Kohei Miura

Reaction of N,N’-dimethylformamide and divalent viologen molecule to generate an organic dopant for molybdenum disulfide

Tuning the carrier concentration is essential for semiconducting materials to apply optoelectronic devices. Molybdenum disulfide (MoS2) is a semiconducting material composed of atomically thin (∼0.7 nm thickness) layers. To dope thin MoS2, instead of using conventional atom/ion injection processes, a surface charge transfer method was successfully applied. In this study, we report a simple preparation method of a molecular dopant applicable to the doping process. The method follows a previous report for producing a molecular dopant, benzyl viologen (BV) which shows electron doping to MoS2. To prepare dopant BV molecules, a reduction process with a commercially available divalent BV by sodium borohydride (NaBH4) is required; however, the reaction requires a large consumption of NaBH4. NaBH4 drastically reacts with the solvent water itself. We found a reaction process of BV in an organic solvent, N,N’-dimethylformamide (DMF), by adding a small amount of water dissolving the divalent BV. The reaction is mild (at room temperature) and is autonomous once DMF comes into contact with the divalent BV aqueous solution. The reaction can be monitored with a UV-Vis spectrometer, and kinetic analysis indicates two reaction steps between divalent/monovalent/neutral viologen isomers. The product was soluble in toluene and did not dissolve in water, indicating it is similar to the reported dopant BV. The synthesized molecule was found to act as a dopant for MoS2 by applying a metal-oxide-semiconductor field-effect-transistor (MOSFET) structure. The process is a general method and applicable to other viologen-related dopants to tune the electronic structure of 2D materials to facilitate generating atomically thin devices.

Tuning Transition-Metal Dichalcogenide Field-Effect Transistors by Spontaneous Pattern Formation of an Ultrathin Molecular Dopant Film

Spontaneous pattern formation is an energetically favorable process and is shown in nature in molecular-scale assembly, biological association, and soft material organizations. The opposite regime, the artificial process, which is widely applied to the fabrication of semiconducting devices, such as lithographic techniques, requires enormous amounts of energy. Here, we propose a concept of tuning the properties of semiconducting MoS2 and WSe2 devices using the spontaneous pattern formation of adjacent molecular films. The film used was a 10 nm thick ultrathin film of a molecular electron dopant, which exhibited spontaneous pattern formation and dynamically transformed the morphology of tiny holes, a network, a maze, and dots on substrates, including SiO2, MoS2, and WSe2. These patterns were exhibited only when the film came in contact with water and was tuned with temperature and time. The specific lengths of the patterns were less than 200 nm, which is sufficiently smaller than the exfoliated ∼10 μm semiconducting MoS2 and WSe2 flakes. The properties of the field-effect devices of MoS2 and WSe2 were found to be modified according to the pattern formation process of the ultrathin molecular film on the device. This concept applies the spontaneous patterning phenomena shown in nature to the fabrication and optimization of electronic devices by using molecular films and their responses to the external environment.

Origin of the photoinduced current of strongly correlated YMnO3 ferroelectric epitaxial films

We have studied the photoinduced carrier generation and the carrier emission resulting in a photoinduced current using strongly correlated YMnO3 ferroelectric thin films. The unipolar material YMnO3 is suitable for studying the effect of the ferroelectric polarization on the photoinduced current. A clear relationship between the direction of the polarization and the photoinduced current was recognized using (0001)YMnO3 epitaxial films. The current switching corresponding to the polarization switching is also observed under white light illumination. To study the origin of the photoinduced current that originated from the photoinduced carrier generation, the light energy dependence of the photoinduced current was investigated. A small peak at 1.75 eV and a broad peak at around 2.5 eV are observed at room temperature. The peak at 1.75 eV corresponds to the optical absorption at 1.7 eV generated by the electron transition between the Mn 3d (e2g state)/O 2p hybridized band and upper Mn 3d (3z 2 − r 2) (a1g state) orbital. The broad peak of the photoinduced current corresponds to the broad photoluminescence excitation spectrum at around 2.5 eV, which is never observed in absorption measurement but reported as the hidden optical channel. The origin of the photoinduced current of YMnO3 is discussed in relation to the carrier generation and the emission processes.