钙钛矿太阳能电池缺陷钝化技术的研究进展

有机无机杂化钙钛矿太阳能电池具有极低制造成本和高功率转换效率的特点,发展前景广阔.薄膜缺陷长期制约钙钛矿太阳能电池光电转换效率和器件稳定性的发展,本文综述了近年行业对各功能薄膜缺陷的深化认识及其钝化技术的最新研究进展.     

具有黄光发射的有机-无机层状钙钛矿材料的合成

通过溶液法,合成了一种有机-无机杂化钙钛矿材料[C6H10(NH2)3]2Pb2Brs(H2O)(1).单晶衍射分析表明,该化合物存在两种不同的Pb原子,一种Pb原子与六个Br原子相连形成了典型的八面体,一种Pb原子与五个Br原子及一个配位水分子形成了扭曲的八面体,两种八面体通过共顶点Br相连接形式了无机阴离子层.有机胺阳离子分布在层与层之间,该化合物具有典型的有机-无机杂化层状钙钛矿结构,表现出特征的二维量子限域效应,该化合物具有很好的光致发光性能,其发射峰位于566 nm,表现出很强的宽光谱黄光发射,量子产率为1.2;.研究发现该发光来源于八面体结构扭曲引起的激子自捕获.     

碳电极钙钛矿太阳能电池光吸收层厚度对光伏性能的影响研究

本文使用两步法,通过控制PbI₂(DMSO)溶液的浓度制备了不同厚度的有机-无机杂化钙钛矿(MAPbI₃)光吸收层薄膜,并组装了大面积基于碳电极且无空穴传输层的钙钛矿太阳能电池。对不同厚度MAPbI₃光吸收层薄膜的晶相、光吸收性质、表面形貌、元素组成进行分析,并进一步测试了基于MAPbI₃薄膜制备的钙钛矿太阳能电池的光伏性能。结果表明,MAPbI₃光吸收层薄膜厚度与PbI₂(DMSO)浓度呈正相关关系,浓度为1.3 mol/L的PbI₂溶液制备的MAPbI₃薄膜厚度约为350 nm,具有较好的结晶度和光吸收强度,且薄膜表面致密平整,无明显缺陷,基于350 nm MAPbI₃光吸收层的钙钛矿太阳能电池获得了8.48%的光电转换效率。     

钙钛矿薄膜的气相法制备及光伏应用的研究进展

近几年,有机-无机杂化钙钛矿太阳电池迅速兴起并且获得了媲美硅基电池的效率,受到了学术界以及产业界的高度关注.随着效率的提高,如何解决稳定性、大面积制备等问题也迅速被提上日程.汽相薄膜制备方法是目前广泛应用于制备大面积致密半导体薄膜及器件的一种工业技术.自2013年Snaith团队成功实现钙钛矿薄膜的真空汽相沉积以来,汽相制备技术在钙钛矿薄膜及器件制备领域也获得越来越多的研究.本论文将对气相法制备钙钛矿薄膜和器件的研究进行综述.重点介绍气相法制备方法的发展及汽相制备方法中一些共有的物理问题,包括MAI分子蒸发的弥散性问题;真空度对分子扩散及薄膜形态的影响以及温度对固态反应的影响.最后将简单讨论进一步提高材料和器件特性可以采取的方案.     

碱金属碘化物后处理制备大晶粒CH3NH3PbI3钙钛矿薄膜,

有机-无机杂化钙钛矿太阳电池作为一种低成本、高效的光伏技术具有巨大的发展潜力,制备大晶粒、致密的钙钛矿吸收层仍然是获得高效钙钛矿太阳电池的关键因素.本文采用简单碱金属碘化物(NaI,KI,CsI)后处理方法诱导CH3NH3PbI3薄膜二次结晶,成功制备了微米级大晶粒、致密的CH3 NH3 PbI3钙钛矿薄膜.与KI相比,NaI和CsI更有利于促进钙钛矿薄膜晶粒长大.并且碱金属碘化物后处理能够钝化晶界,降低钙钛矿薄膜内的缺陷.最后,碱金属掺杂对CH3NH3PbI3带隙的影响很小,不改变其接近单节电池带隙的最优值.因此,碱金属碘化物后处理是进一步提高钙钛矿太阳电池的有效方法.     

钙钛矿太阳能电池中电子传输层现状研究

有机-无机杂化钙钛矿型太阳能电池(简称钙钛矿太阳能电池)的最高光电转换效率已经达到25.5%,是最有希望取代硅基太阳能电池并实现广泛应用的太阳能电池之一。作为钙钛矿太阳能电池的基本组成部分,电子传输层对电池的性能起着至关重要的作用。本文阐述了钙钛矿太阳能电池中电子传输层的种类、尺寸以及界面修饰等对器件性能的影响,为继续提升钙钛矿太阳能电池性能提供参考。     

柔性钙钛矿太阳能电池的研究进展

柔性钙钛矿太阳能电池因质轻、价廉的优点,有望实现大规模卷对卷应用生产和制成可穿戴移动式电源的目标,因而在有机-无机杂化钙钛矿太阳能电池研究领域占据着重要地位.目前该类电池的最高光电转换效率已超过16;.本文综述了近年以不同柔性基底材料制备的钙钛矿电池的研究进展,详细阐述了不同条件制备的电池各功能层及基底柔韧性对电池性能的影响,并探讨了未来柔性电池产业化面临的关键性问题,最后展望了柔性钙钛矿电池的发展趋势.     

钝化剂乙酰水杨酸对钙钛矿太阳能电池性能影响的研究

有机-无机杂化钙钛矿太阳能电池因其优异的光电性能和低廉的制备成本,成为目前光伏领域内的研究热点。然而,钙钛矿薄膜表面和晶界处存在大量缺陷,这易于导致载流子非辐射复合,并进而影响太阳能电池的光电转换效率。本工作通过在两步法制备钙钛矿的铅盐前驱液中引入钝化剂乙酰水杨酸(acetylsalicylic acid, ASA),利用吸收/光致发光光谱、扫描电镜和电学测试等技术手段研究了ASA分子对钙钛矿薄膜质量与器件性能的影响。结果表明:适量的ASA分子可以通过路易斯酸碱相互作用增大钙钛矿晶粒尺寸,并有效降低钙钛矿薄膜的缺陷密度;当ASA的浓度为2.5 mmol/L时,所制得的钙钛矿电池取得了19.83%的最高光电转换效率,明显高于对照器件的转换效率(17.47%)。本工作首次报道了ASA对钙钛矿薄膜缺陷的良好钝化效果,并为提高钙钛矿太阳能电池性能提供了一种简单有效的制备方法。     

压强对有机-无机杂化钙钛矿(MAPbBr3)电子结构调制的第一性原理研究

自2009年以来,有机-无机杂化钙钛矿作为光吸材料的新型太阳能电池受到了广泛关注.在基于密度泛函理论(DFT)的第一性原理计算的基础上,利用VASP软件包,通过改变钙钛矿MAPbBr3(CH3NH3PbBr3)的晶格常数进行加压模拟计算,系统的研究了压强作用下钙钛矿材料的电子结构的变化.压强作用下带隙值变化的物理机制可以通过MA阳离子和PbBr6正八面体无机笼之间的氢键作用进行半定量的描述.在压强作用下,Br原子通过靠近氨末端的H原子而响应,会引起了PbBr6八面体发生不同程度的倾斜和扭曲,导致体系的晶格对称性发生破坏,使得Pb、Br原子之间的电荷密度函数发生变化,进而影响钙钛矿MAPbBr3在不同压强下的电子结构以及光学性质的变化.     

基于蒙脱石和层状双氢氧化物纳米剥离的层层自组装异构薄膜制备

以乙酸乙酯为剥离介质,采用超声法剥离有机蒙脱石(CTA-MMT)和层状双氢氧化物(MgAl-SDS-LDH),以聚乙烯醇(PVA)为交联剂,采用层层自组装(LBL)的方法制备了蒙脱石-层状双氢氧化物异构薄膜(PVA/MMT/PVA/LDH)n.采用X射线衍射分析(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、原子力显微镜(AFM)和紫外-可见光分光光度计对样品进行了表征.结果表明,超声剥离处理后的CTA-MMT和MgAl-SDS-LDH片层厚度分别达到17 nm和12 nm.(PVA/MMT/PVA/LDH)n异构薄膜层间距为1.81 nm,一个组装循环得到以MMT和LDH纳米片层构成薄膜单循环片层,厚度约为170 nm.薄膜对264 nm左右的光呈现强烈的吸收带,并且吸收强度与薄膜厚度之间呈线性关系,表明薄膜单元层具有良好均一性.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structures of the cis and trans isomers of a tetrathia[3.3.3.3]cyclophane

Both the cis and trans isomers of 3,11,18,26-tetrathiatricyclo[26.2.2.1^5,9.2^13,16.1^20,24] hexatriaconta-5,7,9,20,22,24-hexene have been prepared and structurally characterized. Each of these centrosymmetric tetrathia dimers includes two cyclohexane rings in chair conformations with either 1,4-cis or 1,4-trans bonding and two meta-substituted benzene rings. The cis isomer packs into the monoclinic space group P2₁/a with a = 10.485(3)Å, b = 10.3956(18)Å, c = 14.1343(10)Å, = 105.200(13)°, Z = 2 and refined to an R factor of 0.046. The trans isomer crystallizes in the monoclinic space group P2₁/c with a = 10.7217(12)Å, b = 5.6797(7)Å, c = 25.415(5)Å, = 96.001(12)°, Z = 2 and refined to an R factor of 0.043. In the cis structure each benzene ring faces a cyclohexane ring while in the trans structure the cyclohexane rings face one another.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

电沉积法制备ZnO纳米棒阵列及其发光特性

本文以掺F的SnO2导电玻璃为基板,以硝酸锌水溶液为电解液,采用三电极恒电位体系电沉积制备ZnO纳米棒阵列,系统考察了硝酸锌浓度和沉积电位等工艺参数对ZnO纳米棒阵列的微观形貌及其发光性能的影响规律.结果表明,硝酸锌浓度和沉积电位对纳米棒阵列的形貌有显著影响,控制适宜的工艺条件可以制备出直径分布均匀、结晶性好且纯度高的六方纤锌矿ZnO纳米棒阵列.荧光光谱分析表明,电沉积制备出的ZnO纳米棒阵列在385 nm附近有一个强荧光发射峰,且发光性能稳定、对纳米棒阵列微观形貌的细微变化不敏感,使其在发光二极管和激光器等领域具有广阔的应用前景.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.