Synthetic Route of Layered Titanium Nitride Chloride TiNCl Using Sodium Amide

Scanning tunneling microscopy and spectroscopy (STM/STS) and break-junction tunnel spectroscopy (B.TTS) measurements are performed on the pristine layered α-TiNCl semiconductor (pri-TiNCl), being the precursor of superconducting nitride chlorides. The STM topography of pri-TiNCl shows basic crystal structures with the lattice periods of a0≈ 0.38 nm and b0≈ 0.31 nm, ensuring that a clean a–b surface of micro-single crystals is obtained. From the STS measurements, the averaged conductance versus voltage dependence dI/dV(V) reveals kink structures at relatively high bias voltages of |F| ∼ −50 mV and −100 mV. The spatial (r-) conductance distributions dI/dV (V, r) (dI/dV maps) proportional to those of quasiparticle local densities of states (LDOSes) exhibit the bias-independent streak structures with the period of (4.8 ± 0.2) b0, which are predominantly observed within the range of |V| < 95 mV. The temperature dependence of the dI/dV B.TTS spectra shows the gap structure with the energy scale of 4Σ = 180 meV vanishing at Ts ∼ 120 K. Thus, the ratio of the gap Σ to the transition temperature Ts is 2Σ/kBTs ∼ 10. Here, kB is the Boltzmann constant. Such a ratio is typical of the pseudogap features in cuprate superconductors and dielectric gap characteristics in layered chalcogenides with charge-density waves.

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Superconductivity in the α-Form Layer Structured Metal Nitride Halide

Tanaka

Kataoka

Yokoya

2022

Condensed Matter

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Layered metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) have two polymorphs, including α- and β-forms, which have the FeOCl and SmSI structures, respectively. These compounds are band insulators and become metals and show superconductivity after electron doping by intercalating alkali metals between the layers. The superconductivity of β-form had been extensively characterized from decades ago, but it is not easy to consistently interpret all experimental results using conventional phonon-mediated Bardeen–Cooper–Schriefer mechanisms. The titanium compound TiNCl crystallizes only in the α-form structure. TiNCl also exhibits superconductivity as high as ~16 K after electron doping by intercalating metals and/or organic basis. It is important to compare the superconductivity of different M–N networks. However, α-form compounds are vulnerable to moisture, unlike β-form ones. The intercalation compounds are even more sensitive to humid air. Thus, there are few experimental studies on the superconducting mechanism of α-form, although it has been discussed for exotic Cooper-pairing mechanisms. This short review gathers the recent progress in experimental studies of TiNCl.

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Synthetic Route of Layered Titanium Nitride Chloride TiNCl Using Sodium Amide

Cited by 4 publications

References 32 publications

Modification of the synthesis of layered titanium chloride nitride

Modification of the synthesis of layered titanium chloride nitride

Observation of periodic structures and pseudogaps in pristine compound α-TiNCl by STM/STS and break junction methods

Superconductivity in the α-Form Layer Structured Metal Nitride Halide

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