Glass formation and physical properties of Sb2S3–CuI chalcogenide system

Novel chalcogenide glasses of pseudo-binary(100-x)Sb₂S_3-xCuI systems were synthesized by traditional meltquenching method.The glass-forming region of Sb₂S₃-CuI system was determined ranging from x=30 mol% to 40 mol%.CuI acts as a non-bridging modifier to form appropriate amount of [SbSI] structural units for improving the glass-forming ability of Sb₂S₃.Particularly,as-prepared glassy sample is able to transmit light beyond 14 μm,which is the wider transparency region than most sulfide glasses.Their physical properties,including Vickers hardness(Hv),density(ρ),and ionic conductivity(σ) were characterized and analyzed with the compositional-dependent Raman spectra.These experimental results would provide useful knowledge for the development of novel multi-spectral optical materials and glassy electrolytes.     

Structural and electrical investigation of (Ag3AsS3)x(As2S3)1?x superionic glasses

Structural studies of (Ag₃AsS₃) _x (As₂S₃)_1−x chalcogenide superionic glasses in the compositional range x = 0.3–0.9 were performed by scanning electron microscopy. Temperature and compositional dependences of transmission coefficient, electrical conductivity, and activation energy were investigated     

Biomolecule-assisted hydrothermal synthesis of Sb2S3 and Bi2S3 nanocrystals and their elevated-temperature oxidation behavior for conversion into α-Sb2O4 and Bi2O3

We have developed a novel biomolecule-assisted hydrothermal method to prepare Sb₂S₃ and Bi₂S₃ nanocrystals with various sizes and shapes, in which cysteine combined with other sulfur source can exert the synergistic effect on products. The samples were characterized XRPD, TEM, HRTEM, FESEM, and PL techniques. First, we prepared a series of Sb₂S₃ and Bi₂S₃ nanocrystals by simply adjusting the composition of sulfur sources under hydrothermal conditions. Then, we studied the elevated-temperature oxidation behavior of these sulfides in air, which can lead to the formation of α-Sb₂O₄ and Bi₂O₃ samples at 600 °C for 3 h. The optical properties of the α-Sb₂O₄ and Bi₂O₃ samples were also discussed.     

Effect of Cd and Pb impurities on the optical properties of?fresh?evaporated amorphous (As2Se3)90Ge10 thin films

Transmission spectra (400–1500 nm) of thermally evaporated amorphous [(As₂Se₃)₉₀Ge₁₀]₉₅M₅ thin films have been analyzed to study the effect of impurities (M = Cd and Pb) on their optical properties. The refractive index increases with addition of metal impurities. The dispersion of refractive index has been studied using Wemple–DiDomenico single oscillator model. The optical gap has been estimated using Tauc’s extrapolation and was found to decrease with the addition of metal impurities from 1.46 to 1.36 eV (Cd) and 1.41 eV (Pb) with an uncertainty of ±0.01 eV. The change in optical properties with metal impurities has been explained on the basis of density, polarizability and bond energy of the system.     

Models of optical absorption in amorphous semiconductors at the absorption edge — A review and re-evaluation

Davis-Mott and Tauc models of optical absorption at the absorption edge in the high absorption coefficient region (10⁴cm^–1) are carefully reviewed with regard to their theoretical foundations, assumptions, mathematical derivations, and results. The full implications of these models are exploited, and it is found that the Davis-Mott model for negligible matrix elements between localised states could account for the cubic power law behaviour of with photon energy of some amorphous semiconductors such as a-Si. A fractional power law to find the optical band gapE _opt, of the form [ (–E _opt)^r; 2r3] based on Davis-Mott model is proposed in which the indexr can be a function of disorder. The Tauc model has further been extended to the case of negligible matrix elements between localised states, in which the same square power law for vs. with the same meaning of the optical gap as in the original Tauc model has resulted. A consideration of the case of unequal matrix elements for those transitions between localised states and those between extended states is also included. The meaning ofE _opt has been re-assessed and it is emphasized that it is an extrapolation of delocalised states to the zero of the density of states rather than a threshold energy for the onset of some kind of optical transitions.This paper is cordially dedicated to Professor C. A. Hogarth who taught us the Physics of amorphous materials.     

Solvent effects on the S0→S2 absorption spectra of β-carotene

Absorption spectra of β-carotene in 31 solvents are measured in ambient conditions. Solvent effects on the 0-0 band energy, the bandwidth, and the transition moment of the S 0 → S 2 transition are analysed. The discrepancies between published results of the solvent effects on the 0-0 band energy are explained by taking into account microscopic solute-solvent interactions. The contributions of polarity and polarizability of solvents to 0-0 band energy and bandwidth are quantitatively distinguished. The 0-0 transition energy of the S 2 state at the gas phase is predicted to locate between 23000 and 23600 cm-1 .     

Theoretical investigation on the optical absorption spectra and local lattice structure of α-Al2O3:Yb crystals

In this paper, the optical absorption spectra of Yb³⁺ in the α-Al₂O₃ crystal are reasonably explained by using the superposition model and local lattice structure analysis. Based on these studies, we find that the local geometrical structure around the Yb³⁺ ions possesses an elongated trigonal distortion above the O²⁻-triangle and a compressed trigonal distortion in the lower one.     

Solvent effects on the S0→S2 absorption spectra of β-carotene

Absorption spectra of β -carotene in 31 solvents are measured in ambient conditions. Solvent effects on the 0--0 band energy, the bandwidth, and the transition moment of the S₀ → S₂ transition are analysed. The discrepancies between published results of the solvent effects on the 0--0 band energy are explained by taking into account microscopic solute-solvent interactions. The contributions of polarity and polarizability of solvents to 0--0 band energy and bandwidth are quantitatively distinguished. The 0--0 transition energy of the S₂ state at the gas phase is predicted to locate between 23000 and 23600~cm^-1.     

(Sb2Te3)0.75(1－x)(Bi2Te3)0.25(1－x)(Sb2Se3)x机械合金化粉体的制备及其冷压烧结样品的热电性能研究

采用机械合金化法制备了p型赝三元(Sb₂Te₃-Bi₂Te₃-Sb₂Se₃)合金粉体，对其进行XRD分析表明Te，Bi，Sb，Se单质粉末，经100h球磨后实现了合金化；SEM分析表明所得机械合金化粉体材料颗粒均匀、细小，颗粒尺寸在10nm到100nm量级.使用这种粉体制备了冷压烧结块体样品，在室温下测量了温差电动势率(α)和电导率(σ)，研究了烧结温度对材料热电性能的影响，结果表明在低于300℃的烧结温区，样品室温下的热电性能随烧结温度的升高不断提高，功率因子(α²σ)由未烧结样品的0.59μW cm^-1K^-2升高到在300℃下烧结样品的15.9μW cm^-1K^-2，这一结果对确定材料的最佳烧结温度具有重要意义. 关键词： 赝三元热电材料 机械合金化 冷压 烧结     

Observation of simultaneous ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) transitions enhanced by the resonance dipole-dipole interaction with the ν1 + ν3 and ν2 + ν3 states of the SF6 molecule

IR spectra of the solution of SF₆ molecules in liquid NF₃ at 84 K have been recorded. In a solvent transmission window of 1500–1750 cm⁻¹, two wide absorption bands with pronounced peaks in the high-frequency part are observed. The profile of these bands is explained by the influence of the resonance dipole-dipole (RDD) interaction of the states of the simultaneous transition ν₁(SF₆) + ν₃(NF₃) and ν₂(SF₆) + ν₃(NF₃) with the states (ν₁ + ν₃) and (ν₂ + ν₃) of the SF₆ molecules, respectively. The use of three isotopic modifications ³²SF₆, ³³SF₆, and ³⁴SF₆ has allowed us to vary the resonance detuning and thus to change the strength of the RDD interaction. With the liquid near the melting point being represented as a close-packed cubic crystal, the profile was calculated and its spectral characteristics were determined. The frequencies of the main peaks coincide with the experimental values accurate to the error.     

掺杂As2S8非晶态薄膜波导的光阻断效应

实验研究了未掺杂和低浓度掺锡和掺磷的As₂S₈薄膜波导的光阻断效应,提供了三种样品的光阻断响应曲线、室温退激实验数据和光谱测试数据. 结果表明,掺锡样品可以明显提升毫秒级响应的快过程恢复作用,同时还具有减少残留传输损耗的效果,掺磷的效果则相反. 结合实验结果给出了分析讨论. 关键词： 光波导技术 硫属化合物玻璃 光阻断效应 掺杂     

基于AZ5214光致保护层的As2S3硫系脊型波导制备

实验研究发现AZ5214光刻胶在一定曝光剂量下显影后会留存一定厚度的底膜,该底膜可以在干法刻蚀过程中避免As-S薄膜与碱性显影液直接接触,减轻薄膜表面损伤,起到保护作用。基于此,采用该底膜作为保护层制备As₂S₃脊型波导,研究结果表明,在AZ5214光刻胶匀胶厚度为2.1μm、紫外曝光剂量为200 mJ/cm²、显影时间为45 s的条件下会留存约为220 nm厚的光致保护层,该条件下保护层均匀性较好,且在刻蚀阶段可以完全去除。实验表明利用此保护层制备的As₂S₃脊型波导具有良好的形貌特征,波导脊宽约为3μm、脊高约为800 nm的As₂S₃脊型波导的传输损耗约为0.74 dB/cm@1 550 nm。     

中红外波段As2S3光子晶体光纤中受激布里渊散射的研究(英文)

通过有限元方法研究了As₂S₃光子晶体光纤在2μm至6μm波段的受激布里渊散射。数值结果表明,当空气占空比小于0.6时,所提出的光子晶体光纤可保持单模工作。布里渊频移主要受泵浦波长和光纤结构的影响,泵浦波长从2μm增加到6μm时,布里渊频移减小了4.16 GHz;而当空气占空比由0.5增加到0.6时,布里渊频移变化量仅为兆赫兹量级。布里渊增益谱的半高全宽取决于声子寿命,泵浦波长为2μm时布里渊增益谱的半高全宽是泵浦波长为6μm时的9倍。在空气填充率为0.5和0.6的情况下,提出的光子晶体光纤的最大布里渊增益分别为2.413×10^-10 m/W和2.429×10^-10 m/W。在光纤有效长度相同的条件下,布里渊阈值与泵浦波长正相关,在空气填充率为0.5和0.6的光子晶体光纤中,使用6μm泵浦时的布里渊阈值比使用2μm时分别增大了27.8%和19.6%。这些数值结果对于中红外波段设计和制造基于所提出光纤的光学设备或光学传感器具有重要意义。     

High-resolution infrared analysis of the ν7 band of cis-ethylene-d2 (cis-C2H2D2)

The spectrum of the ν₇ band of cis-ethylene-d₂ (cis-C₂H₂D₂) has been recorded with an unapodized resolution of 0.0063 cm⁻¹ in the 740-950 cm⁻¹ region using a Bruker IFS 125 HR Fourier transform infrared spectrometer. By fitting 2186 infrared transitions of ν₇ with a standard deviation of 0.00060 cm⁻¹ using a Watson’s A-reduced Hamiltonian in the I^r representation, accurate rovibrational constants for ν₇ = 1 state have been derived. The band center of ν₇ has been found to be 842.20957 ± 0.00004 cm⁻¹. In a simultaneous fit of 1331 infrared ground state combination differences from the present ν₇ transitions, together with 22 microwave frequencies, ground state constants have been improved. The rms deviation of the ground state fit was 0.00027 cm⁻¹.     

Luminescence studies of Nd- and Yb-doped α-Y(IO3)3 and β-Y(IO3)3, transparent host matrix in the mid- and beginning of the far-infrared

α-Y(IO₃)₃ and β-Y(IO₃)₃ are transparent until 12.8 and 13.4 μm, respectively; thus they are interesting as a potential laser matrix in the mid- and beginning of the far-infrared. So, in order to investigate the properties of lanthanides- doped anhydrous yttrium iodate, polycrystalline samples of α-Y_1−xNd_x(IO₃)₃ (0.01?x?0.05), β-Y_1−xNd_x(IO₃)₃ (0.001?x?0.1), α-Y_1−xYb_x(IO₃)₃ (0.01?x?0.33) and β-Y_1−xYb_x(IO₃)₃ (0.01?x?0.25) were synthesized. For Nd³⁺ ions, fluorescent emissions from the ⁴F_3/2 multiplet were observed at 300 K under pulsed laser excitations at 750 nm and for Yb³⁺, fluorescent emissions from the ²F_5/2 multiplet were observed at 300 K under pulsed laser excitations at 980 nm. The decays of all these emissions were measured. They are exponential and the fluorescence lifetimes are in the range 0.093-0.193 ms for Nd³⁺ and 0.370-0.541 ms for Yb³⁺, depending on the nature of the host and the concentration of doping.     

Antiferromagnetic transition and electrical conductivity in α-Gd2S3

Magnetic susceptibility and electrical resistivity of α-Gd₂S₃ with an orthorhombic structure (space group: Pnma) have been measured for powder and single-crystal samples. While the magnetic susceptibility of powder sample exhibits a broad peak having a maximum at 4.2 K, the susceptibility for a single crystal with an applied magnetic field along the b-axis demonstrates a sharp drop below 10 K. Nevertheless, the susceptibility with the field perpendicular to the b-axis keeps increasing with decreasing temperature even below 10 K. The electrical resistivity ρ for the powder sample of 4.2×10³ Ω cm around room temperature increases with decreasing temperature and shows a slight discontinuity at about 65 K. In both regions above and below 65 K, is proportional to T^−1/4 with respective coefficients, which is associated with Mott variable-range hopping conductivity. The resistivity of a single crystal along the b-axis is considerably smaller than the value for the powder sample as 0.35 Ω cm at room temperature, and its temperature dependence is fairly weak. While cooling, the resistivity first decreases down to 240 K and then keeps the value independent of the temperature down to 140 K, and subsequently rises gently below 140 K.     

Infrared spectra of two isomers of OCS-C2H2 and OCS-C2D2 in the region of OCS ν1 fundamental

Infrared spectra of OCS-C₂H₂ and OCS-C₂D₂ complexes in the region of the C-O stretching fundamental of OCS (∼2060 cm⁻¹) are studied in a pulsed supersonic slit-jet expansion using a tunable diode laser. For each complex, two bands are observed and assigned to distinct near-parallel and the T-shaped isomers. Ground state parameters were previously determined from microwave studies, so analysis of the infrared spectra gives information on the vibrational shifts upon complex formation as well as rotational and centrifugal distortion parameters for the excited states. All four bands show a red shift with respect to the monomer band origin, with the T-shaped isomer having a much larger shift than the near-parallel isomer. Disappearance of the T-shaped isomer when argon is used as a carrier gas supports the notion that the near-parallel isomer is the lowest energy form of the complex.     

The simulation of infrared bands from the analyses of rotational spectra: the 2ν9-ν9 and ν5-ν9 hot bands of HNO3

The results of millimeter and submillimeter wave rotational spectroscopy are used to simulate the complex structure of the 2ν₉-ν₉ and ν₅-ν₉ hot bands. The comparison data were obtained with a high-resolution Bruker FTIR. The combination of the quality of these data and the complexity of the spectra of these interacting states represents a stringent test for the simulation. It is shown that the agreement is very good and that this approach is generally advantageous. From this simulation, the ratios of the transition dipole moments for the 2ν₉-ν₉ and ν₅-ν₉ hot bands with respect to the ν₉ fundamental band were found to be 1.38(11) and 0.67(20), respectively. Using these results, the calculated integrated band intensities for the hot bands at were determined to be and . These results were used to successfully simulate high-resolution stratospheric spectra obtained from a balloon flight of the FIRS-2 spectrometer. The more general problem of the rotation-vibration database and the optimal use of both microwave and infrared data to define it is discussed. It is concluded that it is best if the combination of data takes place at the level of the original spectra.     

High resolution Fourier transform infrared spectra and analysis of the ν14, ν15 and ν16 bands of azetidine

Rotationally resolved vibrational spectra of the three lowest frequency bands of the four-membered heterocycle azetidine (c-C₃H₆NH) have been collected with a resolution of 0.00096 cm⁻¹ using the far infrared beamline at the Canadian Light Source synchrotron. The modes observed correspond principally to motions best described as: β-CH₂ rock (ν₁₄) at 736.701310(7) cm⁻¹, ring deformation (ν₁₅) at 648.116041(8) cm⁻¹, and the ring puckering mode (ν₁₆) at 207.727053(9) cm⁻¹. A global fit of 14 276 rovibrational transitions from the three bands provided an accurate set of ground state spectroscopic constants as well as excited state parameters for each of the three vibrational modes. The ground state structure was determined to be that of the puckered conformer having the NH bond in an equatorial arrangement.     

UV–visible,infrared absorption spectra of undoped and TiO2-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and TiO₂-doped lead phosphate glasses were prepared. Ultraviolet (UV)–visible and Fourier transform-infrared (IR) absorption spectra of the prepared samples were measured before and after being subjected to doses of 30 and 60 kGy of gamma irradiation. The parent undoped lead phosphate glass reveals charge transfer UV absorption bands which are attributed to the presence of unavoidable iron impurities contaminated within the raw materials used for the preparation of the glasses and the sharing of divalent lead (Pb²⁺) ions. Experimental spectral data indicate that the doped titanium ions are involved in such glasses in two valences, namely the trivalent and tetravalent states. The predominant trivalent titanium (Ti³⁺) ions are characterized by its purple color and exhibiting two visible absorption bands at about 500–550 and 700–720 nm. The lesser tetravalent titanium (Ti⁴⁺) ions belong to the d⁰ configuration and generally exhibit only an UV absorption band. Spectral data show that gamma irradiation causes noticeable changes in the undoped and TiO₂-doped samples in the UV range while the effects are limited in the visible range. The observed changes in the UV region are attributed to photochemical reactions while TiO₂-doped samples show retardation or shielding toward continuous gamma irradiation together with the sharing of heavy Pb²⁺ ions. IR absorption spectra reveal the vibrations of several phosphate groups including the metaphosphate chains as the main structural building units together with the possible Pb?O vibrations.