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1.
The method of annihilating positrons in positron annihilation lifetime measuring mode is applied to study mechanism of rare‐earth doping in Ga‐codoped arsenic selenide As2Se3 glass modified with Sb. The atomic‐deficient structure of parent As2Se3 glass is imagined as containing positron‐trapping sites in the form of free‐volume voids within cycle‐type arrangement of corner‐sharing trigonal AsSe3/2 pyramids, composed of atomic‐accessible geometrical holes arrested by surrounding atomic‐inaccessible Se‐based bond‐free solid angles. The Ga codoping in As2Se3 glass causes gradual decrease in trapping rate and fraction of trapped positrons due to agglomeration of free‐volume voids. Partial As‐to‐Sb replacement in Ga‐codoped As‐Se glasses leads to better stability against crystallization processes and possibility to further rare‐earth doping without principal changes in the type of positron‐trapping defects. Effect of 500 wppm of Pr3+ in Ga2(As0.28Sb0.12Se0.60)98 glass is explained in terms of competitive contribution of changed occupancy sites in Ga‐modified glassy network available for rare‐earth ions and annihilating positrons.  相似文献   

2.
Gallium (Ga) helps solubilize rare‐earth ions in chalcogenide glasses, but has been found to form the dominant crystallizing selenide phase in bulk glass in our previous work. Here, the crystallization behavior is compared of as‐annealed 0–3000 ppmw Dy3+‐doped Ge–As–Ga–Se glasses with different Ga levels: Ge16.5As(19?x)GaxSe64.5 (at.%), for x = 3 and 10, named Ga3 and Ga10 glass series, respectively. X‐ray diffraction and high‐resolution transmission electron microscopy are employed to examine crystals in the bulk of the as‐prepared glasses, and the crystalline phase is proved to be the same: Ge‐modified, face centered cubic α‐Ga2Se3. Light scattering of polished glass samples is monitored using Fourier transform spectroscopy. When Ga is decreased from 10 to 3 at.%, the bulk crystallization is dramatically reduced and the optical scattering loss decreases. Surface defects, with a rough topology observed for both series of as‐prepared chalcogenide glasses, are demonstrated to comprise Dy, Si, and [O]. For the first time, evidence for the proposed nucleation agent Dy2O3 is found inside the bulk of as‐prepared glass. This is an important result because rare‐earth ions bound in a high phonon–energy oxide local environment are, as a consequence, inactive mid‐infrared fluorophores because they undergo preferential nonradiative decay of excited states.  相似文献   

3.
Pulsed laser deposition was used to prepare amorphous thin films from (GeSe2)100?x(Sb2Se3)x system (x = 0, 5, 10, 20, 30, 40, 50, and 60). From a wide variety of chalcogenide glass‐forming systems, Ge–Sb–Se one, especially in thin films form, already proved to offer a great potential for photonic devices such as chemical sensors. This system has a large glass‐forming region which gives the possibility to adjust the chemical composition of the glasses according to required physical characteristics. The chemical composition of fabricated thin films was analyzed via X‐ray photoelectron spectroscopy (XPS) and compared to energy dispersive spectroscopy (EDS) data. The results of both techniques agree well: a small deficiency in chalcogen element and an excess of antimony was found. The structure of as‐deposited thin films has been investigated by XPS. The presence of the two main structural units, [GeSe4] and [SbSe3] proposed by Raman scattering spectroscopy data analysis, was confirmed by XPS. Moreover, XPS core level spectra analysis revealed the presence of M–M bonds (M = Ge, Sb) in (Ge,Sb)–Ge–(Se)3 and (Ge,Sb)–Sb–(Se)2 entities that could correspond to Ge‐based tetrahedra and Sb‐based pyramids where one of its Se atoms at corners is substituted by Ge or Sb ones. The content of depicted M–M bonds tends to increase with introduction of antimony in the amorphous network of as‐deposited thin films from x = 0 to x = 40 and then it decreases. XPS analysis of as‐deposited thin films shows also the presence of the (Ge,Sb)–Se–(Ge,Sb) and Se–Se–(Ge,Sb) entities.  相似文献   

4.
For fiber‐optic mid‐infrared bio‐ and chemical‐sensing, Ge–Sb–Se glass optical fibers are more attractive than Ge–As–Se because of: (i) lowered toxicity and (ii) lower phonon energy and hence transmission to longer wavelengths, with potential to reach the spectral “fingerprint region” for molecular sensing. There is little previous work on Ge–Sb–Se fibers. Here, fibers are fabricated from two glass compositions in the GexSb10Se90?x atomic (at.) % series. Both glass compositions are of similar mean‐coordination‐number, lying in the overconstrained region, yet of different chemical composition: stoichiometric Ge25Sb10Se65 at. % and non‐stoichiometric Ge20Sb10Se70 at. %. Thermal analysis on bulk glasses has previously shown that the former exhibited the maximum glass stability of the series. However, during fiber‐drawing of Ge25Sb10Se65 at. %, the preform tip is found to undergo surface‐devitrification to monoclinic GeSe2 alone, the primary phase, no matter if the preform is an annealed, as‐melted rod or annealed, extruded rod. The heating rate of the preform‐tip to the fiber‐drawing temperature is estimated to be up to ~100°C/min to ~490°C. Lower heating rates of 10°C/min using thermal analysis, in contrast, encourage crystallization of both Sb2Se3 and GeSe2. The non‐stoichiometric: Ge20Sb10Se70 at. % composition drew successfully to low optical loss fiber, no matter whether the preform was an annealed, as‐melted rod or annealed, extruded rod.  相似文献   

5.
This work reports on process‐induced impurities in rare‐earth ion: Dy3+‐doped selenide chalcogenide glasses, which are significant materials for active photonic devices in the mid‐infrared region. In particular, the effect of contamination from the silica glass ampoule containment used in chalcogenide glass synthesis is studied. Heat‐treating Dy‐foil‐only, and DyCl3‐only, separately, within evacuated silica glass ampoules gives direct evidence of silica ampoule corrosion by the rare‐earth additives. The presence of [Ga2Se3] associated with [Dy] on the silica glass ampoule that has been contact with the chalcogenide glass during glass melting, is reported for the first time. Studies of 0–3000 ppmw Dy3+‐doped Ge16.5As9Ga10Se64.5 glasses show that Dy‐foil is better than DyCl3 as the Dy3+ additive in Ge‐As‐Ga‐Se glass in aspects of avoiding bulk crystallization, improving glass surface quality and lowering optical loss. However, some limited Dy/Si/O related contamination is observed on the surfaces of Dy‐foil‐doped chalcogenide glasses, as found for DyCl3‐doped chalcogenide glasses, reported in our previous work. The surface contamination indicates the production of Dy2O3 and/or [≡Si‐O‐Dy=]‐containing particles during chalcogenide glass melting, which are potential light‐scattering centers in chalcogenide bulk glass and heterogeneous nucleation agents for α‐Ga2Se3 crystals.  相似文献   

6.
In this work, Pr3+ ion-doped Ge20Ga15−xSbxSe65 (x = 0, 5, 10, in mol%), Ge20Sb15−yInySe65 (y = 5, 10, in mol%), Ge20Ga15−zInzSe65 (z = 0, 5, 10, in mol%), and Ge20Ga5Sb10Se60I5 glasses were prepared. The structural units, thermal properties, and optical properties of these glasses were analyzed. In addition, a comprehensive comparison study of the effects of metal ions (Sb, Ga, and In), S/Se ratio, and I content on the mid-infrared (MIR) luminescence of Pr3+ ions was conducted. Under a 1.55-μm laser pump, 0.2 mol% of Pr3+ ion-doped chalcogenide glasses performed strong photoluminescence in the wavelength range of 3.5-5.5 μm. Results indicated that the Sb-containing glass performed the strongest emission intensity among the studied glasses. Moreover, halogen element I can reduce the phonon energy of the matrix, which is beneficial to the luminescence of Pr3+ ions and provide significant possibilities for developing MIR lasers and amplifiers.  相似文献   

7.
《Ceramics International》2022,48(18):25756-25763
In order to improve the fiber drawing performances including the anti-crystallization in fiber drawing process and the mechanical properties, the fourth component of antimony (Sb) was introduced into Ga0.8As39.2S60 glass, and a serial Ga0.8As39.2-xSbxS60 (x = 0, 1, 3,5, 7, 9 and 11) novel chalcogenide glasses doped with 3000 ppmw Dy3+ ions were prepared. The influences of antimony content on the physical properties, spectroscopic properties and fiber forming ability of glass were investigated. The experiment results indicate that the introduction of moderate antimony into glass effectively improves the fiber drawing performance and the spectroscopic properties of Dy3+ ions. The Ga0.8As34.2Sb5S60 composition glass possesses the best performance and it is recommended a good candidate for mid-infrared laser working medium.  相似文献   

8.
《Ceramics International》2022,48(15):21663-21670
In this study, two series of GaxSb40-xS60 (x = 4, 6, 8, 10 mol%) and GaySb36S64-y (y = 3, 5, 6 mol%) glasses were prepared and the relationship between their compositional and acousto-optic (AO) properties was investigated systematically for the first time. In the GaySb36S64-y system, the AO figure of merit (M2) increased as the Ga increased, and the maximum M2 of the Ga6Sb36S58 glass was 455.78 × 10?18 s3/g, which is ~301 times greater than that of fused silica and ~2.5 times greater than that of As2S3 chalcogenide (ChG) glass at 1550 nm. However, its thermo-optic coefficients (dn/dT) varied greatly (32.1 × 10?6 °C?1–57.2 × 10?6 °C?1), and acoustic attenuations (α) at 10 MHz were high, from 5.446 dB/cm to 7.274 dB/cm. In the GaxSb40-xS60 glass system, the M2 value and α at different ultrasonic frequencies gradually decreased with the improvement of Ga. Compared with the GaySb36S64-y system, the GaxSb40-xS60 glass system had lower α (at 10 MHz) and dn/dT, which are 5.001 dB/cm–5.563 dB/cm and 17.3 × 10?6 °C?1–55.6 × 10?6 °C?1, respectively. These results provide a significant reference for the further development of novel ChG glasses and help expand their application fields.  相似文献   

9.
Chalcogenide glasses and more importantly their glass‐ceramics counterparts have been an interesting but very peculiar class of thermoelectric materials, with inherently low thermal conductivity (<0.3 W/m·K). In this study, we report on the fabrication of glasses in the ternary system Cu‐As‐Te (CuxAs55?xTe45 [5≤x≤20], Cu15As85?yTey [45≤y≤70], and Cu20As80?yTey [45≤y≤65]) by melt‐quenching and subsequent spark plasma sintering treatment. Their thermal and structural properties have been studied by differential scanning calorimetry and Raman spectroscopy, leading to give insights into the structural evolution of the glassy matrix. Coupling this information with the analysis of their electrical transport properties allowed us to deepen further our understanding of the compositional effect on their thermoelectric properties, and indirectly how the evolution of their electronic band structure is at play. Despite exhibiting low ZT values by themselves, Cu‐As‐Te glasses may still be interesting candidates for thermoelectricity through partial crystallization for which knowing the relationship between composition and properties remains essential.  相似文献   

10.
A systematic investigation is presented, for the first time, of a 1000 ppmw (parts per million, by weight) Dy3+-doped Ge–As–Ga–Se chalcogenide glass series, with a fixed low Ga content of 1 atomic% (at. %), suitable for active mid-infrared fiber optics. Seven glasses constitute the series, which have increasing average coordination number from 2.49 to 2.61, in steps of 0.02, with the GeSe2, As2Se3, and Ga2Se3 stoichiometries kept. Glass formation is confirmed using X-ray diffraction and differential scanning calorimetry. Fourier transform infrared spectroscopy is reported for the series. Parallel plate viscometry enables prediction of fiber-drawing temperatures and, with differential thermal analysis, determines the potential for fiber fabrication. X-ray diffraction of samples after parallel-plate viscometry shows that Ge25As9Ga1Se65 (at. %) alone, in the glass-series, devitrifies to form the single-crystalline phase: monoclinic-GeSe2; scanning electron microscope imaging suggests that this phase is both surface and bulk grown. Overall, the recommended host glass at. % compositions for doping with rare-earth ions and drawing to active mid-infrared fiber are: Ge17.5As18Ga1Se63.5, Ge15As21Ga1Se63, and Ge12.5As24Ga1Se62.5.  相似文献   

11.
Series of glassy and glass‐ceramic samples in the GeSe2–Ga2Se3–NaI system is prepared by melt‐quenching technique and the glass‐forming region is well‐defined by XRD investigations. Na‐ion conduction behavior is systemically studied by impedance measurements. For the glasses in the series (100?2x)GeSe2xGa2Se3xNaI, ionic conductivities increased with increasing x, whereas the attributed activation energy of ion conduction decreases. The enhanced mechanism is discussed by employing Raman spectra. In addition, the effect of the crystal phases NaI and Ga2Se3 on the ionic conduction behavior in the (70?x)GeSe2xGa2Se3–30NaI samples is discussed. Although it shows that the poorly conducting crystallites of NaI and Ga2Se3 have a negative effect on the ionic conductivities in this series, the highest ionic conductivity of 1.65 × 10?6 S/cm is obtained in the 45GeSe2–25Ga2Se3–30NaI glass. Finally, this study also demonstrates a possible way to search appropriate Na‐ion solid electrolytes for all‐solid‐state batteries.  相似文献   

12.
We explored the structure and physical properties of Ge15Sb20Se65‐xSx (with x = 0, 16.25, 32.5, 48.75, and 65) glasses in order to screen the best compositions for the applications in photonics, since the laser damage thresholds in Se‐based glasses are too low although their optical nonlinearities are high. We found that, linear and nonlinear refractive index of the glasses decreased, but glass transition temperature Tg, optical bandgap Eg and the laser damage threshold increased with increasing S content. We further employed Raman scattering and high‐resolution X‐ray photoelectron spectra to probe the structure of the glasses. Through the analysis of the evolution of the different structural units in the glasses, it was concluded that, the heteropolar bonds (Ge–Se/S, Sb–Se/S) were dominated in these glasses. With the increase in chalcogen Se/S ratio, the number of the Se‐related chemical bonds (Ge–Se, Sb–Se and Se–Se) increased and that of S‐related chemical bond (Ge–S, Sb–S and S–S) decreased gradually, and Ge was prior to bond with S rather than Se. The elemental substitution thus had negligible effect on the glass structure. The change of the physical properties was mainly due to the difference of the strength of the chemical bonds between S–Ge(Sb) and Se–Ge(Sb).  相似文献   

13.
Tellurium based glasses have interesting thermoelectric characteristics. However, their high electrical resistivity is still an obstacle to considering them for thermoelectric applications. In this work, the (Te85Se15)60???0.6xAs40???0.4xCux glass system was studied. This revealed that Cu can act as glass former and increase both glass thermal stability and electrical conductivity. The best candidate, (Te85Se15)45As30Cu25, was chosen to prepare composites with Bi0.5Sb1.5Te3 using spark plasma sintering. These glass ceramic samples exhibited a much better thermoelectric performance. Glass ceramics with 50?mol. % of Bi0.5Sb1.5Te3 show a maximum ZT value equal to 0.37 at 413?K. Meanwhile, the advantages of glass including low sintering temperature and high formability are well maintained.  相似文献   

14.
Laser ablation of Ga-Sb-Te chalcogenide thin films prepared by radiofrequency magnetron co-sputtering was monitored with quadrupole ion trap time-of-flight mass spectrometry (QIT-TOF-MS). The mass spectra of 11 thin films of various compositions (Ga: 0–53.1, Sb: 0–52.0, and Te: 0–100.0 at. %) were recorded. Several series of unary (Gax, Sby, and Tez) binary (GaxSby, GaxTez, and SbyTez), and ternary GaxSbyTez clusters were identified in both positive and negative ion modes. Stoichiometry of observed clusters was determined. Up to 18 binary clusters (positively and negatively charged) were detected for thin film with low Sb content of 6.5 at. %. The highest number (4) of ternary clusters was observed for thin film with high Te content of 66.7 at. %. The number of generated clusters and their peaks intensity varied according to the chemical composition of thin films. Altogether, 41 clusters were detected. The laser ablation monitoring shows laser-induced fragmentation of thin film structure. The relation of clusters stoichiometries to the chemical composition of thin films is discussed. The fragmentation can be diminished by covering a surface of thin films with paraffin's, glycerol, or trehalose sugar thin layers. The stoichiometry of generated clusters shows partial structural characterization of thin films.  相似文献   

15.
Two valence states of tin atoms in (As2Se3)1 ? z (SnSe)z ? x(GeSe)x and (As2Se3)1 ? z (SnSe2)z ? x(GeSe2)x glasses are identified by Mössbauer and photoelectron spectroscopy. It is demonstrated that the presence of doubly charged tin ions in the structural glass network does not give rise to impurity conduction or impurity optical absorption. The inference is made that these glasses can be treated as semiconductor solid solutions.  相似文献   

16.
Laser Desorption Ionization Time‐of‐Flight Mass Spectrometry was exploited for the characterization of Ge–As–Se chalcogenide glasses and corresponding thin films fabricated using pulsed laser deposition. Main achievement of the paper is the determination of laser generated clusters’ stoichiometry. The clusters observed were Asb+ (b = 1–3), Se2?, binary AsbSe+ (b = 1–3), AsbSec? (b = 1–3, c = 1–4), Ge2Sec? (c = 2–3), As3Se2+, Ge2Asb? (b = 2–3), Ge3Asb? (b = 1–2), Ge3Se4?, As5Sec? (c = 4–5), GeAsSe4?, GeaAsSe5? (a = 1–4), GeAs2Se3?, GeAs3Se2?, Ge2As2Se2?, Ge2AsSec? (c = 6–7), and GeAs3Sec? (c = 5–6) (in positive as well as in negative ion mode). The stoichiometries of identified species are compared with the structural units of the glasses/thin films revealed via Raman scattering spectra analysis. Some species are suggested to be fragments of bulk glass as well as thin films. Described method is useful also for the evaluation of the contamination of chalcogenide glasses or their thin films.  相似文献   

17.
The standard method-recording of X-ray fluorescence spectra of a standard Ge0.2As0.4Se0.4 alloy followed by evaluation of its component spectral fractions and by building of dependences x XRF = f(x) and y XRF = f(y) for the As x (Ge y Se1 ? y )1 ? x system—was employed to determine the quantitative contents of arsenic, germanium, and selenium in the Ge t As s Se1 ? t ? s glassy alloys with X-ray fluorescence analysis. The accuracy of the composition’s determination was ±0.0005 for both x and y. However, it was not possible to use the external standard method for determining the tellurium in As y Se1 ? y )1 ? x Te x alloys because tellurium, arsenic, and selenium had significantly different X-ray fluorescence characteristics and, hence, substitution of the arsenic or selenium for tellurium at a fixed y resulted in tellurium emission fraction changing.  相似文献   

18.
The acousto-optic parameters of Ge10As90−xTex (x = 30, 40, 50, 60, 70 mol%) and Ge10As20Te70−ySey (y = 20, 30, 40, 50 mol%) glasses, were studied systematically to compare the pros and cons of Te-based and Se-based chalcogenide glasses in acousto-optic performance, as well as the thermomechanical properties. In the Ge10As90−xTex system, the acousto-optic figure of merit (M2) increased with increased Te content, and the maximum M2 of 2279 × 10−18 s3/g, which is 13 times that of commercial single-crystal Ge, obtained in Ge10As20Te70 at 10.6 μm. However, its thermal properties and elastic modulus decreased and the acoustic attenuation (α) at different ultrasonic frequencies increased accordingly. In the Ge10As20Te70−ySey system, the thermomechanical performance of the glasses improved with the introduction of Se element, the overall α was lower than that of Te-based chalcogenide glasses, and the minimum α was 5.29 dB/cm at 30 MHz ultrasonic frequency, although its M2 was inferior to that of Te-based chalcogenide glasses. Additionally, the difference in the α of these glasses was smaller at low ultrasonic frequencies than at high ultrasonic frequencies. This work will promote the practical application of chalcogenide glasses as promising materials with outstanding acousto-optic properties in low ultrasonic frequency acousto-optic devices.  相似文献   

19.
Na‐ion conducting Na1+x[SnxGe2?x(PO4)3] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe2(PO4)3 (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe2(PO4)3] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO6) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO4). The highest bulk Na+ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na1.5[Sn0.5Ge1.5(PO4)3]) of tetrahedral Ge4+ ions by Sn4+ on Na–Ge–P network. CV studies of the best conducting Na1.5[Sn0.5Ge1.5(PO4)3] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.  相似文献   

20.
This paper reports on the results of an investigation into the concentration behavior of the glass-forming ability, heat resistance, glass transition temperature, density, refractive index, transparent spectral region, and impurity optical absorption of glasses in the Ga4Ge21Se50-Sb2Se3 system. The data obtained indicate that glasses in the Ga4Ge21Se50-Sb2Se3 system with a high Sb2Se3 content are of interest as materials for use in fiber optics.  相似文献   

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