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1.
The characteristic A1 peak at 199 cm−1 in the Raman spectrum of amorphous GeSe2 were compared with the peaks at 211 and 216 cm−1 in the spectrum of crystalline GeSe2. It was proved that the crystalline 216 cm−1 peak is an intrinsic mode which is enhanced by the bulk exciton transition. From a model calculation using a valence force field and bond polarizability, the 211 cm−1 peak was assigned to in-phase breathing vibrations extended along the GeSe4 tetrahedral chain structure, while the 216 cm−1 peak was attributed to in-phase breathing vibrations quasi-localized at the GeSe4 edge-sharing tetrahedra. The phonon density of states in the crystal has a doublet peak similar to the amorphous Raman spectrum. A correspondence between the amorphous and the crystalline Raman spectra was proposed.  相似文献   

2.
The laser irradiated crystallization process in amorphous GeSe2 was studied by Raman scattering to discriminate between thermal and photo-induced contributions. Amorphous GeSe2 crystallizes into a low-temperature (LT) form, LT-GeSe2, and a high-temperature (HT) form, HT-GeSe2. An amorphous sample was annealed at various temperatures and times in an electric furnace with and without laser irradiation. The laser power was adjusted to about 20 mW having a 0.4 mm spot size to determine the photo-induced effect. The difference between the thermal and laser irradiated crystallization process was discussed by considering the activation energy of crystallization. The activation energy due to laser irradiation above the band-gap energy was found to be smaller than that for the pure thermal crystallization process. We present a model for the photo-enhanced effect in which the lone-pair electrons of Se atoms are excited by the photons and the bond switching or atomic rearrangement occurs when the electrons relax through an electron–phonon interaction.  相似文献   

3.
The Raman scattering spectra of various forms of GeSe2, such as amorphous films, single crystals, and small crystals prepared by a gas-evaporation deposition technique, are investigated with an excitation photon energy ranging from 2.1 to 2.8 eV. In the spectra of the crystals, there are two Raman bands, originating from two types of breathing vibrations of the GeSe4/2 tetrahedra: one is spread over the corner-sharing tetrahedra and the other is quasi-localized on the edge-sharing tetrahedra. In addition to the resonant Raman scattering related to the edge-sharing tetrahedra through the exciton transition observed with 2.71 eV excitation in the single crystals, a new resonant spectrum is found only in the small crystals with 2.54 eV excitation. With increasing disorder in the crystals, the intensity ratio between the two breathing vibration bands increases in the off-resonant excitation region. The Raman spectra in the amorphous states are ascribed to the breathing vibrations of GeSe4/2 tetrahedra which form a medium-range structure topologically similar to that of crystalline fragments.  相似文献   

4.
The interest in superionic systems has increased in recent years because of the potential application of these materials as solid electrolytes. In this field, amorphous materials present important advantages when compared to the crystalline solids: larger conductivity, isotropy and absence of grain boundaries. In this work, amorphous alloys of compositions (Ge25Se75)100−yAgy with y=10, 15, 20 and 25 at.% have been studied. Amorphous samples in bulk were obtained from the liquid by water quenching (melt-quenching technique). The crystallization kinetics of the amorphous alloys have been studied under continuous heating and isothermal conditions by means of differential scanning calorimetry. A glass transition and two exothermic transformations were observed in all the samples. The quenched samples and the crystallization products have been characterized by X-ray diffraction. The primary crystallization of the ternary phase Ag8GeSe6 and the secondary phase GeSe2 was observed. The glass and crystallization temperatures, the activation energy and the crystallization enthalpy are reported. The first step of the crystallization of the Ag8GeSe6 phase in all the (Ge25Se75)100−yAgy samples is modelled taking into account the Johnson–Mehl–Avrami–Kolmogorov theory and considering that the changes in the composition only modify the viscosity of the undercooled liquid. The transformation diagrams (TTT and THRT) are calculated and the glass forming ability is analyzed. The experimental results are discussed and correlated with the structures proposed for the glass. The present results and conclusions are also compared with those reported by other authors.  相似文献   

5.
《Journal of Non》2000,270(1-3):137-146
The Ge25Ga5Se70 and Ge30Ga5Se65 pure and Pr3+-doped glasses were prepared by direct synthesis from elements and PrCl3. It was found that up to 1 mol% PrCl3 can be introduced in the Ge25Ga5Se70 and Ge30Ga5Se65 glasses. Both types of glasses with overstoichiometric and substoichiometric content of Se were homogeneous and of black color. The optical energy gap is Eoptg=2.10 eV, and the glass transition temperature is Tg=543 K for Ge25Ga5Se70 and Tg=633 K for Ge30Ga5Se65. The long-wavelength absorption edge is near 14 μm and it corresponds to multiphonon processes. Doping by Pr3+ ions creates absorption bands in transmission spectra, which can be assigned to the electron transitions from the ground 3H4 level to the higher energy levels of Pr3+ ions 3H5, 3H6, 3F2, 3F3 and 3F4, respectively. By excitation with YAG:Nd laser line (1064 nm), two intense luminescence bands (1343 and 1601 nm) were excited. The first band can be ascribed to electron transitions between 1G4 and 3H5 energy levels of Pr3+ ions. Full width at half of maximum (FWHM) of the intensity of luminescence was found to be 70 nm for (Ge25Ga5Se70)1 − x(PrCl3)x and (Ge30Ga5Se65)1 − x(PrCl3)x glasses. The FWHM in selenide glasses is lower than in halide and sulphide glasses. The second luminescence band (1601 nm) can be probably ascribed to the transitions between 3F3 and 3H4 energy levels of Pr3+ ions. The absorption and luminescence spectra of Pr3+ ions in studied glasses are slightly influenced by stoichiometry of glassy matrix. The Raman spectra of studied glasses were deconvoluted and assignment of Raman bands to individual vibration modes of basic structural units was suggested. The structure of studied glasses is mainly formed by corner-sharing and edge-sharing GeSe4 tetrahedra. The vibration modes of Ga-containing structural units were not found, they are apparently overlapping with Ge-containing structural units due to small difference between atomic weights of Ge and Ga. In the glasses with substoichiometry of Se, the Ge–Ge bonds of Ge2Se6 structural units were found. In Se-rich glasses the Se–Se vibration modes were found. In all studied glasses also ‘wrong' bonds between like atoms were found in small amounts. Maximum phonon energy of studied glasses is 320 cm−1.  相似文献   

6.
Binary glasses containing no modifying oxides, such as SiO2---GeO2, SiO2---B2O3, SiO2---P2O5, GeO2---B2O3, Al2O3---P2O5 and ternary glasses SiO2---GeO2---P2O5, Al2O3---B2O3---P2O5, B2O3---SiO2---P2O5, Al2O3---ZrO2---P2O5 have been prepared by melting and CVD methods. The Raman spectra have also been measured. Structural characteristics of SiO2, GeO2, B2O3, P2O5 in different glass systems are analysed. There exist coordination number changes in B2O3- and GeO2-containing glasses and linkage changes between tetrahedra (SiO4) and (PO4) in SiO2 and P2O5 containing glasses. The structure of Al2O3 containing glasses is homogeneous and the structure of B2O3 containing glasses is inhomogeneous. These experimental results are in coincidence with the X-ray small angle scattering analysis.  相似文献   

7.
为寻求新型热障涂层用陶瓷材料,本文采用高温固相烧结法制备了(Sm0.5Gd0.2Nd0.3)2(Hf0.3Ce0.7)2O7复合氧化物。利用XRD分析了其晶体结构,SEM分析其显微组织,膨胀仪测试其热膨胀性能,激光热导仪测试其热扩散系数。结果表明,成功制备了具有单一萤石晶体结构的(Sm0.5Gd0.2Nd0.3)2(Hf0.3Ce0.7)2O7复合氧化物。其显微组织结构致密,晶界清晰无其他相存在。由于复杂的元素组成和较大的原子量,其热导率明显低于7YSZ和Sm2Ce2O7。其较低的热膨胀系数则归因于B位离子较小的离子半径,但其热膨胀系数依然满足热障涂层的要求。  相似文献   

8.
为克服TiO2纳米管在光电转换时电子-空穴复合率高和吸收光谱范围窄的缺陷,利用多酸H4SiW12O40(SiW12)和CsPbI3量子点对其协同修饰,采用电沉积法将SiW12沉积在TiO2纳米管上,制备了SiW12/TiO2纳米管复合薄膜;使用高温热注射法合成出CsPbI3量子点,再通过化学浴沉积法沉积CsPbI3量子点到复合薄膜上,得到SiW12/CsPbI3/TiO2纳米管复合薄膜,探究SiW12沉积时间、CsPbI3沉积次数对TiO2纳米管光电性能的影响。利用扫描电子显微镜(SEM)、能谱仪(EDS)、透射电子显微镜(TEM)、X射线衍射(XRD)仪、红外分光光度计(FT-IR)、紫外-可见分光光度计(UV-Vis)对薄膜进行表征,使用电化学工作站测试薄膜的光电化学性能。结果表明:TiO2纳米管沉积多酸SiW12和CsPbI3量子点后,光吸收范围扩大、电荷转移电阻降低,光电转换效率得到显著提升,最高达到0.52%。说明SiW12和CsPbI3的协同作用很好地抑制了TiO2纳米管电子-空穴的复合,并拓宽了吸收光谱范围,提高了TiO2纳米管的光电转换效率。  相似文献   

9.
Study of electrical properties of two series of glasses (ZrF4)54(BaF2)30(ThF4)5(LaF3)3(RbF)8(1−x)(RbCl)8x (0 x 1) and (ZrF4)50(BaF2)30(ThF4)5(LaF3)3(RbF)12(1−x)(RbCl)12x (0 x 1) demonstrates the existence of a mixed mobile anion effect in these anion-conducting glasses. The effective medium approach has been applied to these materials: a satisfactory fitting is obtained as a function of the Cl/(Cl + F) ratio and temperature; the ionic transport in these glasses takes place along preferential pathways.  相似文献   

10.
本文对TOPCon电池发射结的叠层钝化膜进行了研究,对比了3种不同叠层钝化膜(SiO2/SiNx、Al2O3(1.5 nm)/SiNx、SiO2/Al2O3(1.5 nm)/SiNx)的钝化性能。结果表明:Al2O3(1.5 nm)/SiNx的钝化性能优于SiO2/SiNx,SiO2/Al2O3(1.5 nm)/SiNx的钝化水平最佳,隐开路电压均值可达到705 mV。基于Al2O3/SiNx叠层膜研究了Al2O3厚度(1.5 nm、3 nm和5 nm)对钝化性能和电池转换效率的影响。当Al2O3厚度由1.5 nm增加到3 nm时,钝化性能得到明显提升,隐开路电压均值提高了20 mV,达到707 mV,对应电池的光电转换效率升高了0.23个百分点,与SiO2/Al2O3(1.5 nm)/SiNx叠层膜电池的转换效率持平。然而,当Al2O3厚度继续增加至5 nm时,隐开路电压均值保持不变。因此可以使用Al2O3(3 nm)/SiNx叠层膜代替SiO2/Al2O3(1.5 nm)/SiNx叠层膜,不仅简化了电池的工艺步骤,而且降低了生产成本。  相似文献   

11.
以Ni3[Ge2O5](OH)4为载体,氟钛酸铵为原料,采用水热辅助液相沉积法制备了纳米TiO2/ Ni3[Ge2O5](OH)4复合材料。通过X射线衍射(XRD)、拉曼光谱分析(RM)、场发射扫描电子显微镜(FE-SEM)、高分辨透射电镜(HTEM)、紫外-可见吸收光谱(UV-Vis)等表征手段对样品的物相组成、结构特性及微观形貌做了检测分析,并且探究了不同二氧化钛负载量对纳米TiO2/Ni3[Ge2O5](OH)4复合材料光降解亚甲基蓝能力的影响规律。结果表明,实验实现了纳米TiO2与Ni3[Ge2O5](OH)4的紧密复合与有效分散,TiO2为锐钛矿型结构,平均粒径20 nm。该复合材料能够有效抑制光生载流子的复合,改善材料的吸附性能,提高材料的光催化效率。当复合材料中TiO2与Ni3[Ge2O5](OH)4的摩尔比为3.1∶1时,材料对亚甲基蓝的光催化效率最高,90 min亚甲基蓝的光降解率为99.81%。  相似文献   

12.
刘朋  陈洪霞 《人工晶体学报》2021,50(8):1444-1451
多齿配体2-咪唑乙酸(Hima)、4,4'-连吡啶分别与金属盐Pb(NO3)2和AgNO3反应,得到[Pb2(4,4'-bipy)(ima)(NO3)3]n(1, 3D framework)和[Ag4(4, 4'-bipy)3(ima)2(NO3)2(H2O)2]n(2, 3D framework)两个配位聚合物。根据配位聚合物的结构特点,研究了这两个配位聚合物荧光性质等物理化学性能。配位聚合物1在最大激发波长(λex=346 nm)激发下,荧光的最大发射波长为552 nm,配位聚合物2在最大激发波长(λex=369 nm)激发下,荧光的最大发射波长为444 nm。这可能是由于金属和配体之间发生了电荷转移(LMCT)。  相似文献   

13.
本文以Al(OH)3、煅烧Al2O3和纳米Al2O3为铝源,在KCl和LiCl的混合熔盐介质中,800~1 200 ℃温度范围内保温3 h合成超细ZnAl2O4粉体。采用XRD、SEM、激光粒度仪和比表面分析仪等重点分析了铝源种类对ZnAl2O4粉体合成温度、产物物相组成以及显微形貌的影响。在此基础上探讨了反应温度、熔盐与原料的质量比(Ws/Wr)对粉体合成的影响。结果表明:铝源种类显著影响ZnAl2O4的开始形成温度和粉体性能,相比于煅烧Al2O3,以Al(OH)3和纳米Al2O3为铝源生成ZnAl2O4的速率较快,在900 ℃时即可合成出单相ZnAl2O4。以煅烧Al2O3粉为铝源,当Ws/Wr为3∶1时,在1 000 ℃合成ZnAl2O4粉体的分散性最佳,而温度过高易造成粉体团聚长大。适当的Ws/Wr有利于ZnAl2O4的生成,当Ws/Wr为4∶1时合成的ZnAl2O4粒径最小。ZnAl2O4粉体均在一定程度保持着初始铝源的尺寸和形貌,表明熔盐法合成ZnAl2O4的机理主要遵循着“模板合成机理”。  相似文献   

14.
The enthalpy relaxation behaviour of metal-metalloid type (Fe0.5Co50.5)83P17 and metal-metal type (Fe0.5Co0.5) 90-Zr10 amorphous alloys was investigated with a DSC measurement. The annealing temperature (Ta) dependence of the annealing-induced reversible enthalpy relaxation evaluated with an endothermic showed the maximum at thesame Ta for the two alloys, but the magnitude of the relaxation was considerably smaller for the (Fe0.5Co0.5)90Zr10 alloy. Moreover, it was found that the amorphous (Fe0.5Co0.5)90Zr10 alloy has a larger atomic packing density and a higher activation energy of the enthalpy relaxation than the amorphous (Fe0.5Co0.5)83P17 alloy. Rhe small enthalpy relaxation and high activation energy for the amorphous (Fe0.5Co0.5)90Zr10 alloy were ascribed to the highly packed structure of the metal-metal type amorphous alloy.  相似文献   

15.
通过高温固相法合成Pr3+不同掺杂浓度的K2LaBr5多晶料,采用垂直坩埚下降法生长出K2LaBr5∶Pr单晶,并对晶体进行一系列加工,得到ø12 mm×5 mm的圆柱透明晶体。该晶体属于正交晶系,晶胞参数为a=1.336 0 nm,b=0.992 7 nm,c=0.846 2 nm,Z=4,晶体密度为3.908 g/cm3,熔点为607 ℃。测试了该晶体的X射线粉末衍射、X射线激发发射光谱、光致发光光谱、透过率等。在紫外光以及X射线的激发下,K2LaBr5∶Pr晶体在480~750 nm波长范围内呈现蓝光(3P13H4)、绿光(3P03H4,3P13H5)、橙光(3P13H6,3P13F2)、红光(3P03F2,3P13F3)、深红光(3P13F4),及紫光(3P03F4)等多个可见波长的光输出,表明该晶体具有优良的发光性能。在X射线的激发下,在360~440 nm范围内还观察到一个宽带4f 5d-4f2发射跃迁。稳态瞬态荧光光谱分析仪测出光致衰减时间为10 μs左右,紫外可见分光光度计则测出晶体在可见光波段的透过率达到88%。  相似文献   

16.
为将Ca(H2PO4)2制备KH2PO4过程中的石膏资源化利用,以H3PO4与CaCO3反应制备Ca(H2PO4)2溶液,并与K2SO4溶液反应,进行Ca(H2PO4)2-H3PO4-K2SO4体系中石膏晶型和形貌调控研究。结果表明:通过改变反应时间、反应温度、SO2-4过量系数和CaO含量等参数可对Ca(H2PO4)2-H3PO4-K2SO4体系中石膏晶型和形貌进行调控,制得短柱状α-CaSO4·0.5H2O。体系在温度高于95 ℃和CaO含量为3.0%~5.0%(质量分数,下同)时形成α-CaSO4·0.5H2O,在CaO含量为5.5%主要形成CaSO4·2H2O;反应时间长于20 min和SO2-4过量系数大于1.4将形成K2SO4(CaSO4)5·H2O,导致石膏晶体表面缺陷增加。本实验条件下,适宜反应条件为:反应时间10 min、反应温度95 ℃、SO2-4过量系数1.2和CaO含量5.0%,此条件下可制得长度42~70 μm、直径13~24 μm的短柱状α-CaSO4·0.5H2O,其抗折和抗压强度分别可达5.61 MPa和33.74 MPa,滤液中钾收率和脱钙率分别可达94.23%和83.80%。  相似文献   

17.
The 11B, 27Al, 29Si and 31P magic angle spinning (MAS) NMR spectra of MO–P2O5, MO–SiO2–P2O5 and MO(M2O)–SiO2–Al2O3–B2O3 (M=Mg, Ca, Sr and Ba, M=Na) glasses were examined. In binary MO–P2O5 (M=Ca and Mg) glasses, the distributions of the phosphate sites, P(Qn), can be expressed by a theoretical prediction that P2O5 reacts quantitatively with MO. In the ternary 0.30MO–0.05SiO2–0.65P2O5 glasses, the 6-coordinated silicon sites were detected, whose population increases in the order of MgOxCaO–0.05SiO2–(0.95−x)P2O5 glasses, its population increases with an increase in f (=([P2O5]−[MO]−[B2O3]−[Na2O])/[SiO2]) and has maximum at f=9. The signal due to the 5-coordinated silicon atoms is also observed when x is smaller than 0.45. When three network-forming oxides such as SiO2, Al2O3 and B2O3 coexist, Al2O3 reacts preferably with MO. The populations of 4-coordinated boron atoms, N4, are expressed well with r/(1−r), where r=([Na2O]−[Al2O3])/([Na2O]−[Al2O3]+[B2O3]). The correlation of the Raman signal at 1210 and 1350 cm−1 with the NMR signal of Si(Q6) at −215 ppm is also seen.  相似文献   

18.
CsxWO3纳米棒因其优异的近红外吸收性能得到研究人员的广泛关注,但目前水热法合成CsxWO3纳米棒存在易形成等轴状纳米颗粒,或合成温度高,需要后续处理等问题。本文以钨酸铵((NH4)6 W7O24·6H2O)、氯化铯(CsCl)、盐酸(HCl)和油胺(C18H37N)为原料,在220 ℃水热反应24 h合成了直径和长度分别为10~20 nm和100~250 nm的Cs0.2WO3纳米棒。研究了溶剂、合成路径以及HCl对Cs0.2WO3纳米棒的物相和形貌的影响,探讨了Cs0.2WO3纳米棒的形成机理,测试了Cs0.2WO3纳米棒的红外吸收性能。结果表明:过少和过量的HCl不利于合成Cs0.2WO3,改变HCl和CsCl的加入顺序,降低(NH4)6 W7O24·6H2O、CsCl和HCl间的反应速率,有助于合成Cs0.2WO3纳米棒,且Cs0.2WO3纳米棒的红外吸收性能优于等轴状纳米颗粒。  相似文献   

19.
李东  高彩云 《人工晶体学报》2020,49(12):2350-2357
以钨酸(H2WO4)为钨前驱体,十二烷胺(DDA)为模板剂,利用模板剂的结构导向功能,合成了比表面积为57.3 m2·g-1的介孔三氧化钨(DDA-WO3),是未用DDA制备的非介孔WO3(H2WO4-WO3)的2.35倍。X射线衍射(XRD)结果表明,400 ℃下煅烧的DDA-WO3是具有单斜晶型结晶孔壁的无序介孔结构。此外,400~550 ℃下煅烧的DDA-WO3的结晶度均高于同条件的H2WO4-WO3。400 ℃下的DDA-WO3/FTO(掺氟氧化锡)在1.0 V的Ag/AgCl偏压作用下,可以产生0.18 mA·cm-2的饱和光电流,是H2WO4-WO3/FTO(0.06 mA·cm-2)的3倍。增强的光电化学(PEC)活性主要因为DDA-WO3/FTO的大表面积降低了低结晶度对PEC性能的不利影响,成为影响PEC活性的主要因素。500 ℃煅烧导致了DDA-WO3/FTO介孔结构的坍塌,但高的结晶度仍然保持其优越的PEC催化活性。  相似文献   

20.
Nickel-incorporated FeS2 single crystals with various Ni compositions of Fe0.99S2:Ni0.01, Fe0.98S2:Ni0.02, Fe0.96S2:Ni0.04, and Fe0.9S2:Ni0.1 were grown by chemical vapor transport (CVT) method using ICl3 as a transport agent. Physical properties of the Ni-incorporated FeS2 single crystals were characterized using X-ray diffraction, Raman spectroscopy, electrical conductivity, and photoconductivity (PC) measurements. By means of the analyses of the X-ray diffraction patterns, the whole series of Ni-doped FeS2 single crystals were determined to be single-phase and isostructural. Raman spectroscopy of the Ni-doped FeS2 crystals was carried out at room temperature. Raman resonant peaks of the Ni-doped FeS2 crystals demonstrate an energy red-shift behavior with respect to the increase of the dopant densities. Conductivity measurements show the resistivity of the Ni-doped FeS2 decreased as the doping concentration of Ni is increased. Nickel is an n-type dopant, which behaves like a donor level existed near the conduction band edge of the synthetic FeS2. On the other hand, dopant effect of nickel on the synthetic FeS2 also destroys the photoconductive sensitivity in the photoconductivity measurements.  相似文献   

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