Combinatorial screening of halide perovskite thin films and solar cells by mask-defined IR laser molecular beam epitaxy.

As an extension of combinatorial molecular layer epitaxy via ablation of perovskite oxides by a pulsed excimer laser, we have developed a laser molecular beam epitaxy (MBE) system for parallel integration of nano-scaled thin films of organic-inorganic hybrid materials. A pulsed infrared (IR) semiconductor laser was adopted for thermal evaporation of organic halide (A-site: CH3NH3I) and inorganic halide (B-site: PbI2) powder targets to deposit repeated A/B bilayer films where the thickness of each layer was controlled on molecular layer scale by programming the evaporation IR laser pulse number, length, or power. The layer thickness was monitored with an in situ quartz crystal microbalance and calibrated against ex situ stylus profilometer measurements. A computer-controlled movable mask system enabled the deposition of combinatorial thin film libraries, where each library contains a vertically homogeneous film with spatially programmable A- and B-layer thicknesses. On the composition gradient film, a hole transport Spiro-OMeTAD layer was spin-coated and dried followed by the vacuum evaporation of Ag electrodes to form the solar cell. The preliminary cell performance was evaluated by measuring I-V characteristics at seven different positions on the 12.5 mm × 12.5 mm combinatorial library sample with seven 2 mm × 4 mm slits under a solar simulator irradiation. The combinatorial solar cell library clearly demonstrated that the energy conversion efficiency sharply changes from nearly zero to 10.2% as a function of the illumination area in the library. The exploration of deposition parameters for obtaining optimum performance could thus be greatly accelerated. Since the thickness ratio of PbI2 and CH3NH3I can be freely chosen along the shadow mask movement, these experiments show the potential of this system for high-throughput screening of optimum chemical composition in the binary film library and application to halide perovskite solar cell.

Development of a new laser heating system for thin film growth by chemical vapor deposition.

We have developed a new laser heating system for thin film growth by chemical vapor deposition (CVD). A collimated beam from a high-power continuous-wave 808 nm semiconductor laser was directly introduced into a CVD growth chamber without an optical fiber. The light path of the heating laser inside the chamber was isolated mechanically from the growth area by bellows to protect the optics from film coating. Three types of heat absorbers, (10 × 10 × 2 mm(3)) consisting of SiC, Ni/NiO(x), or pyrolytic graphite covered with pyrolytic BN (PG/PBN), located at the backside of the substrate, were tested for heating performance. It was confirmed that the substrate temperature could reach higher than 1500 °C in vacuum when a PG/PBN absorber was used. A wide-range temperature response between 400 °C and 1000 °C was achieved at high heating and cooling rates. Although the thermal energy loss increased in a H(2) gas ambient due to the higher thermal conductivity, temperatures up to 1000 °C were achieved even in 200 Torr H(2). We have demonstrated the capabilities of this laser heating system by growing ZnO films by metalorganic chemical vapor deposition. The growth mode of ZnO films was changed from columnar to lateral growth by repeated temperature modulation in this laser heating system, and consequently atomically smooth epitaxial ZnO films were successfully grown on an a-plane sapphire substrate.

Communication: The reason why +c ZnO surface is less stable than -c ZnO surface: first-principles calculation.

It has been experimentally shown that an O(-c)-polar ZnO surface is more stable than a Zn(+c)-polar surface in H(2) ambient. We applied first-principles calculations to investigating the polarity dependence on the stability at the electronic level. The calculations revealed that the -c surface terminated with H atom was stable maintaining a wurtzite structure, whereas the +c surface was unstable due to the change of coordination numbers of Zn at the topmost surface from four (wurtzite) to six (rock salt). This causes the generation of O(2) molecules, resulting in instability at the +c surface.

High-performance organic field-effect transistors based on pi-extended tetrathiafulvalene derivatives.

Aromatic ring-condensed TTF derivatives exhibited excellent p-type FET performances in thin films. Introduction of fused benzene and pyrazine rings to the TTF skeleton was effective to enhance the intermolecular interactions and stability to oxygen. Ordered molecular alignment was confirmed by XRD studies. A pi-stacking structure was observed in the single crystal of diquinoxalinoTTF.

Crystal-face dependences of surface band edges and hole reactivity, revealed by preparation of essentially atomically smooth and stable (110) and (100) n-TiO(2) (rutile) surfaces.

Essentially atomically smooth (100) and (110) n-TiO(2) (rutile) surfaces were prepared by immersion of commercially available single-crystal wafers in 20% HF, followed by annealing at 600 degrees C in air. The obtained surfaces were stable in aqueous solutions of pH 1-13, showing no change in the surface morphology on an atomic level, contrary to atomically flat surfaces prepared by ion sputtering and annealing under UHV. The success in preparation of the atomically smooth and stable n-TiO(2) surfaces enabled us to reveal clear crystal-face dependences of the surface band edges and hole reactivity in aqueous solutions.

Combinatorial solid-state chemistry of inorganic materials.

Throughout history, scientists and engineers have relied on the slow and serendipitous trial-and-error process for discovering and developing new materials. In contrast, an emerging theme in modern materials science is the notion of intelligent design of materials. Pioneered by the pharmaceutical industry and adapted for the purposes of materials science and engineering, the combinatorial approach represents a watershed in the process of accelerated discovery, development and optimization of materials. To survey large compositional landscapes rapidly, thousands of compositionally varying samples may be synthesized, processed and screened in a single experiment. Recent developments have been aided by innovative rapid characterization tools, and by advanced materials synthesis techniques such as laser molecular beam epitaxy which can be used to perform parallel-processed design and control of materials down to the atomic scale. Here we review the fast-growing field of combinatorial materials science, with an emphasis on inorganic functional materials.

Anomalous Hall effect governed by electron doping in a room-temperature transparent ferromagnetic semiconductor.

Ferromagnetic semiconductors are believed to be suitable for future spintronics, because both charge and spin degrees of freedom can be manipulated by external stimuli. One of the most important characteristics of ferromagnetic semiconductors is the anomalous Hall effect. This is because the ferromagnetically spin-polarized carrier can be probed and controlled electrically, leading to direct application for electronics. Control of the Curie temperature and magnetization direction by electronic field, and photo-induced ferromagnetism have been performed successfully using the anomalous Hall effect for group III-V ferromagnetic semiconductors. In these cases, the operation temperature was much below room temperature because of the limited Curie temperature of less than 160 K (ref. 6). Here, we report on the anomalous Hall effect governed by electron doping in a room-temperature transparent ferromagnetic semiconductor, rutile Ti(1-x)Co(x)O(2-delta) (of oxygen deficiency delta). This result manifests the intrinsic nature of ferromagnetism in this compound, and represents the possible realization of transparent semiconductor spintronics devices operable at room temperature.