Counterion Control and the Spectral Signatures of Polarons,Coupled Polarons,and Bipolarons in Doped P3HT Films

When an electron is removed from a conjugated polymer, such as poly(3-hexylthiophene-2,5-diyl) (P3HT), the remaining hole and associated change in the polymer backbone structure from aromatic to quinoidal are referred to as a polaron. Bipolarons are created by removing the unpaired electron from an already-oxidized polymer segment. In electrochemically-doped P3HT films, polarons, and bipolarons are readily observed, but in chemically-doped P3HT films, bipolarons rarely form. This is explained by studying the effects of counterion position on the formation of polarons, strongly coupled polarons, and bipolarons using both spectroscopic and X-ray diffraction experiments and time-dependent density functional theory calculations. The counterion positions control whether two polarons spin-pair to form a bipolaron or whether they strongly couple without spin-pairing are found. When two counterions lie close to the same polymer segment, bipolarons can form, with an absorption spectrum that is blueshifted from that of a single polaron. Otherwise, polarons at high concentrations do not spin-pair, but instead J-couple, leading to a redshifted absorption spectrum. The counterion location needed for bipolaron formation is accompanied by a loss of polymer crystallinity. These results explain the observed formation order of single polarons, coupled single polarons, and singlet bipolarons in electrochemically- and chemically-doped conjugated polymers.     

Silane-Mediated Expansion of Domains in Si-Doped κ-Ga2O3 Epitaxy and its Impact on the In-Plane Electronic Conduction

Unintentionally doped (001)-oriented orthorhombic κ-Ga₂O₃ epitaxial films on c-plane sapphire substrates are characterized by the presence of ≈ 10 nm wide columnar rotational domains that can severely inhibit in-plane electronic conduction. Comparing the in- and out-of-plane resistance on well-defined sample geometries, it is experimentally proved that the in-plane resistivity is at least ten times higher than the out-of-plane one. The introduction of silane during metal-organic vapor phase epitaxial growth not only allows for n-type Si extrinsic doping, but also results in the increase of more than one order of magnitude in the domain size (up to ≈ 300 nm) and mobility (highest µ ≈ 10 cm²V⁻¹s⁻¹, with corresponding lowest ρ ≈ 0.2 Ωcm). To qualitatively compare the mean domain dimension in κ-Ga₂O₃ epitaxial films, non-destructive experimental procedures are provided based on X-ray diffraction and Raman spectroscopy. The results of this study pave the way to significantly improved in-plane conduction in κ-Ga₂O₃ and its possible breakthrough in new generation electronics. The set of cross-linked experimental techniques and corresponding interpretation here proposed can apply to a wide range of material systems that suffer/benefit from domain-related functional properties.     

Room-Temperature Hydrogen Sensor with High Sensitivity and Selectivity using Chemically Immobilized Monolayer Single-Walled Carbon Nanotubes

Although semiconducting single-walled carbon nanotubes (sc-SWNTs) exhibit excellent sensing properties for various gases, commercialization is hampered by several obstacles. Among these, the difficulty in reproducibly fabricating sc-SWNT films with uniform density and thickness is the main one. Here, a facile fabrication method for sc-SWNT-based hydrogen (H₂) sensors with excellent reproducibility, high sensitivity, and selectivity against CO, CO₂, and CH₄ is reported. Uniform-density and monolayer sc-SWNT films are fabricated using chemical immobilized through the click reaction between azide-functionalized polymer-wrapped sc-SWNTs and immobilized alkyne polymer on a substrate before decorating with Pd nanoparticles (0.5–3.0 nm). The optimized sc-SWNT sensor has a high room-temperature response of 285 with the response and recovery times of 10 and 3 s, respectively, under 1% H₂ gas in air. In particular, this sensor demonstrates highly selective H₂ detection at room temperature (25 °C), compared to other gases and humidity. Therefore, the chemical immobilization of the monolayer SWNT films with reproducible and uniform density has the potential for large-scale fabrication of robust room-temperature H₂ sensors.