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.     

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.     

金属前驱体比例和硫化温度对Cu-Sn-S薄膜特性的影响

使用射频磁控溅射在镀Mo的玻璃基底上制备了Cu/Sn化学计量比为1.4 ～2.0的金属前驱体薄膜.经过400℃、450℃和500 ℃硫化后获得了一系列Cu-Sn-S薄膜.采用X射线衍射、X射线光电子能谱、拉曼光谱、原子力显微镜和紫外可见近红外分光光度计对样品进行了表征.结果表明:硫化温度与前驱体中Cu/Sn化学计量比对Cu-Sn-S薄膜的结构、化学组分和光学性能影响较大.当硫化温度为450℃,前驱体中Cu/Sn化学计量比为1.4∶1时,能得到近乎单一相、四方结构的Cu2SnS3薄膜,光学带隙为1.01 eV.过高的Cu/Sn化学计量比或硫化温度都会导致Cu3SnS4或Cu4SnS4的出现.     

单质靶溅射制备CZTS薄膜及太阳电池

采用单质靶磁控溅射制备Cu2ZnSnS4 (CZTS)薄膜,研究了薄膜的元素组分、升温速率、硫化温度对薄膜表面平整性以及晶粒尺寸的影响.通过SEM与AFM表征薄膜的表面形貌与表面粗糙度,用EDS检测薄膜的元素组分.所制备的样品的Cu/(Zn+ Sn)、Zn/Sn处于最优范围.通过XRD及Raman检测薄膜的结晶情况以及薄膜中的二次相,经上述测试分析判定CZTS薄膜品质良好.最终制备出以CZTS为吸收层的薄膜太阳电池,并用Ⅰ～V特性检验了CZTS电池性能参数,得到效率为0.83;的CZTS薄膜太阳电池,并通过改进硫化退火工艺将效率提高至1.58;.     

预制层中Zn和ZnS对CZTS薄膜太阳电池的影响

采用磁控溅射后硫化的方法制备Cu2 ZnSnS4 (CZTS)薄膜,分别用Zn和ZnS作为锌源,在镀钼的钠钙玻璃衬底上以Zn(或ZnS)/Sn/Cu的顺序制备出不同的CZTS薄膜预制层.首先对预制层进行低温合金,然后以硫粉作为硫源进行高温硫化,得到CZTS薄膜.通过X射线衍射仪(XRD)、扫描电镜(SEM)及能谱仪(EDS)分别对所制备薄膜的晶体结构、表面形貌和薄膜组分进行分析表征;并用拉曼光谱表征了CZTS相的纯度.最后用CZTS薄膜制备了太阳电池,发现在预制层中以ZnS作为锌源得到的太阳电池有较高的性能参数,其开路电压:V =651 mV,短路电流密度:Jsc=11.4 mA/cm2,光电转换效率达到2.8;.     

Ce3+掺杂CsPbBr3纳米晶的制备与性能

采用热注入法制备Ce³⁺掺杂CsPbBr₃纳米晶,利用XRD、TEM、XPS、UV-Vis、PL、Time-resolved fluorescence spectroscopy、J-V曲线测试等对样品的晶体结构、微观形貌、化学组成、光吸收性能、发光性能、荧光寿命和荧光太阳能集光器(LSC)的光学效率进行表征。实验结果表明:采用热注入法成功制备出分散性良好、平均晶粒大小为12.26 nm的立方相Ce³⁺掺杂CsPbBr₃纳米晶。Ce³⁺掺杂CsPbBr₃纳米晶的光学带隙和荧光发射峰强度随着Ce/Pb摩尔比的增加呈现先增大后减小的变化趋势,当n(Ce)/n(Pb)=0.25时,光学带隙达到最大为2.416 eV,发光强度最强,荧光发射峰由纯CsPbBr₃纳米晶的515 nm蓝移到510 nm,Ce³⁺掺杂CsPbBr₃纳米晶的发光性能与稳定性均得到增强。Ce³⁺掺杂CsPbBr₃纳米晶与聚苯乙烯溶液制备复合薄膜型LSC器件的光学效率ηopt最高达到6.81%。     

Fe掺杂纳米ZnO的制备及其光催化性能研究

采用改进的溶胶-凝胶法,无需研磨,制备出不同掺杂浓度的纳米Zn1-xFexO(0.00≤x≤O.03)样品.利用TG-DTA对前驱物样品的成分进行了分析,利用XRD,SEM和UV-Vis等方法对煅烧后样品的结构、形貌及光学性质进行了表征.结果显示:80℃烘干后,未掺杂样品前驱物为Zn3(C6H5O7)2,700℃煅烧后,Zn1-xFexO样品均属六方纤锌矿结构,Fe的掺杂没有引入新的杂相,晶粒均呈现为纳米球形颗粒.其具有很宽的光吸收频段和优异的紫外吸收特性,且随Fe浓度的增大光吸收边发生红移.当x=0.007时纳米Zn1-xFexO的光催化性能最好,对甲基橙溶液的降解效率高达99.71;.     

Cu2ZnSnS4纳米片的两步法制备及其光学性能

先后利用化学气相沉积法和液相离子交换法,在FTO导电玻璃基底上两步法制备Cu2ZnSnS4 (CZTS)纳米片,并通过X射线衍射仪(XRD)、拉曼光谱仪(Raman)、扫描电镜(SEM)、透射电镜(TEM)、X射线能谱(EDS)和紫外-可见吸收光谱仪(UV-vis)等表征手段对所得样品的物相结构、微观形貌、化学组分及光学性能进行测试分析.研究结果表明,所得样品为四方晶型CZTS纳米片,对可见光具有良好的全波段吸收,经计算其禁带宽度约1.51 eV.此外,对CZTS纳米片的形成机理进行初步探讨.     

水热法制备纳米Co0.5Zn0.5Fe2O4工艺条件试验研究

采用水热法合成纳米Co0.5Zn0.5Fe2O4粉体,并借助X射线衍射仪(XRD)、透射电子显微镜(TEM)、矢量网络分析仪(VNA)研究工艺条件(晶化温度、晶化时间)对Co0.5Zn0.5Fe2O4物相、形貌及吸波性能的影响.结果表明,当晶化时间为8 h、晶化温度为180℃时制备出纯相的尖晶石结构的纳米Co0.5Zn0.5Fe2O4,样品形貌为类球形,平均粒径为10～15 nm.在1～18 GHz频段内,样品在16.47 GHz处的反射率达到-33.9 dB,吸波性能最好.     

改进的碳铵沉淀法中氧化钇粉体尺寸及形貌的调控研究

以商业氧化钇(Y2 O3)为原材料,采用改进的碳酸盐沉淀工艺合成钇碳酸盐前驱体,经随后的焙烧工艺获得Y2O3产品.X衍射技术(XRD)和扫描电镜(SEM)表征表明:合成的碳酸盐前驱体Y2(CO3)3·2H2O具有类球形形貌、粒度分布均匀,经950℃焙烧2 h,前驱体受热分解为Y2 O3粉体,粉体完整保留了前驱体的形貌特征.同时,基于对NH4 HCO3/NH4+不同摩尔比条件下NH4 HCO3/NH4 NO3混合溶液中pH值变化的理论计算,在保持其他条件不变化条件下,通过改变NH4 HCO3/NH4 NO3混合溶液的加入量以获得不同的稀土碳酸盐沉淀终点pH值,当碳酸盐沉淀过程中pH值从6.0降低至4.7时,可实现超细至大颗粒不同尺寸氧化钇粉体的制备.同时,公斤级的扩大试验证实该工艺具有良好的可推广性.进一步提出NH4+在碳酸氢铵沉淀制备氧化钇工艺中的作用机理:(1)改变反应体系中阳离子和阴离子的组成;(2)显著影响前驱体的晶型;(3)显著影响产品颗粒尺寸大小.     

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...     

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.     

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.     

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.     

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.