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本文针对Sb取代As元素对GexAs(Sb)20Se80–x玻璃阈值行为的影响进行研究. 对理想共价网络玻璃GexAs20Se80–x的玻璃转变温度、密度和折射率等物理参数进行了系统测量, 在其平均配位数为2.4和2.67处验证了转变阈值的存在, 这两个转变分别代表玻璃内部的共价网络结构从欠限制的松散状态到过限制的紧致状态的转变和从二维到三维紧致状态的转变. 但是, 当金属性更强的Sb取代As时, 得到的非理想共价网络玻璃GexSb20Se80–x则会引起转变阈值的变化, 转变阈值改变为化学计量组成. 进一步利用拉曼散射技术对其结构进行表征, 并将拉曼光谱通过分峰拟合分解成不同的结构单元的特征峰, 它们各自的强度变化表现出相同的行为, 这归因于As和Sb的原子半径差异较大所引起的化学效应以及Sb元素具有较强的离子特性.In this paper, We prepare two groups of glasses: one is GexAs20Se80–x with x ranging from 5% to 32.5%, the other is GexSb20Se80–x with x spanning from 5% to 25%, by using the conventional melt-quench method, and investigate the effect of the elemental substitution of Sb for As on the threshold behaviors in GexAs(Sb)20Se80–x glasses. We are to understand to what extent the topological model and chemical order model can explain the correlation between physical properties and glass compositions, and how the chemical composition can affect the glass transition threshold. Glass transition temperature is measured by the differential scanning calorimeter (Mettler-Toledo, DSC1) with different scanning rates ranging from 5 K/min to 30 K/min under a uniform nitrogen gas flow of 50 mL/min, the glass density is measured by a Mettler H20 balance with a MgO crystal used as a reference. Samples of each glass composition are weighed five times and the average density is recorded. The refractive index of the glass at 1.5 um is measured by a Metricon Model 2010 prism coupler. Raman spectra are measured by a T64000 Jobin-Yvon-Horiba micro-Raman spectrometer equipped with a liquid-nitrogen-cooled CCD detector. The 830 nm laser line is used as an excitation source, and the laser power is kept as small as possible to avoid any photo-induced effects. The resolution of the spectrometer is about 0.5 cm–1. The systematic measurements of these physical parameters show that while the transition thresholds at MCN = 2.4 and 2.67 are verified in the Ge-As-Se glasses with ideal covalent network, these two transitions represent the covalent network structure inside the glass from an under-constrained “floppy” network to an over-constrained “rigid” phase and from the two-dimensional to the three-dimensional “stressed rigid” phase respectively. However, when As is substituted by Sb, the the resulting GexSb20Se80–x glass with non-ideal covalent network will change its transition threshold, changing into the chemically stoichiometric composition. We further deconvolve Raman scattering spectra into different structural units and the change of their respective intensity shows the same behavior, which is ascribed to the chemical effect induced by a large difference in atomic radius between As and Sb, and a relatively strong ionic feature of element Sb.
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Keywords:
- chalcogenide glasses /
- glass transition /
- Raman scattering
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图 1 玻璃转变温度随平均配位数和Ge原子含量的变化趋势
Fig. 1. Glass transition temperature as a function of MCN and Ge concentration.
图 2 玻璃密度随平均配位数和Ge原子含量的变化趋势
Fig. 2. Density of the glass as a function of MCN and Ge concentration.
图 3 玻璃折射率随平均配位数和Ge原子含量的变化趋势
Fig. 3. Refractive index of the glass as a function of MCN and Ge concentration.
图 4 GexAs20Se80–x(a)和GexSb20Se80–x(b)玻璃的拉曼散射光谱及其分峰拟合
Fig. 4. Raman scattering spectra of GexAs10Se90-x (a) and GexSb10Se90-x (b) glasses and their decompositions.
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[1] Wang R P 2014 Amorphous Chalcogenides: Advances and Applications (Singapore: Pan Stanford Publisher) pp101–128
[2] Tanaka K, Shimakawa K 2011 Amorphous Chalcogenide Semiconductors and Related Materials (New York: Springer International Publishing) pp110–121
[3] Niu L, Chen Y M, Shen X, Xu T F 2020 Chin. Phys. B 29 087803
Google Scholar
[4] 许思维, 杨晓宁, 杨大鑫, 王训四, 沈祥 2021 物理学报 70 167101
Google Scholar
Xu S W, Yang X N, Yang D X, Wang X S, Shen X 2021 Acta Phys. Sin. 70 167101
Google Scholar
[5] 许思维, 王训四, 沈祥 2023 物理学报 72 017101
Google Scholar
Xu S W, Wang X S, Shen X 2023 Acta Phys. Sin. 72 017101
Google Scholar
[6] Yang A P, Sun M Y, Ren H, Lin H X, Feng X, Yang Z Y 2021 J. Lumin. 237 118169
Google Scholar
[7] Tronc P, Bensoussan M, Brenac A, Sebenne C 1973 Phys. Rev. B 8 5947
Google Scholar
[8] Lucovsky G, Galeener F L, Keezer R C, Geils R H, Six H A 1974 Phys. Rev. B 10 5134
Google Scholar
[9] Philipps J C 1979 J. Non-Cryst. Solids 34 153
Google Scholar
[10] Philips J C 1981 J. Non-Cryst. Solids 43 37
Google Scholar
[11] Tanaka K 1989 Phys. Rev. B 39 1270
Google Scholar
[12] Bulla D A P, Wang R P, Prasad A, Rode A V, Madden S J, Luther-Davies B 2009 Appl. Phys. A 96 615
Google Scholar
[13] Su X Q, Wang R P, Luther-Davies B, Wang L 2013 Appl. Phys. A 113 575
Google Scholar
[14] Wang R P, Smith A, Luther-Davies B, Kokkonen H, Jackson I 2009 J. Appl. Phys. 105 056109
Google Scholar
[15] Wang T, Wei W H, Shen X, Wang R P, Luther-Davies B, Jackson I 2013 J. Phys. D: Appl. Phys. 46 165302
Google Scholar
[16] Wang R P, Smith A, Prasad A, Choi D Y, Luther-Davies B 2009 J. Appl. Phys. 106 043520
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[17] Wei W H, Wang R P, Shen X, Fang L, Luther-Davies B 2013 J. Phys. Chem. C 117 16571
Google Scholar
[18] Georgiev D G, Boolchand P, Micoulaut M 2000 Phys. Rev. B 62 R9228
Google Scholar
[19] Cernosek Z, Cernoskova E, Todorov R, Holubova J 2020 J. Solid State Chem. 291 121599
Google Scholar
[20] Xu S W, Liang T W, Zhu X Y 2023 Chalcogenide Lett. 20 55
Google Scholar
[21] Stevens M, Boolchand P, Hernandez J G 1985 Phys. Rev. B 31 981
Google Scholar
[22] Xu S W, Wang R P, Yang Z Y, Wang L, Luther-Davies B 2015 Appl. Phys. Express 8 015504
Google Scholar
[23] 徐航, 彭雪峰, 戴世勋, 徐栋, 张培晴, 许银生, 李杏, 聂秋华 2016 物理学报 65 154207
Google Scholar
Xu H, Peng X F, Dai S X, Xu D, Zhang P Q, Xu Y S, Li X, Nie Q H 2016 Acta Phys. Sin. 65 154207
Google Scholar
[24] Jackson K, Briley A, Grossman S, Porezag D V, Pederson M R 1999 Phys. Rev. B 60 14985
Google Scholar
[25] Wang R P, Zhou G W, Liu Y L, Pan S H, Zhang H Z, Yu D P, Zhang Z 2000 Phys. Rev. B 61 16827
Google Scholar
[26] Xu S W, Wang L, Shen X 2015 Acta Phys. Sin. 64 223302 [许思维, 王丽, 沈祥 2015 物理学报 64 223302]
Google Scholar
Xu S W, Wang L, Shen X 2015 Acta Phys. Sin.64 223302 Google Scholar
[27] Yang G, Bureau B, Rouxel T, Gueguen Y, Gulbiten O, Roiland C, Soignard E, Yarger J L, Troles J, Sangleboeuf J C, Lucas P 2010 Phys. Rev. B 82 195206
Google Scholar
[28] Xu S W, Wang R P, Yang Z Y, Wang L, Luther-Davies B 2016 Chin. Phys. B 25 057105
Google Scholar
[29] Wang Y, Matsuda O, Inoue K, Yamamuro O, Matsuo T, Murase K 1998 J. Non-Cryst. Solids 232 702
Google Scholar
[30] Bhosle S, Gunasekera K, Boolchand P, Micoulaut M 2012 Int. J. Appl. Glass. Sci. 3 205
Google Scholar
[31] Saffarini G 1994 Solid State Commun. 91 577
Google Scholar
[32] Giridhar A, Narasimham P S L, Mahadevan S 1981 J. Non-Cryst. Solids 43 29
Google Scholar
[33] Opletal G, Drumm D W, Petersen T C, Wang R P, Russo S P 2015 J. Phys. Chem. A 119 6421
Google Scholar
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