CZTSe/Cd1-xZnxS界面能带结构研究

严重的开路电压损耗是限制铜锌锡硫(硒)薄膜太阳电池性能提升的关键问题,其吸收层和缓冲层界面的能带结构有待进一步优化.针对此问题,本文对CZTSe/Cd1-xZnxS界面的能带结构进行了研究.首先,模拟计算了化学水浴法制备Cd1-xZnxS薄膜所需的溶液体系条件,通过椭偏仪和SEM测试结果分析了不同Cd/Zn比例的Cd1-xZnxS缓冲层形貌、光学特性以及禁带宽度.然后,对CZTSe/Cd1-xZnxS界面进行了XPS测试分析,发现CZTSe/Cd0.9Zn01S界面最为匹配,其导带失调值约为0.3 eV.最后对电池器件进行了制备与测试,得到的CZTSe/Cd0.9Zn0.1S结构的太阳电池比CZTSe/CdS结构具有更高的开路电压,达到了394 mV,转换效率达到了5.78;.     

溅射硒化物靶与金属单质靶制备Cu2 ZnSnSe4薄膜及电池的比较研究

采用磁控溅射SnSe-ZnSe-Cu硒化物靶和Sn-Zn-Cu金属单质靶的方法制备两种Cu2 ZnSnSe4(CZTSe)预制层,并将两种预制层采用相同的硒化工艺制备出CZTSe薄膜吸收层.分别采用XRD、Raman、SEM、EDS等分析了薄膜的晶体结构、相的纯度、表面及截面形貌和元素组分,结果发现采用硒化物靶制备的CZTSe吸收层薄膜更为平整致密且无明显孔洞.同时采用Hall测试和J-V测试对太阳电池薄膜的电学性质进行了表征,结果表明硒化物靶制备的CZTSe太阳电池的电流密度以及光电转化效率要高于金属单质靶,金属单质靶制备的CZTSe薄膜电池的开路电压为356 mV,短路电流密度为20.61 mA/cm2,光电转换效率为2.18;,而硒化物靶制备的CZTSe薄膜电池的开路电压为354 mV,短路电流密度为28.41 mA/cm2,光电转换效率为3.33;.     

化学浴法制备CdS薄膜及其光电性能研究

本文用氯化镉、氯化铵、硫脲和氨水的溶液体系采用化学浴沉积法合成CdS薄膜,制备出均匀、致密的CdS薄膜,通过XRD、SEM、EDS、紫外可见吸收光谱等表征手段研究了CdS薄膜的晶体结构,表面形貌,元素比例和光电性能.发现在不同水浴温度下都成功制备了CdS薄膜,其中75℃制备的CdS薄膜最为均匀致密且其XRD衍射峰强度最强,光吸收边在500 nm附近,禁带宽度大约为2.52 eV.这些CdS薄膜的光电响应大,暗态及光照下的电导率分别为1×10-4S·cm-1和1.04×10-2 S · cm-1.用它们制备的CdS/CZTS异质结太阳电池具有明显的光伏效应.     

沉积时间对Zn(O,S)薄膜性能及Cu2ZnSnSe4薄膜电池的影响

无镉材料Zn(O,S)因其带隙宽且可调节、无毒无害等优点被作为缓冲层材料重点研究,通过化学水浴法制备Zn(O,S)薄膜,研究了沉积时间的不同(20~35 min)对Zn(O,S)薄膜的成分、结构特性、光学性能及形貌的影响.通过XRD测试可知,水浴法制备的Zn(O,S)薄膜为非晶态.通过透反射谱测试可知,薄膜的光学透过率较高(>80;).通过表面形貌测试可知,30 min时Zn(O,S)薄膜为致密均匀的小颗粒.将Zn(O,S)薄膜应用在CZTSe电池中,在30 min时获得较高器件转换效率5.37;.     

CdS纳米晶颗粒薄膜的制备及其光学特性研究

采用化学浴沉积法,以CdCl2·H2O、CS(NH2)2、NH4Cl、NH3·H2O和去离子水作为反应前驱物,在不同的氨水浓度下制备CdS纳米晶颗粒薄膜.通过扫描电镜、X射线衍射、X射线能量色散谱、紫外-可见光透射光谱、椭圆偏振光谱等方法,研究了反应前驱物中氨水浓度对CdS纳米晶颗粒薄膜的表面形貌、晶体结构、S/Cd原子比、光透过率、光学带隙、折射率、消光系数和光学吸收边等物理性能的影响.结果表明:反应前驱物中氨水浓度在0.4～1.0mol/L范围内,可以在衬底上形成均匀致密的CdS纳米晶颗粒薄膜.随着氨水浓度的增加,CdS纳米晶的平均晶粒尺寸逐渐减少,S/Cd原子比逐渐增加,由富Cd型转变为富S型,禁带宽度逐渐增加.在500～1000 nm波段内,折射率的平均值为1.75;消光系数k小于0.07.     

不同硫化温度对Cu2ZnSnS4薄膜质量及太阳能电池性能的影响

采用ZnS-Sn-CuS作为靶材,利用磁控溅射技术制备了Cu2ZnSnS4 (CZST)薄膜材料及太阳电池,重点研究了不同硫化温度对CZTS薄膜质量及太阳电池性能的影响.利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能谱仪(EDS)、显微拉曼光谱仪(Raman)和紫外可见分光光度计(UV-Vis)分别表征了不同硫化温度下制备的CZTS薄膜的晶相结构、表面形貌、化学组分、相的纯度和光学性能.结果表明:在580℃下所制备的CZTS薄膜光滑致密、结晶质量好,同时化学组分属于贫铜富锌,而且无其他二次相,禁带宽度约为1.5 eV.符合高效率太阳电池吸收层的要求.将CZTS吸收层按照SLG/Mo/CZTS/CdS/i-ZnO/ITO/ Al的结构制备成面积为0.12 cm2的电池并进行Ⅰ-Ⅴ测试.测试结果表明,在580℃硫化后制备的CZTS薄膜太阳电池具有最高的转换效率为3.59;.     

铜蒸发温度对共蒸发法制备Cu2ZnSnSe4太阳电池的影响

由于Cu元素的含量对Cu2ZnSnSe4(CZTSe)化合物的薄膜性质及电池性能都有影响,本文主要研究了不同铜蒸发温度对CZTSe薄膜性质及电池性能的影响.研究表明:当铜蒸发温度较低时(1400 ℃),CZTSe薄膜中含有SnSe相,同时薄膜呈N型;随着铜蒸发温度的提高,CZTSe薄膜的结晶质量明显提升.但当铜蒸发温度过高时(1500 ℃),薄膜中含有CuxSey相.二次相SnSe与CuxSey的存在都会使电池失效.最终通过优化铜的蒸发温度,在较合适的1450 ℃ 铜蒸发温度条件下制备出效率为2.63;(有效面积0.34 cm2)的CZTSe太阳电池.     

用于HIT太阳能电池的非晶硅薄膜制备与性能研究

采用射频等离子体增强化学气相沉积技术(RF-PECVD),在不同硅烷浓度下制备本征非晶硅薄膜,研究薄膜材料的微结构和光电性能.研究表明,在硅烷浓度为5;时,制备的薄膜材料处于非晶/微晶相过渡区域,具有宽光学带隙、低吸收系数、较高电导率和较好的致密性.作为钝化层应用到HIT太阳电池中,具有良好的钝化效果,在n型单晶硅衬底上制备出了效率为13.92;的太阳电池.     

溅射功率对硫化镉薄膜结构和光电性能的影响

在玻璃衬底上采用射频磁控溅射方法制备了硫化镉(CdS)薄膜,研究了溅射功率对CdS薄膜的结构、表面形貌、光学特性和电学性质的影响.XRD测量表明制备的CdS薄膜均为六方纤锌矿结构的多晶薄膜.随着功率从40 W增加到80 W,H(102)面的峰呈现增强再逐渐减弱的趋势.60 W时薄膜的衍射峰最强,结晶度最好.同时,薄膜的晶粒尺寸随着功率增加先增大再减小.从SEM图像可以看出,制备的薄膜均匀致密且无针孔的出现.在可见光范围内,薄膜的平均透射率都在70;以上.随着功率的增加,薄膜带隙在2.25～2.41 eV的范围内变化,而暗电导率呈现先增加再减少的趋势.     

CdS薄膜中"白斑"的研究

本论文对CdS薄膜中的"白斑"进行了研究.化学水浴沉积法(CBD)制备CdS薄膜所需要的化学反应物包括硫脲、氨水、镉盐和铵盐等.文中采用两种镉盐和铵盐来沉积CdS薄膜:氯化镉和氯化铵,乙酸镉和乙酸铵.所沉积的CdS薄膜的表观形貌由SEM表征,成分由EDX表征.当镉盐和铵盐分别采用氯化镉和氯化铵时,生成的薄膜中存在大量的"白斑".这些"白斑"的成分不是CdS,而是(CdCl)2S.增加氨水的浓度可以大大减少这些"白斑",但是不能彻底消除这些"白斑".当镉盐和铵盐分别采用乙酸镉和乙酸铵时,生成的薄膜均匀、平整,薄膜中根本就不存在所谓的"白斑".因此,沉积CdS薄膜时,镉盐和铵盐不宜采用氯化镉和氯化铵,应该采用乙酸镉和乙酸铵.     

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...     

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.     

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.     

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.     

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.     

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.     

Mechanism of thermal expansion of structural modifications of zinc pyrovanadate

Crystal chemical characteristics of the α and β modifications of Zn₂V₂O₇ are calculated based on in situ high-temperature X-ray measurements. The expansion of the structure is found to be strongly anisotropic up to the negative volumetric thermal expansion of the α-Zn₂V₂O₇ unit cell in the temperature range of 300–600°С, α _V =–17.94 × 10^–6 1/K. The transformations of the “hard” and “soft” sublattices with an increase temperature and at the phase transition are considered in detail. It is shown that the negative volumetric thermal expansion of α-Zn₂V₂O₇ is due to the degeneracy of the zigzag-like shape of zinc–oxygen columns at constant distances between their vertices.