简易溶液法快速制备Cu2ZnSnS4纳米晶工艺研究

采用一种简易溶液法成功快速制备出低成本薄膜太阳能电池用Cu2ZnSnS4(CZTS)纳米晶.探讨合成温度和时间对CZTS纳米晶的结构、形貌、元素比例及光学特性的影响,实现可控的CZTS纳米晶合成.以上特性分别采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能量色散谱仪(EDX)、紫外-可见光谱仪(UV-vis)进行表征.结果表明:温度为250℃,时间为1h时可获得锌黄锡矿结构,团聚颗粒约为200～500 nm,化学计量比约为Cu∶ Zn∶ Sn∶S=2.17∶ 1∶1.23∶4.69,禁带宽度为1.5 eV的纳米晶,适合印刷法制备CZTS薄膜太阳能电池吸收层.     

微波水热法制备ZnO纳米晶

采用微波水热(microwave hydrothermal,M-H)法在MDS-6型温压双控微波水热反应仪中成功地制备出平均晶粒尺寸为30 nm且呈现棒状形貌的ZnO纳米晶.并在一定的水热温度和反应时间下系统研究了微波水热反应过程中[Zn2+]离子浓度、反应釜填充比、反应物浓度比[Zn2+]/[OH]等工艺因素对ZnO纳米晶的晶粒尺寸及形貌的影响.采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)和透射电子显微镜(TEM)对所制备的ZnO纳米晶进行表征.结果表明:所制备ZnO的平均晶粒尺寸约为30 nm,ZnO纳米晶呈现棒状形貌.随着[Zn2+]离子浓度的增加,ZnO纳米晶的晶粒尺寸先减小后增大;随着反应釜填充比和反应物浓度比[Zn2+]/[OH]的增大,ZnO纳米晶的晶粒尺寸先减小后增大,并逐渐趋于稳定.制备ZnO纳米晶的最佳反应条件为:[Zn2+]=1.6 mol·L-1;反应釜填充比=70;;[Zn2+]/[OH]=1/2.     

Cu2ZnSnS4纳米晶的溶剂热法制备和表征

利用溶剂热制备了Cu2ZnSnS4 (CZTS)球形纳米晶.采用X射线衍射(XRD)、拉曼光谱、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、能量色散谱(EDS)和紫外-可见分光光度计对产物的物相结构、形貌、化学组分及光学性能进行表征.结果表明:所制备的CZTS球形纳米晶具有锌黄锡矿结构,球形颗粒的直径为190～300 nm,每个球形颗粒是由很多平均尺寸大约24 nm的纳米晶构成.纳米晶具有锌黄锡矿结构,其禁带宽度约为1.55 eV.同时研究了反应前驱溶液中不同量的硫脲和氯化锌对所制备的CZTS纳米颗粒的结构、原子组分比和形貌的影响规律,并对其形成机理进行了初步探讨.     

微波辅助溶剂热法制备纳米Fe3O4团簇

采用微波辅助溶剂热法制备了纳米Fe3O4团簇,其中乙二醇和二甘醇作为反应溶剂和还原剂,乙酸钠和聚乙烯吡咯烷酮(PVP)作为表面活性剂和稳定剂.采用X射线衍射仪(XRD)、透射电镜(TEM)对样品的结构和形貌进行了表征,利用样品振动磁强计(VSM)对样品的磁学性能进行了表征.结果表明,微波加热2h和4h,获得的是尺寸为40 ～ 50 nm的纳米Fe3O4团簇,而在微波加热5 min的条件下,获得的是10 nm的Fe3O4纳米颗粒.所制备样品在室温下表现出超顺磁性.     

爆轰法合成超小TiO2的光催化性能分析

颗粒尺寸是影响TiO2光催化活性的重要因素,颗粒越小其光催化效率越高.在密闭的反应釜内引爆用含钛前驱体、硝酸铵、黑索金与一定量的聚苯乙烯小球制备的浆状混合炸药制备了超小的TiO2纳米颗粒.研究了炸药配比对TiO2的形貌、分散性、颗粒尺寸的影响,并通过降解甲基橙溶液表征超小TiO2的光催化性能.结果发现:制备的TiO2由金红石相与锐钛矿相组成,大部分颗粒呈球形或不规则四边形,尺寸在10nm左右,少量颗粒尺寸大于20nm,结晶度较好.炸药配比对TiO2的结晶度、颗粒大小、分散性等有较大影响.TiO2的禁带宽度在2.8eV左右,低于锐钛矿相与金红石相的禁带宽度,能够提高太阳光的利用率.爆轰制备的超小TiO2催化降解甲基橙溶液50min时,甲基橙的降解率为30;,明显高于爆轰法制备的颗粒较大的TiO2与铜粒子掺杂的纳米TiO2的光催化速率,光催化性能得到明显提高.     

超声波协同微波溶剂热合成工艺对FeS2性能影响的研究

以FeSO4·7H2O和Na2S2O3·5H2O为原料、乙二醇为溶剂,采用超声波协同微波溶剂热法制备了黄铁矿型FeS2粉体.研究了反应温度、反应时间对产物物相及形貌的影响,并通过添加表面活性剂对产物的形貌进行了控制.结果表明:采用该合成方法,于130℃反应温度下反应30 min可以获得组成接近化学计量比、结晶度较好的黄铁矿型FeS2粉体,其形貌为由片状聚集而成的花球状,该样品在紫外-可见光区具有良好的光吸收性能,禁带宽度约1.55 eV.添加SDS、SDBS和CTAB均使得FeS2的光催化活性降低,但SDBS的加入,有效提高了产物的比表面积从而使得产物对亚甲基蓝的吸附作用增强.     

MgZnO/ZnO异质结构的发光性质研究

本文利用等离子体辅助分子束外延(P-MBE)技术在蓝宝石 (Al2O3) 衬底上生长了Mg0.12Zn0.88O(100nm)/ZnO (20nm) /Mg0.12Zn0.88O (40nm) 异质结构,测得样品的X射线衍射谱表明,在34.56°的位置出现很强的(002)方向衍射峰,其半高宽度为0.20°,比Mg0.12Zn0.88O合金薄膜的半高宽度0.15°明显展宽.通过光致发光谱研究了MgZnO/ZnO/MgZnO异质结构的光学性质,室温下测得在370nm(3.35eV)位置有很强的紫外发光,而在348nm (3.56eV)的位置处有一个较弱的发光,这两个峰分别被归结于来自ZnO层和MgZnO盖层的发光.室温下的吸收光谱中,在上述两个峰的位置附近分别存在很明显的吸收,指示了带边吸收来自于MgZnO和ZnO两种材料.通过变温发光谱研究了异质结构中载流子弛豫、复合的规律.随着温度增加,来自于ZnO层和MgZnO层的发光强度比增加,这归结为MgZnO/ZnO异质结构存在界面势垒所致.     

低温磁控溅射法制备氧化锌薄膜的光学性能研究

采用射频磁控溅射法,在较低的衬底温度(100℃)下,改变溅射时间,制备了一组氧化锌(ZnO)薄膜.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、原子力显微镜(AFM)、X射线能谱仪(EDS)、傅里叶红外光谱(FTIR)、拉曼光谱和紫外-可见分光光度计对制备的ZnO薄膜的微观结构、形貌和光学特性进行了研究.XRD图谱表明,制备的ZnO薄膜具有良好的结晶性和c轴择优取向,随着溅射时间的增加,(002)衍射峰的强度先增大后降低,溅射时间为40 min时,(002)衍射峰的强度达到最大,衍射峰半高宽最小;AFM测试表明制备的ZnO薄膜表面呈现球状颗粒,随着溅射时间的延长,薄膜的颗粒尺寸和表面均方根粗糙度均逐渐变大;EDS结果显示溅射时间较长(40 min和60 min)的ZnO薄膜,O和Zn的原子比更接近1:1.FTIR光谱中,发现位于408 cm-1附近的ZnO的E1(TO)声学模式和位于380 cm-1处的A1(TO)模式;拉曼光谱中,观测到了分别位于99 cm-1和438 cm-1处的ZnO的E2(Low)和E2(high)模式拉曼特征峰;紫外-可见透过光谱显示,在可见光范围,ZnO薄膜具有高的透光率,平均透光率高于90;,ZnO薄膜的光学禁带宽度范围为3.27～3.28 eV,溅射时间为40 min时,ZnO薄膜的光学禁带宽度最接近单晶ZnO的.     

片状ZnO单晶的光电性能研究

通过SEM、TG、XRD、IR、UV-Vis研究了用均匀沉淀法制备的片状ZnO单晶的结晶学和光电性能.结果显示:片状ZnO是结晶良好的晶体,属纤锌矿结构,对中红外和可见光透射率很高,达80;以上,而对近紫外光的透射率仅为6;.片状ZnO单晶的晶格常数为a＝0.3246 nm,c＝0.5207 nm,禁带宽度为3.25 eV.     

水热法辅助溶胶-凝胶法制备Al∶ZnO纳米棒阵列及发光性能研究

采用水热法结合溶胶-凝胶法在SiO2基片上制备了不同Al含量掺杂的ZnO纳米棒阵列.通过X射线衍射仪(XRD),电子扫描显微镜(SEM),透射光谱和光致发光光谱仪(PL)等测量手段,分析了Zn1-xAlxO薄膜样品的微结构、表面形貌、透射及光致发光特性.结果表明,制备出的Zn1-xAlxO薄膜具有良好的结晶质量和明显的沿(002)方向择优取向生长.透射谱分析显示,样品的吸收边随Al含量的增加出现明显的红移现象.PL谱分析表明,掺杂Al以后,薄膜出现强的橙红光发射光谱带,通过谱线拟合,发现在可见光波段的缺陷发光主要是位于能量为1.92eV和2.15 eV的红光及黄光发射,主要发光机理为Zn,缺陷发射.     

Modelling of mechanism of agglomeration of KCl crystallization

The article presents an analysis into agglomeration during KCl vacuum crystallization. The theoretical and experimental investigations into the mechanism of agglomeration during mass crystallization result in an extension of the growth phenomena within the known model equations. The basis for this is essentially constituted by the collision model concepts of the theory of floculation in disperse systems. The parameters derived from the microprocess analysis (energy dissipation, content of solids, growth rate of individual grains) lead to model equations which are confirmed by laboratory and test trials.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

Velocities of Disappearance and Lifetime of Faces of Growing Crystals

The formulae for absolute R_disap and relative R velocities of disappearance and lifetime τ of faces of growing crystals have been derived for stationary growth. It was shown that the quantities are determined by the relative growth velocity R_A/R_critA of the vanishing face A with respect to the critical growth velocity R_critA and by the geometry of a crystal expressed by the trigonometric functions of interfacial angles β and γ formed between face A and the adjacent faces. R increases and τ decreases with the increase in R_A/R_critA to certain limiting values. The calculations have been verified and illustrated by the experimental results for triclinic potassium bichromate (KBC) crystals. Results enable ones to predict values of velocities of disappearance and lifetimes of undesirable, supplementary faces of any real crystal.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.