Nobuo Ueno

We identify a universality in the Fermi level change of Van der Waals interacting semiconductor interfaces-based Schottky junctions. We show that the disappearing of quasi-Fermi level pinning at a certain thickness of semiconductor films for both intrinsic (undoped) and extrinsic (doped) semiconductors, over a wide range of bulk systems including inorganic, organic, and even organic-inorganic hybridized semiconductors. The Fermi level (EF) position located in the energy bandgap was dominated by not only the substrate work function, but also the thickness of semiconductor films, in which the final EF shall be located at the position reflecting the thermal equilibrium of semiconductors themselves. Such universalities originate from the charge transfer between the substrate and semiconductor films after solving one-dimensional Poisson's equation. Our calculation resolves some of the conflicting results from experimental results determined by using ultraviolet photoelectron spectroscopy (UPS) and unifies the general rule on extracting EF positions in energy bandgaps from (i) inorganic semiconductors to organic semiconductors and (ii) intrinsic (undoped) to extrinsic (doped) semiconductors. Our findings shall provide a simple analytical scaling for obtaining the quantitative energy diagram regarding thickness in the real devices, thus paving the way for a fundamental understanding of interface physics and designing functional devices.

Metal halide perovskites are one of the most promising materials for optoelectronic applications owing to their unique optoelectronic properties. In the pursuit of achieving the efficient perovskite light‐emitting diodes (PeLEDs), the critical role of crystallization dynamics on luminescence properties of cesium lead bromide (CsPbBr₃) perovskite films has been clarified based on the characterizations of in situ photoelectron spectroscopy, synchrotron‐based grazing incidence X‐ray diffraction, and device fabrication. The crystallinity and crystal orientation of CsPbBr₃ perovskite films has been effectively controlled when tuning the underlayer of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) with the ethanolamine modification. The fast crystallization with the formation of pure cubic phase (α‐CsPbBr₃) reveals a substantial boost in luminance and device efficiency of PeLEDs, whereas the performance degradation occurs due to the phase transition from α‐CsPbBr₃ to orthogonal phase (γ‐CsPbBr₃) along with the appearance of PbBr₂. The decomposition of organic additives in the perovskite films is a key factor that results in this phase transition, which changes the absorption and band gap as confirmed by the density functional theory calculation. These experimental and theoretical findings provide a better understanding of the crystallization dynamics of perovskite emitters and their influence on device performance by tuning the substrate properties.

The conduction band dispersion in methylammonium lead iodide (CH₃NH₃PbI₃) was studied by both angle-resolved two-photon photoelectron spectroscopy (AR-2PPE) with low photon intensity (∼0.0125 nJ/pulse) and angle-resolved low-energy inverse photoelectron spectroscopy (AR-LEIPS). Clear energy dispersion of the conduction band along the Γ-M direction was first observed by these independent methods under different temperatures, and the dispersion was found to be consistent with band calculation under the cubic phase. The effective mass of the electrons at the Γ point was estimated to be (0.20 ± 0.05)m₀ at the temperature of 90 K. The observed conduction band energy was different between the AR-LEIPS and AR-2PPE, which was ascribed to the electronic-correlation-dependent difference of initial and final states probing processes. The present results also indicate that the surface structure in CH₃NH₃PbI₃ provides the cubic-dominated electronic property even at lower temperatures.

The conduction band structure in methylammonium lead iodide (CH3NH3PbI3) was studied both by angle-resolved two-photon photoemission spectroscopy (AR-2PPE) with low-photon intensity and angle-resolved low-energy inverse photoelectron spectroscopy (AR-LEIPS). Clear energy dispersion of the conduction band along the {\Gamma}M direction was observed by these independent methods under different temperatures, and the dispersion was found to be consistent with band calculations under the cubic phase. The effective mass of the electrons at the {\Gamma} point was estimated to be (0.20+-0.05)m0 at 90 K. The observed energy position was largely different between the AR-LEIPS and AR-2PPE, demonstrating the electron correlation effects on the band structures. The present results also indicate that the surface structure in CH3NH3PbI3 provides the cubic-dominated electronic property even at lower temperatures.

Methodologies and experimental achievements for exploration into electronic band structures of organic semiconductor and hybrid perovskite single crystals are reviewed.

Doped organic semiconductors typically exhibit a thermal activation of their electrical conductivity, whose physical origin is still under scientific debate. In this study, we disclose relationships between molecular parameters and the thermal activation energy (E_A) of the conductivity, revealing that charge transport is controlled by the properties of host–dopant integer charge transfer complexes (ICTCs) in efficiently doped organic semiconductors. At low doping concentrations, charge transport is limited by the Coulomb binding energy of ICTCs, which can be minimized by systematic modification of the charge distribution on the individual ions. The investigation of a wide variety of material systems reveals that static energetic disorder induced by ICTC dipole moments sets a general lower limit for E_A at large doping concentrations. The impact of disorder can be reduced by adjusting the ICTC density and the intramolecular relaxation energy of host ions, allowing an increase of conductivity by many orders of magnitude.

Solar cells incorporating organic–inorganic perovskites, especially methylammonium lead iodide (CH₃NH₃PbI₃), have recently shown remarkable performances and therefore attracted wide interest. For understanding the origin of the high performance, the effective charge carrier masses of CH₃NH₃PbI₃ are critical. However, reliable experimental data on its electronic band structure, which determines the effective mass, is yet to be provided. Here, the electronic structure of CH₃NH₃PbI₃ single crystals is studied by using angle‐resolved photoelectron spectroscopy on cleaved crystal surfaces after characterizing the surface structure by low‐energy electron diffraction. Coexisting cubic and tetragonal phases of CH₃NH₃PbI₃ are found in diffraction patterns. Moreover, a clear band dispersion of the top valence band is observed along directions parallel to different high‐symmetry points of the cubic structure, in consistence with theoretical calculations. Based on these values, the effective hole mass is then estimated to be 0.24(±0.10)m₀ around the M point and 0.35(±0.15)m₀ around the X point, which are significantly lower than in organic semiconductors. These results reveal the physical origin of the high performance of solar cells incorporating perovskite materials compared to pure organic semiconductors.