The photocurrent generation in photovoltaics relies essentially on the interface of p-n junction or Schottky barrier with the photoelectric efficiency constrained by the Shockley-Queisser limit. The recent progress has shown a promising route to surpass this limit via the bulk photovoltaic effect for crystals without inversion symmetry. Here we report the bulk photovoltaic effect in two-dimensional ferroelectric CuInP2S6 with enhanced photocurrent density by two orders of magnitude higher than conventional bulk ferroelectric perovskite oxides. The bulk photovoltaic effect is inherently associated to the room-temperature polar ordering in two-dimensional CuInP2S6. We also demonstrate a crossover from two-dimensional to three-dimensional bulk photovoltaic effect with the observation of a dramatic decrease in photocurrent density when the thickness of the two-dimensional material exceeds the free path length at around 40 nm. This work spotlights the potential application of ultrathin two-dimensional ferroelectric materials for the third-generation photovoltaic cells.
We have investigated systematically the morphology of thin films spin-coated from solutions of a semicrystalline diblock copolymer, poly(L-lactic acid)-block-polystyrene (PLLA-b-PS), in solvents with varying selectivity. In neutral solvents (chloroform and tetrahydrofuran (THF)), a spinodal-like pattern was obtained and the pattern boundary was sharpened by diluting the solution. Meanwhile, loose spherical associates, together with larger aggregates composed of these associates by unimer bridges, formed partly due to crystallization of the PLLA blocks in relatively concentrated solutions. In slightly PS-selective solvent (e.g., benzene), both loose and compact spherical micelles were obtained, depending on the polymer concentration, coexisting with unimers. When enhancing the selectivity with mixed solvents, for example, mixing the neutral solvent and the slightly selective solvent with a highly PS-selective solvent, CS 2, loose assemblies (nanorods in CS2/THF mixtures and polydisperse aggregates in CS2/benzene mixtures) and well-developed lamellar micelles were obtained. For the lamellar micelles observed, a collapsed corona model is proposed to describe the geometry of dry platelets spin-coated on the substrates instead of the swollen coils in solutions.
Two-dimensionally ordered honeycomb structures have been prepared on dodecanethiol-capped gold nanoparticle films by blowing moist air across the surface of the nanoparticle solution. The pore morphology can be altered from circle to ellipse with tunable aspect ratios by carefully controlling the direction and velocity of airflow. The formation mechanisms of different surface morphologies have been discussed in terms of the surface and interfacial tension.
Ordered macroporous materials recently have attracted much attention. A method that utilizes the condensation of monodisperse water droplets on a polymer solution is proposed for the preparation of honeycomb microporous films. Our results show that it is a general method that can be used for patterning a wide range of polymers. The presence of water vapor and polymer is necessary for the formation of regular holes in films. The formation of hexagonal packing instead of other kinds of packing takes place because the hexagonal packing has the lowest free energy. The formation mechanisms of regular hole pattern and imperfections in the hexagonal packing are proposed.Hexagonal hole structures in a PMMA film.magnified imageHexagonal hole structures in a PMMA film.
Room-temperature ferroelectricity in two-dimensional materials offer a potential route for developing atomic-scale functional devices beyond Moore's law.However, as a key for the technology implementations of ferroelectrics in electronics, the controllable generation of uniform domains remains challenging in two-dimensional ferroelectrics at current stage because domain engineering through an external electric field at 2D limit inevitably leads to large leakage current and material break-down. Here, we demonstrate a voltage-free method, the flexoelectric effect, to artificially generate largescale stripe domains in two-dimensional ferroelectric CuInP2S6 with single domain lateral size at the scale of several hundred microns. With giant strain gradients (~10 6 m -1 ) at nanoscale, we mechanically switch the out-of-plane polarization in ultrathin CuInP2S6. The flexoelectric control of ferroelectric polarization is understood with a distorted Landau-Ginzburg-Devonshire double well model as evidenced by the shifted ferroelectric hysteresis loops and the first-principle calculations. Through substrate mechanical strain engineering, the stripe domain density is controllable. Our results not only highlight the potential of developing van der Waals ferroelectrics-based memories but also offer the opportunity to study ferroelectric domain physics in two-dimensional materials.
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