The experimental mapping of the band structure of TiS3(001), by momentum resolution nanospot angle resolved photoemission, is presented. The experimental band structure, derived from angle-resolved photoemission, confirms that the top of the valence band is at the center of the Brillouin zone. This trichalcogenide has a rectangular surface Brillouin zone where the effective hole mass along the chain direction is −0.95 ± 0.09 me, while perpendicular to the chain direction, the magnitude of the effective hole mass is much lower at −0.37 ± 0.1 me. The placement of the valence band well below the Fermi level suggests that this is an n-type semiconductor.
The interfaces of layered trichalcogenide TiS3(001), with metals Au and Pt, were examined using X-ray photoemission spectroscopy. In spite of the fact that both Au and Pt are large work function metals, no evidence of Schottky barrier formation was found with this n-type semiconductor. Two- and four-terminal field-effect transistor measurements performed on exfoliated few-nm-thick TiS3 crystals using pure Au contacts indicate that Au forms an Ohmic contact on TiS3(001), with negligible contact resistance. The absence of appreciable Schottky barrier formation is attributed to strong interactions with sulfur at the metal-semiconductor interface.
The band structure of the quasi-one-dimensional transition metal trichalcogenide ZrS 3 (001) was investigated using nanospot angle resolved photoemission spectroscopy (nanoARPES) and shown to have many similarities with the band structure of TiS 3 (001). We find that ZrS 3 , like TiS 3 , is strongly n-type with the top of the valence band ∼1.9 eV below the Fermi level, at the center of the surface Brillouin zone. The nanoARPES spectra indicate that the top of the valence band of the ZrS 3 ( 001) is located at Γ. The band structure of both TiS 3 and ZrS 3 exhibit strong in-plane anisotropy, which results in a larger hole effective mass along the quasi-one-dimensional chains than perpendicular to them.
Photocurrent production
in quasi-one-dimensional (1D) transition-metal trichalcogenides, TiS3(001) and ZrS3(001), was examined using polarization-dependent
scanning photocurrent microscopy. The photocurrent intensity was the
strongest when the excitation source was polarized along the 1D chains
with dichroic ratios of 4:1 and 1.2:1 for ZrS3 and TiS3, respectively. This behavior is explained by symmetry selection
rules applicable to both valence and conduction band states. Symmetry
selection rules are seen to be applicable to the experimental band
structure, as is observed in polarization-dependent nanospot angle-resolved
photoemission spectroscopy. Based on these band symmetry assignments,
it is expected that the dichroic ratios for both materials will be
maximized using excitation energies within 1 eV of their band gaps,
providing versatile polarization sensitive photodetection across the
visible spectrum and into the near-infrared.
The increasing interest in spin-based electronics has led to a vigorous search for new materials that can provide a high degree of spin polarization in electron transport. An ideal candidate would act as an insulator for one spin channel and a conductor or semiconductor for the opposite spin channel, corresponding to the respective cases of half-metallicity and spin-gapless semiconductivity. Our first-principle electronic-structure calculations indicate that the metallic Heusler compound Ti2MnAl becomes half-metallic and spin-gapless semiconducting if half of the Al atoms are replaced by Sn and In, respectively. These electronic structures are associated with structural transitions from the regular cubic Heusler structure to the inverted cubic Heusler structure.
The surface termination of In4Se3(001) and the interface of this layered trichalcogenide, with Au, was examined using x-ray photoemission spectroscopy. Low energy electron diffraction indicates that the surface is highly crystalline, but suggests an absence of C2v mirror plane symmetry. The surface termination of the In4Se3(001) is found, by angle-resolved x-ray photoemission spectroscopy, to be In, which is consistent with the observed Schottky barrier formation found with this n-type semiconductor. Transistor measurements confirm earlier results from photoemission, suggesting that In4Se3(001) is an n-type semiconductor, so that Schottky barrier formation with a large work function metal, such as Au, is expected. The measured low carrier mobilities could be the result of the contacts and would be consistent with Schottky barrier formation.
Theoretical and experimental investigations of various exfoliated samples taken from layered In4Se3 crystals are performed. In spite of the ionic character of interlayer interactions in In4Se3 and hence much higher calculated cleavage energies compared to graphite, it is possible to produce few‐nanometer‐thick flakes of In4Se3 by mechanical exfoliation of its bulk crystals. The In4Se3 flakes exfoliated on Si/SiO2 have anisotropic electronic properties and exhibit field‐effect electron mobilities of about 50 cm2 V−1 s−1 at room temperature, which are comparable with other popular transition metal chalcogenide (TMC) electronic materials, such as MoS2 and TiS3. In4Se3 devices exhibit a visible range photoresponse on a timescale of less than 30 ms. The photoresponse depends on the polarization of the excitation light consistent with symmetry‐dependent band structure calculations for the most expected ac cleavage plane. These results demonstrate that mechanical exfoliation of layered ionic In4Se3 crystals is possible, while the fast anisotropic photoresponse makes In4Se3 a competitive electronic material, in the TMC family, for emerging optoelectronic device applications.
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