselenide. Feeding of metals and chalcogens continuously to the interface between a single-crystal Ni substrate and grown layers ensured consistent 3R stacking sequence and controlled thickness from a few to 15,000 layers. Comprehensive characterizations confirmed the large-scale uniformity, high crystallinity, and phase purity of these films. The as-grown 3R-MoS ₂ exhibited room-temperature mobilities up to 155 and 190 square centimeters per volt second for bi- and trilayers, respectively. Optical difference frequency generation with thick 3R-MoS ₂ showed markedly enhanced nonlinear response under a quasi–phase matching condition (five orders of magnitude greater than monolayers).

Optical phase matching involves establishing a proper phase relationship between the fundamental excitation and generated waves to enable efficient optical parametric processes. It is typically achieved through birefringence or periodic polarization. Here, we report that the interlayer twist angle in two-dimensional (2D) materials creates a nonlinear geometric phase that can compensate for the phase mismatch, and the vertical assembly of the 2D layers with a proper twist sequence generates a nontrivial “twist-phase-matching” (twist-PM) regime. The twist-PM model provides superior flexibility in the design of optical crystals, which can be applied for twisted layers with either periodic or random thickness distributions. The designed crystal from the twisted rhombohedral boron nitride films within a thickness of only $3.2\mathrm{\mu }\mathrm{m}$ is capable of producing a second-harmonic generation with conversion efficiency of $\sim 8\%$ and facile polarization controllability that is absent in conventional crystals. Our methodology establishes a platform for the rational design and atomic manufacturing of nonlinear optical crystals based on abundant 2D materials.

The anomalous photovoltaic effect (APE) in polar crystals is a promising avenue for overcoming the energy conversion efficiency limits of conventional photoelectric devices utilizing p-n junction architectures. To facilitate effective photocarrier separation and enhance the APE, polar materials need to be thinned down to maximize the depolarization field. Here, we demonstrate Janus MoSSe monolayers (~0.67 nm thick) with strong spontaneous photocurrent generation. A photoresponsivity up to 3 mA/W, with ~ 1% external quantum efficiency and ultrafast photoresponse (~50 ps) were observed in the MoSSe device. Moreover, unlike conventional 2D materials that require careful twist alignment, the photovoltage can be further scaled up by simply stacking the MoSSe layers without the need for specific control on interlayer twist angles. Our work paves the way for the development of high-performance, flexible, and compact photovoltaics and optoelectronics with atomically engineered Janus polar materials.

One-dimensional transition metal dichalcogenides exhibiting an enhanced bulk photovoltaic effect have the potential to exceed the Shockley–Queisser limit efficiency in solar energy harvest within p - n junction architectures. However, the collective output of these prototype devices remains a challenge. We report on the synthesis of single-crystalline WS ₂ ribbon arrays with defined chirality and coherent polarity through an atomic manufacturing strategy. The chirality of WS ₂ ribbon was defined by substrate couplings into tunable armchair, zigzag, and chiral species, and the polarity direction was determined by the ribbon-precursor interfacial energy along a coherent direction. A single armchair ribbon showed strong bulk photovoltaic effect and the further integration of ~1000 aligned ribbons with coherent polarity enabled upscaling of the photocurrent.

Scalable quantum photonic devices drive the development of compact sources of entangled photons, which are pivotal for quantum communication, computing, and cryptography. In this work, we present entangled photon pair generation in rhombohedral boron nitride (r-BN), leveraging its unique optical and structural properties. Unlike conventional hexagonal boron nitride, which suffers from reduced nonlinear response due to centrosymmetric structure in even-layered stacks, r-BN features interlayer ABC stacking and maintains robust in-plane inversion symmetry. These characteristics lead to highly efficient entangled photon generation. Our system demonstrates an entangled photon pair generation rate up to 8667 Hz/(mW·mm) and offers a tunable platform for Bell state generation by simply adjusting the pump polarization, without compromising the entanglement quality or generation efficiency. The polarization entangled state is measured with a fidelity up to 94%. This advancement not only marks a significant step towards ultrathin, scalable quantum devices but also establishes r-BN as a promising candidate for on-chip integrated quantum optical applications.