Far infrared absorption of a-GeSe

Far infrared absorption measurements have been made on a series of a-Ge_xSe_1?x films with near equiatomic compositions. The only sharp feature is an absorption line at 260cm^-1, and the compositional dependance of this feature is correctly described by a model in which the Ge(Se) atoms are 4(2) fold co-ordinated. There is no evidence in our amorphous samples of any absorption band in the frequency range (160?190cm^?1) of the major IR active modes of 3:3 fold co-ordinated crystalline GeSe.     

Evidence for insulator–metal transition in amorphous chalcogenide Se–Ge–Te films

The temperature dependence of the dc conductivity and thermoelectric power was determined for five different amorphous chalcogenide Se–Ge–Te films, with Ge?=?3.0–22?at.%, Se?=?0–97?at.% and Te?=?0–97?at.%. The films were prepared by thermal evaporation of GeSe₄, GeTe₄ and GeSe₂Te₂ quenched bulk materials. Values of the activation energy calculated from the temperature dependence of both electrical conductivity and thermoelectric power showed a decrease with increasing Ge content in the Se–Ge films as well as with replacement of Te for Se in the Se–Ge–Te films. The results showed an Anderson transition, with the conductivity showing insulating behaviour on the Ge–Se side to metallic behaviour at the binary composition Ge–Te. The radius of localization was obtained for the different compositions investigated. The wave function associated with the charge carriers at the composition Ge_3.3Te_96.7 is non-localized. A minimum metallic conductivity of 237?±?5?(Ω?cm)^?1 was found.     

First evidence for vibrational excitations of large atomic clusters in amorphous semiconductors

Raman and depolarization spectra of GeSe₂ alloyed with Se or As₂Se reveal a sharp vibrational doublet, only one component of which can be attributed to a vibrational excitation of the GeSe₂ local atomic cluster. The composition dependence of the intensity and polarization of the second feature identify it as an excitation involving a substantially larger cluster with high symmetry. The large cluster is a ring of Ge atoms inter-connected through single Se atoms     

Glass formation and vibrational properties in the (Ge,Sn) system

The glass forming tendency and infrared reflectance spectra are investigated in the (Ge, Sn) system. It is found that the glass formation of the SnSe system is much more difficult than that of the Ge system. This is mainly ascribed to the ionicity difference between GeSe and SnSe bonds. Infrared spectra in the glassy Ge_1-xSe_x system at the composition 0.67<x<1.0 indicate the presence of clusters within which the atomic connectivity is similar as in the glassy GeSe₂. The vibrational modes caused by the $\text{SnSe}{}_{\mathrm{<mtext>4</mtext><mtext>2</mtext>}}$ tetrahedron are found in the glassy (Ge, Sn)-Se system. It is suggested that tin atoms are mainly incorporated into the clusters. Importance of the medium range order is discussed in the formation of the glasses.     

GeTe和GeSe 分子在外电场下的特性研究

对Ge原子采用6-311++G^**基函数,Te和Se原子采用SDB-cc-pVTZ基函数,利用密度泛函理论的局域自旋密度近似方法优化得到了GeTe和GeSe分子的稳定构型,并计算了外电场作用下GeTe和GeSe基态分子的平衡核间距、总能量、最高已占据分子轨道能量E_H、最低未占分子轨道能量E_L、能隙、谐振频率和红外谱强度. 在上述计算的基础上利用单激发组态相互作用-局域自旋密度近似方法研究了GeTe和GeSe分子在外电场下的激发特性. 结果表明:随着正向电场强度的增大,分子核间距逐渐增大,分子总能量逐渐降低,谐振频率逐渐减小,红外谱强度则逐渐增大. 在0-2.0569×10¹⁰ V·m^-1的电场范围内,GeTe分子的E_H 均高于GeSe分子的E_H;随着正向电场的增大,GeTe与GeSe的E_H差逐渐变大,GeTe的E_L低于GeSe的E_L,它们的E_L均随正向电场的增大而增大. 无外场时,GeTe分子的能隙比GeSe分子的能隙要小;在外电场反向增大的过程中, GeTe和GeSe的分子能隙始终减小. 外电场的大小和方向对GeTe和GeSe分子的激发能、振子强度及跃迁的波长均有较大影响. 关键词： GeTe GeSe 外电场 激发态     

Influence of S→Se substitution on chemical and physical properties of Cu7Ge(S1−xSex)5I superionic solid solutions

Phase diagram of Cu₇GeS₅I-Cu₇GeSe₅I superionic system was investigated by the differential thermal analysis (DTA). Chemical interaction in Cu₇GeS₅I-Cu₇GeSe₅I system was studied by X-ray phase analysis (XPA), microstructural analysis, and density determination. Compositional behaviour of diffuse reflection spectra and energy gap due to S→Se anion substitution in Cu₇Ge(S_1−xSe_x)₅I solid solutions are discussed.     

Influence of Se atoms on the properties of amorphous Ge

Electron spin resonance (ESR), electrical and optical measurements have been made for Ge_1?xSe_x (0?x?0.35) films in order to elucidate relations between tetrahedrally bonded amorphous semiconductors and chalcogenide amorphous semiconductors. The ESR signal due to dangling bonds in amorphous Ge decreases by increasing Se content. For more than about 20 at. % Se, the electrical conductivity is the activation type and the optical gap increases with the increase of Se content. The model of charged dangling bonds by Street and Mott seems to explain the experimental results.     

Coordination dependent vibrational properties of amorphous semiconductors alloys

The i.r., Raman and depolarization spectra of the amorphous pseudo-binary alloy systems (GeS₂)_1-χ(As₂S₃)_χ and (GeSe₂)_1-χ(As₂Se₃)_χ are reported here. In contrast to the one-mode behavior that is anticipated on the basis of the mass ratio of the alloy atoms (Ge/As), two bond-stretching modes are observed in both the i.r. and Raman spectra. This new type of phonon behavior is interpreted in terms of differences in the local coordination via a chemical bonding model.     

Defects in a disordered world: the structure of glassy GeSe2

The full set of partial structure factors for the prototypical network glass GeSe2 was measured using the method of isotopic substitution in neutron diffraction. The basic building block of the network is the Ge(Se(1/2))(4) tetrahedron in which 34(5)% of the Ge reside in edge-sharing configurations. The intrinsic chemical order of the glass is, however, broken with a maximum of 25(5)% Ge and 20(5)% Se being involved in homopolar bonds at distances of 2.42(2) and 2.32(2) A, respectively.     

Third-order nonlinear optical properties of GeSe2-Ga2Se3-PbI2 glasses

The third-order nonlinear optical (NLO) properties of new selenium-based GeSe₂-Ga₂Se₃-PbI₂ glasses have been measured using the optical Kerr effect (OKE) technique, with picosecond and femtosecond laser pulses. The 0.70GeSe₂-0.15Ga₂Se₃-0.15PbI₂ glass has the largest third-order optical nonlinear susceptibility in GeSe₂-Ga₂Se₃-PbI₂ glass system with χ⁽³⁾ of 5.28×10¹² esu. In addition, the response time of glasses is sub-picosecond, which is predominantly associated with electron cloud. Local structure of the glasses has been identified by using Raman studies, while the origins of the observed nonlinear optical response are discussed. The [Ge(Ga)Se₄] tetrahedral and lone-pair electrons from highly polarizable Pb atom in glasses play an important role in enhanced NLO response. These results as well as their good chemical stability indicate that GeSe₂-Ga₂Se₃-PbI₂ glasses are promising materials for photonic applications of third-order nonlinear optical signal processing.     

Influence of thickness on the optical properties of amorphous GeSe2 thin films: analysis using Raman spectra,Urbach energy and Tauc parameter

An analysis is reported of thickness-induced defects in amorphous GeSe₂ thin films deposited by the vacuum evaporation technique. X-ray diffraction studies confirmed the amorphous nature of the thin films. Optical absorption measurements revealed an indirect transition with an energy gap that increases with film thickness. A blue shift in optical transmittance edges was observed in annealed GeSe₂ thin films. The obtained lower values of Urbach energy (E _U) indicate that as thickness increases more ordered films can be produced. Raman spectra suggest that annealing promotes corner-sharing GeSe_4/2 tetrahedra and edge-sharing Ge₂Se_8/2 bi-tetrahedra bonding and leads to the reduction in disorder in bonding network, which is amply supported by the way of increase in band gap, increase in Tauc parameter (B ^1/2) and reduction in E _U from the analysis of transmittance spectra. Increasing the thickness promotes tetrahedral and bi-tetrahedral bonding through the reduction in bonding defects.     

Comparison of site-specific valence band densities of states determined from Auger spectra and XPS-determined valence band spectra in GeS (001) and GeSe (001)

Auger lineshapes of the Ge M₁M_4,5V and M₃M_4,5V and Se _M1M_4,5V transitions in GeS (001) and GeSe (001) are measured and compared to XPS valence band spectra. Distortions in both types of spectra due to inelastic scattering, analyzer and source broadening, and core level lifetime broadening are removed by deconvolution techniques. The valence band consists of three main peaks at ?2 eV, ?8 eV, and ?13 eV. There is excellent agreement of peak positions in AES and XPS spectra. The Auger lineshapes can be interpreted in terms of site-specific densities of states. They indicate that the states at ～?8 eV and at ～?13 eV are associated with the cation and anion sites respectively. The bonding p-like states at the top of the valence band have both cation and anion character. The Auger lineshapes indicate that the states closest to the valence band maximum are preferentially associated with Ge.     

新型GeSe2-In2Se3-AgI玻璃性能研究

采用传统熔融-淬冷法制备了一系列新型(100-x) (4GeSe₂-In₂Se₃) -xAgI(x=20,30,40 mol%)硫系玻璃样品.利用X射线衍射分析、差热分析、可见-近红外吸收光谱、红外透过光谱、喇曼分析等技术手段研究了该玻璃系统的组成、结构、热稳定性和光学特性等.利用Tauc方程计算出了样品的间接带隙;测试了部分样品在不同升温速率下的差示扫描量热曲线,并采用Kissinger法计算了玻璃样品的析晶活化能.X射线衍射数据表明,该玻璃体系在较宽的组分范围内有良好的非晶特性,成玻范围较宽;差热分析和析晶动力学研究表明,玻璃样品70(4GeSe₂-In₂Se₃)-30AgI具有较好的热稳定性(ΔT=114℃)和较高的活化能(E_a=320.4 kJ/mol).随着AgI含量的增加,玻璃的短波吸收限蓝移,并且光学带隙有增大的趋势.此外,红外透过光谱分析表明该玻璃体系具有良好的红外透过性能,其红外截止波长不会随着AgI含量的增加而发生明显变化,皆为16μm左右.     

Multicomponent GeSe2-CdI2-TeO2 (Bi2O3) systems: glass formation and properties

The glass-forming regions of the GeSe₂-CdI₂-TeO₂ (I), GeSe₂-CdI₂-Bi₂O₃ (II) and GeSe₂-TeO₂-Bi₂O₃ (III) systems have been determined. The obtained glassy phases have been characterized by their basic physicochemical parameters such as temperatures of glass transition, crystallization, and melting, density and microhardness. The phase T-X diagram of the GeSe₂-CdI₂ system, which is the basic joint line for systems I and II, has been specified. Three non-variant equilibria (two eutectic and one syntectic) have been observed at temperatures 350, 280 and 375 °C for compositions containing 15, 95 and 33.3 mol% GeSe₂, respectively. A new intermediate phase with probable composition of 2CdI₂·GeSe₂ has been formed.     

Isomere Wirkungsquerschnittsverhältnisse beim thermischen Neutroneneinfang im Bereich der 2p 1/2 und 1g 9/2 Schalenmodellzustände

Thermal capture cross sections and isomeric cross section ratios in thermal neutron capture were determined for even-even nuclei in the region of the 2p _1/2-1g _9/2 neutron shell. Capture cross sections for formation of Zn 69 ^m , Zn 71 ^m , Zn 71, Ge 71, Ge 75 ^m , Ge 77 ^m , Se 77 ^m , Se 79 ^m , Se 83 ^m , Se 83, Sr 85 ^m and Sr 87 ^m were measured by the activation method. From these data and additional measurements of cross section ratios the isomeric ratios for thermal capture in Zn 68, Zn 70, Ge 70, Ge 74, Ge 76, Se 76, Se 78, Se 80, Se 82 and Sr 84 were determined. In addition epithermal capture isomer ratios were determined for Zn 68, Ge 74, Ge 76, Se 80 and Sr 84. The isomer ratios are compared with calculations based on the statistical model ofHuizenga andVandenbosch. With the exception of Se 80 the measured ratios can be explained theoretically with reasonable values of the spin-cutoff-factorσ and gamma-ray multiplicityN, however there seems to be unexplained difference in eitherσ orN between the two groups of nuclei leading to either 1/2–7/2 or 1/2–9/2 isomers.     

Variation of band gap in Se-based chalcogenide glasses

The random network model for amorphous alloys proposed by White has been developed for the system irradiated with light. The model suggests that the photobleaching in GeSe₂ film and the photodarkening in AsSe film may be due to change in the number of the bonds.     

Reaction-diffusion-induced explosive crystallization in a metal–selenium nanometer film structure

Experimental data for reaction-diffusion-induced explosive crystallization in a nanodimensional metal (Cu, Ag)/selenium structure are presented. It is found that after the metal layer has completely diffused into the amorphous Se film, the electrical potential rises from 0.14 to 1.21 V in the Cu(30 nm)/Se(140 nm) heterolayer and from 0.01 to 1.17 V in the Ag(30 nm)/Se(140 nm) heterolayer. The metals diffusing into the amorphous Se layer interact with Se, forming nuclei of a new phase (CuSe or Ag₂Se). The intense growth of the CuSe and Ag₂Se crystallization centers results in a considerable liberation of latent energy in the form of phase transformation heat and in explosive growth of CuSe and Ag₂Se nanocrystalline particles. The mean size of CuSe and Ag₂Se crystallites equals 25 and 50 nm, respectively.     

Effects of Ge doping on the properties of Sb2Te3 phase-change thin films

Ge-doped Sb₂Te₃ films were prepared by magnetron sputtering of Ge and Sb₂Te₃ targets on SiO₂/Si (1 0 0) substrates. The effect of Ge doping on the structure was studied in details by X-ray diffraction, differential scanning calorimetry, and X-ray photoelectron spectroscopy measurements. It is indicated that Ge atoms substitute for Sb/Te in lattice sites and form Ge-Te bonds, moreover, a metastable phase was observed in Ge-doped specimens. Both crystallization temperature and resistivity of amorphous Sb₂Te₃ increase after Ge doping, which are beneficial for improving room temperature stability of the amorphous state and reducing the SET current of chalcogenide random access memory.     

Amorphous Ge1−ySey alloys: ESR study of gap states

We have measured the ESR spectra of evaporated amorphous Ge_1−ySe_y alloy films. We find that with the addition of Se to aGe the spin density drops, the g-value decreases from 2.0233 ± 0.0007 to 2.012 ± 0.002 and there is an increase in asymmetry and linewidth. The results indicate that the Fermi level shifts into the conduction band tail with the addition of as little as 5 at. % Se and that the introduction of Se permits a significant reduction in the dangling bond density.     

新型GeSe2-In2Se3-AgI玻璃性能研究

采用传统熔融-淬冷法制备了一系列新型(100-x)(4GeSe2-In2Se3)-xAgI(x=20,30,40mol%)硫系玻璃样品.利用X射线衍射分析、差热分析、可见-近红外吸收光谱、红外透过光谱、喇曼分析等技术手段研究了该玻璃系统的组成、结构、热稳定性和光学特性等.利用Tauc方程计算出了样品的间接带隙;测试了部分样品在不同升温速率下的差示扫描量热曲线,并采用Kissinger法计算了玻璃样品的析晶活化能.X射线衍射数据表明,该玻璃体系在较宽的组分范围内有良好的非晶特性,成玻范围较宽;差热分析和析晶动力学研究表明,玻璃样品70(4GeSe2-In2Se3)-30AgI具有较好的热稳定性(ΔT=114℃)和较高的活化能(Ea=320.4kJ/mol).随着AgI含量的增加,玻璃的短波吸收限蓝移,并且光学带隙有增大的趋势.此外,红外透过光谱分析表明该玻璃体系具有良好的红外透过性能,其红外截止波长不会随着AgI含量的增加而发生明显变化,皆为16μm左右.