Homopolar bonds in Se-rich Ge-As-Se chalcogenide glasses

We have prepared three groups of Ge–As–Se glasses in which the Se content is 5.5 mol%, 10 mol%, and 20 mol%rich, respectively. We explored the possibility of suppressing the formation of the Ge–Ge and As–As homopolar bonds in the glasses. Thermal kinetics analysis indicated that the 5.5 mol% Se-rich Ge_（11.5）As_（24）Se_（64.5） glass exhibits the minimum fragility and thus is most stable against structural relaxation. Analysis of the Raman spectra of the glasses indicated that the Ge–Ge and As–As homopolar bonds could be almost completely suppressed in 20 mol% Se-rich Ge_（15）As_（14）Se_（71） glass.

Variable angle spectroscopic ellipsometry and its applications in determining optical constants of chalcogenide glasses in infrared

The principle of variable angle spectroscopic ellipsometry（VASE） and the data analysis models, as well as the applications of VASE in the characterization of chalcogenide bulk glasses and thin films are reviewed. By going through the literature and summarizing the application scopes of various analysis models, it is found that a combination of various models, rather than any single data analysis model, is ideal to characterize the optical constants of the chalcogenide bulk glasses and thin films over a wider wavelength range. While the reliable optical data in the mid-and far-infrared region are limited, the VASE is flexible and reliable to solve the issues, making it promising to characterize the optical properties of chalcogenide glasses.

Research progress of third-order optical nonlinearity of chalcogenide glasses

Chalcogenide glasses （ChGs） are a promising candidate for applications in nonlinear photonic devices. In this paper, we review the research progress of the third-order optical nonlinearity （TONL） of ChGs from the following three aspects： chemical composition, excitation condition, and post processing. The deficiencies in previous studies and further research of the TONL property of ChGs are also discussed.

PHASE SEPARATION AND CRYSTALLIZATION OF CHALCOGENIDE GLASSES

In this paper the experimental results associated until the phase separation and nucleation and crystallization of chalcogenidc glasses are described. Experi-ments demonstrate that the phas separation may be affected by small amount of additives. It has been found that some chalcogenide glasses could be converted into glass-ceramics without phase separation. The different mechanisms of nucleated crystallization of chalcogenide glasses are discussed and propossed.

Hot-embossing fabrication of chalcogenide glasses rib waveguide for mid-infrared molecular sensing

Chalcogenide glasses have shown promise in fabricating mid infrared（MIR） photonic sensing devices due to their excellent optical properties in MIR. In addition, the glass transition temperature of chalcogenide glasses are generally low,making them ideal to create the high-throughput patterns of micro-scale structures based on hot embossing that is alternative to the standard lithographic technology. In this paper, we outline the research progress in the chalcogenide waveguide based on the hot embossing method, and discuss the problems remaining to be solved and the possible solutions.

The First Sharp Diffraction Peak in the Total Structure Function of Amorphous Chalcogenide Glasses: Anomalous Characteristics and Controversial Views

Anomalous structural characteristics of the so-called first sharp diffraction peak (FSDP) that arises in the total static structure functions of network-forming glasses and liquids at around 1-2 A-1 have been reviewed and discussed in details. Unlike other peaks in the static structure functions, the FSDP has anomalous dependencies on temperature, pressure and composition. Despite the fact that the FSDP is considered as a signature of intermediate range order (IRO) in network-forming glasses and liquids, its structural origin remains unclear and till now, it forms a subject of debate. A brief account for some anomalous characteristics of the FSDP followed by the different controversial interpretations about its structural origin has been reviewed and discussed. Some of the interpretations that seem to be inconsistent with recent experimental results have been ruled out. The most likely structural origins for the occurrence of the FSDP have been highlighted and discussed in details.

Laser-Induced Phase Transformation in Chalcogenide Glasses Investigated by Micro-Raman Spectrometer

A 488 nm continuous wave （CW） laser was employed in Raman spectrometer to both induce and characterize phase transformation in chalcogenide glasses. Laser-induced Raman inactive changes, structural evolution, and crystallization were observed at laser-irradiated region in GeS2-Sb2S3 glasses. The composition dependence of laser-induced phase transformation was discussed in terms of thermal stability and microstructural modification. It is strongly suggested from these results that fabrication of passive and active chalcogenide glass waveguides, such as refractive index change and nonlinear optical crystal line, is controllable by selecting appropriate glass composition, and convenient by using common CW lasers.

Nanocrystal-enhanced near-IR emission in the bismuth-doped chalcogenide glasses

Bismuth （Bi）-doped materials have attracted a great deal of attention because of their broadband near- infrared （near-IR） emission around the wavelength utilized in telecommunications. In this study, broad near-IR emission band from 1100 to 1650 nm is generated in the Bi-doped 90GeS2-10Ga2S3 glass and glass-ceramics under 820 nm of light excitation. Based on the analysis of the absorption and emission spectra, the origin of this broadband emission is ascribed to the Bi22- dimers. The precipitation of β-GeS2 nanocrystals drastically enhances the emission intensity and lifetime of Bi-doped chalcogenide glass,

Optical properties and local structure of Dy^(3+)-doped chalcogenide and chalcohalide glasses

Dy^3＋-doped Ge-Ga-Se chalcogenide glasses and GeSe2-Ga2Se3-CsI chalcohalide glasses were prepared. The absorption, emission properties, and local structure of the glasses were investigated. When excited at 808 nm diode laser, intense 1.32 and 1.55 μm near-infrared luminescence were observed with full width at half maximum （FWHM） of about 90 and 50 nm, respectively. The lifetime of the 1.32 μm emission varied due to changes in the local structure surrounding Dy^3＋ ions. The longest lifetime was over 2.5 ms, and the value was significantly higher than that in other Dy^3＋-doped glasses. Some other spectroscopic parameters were calculated by using Judd-Ofelt theory. Meanwhile, Ge-Ga-Se and GeSe2-Ga2Se3-CsI glasses showed good infrared transmittance. As a result, Dy^3＋-doped Ge-Ga-Se and GeSe2-Ga2Se3-CsI glasses were believed to be useful hosts for 1.3 μm optical fiber amplifier.

Photo-induced Phenomena in GeS_4 Glasses

GeS4 bulk glasses were prepared by the melt-quench technique and the samples were irradiated by 532-nm linearly polarized light. After the laser treatment, the photo-induced changes of the samples were investigated by UV-1601 speetrophotometer and optical second-order nonlinear tester. The results show that the transmittance of the samples around 532 nm obviously decreases and Bragg reflector forms, which is due to the production of photon-generated carriers. With the increase of laser pulse energy or the extension of irradiation duration, the Bragg reflector increases and gradually tends to be stable. These can be ascribed to the excitation- capture process of the carriers. After irradiation, the relaxation phenomenon results from the release of part of the absorbed energy in the glass matrix. And the fitting equation of the relaxation process is consistent with a conventional Kohlrausch stretched exponential function. The origin of the second harmonic generation （SHG） is because of the dipole reorientation caused by the photo-induced anisotropy in the glass.

Mid-infrared luminescence of Dy^(3+)-doped Ga_2S_3–Sb_2S_3–CsI chalcohalide glasses

The mid-infrared （MIR） luminescent properties of Dy3＋ ions in a new chalcohalide glass host, Ga2S3-Sb2S3-CsI, are investigated; and the suitability of the doped glass for MIR fiber lasers is evaluated. The Dy3＋-doped chalcohalide glasses exhibit good thermal stability and intense MIR emissions around 2.96 μm and 4.41 μm. These emissions show quantum efficiencies （η） as high as ～ 60%, and have relatively large stimulated emission cross sections （σem）. The low phonon energy （～ 307 cm-1） of the host glass accounts for the intense MIR emissions, as well as the high η. These favorable thermal and emission properties make the Dy3＋-doped Ga2S3-Sb2S3-CsI glasses promising materials for MIR fiber amplifiers or lasers.

Effect of Film Thickness on the Optical Parameters and Electrical Conductivity of Te_(10)Ge_(10)Se_(77)Sb_3 Chalcogenide Glass

Several thin films of Te10Ge10Se77Sb3 chalcogenide glass of different thicknesses (250 nm to 400 nm) were prepared by thermalevaporation under vacuum of 133×10-6 Pa (10-6torr). X- ray diffraction analysis showed the amorphicity of the preparedfilms which become partially crystalline by annealing. Transmittance and reflectance measurements in the spectral range of200 nm to 2500 nm have been carried out at normal incidence. The analysis of the absorption coefficient data showed theexistence of indirect transition for the photon energy E in the range 1~3 eV and direct transition for E >3 eV. From thedetermination of the optical constants (n, k), the dispersion of the refractive index has anomalous behaviour in the region ofthe fundamental absorption edge, and followed by the single- effective oscillator approach.The investigated optical parameterssuch as the optical energy gap Eopt, the high frequency dielectric constant εoo, the oscillator position λo, and the oscillatorstrength So, were significantly affected by the film thickness. The characteristic energy gap obtained from the conductivitymeasurements is nearly half the value of that obtained from the optical data as in the case of thickness 400 nm. The activationenergy is 0.65 eV and the indirect optical gap is 1.32 eV.

Properties and Microstructure of GeS_2-Ga_2S_3-CdS Glasses

The samples of the GeS2-Ga2 S3-CdS pseudo-ternary glassy sysem were prepared by comventional melt-quenching techniques.The microstructure of the GeS2-Ca2 S3-CdS glasses was analyzed thoroughly using Raman spectra and the relationships among the composition,microstructure and properties（such as thermal properties,densities,optical properties）were probed.The experimental results indicate that the GeS2 acts as the network former,the Ga2S3 as the net intermediate,and the CdS as the net modifier,The GeS2 and Ga2S3 exist in the form of [GeS4/2],[GaS4/2]tetrahedra or S3G3（Ga）-（Ga）GeS3 ethane-like units within the glassy network,and the addition of CdS mainly breaks the Ge（Ga）-（Ga）Ge bonds among the ethane -like units,leading to the formation of [GeS4/2].[GaS4/2]tetrahedra.The Tg and Tx have tight relations on the congregated degree of glassy network,however,λvis,n and d are hardly involved into the connectional dependence of the space arrangement.

Structural evolution study of additions of Sb_2S_3 and CdS into GeS_2 chalcogenide glass by Raman spectroscopy

The structures of pseudo-binary GeS2-Sb2S3, GeS2-CdS, Sb2S3-CdS, and pseudo-ternary GeS2-Sb2S3-CdS chalco- genide systems are systematically investigated by Raman spectroscopy. It is shown that a small number of [S3Ge-GeS3] structural units （SUs） and -S-S-/S8 groups exist simultaneously in GeS2 glass which has a three-dimensional continuous network backbone consisting of cross-linked corner-sharing and edge-sharing [GeS4] tetrahedra. When Sb2S3 is added into GeS2 glass, the network backbone becomes interconnected [GeS4] tetrahedra and [SbS3] pyramids. Moreover, Ge atoms in [S3Ge-GeS3] SUs tend to capture S atoms from Sb2S3, leading to the formation of [S2Sb-SbS2] SUs. When CdS is added into GeS2 glass, [Cd4GeS6] polyhedra are formed, resulting in a strong crystallization tendency. In addition, Ge atoms in [S3Ge-GeS3] SUs tend to capture S atoms from CdS, resulting in the dissolution of Ge-Ge bond. Co-melting of Sb2S3 or CdS with GeS2 reduces the viscosity of the melt and improves the homogeneity of the glass. The GeS2 glass can only dissolve up to 10-mol% CdS without crystallization. In comparison, GeS2-SbzS3 glasses can dissolve up to 20-mo1% CdS, implying that Sb2S3 could delay the construction of [Cd4GeS6] polyhedron and increase the dissolving amount of CdS in the glass.

Glass formation and physical properties of Sb_(2)S_(3)–CuI chalcogenide system

Novel chalcogenide glasses of pseudo-binary(100-x)Sb_(2)S_(3-x)CuI systems were synthesized by traditional meltquenching method.The glass-forming region of Sb_(2)S_(3)-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 Sb_(2)S_(3).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.

Ultra-broadband modulation instability gain characteristics in As_2S_3 and As_2Se_3 chalcogenide glass photonic crystal fiber

Based on the designed As2Se3 and As2S3 chalcogenide glass photonic crystal fiber（PCF） and the scalar nonlinear Schrdinger equation,the effects of pump power and wavelength on modulation instability（MI） gain are comprehensively studied in the abnormal dispersion regime of chalcogenide glass PCF.Owing to high Raman effect and high nonlinearity,ultra-broadband MI gain is obtained in chalcogenide glass PCF.By choosing the appropriate pump parameter,the MI gain bandwidth reaches 2738 nm for the As2Se3 glass PCF in the abnormal-dispersion region,while it is 1961 nm for the As2S3 glass PCF.

Study on Elimination of Oxygen Absorption in Chalcogenide Glass

Decreasing the absorption is a key process for chalcogenide glass preparation. The glass character of oxygen absorption and some means to remove the oxygen absorption were introduced.

Flexible one-dimensional photonic crystal films composed of chalcogenide glass and water-soluble polymer for curvature sensing

Curvature sensing plays an important role in structural health monitoring,damage detection,real-time shape control,modification,etc.Developing curvature sensors with large measurement ranges,high sensitivity,and linearity remains a major challenge.In this study,a curvature sensor based on flexible one-dimensional photonic crystal(1D-PC)films was proposed.The flexible 1D-PC films composed of dense chalcogenide glass and water-soluble polymer materials were fabricated by solution processing.The flexible 1D-PC film curvature sensor has a wide measurement range of 33-133 m-1and a maximum sensitivity of0.26 nm/m^(-1).The shift of the transmission peak varies approximately linearly with the curvature in the entire measurement range.This kind of 1D-PC film curvature sensor provides a new idea for curvature sensing and measurement.

Third-order nonlinear wavelength conversion in chalcogenide glass waveguides towards mid-infrared photonics

The increasing demand in spectroscopy and sensing calls for infrared(mid-IR)light sources.Here,we theoretically investigate nonlinear wavelength conversion of Ge_(28)Sb_(12)Se_(60)chalcogenide glass waveguide in the mid-IR spectral regime.With waveguide dispersion engineering,we predict generation of over an octave wavelength(2.8μm-5.9μm)tuning range Raman soliton self-frequency shift,over 2.5 octaves wavelength cover range supercontinuum(1.2μm-8.0μm),as well as single soliton Kerr comb generated in suspended Ge_(28)Sb_(12)Se_(60)waveguide.Our findings evidenced that Ge_(28)Sb_(12)Se_(60)chalcogenide glass waveguides can simultaneously satisfy the generation of Raman soliton self-frequency shift,supercontinuum spectrum,and Kerr frequency comb generation through dispersion engineering towards mid-IR on chip.

Comparative Analysis of Photo-Crystallization in a-Se95Te5 and a-Se95In5 Alloys

We report a comparative study on photo-crystallization in a-Se95 Te5 and a-Se95In5 alloys. The photo-crystallization is achieved by a shining white line on the thin films of these alloys in vacuum for different exposure times. The results indicate that photo-crystallization is fast in a-Se95In5 alloy as compared to a-Se95 Te5 alloy. This is explained in terms of lower thermal stability of a-Se95In5 alloy as compared to a-Se95 Te5 alloy.