咔唑基杂化钙钛矿材料的研究

有机/无机杂化钙钛矿材料是一种综合性能良好的有序复合光电材料。选择具有较大共轭的咔唑类铵盐作为杂化钙钛矿的有机组分,合成氯化锌基杂化钙钛矿[(C_6H_4)_2N(CH_2)_6NH_3]_2ZnCl_4(N6AHMC-ZnCl_4)。发现在该杂化钙钛矿材料中,由于有机/无机协同增强作用,使得该材料在紫外光区239nm、265nm、298nm、336nm和351nm处有较强的吸收峰,在分解温度为243℃条件下的失重率为5%,具有较好的热性能。     

有机/无机杂化钙钛矿(C4H9NH3)2ZnCl4的制备与表征

合成了新型的有机/无机杂化钙钛矿（C4H9NH3）2ZnCl4,采用元素分析、红外光谱和X射线衍射对其结构进行了表征,结果表明这种材料具有规则的层状结构,有序性高,热分析结果表明（C4H9NH3）2ZnCl4在170℃的高温处存在一个固-固相转变。     

有机-无机杂化钙钛矿太阳电池的研究进展

可溶液加工的高效太阳电池及其活性层材料一直是全世界学术界与产业界关注与研究的热点。近年来,由于优异的光吸收特性和载流子传输能力,以及相对简单的制备方法,具有立体三维结构的有机-无机杂化钙钛矿晶体材料在太阳电池中的应用受到越来越多的关注,并在过去的两年内取得了重大的研究进展。有机-无机杂化钙钛矿太阳电池的光电转化效率(PCE)纪录被不断刷新,目前已达19.3%,与无机太阳电池相当。主要从有机-无机杂化钙钛矿材料的结构与性质、有机-无机杂化钙钛矿薄膜材料的制备方法、纳米多孔载体结构和平板结构钙钛矿太阳电池、杂化钙钛矿太阳电池的稳定性4个方面,介绍了有机-无机杂化钙钛矿太阳电池近期的研究进展,并对其发展方向进行了展望。     

反应时间对CH3NH3PbBr3钙钛矿纳米晶形貌及荧光性能的影响

有机-无机杂化钙钛矿(CH_3NH_3PbX_3,X=Cl、Br、I)材料正成为最近全世界研究的热点,在太阳能电池、量子点发光等众多领域有着广泛的应用。本研究重点考察反应时间对热注入法合成的CH_3NH_3PbX_3纳米晶的形貌及荧光性能的影响,并采用吸收光谱、荧光光谱、X射线衍射、透射电镜及扫描电镜等手段对材料进行分析。研究表明,随着反应时间的延长,产物从6nm左右的球状纳米颗粒变为层状纳米片;反应时间继续延长,纳米片的尺寸变大,厚度变厚;同时,产物的吸收峰和荧光发射峰都发生蓝移。通过绝对量子产率的分析,发现反应时间为180s时产物的量子产率最高。     

Cs2AgBiBr6钙钛矿太阳能电池研究进展

近年来,有机–无机杂化钙钛矿太阳能电池以其优异的性能和低廉的制造成本受到了广泛关注。然而,其含有铅元素的毒性以及稳定性阻碍了进一步商业化应用。双钙钛矿材料Cs₂AgBiBr₆具有稳定性优异、毒性低、载流子寿命长和载流子有效质量小的优势,是一种颇具潜力的光伏材料,已被应用于太阳能电池并展现出良好的性能。但是Cs₂AgBiBr₆钙钛矿太阳能电池的光电转换效率还无法与有机–无机杂化钙钛矿太阳能电池相媲美,发展仍面临诸多挑战。本文首先介绍了Cs₂AgBiBr₆的晶体结构及容忍因子等结构参数;然后介绍了溶液法、反溶剂辅助成膜法、气相法、真空辅助成膜法以及喷涂法等薄膜制备工艺的进展,评述了各种薄膜制备工艺的优缺点;接着从元素掺杂、添加剂工程及界面工程(界面能级匹配和界面缺陷钝化)三方面介绍了Cs₂AgBiBr₆钙钛矿太阳能电池的性能优化策略,结合近年来的研究进展进行了评述;最后指出Cs₂AgBiBr     

N掺杂TiO2纳米纤维高可见光催化CO2合成甲醇

采用气相生长法在介孔SiO₂球的表面上制备了ϕ 8~10 nm的TiO₂纳米纤维, 采用相同的方法, 还成功地制备了氮掺杂的TiO₂(N-TiO₂) 纳米纤维, 它具有更高的可见光催化活性。采用X射线光电子能谱(XPS)、紫外光电子能谱(UPS)、X射线衍射(XRD)、扫描电镜(SEM)、透射电子显微镜(TEM)、紫外–可见分光光度计(UV-Vis)、荧光分光光度计(PL)等对样品进行了测试分析。TiO₂纳米纤维具有高结晶度的锐钛矿晶型, 掺氮后的TiO₂纳米纤维带隙变窄, 在可见光波段有明显的吸收, 同时, 光生电子还原能力更强, 大大提高了可见光下催化还原CO₂合成甲醇的产率。在300 W氙灯光照2 h后, 用纯TiO₂纤维催化CO₂合成甲醇, 产率为493.4 μmol•g^-1∙h^-1, 转换频率(TOF) 为0.089 h^-1; 以N-TiO₂为催化剂合成甲醇产率提高了40.1%, 达695.1 μmol∙g^-1∙h^-1, 转换频率(TOF) 提高了40.4%, 为0.125 h^-1。     

福建物构所快速响应的光电探测晶体材料研究取得进展

正近年来无机有机杂化材料表现优异的光电性能,其中的二维层状有机-无机杂化钙钛矿材料由于其量子肼结构特性和组份可调型性在光电探测领域引起了研究者的极大重视;然而,较慢的响应速度(一般在毫秒数量级)制约了其在光电子器件方面的发展。因此,探索开发超快响应的光电探测晶体材料迫在眉睫。中科院福建物构所结构化学国家重点实验室"无机光电功能晶体材料"罗军华研究员团队成功制备出一例基于2D层状无机-有机杂化钙钛矿的超快响应光电探测器件。该器件展现出超快的响应速度(1.52μs),比同类型的光电探测器     

以PVP为软模板构建的层状介孔TiO2及其光催化性能

以聚乙烯吡咯烷酮(PVP)为软模板、硫酸钛为钛源,采用无机沉淀-胶溶法制备了层状介孔PVP-TiO₂。采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、紫外可见吸收光谱(UV-Vis-Abs)、比表面积分析仪(BET)分别对样品的表面形貌、晶相组成、紫外吸收带边、比表面积和孔结构进行了表征分析,对层状结构的形成机理进行了研究。以甲基橙为目标降解物,研究了样品的光催化性能。结果表明：在相同条件下,PVP-TiO₂对甲基橙的最佳降解率达到93.84%,明显高于纯TiO₂。经PVP改性后,TiO₂试样出现了层状介孔结构,结晶度和晶粒尺寸均减小,促进了锐钛矿向金红石相的转变,并且PVP的引入使得TiO₂的光吸收带边发生了一定的蓝移。     

CsPbI2Br无机钙钛矿太阳能电池稳定性的研究进展

有机-无机杂化钙钛矿材料中易挥发的有机成分(MA⁺,FA⁺)用高耐热性无机金属铯离子(Cs⁺)取代,用其制备的太阳能电池具有优异的热稳定性。自2016年以来,以CsPbI₂Br材料作为光活性层的无机钙钛矿太阳能电池(IPSCs)的光电转换效率(PCE)从9.84%提高到18.06%,但是IPSCs的稳定性问题仍然制约其商业化。本文总结和分析了影响CsPbI₂Br IPSCs稳定性的因素,从制备工艺、离子掺杂、界面优化等方面评述了近年来IPSCs稳定性的研究进展,并展望了CsPbI₂Br IPSCs的研究趋势和发展方向。     

Mg掺杂TiO2纳米晶光氧化还原染料的可逆颜色转变研究

由于非直接接触、远程控制、高效及快捷的优点, 光可逆颜色转换材料在信息存储、显示器件、传感器等领域有着重要应用。复合无机材料和有机材料, 实现协同增效, 是新型光驱动可逆颜色转换材料的研究热点之一。本研究采用一步液相合成法制备粒径约为5 nm的锐钛矿型Mg²⁺掺杂TiO₂纳米晶, 通过X射线衍射、透射电子显微镜、X射线光电子能谱、红外光谱和拉曼光谱等表征手段确认材料的组成结构, 并对比研究了Mg²⁺掺杂TiO₂对亚甲基蓝(MB)光可逆颜色转换性能的增强效应。结果表明, 掺杂Mg²⁺在TiO₂晶格中能产生杂质能级, 有效抑制了光生载流子的复合, 提高了TiO₂光氧化还原MB的活性; 另一方面, 掺杂Mg²⁺降低了TiO₂纳米晶的吸收波长, 在可见光照射下能够有效地抑制MB向还原态LMB的转变, 提高系统着色速率。这种基于碱金属掺杂TiO₂纳米晶的光可逆颜色转换材料在许多光电子器件领域具有潜在的应用价值。     

Excitons in self-organized layered perovskite films prepared by the two-step growth process

Thin films of microcrystalline (C₈H₁₇NH₃)₂PbBr₄ were prepared by a two-step growth process as follows: (1) deposition of PbBr₂ films on substrates and (2) self-organized growth of layered perovskite compounds by exposing the PbBr₂ film to C₈H₁₇NH₃Br vapor in a vacuum chamber. As-synthesized (C₈H₁₇NH₃)₂PbBr₄ films were characterized by using X-ray diffraction, temperature dependence in optical absorption and photoluminescence spectra. (C₈H₁₇NH₃)₂PbBr₄ films created by this synthesis approach were found to microcrystalline form, single phase and highly oriented with a c-axis perpendicular to the substrate surface. (C₈H₁₇NH₃)₂PbBr₄ films showed clear exciton absorption and photoluminescence even at room temperature in the near-ultraviolet region. Exciton binding energy of (C₈H₁₇NH₃)₂PbBr₄ was estimated about 200 meV.     

高稳定性(EDA)(FA)2[Pb3I10]层状钙钛矿薄膜的制备与表征

为了提高钙钛矿太阳能电池在潮湿环境中的稳定性, 采用一步法, 通过在DMF中混合(EDA)I₂、(FA)I和PbI₂, 将乙二胺离子引入钙钛矿晶格, 成功制备了一种具有较高稳定性的二维片层状的钙钛矿结构薄膜。通过原位掠入射X射线衍射(GIXRD)、X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见吸收光谱(UV-Vis)和原子力显微镜(AFM)等方法检测分析(EDA)(FA)₂[Pb₃I₁₀]在低湿度及高湿度环境下的结构、形貌以及光学性能变化。结果表明: 制备的 (EDA)(FA)₂[Pb₃I₁₀]薄膜在相同湿度环境下比当前广泛应用于钙钛矿太阳能电池的甲胺铅碘薄膜(CH₃NH₃PbI₃)稳定性更高; 薄膜的光学带隙约为1.67 eV, 与太阳能电池最佳带隙比较接近。另外, (EDA)(FA)₂[Pb₃I₁₀]薄膜在可见光范围吸光性能较好; 薄膜的粗糙度很小, 适合制备太阳能电池, 而且, 成本较硅基太阳能电池低廉, 在分子水平较CH₃NH₃PbI₃的可调谐性更大, 使钙钛矿太阳能电池在未来大面积应用成为可能。     

Synthesis of halide perovskite microwires via methylammonium cations reaction

Low-dimensional halide perovskites (HPs) have received considerable attention in recent years due to their novel physical properties such as compositional flexibility, high quantum yield, quantum size effects and superior charge transport. Here we show room temperature solution synthesis of 1D organic–inorganic lead bromide perovskite microwires (MWs). Our method uses acetone as a reactant, and when CH₃NH₃PbBr₃ is immersed, acetone reacts with CH₃NH₃⁺ cations in the CH₃NH₃PbBr₃ single crystal by the dehydration condensation. The reaction generates a large (CH₃)₂C=NHCH₃⁺ A-site which cannot be accommodated by the cuboctahedron formed by the corner-sharing [PbBr₆]⁴⁻ octahedral, leading to the transition of corner-sharing octahedra to face-sharing triangular prism and the crystal structure transformation from 3D to 1D. The formation process of (CH₃)₂C=NHCH₃PbBr₃ MWs does not involve any ligands, templates or catalysts. A two-terminal memory device was constructed using the (CH₃)₂C=NHCH₃PbBr₃ MWs, showing great potential of the method in fabrication of electronic and optoelectronic devices.     

RADIATION CHEMICAL AND PHOTOPHYSICAL PROPERTIES OF C60(C4H8SO3Na)n IN AQUEOUS SOLUTION: A LASER FLASH PHOTOLYSIS AND PULSE RADIOLYSIS STUDY

Optical absorption studies on aqueous solutions of C₆₀(C₄H₈SO₃Na)_n (n = 4-6) revealed deviation from the Beer-Lambert law in the 250-350 nm region, which is assigned to the formation of solute aggregates at concentrations higher than 1 × 10^-3 mol dm^-3. Dynamic light scattering experiments showed aggregates with an average size of ∼100 nm. The solute has a broad weak fluorescence emission (ϕ_f = 1.8 × 10^-3) in the 450-650 nm region, which remained independent of solute concentration. The broad transient absorption band in the 450-900 nm region (ε₆₆₀ = 2170 dm³ mol^-1 cm^-1), which formed immediately on laser flash photolysis (λ_ex = 355 nm, 35 ps), is assigned to singlet-singlet transition. It decays to a triplet excited state whose absorption is observed to depend strongly on solute concentration. In dilute solutions, an absorption band with λ_max = 590 nm is seen, and at high solute concentration a broad absorption in the 500-900 nm region is observed. The e_aq^- reacts with the solute with a bimolecular rate constant of 1.7 × 10⁸ dm³ mol^-1 s^-1 and forms weak broad absorption bands at 440, 540, 620, 870, 940, and 1020 nm. Isopropanol radicals also react with the solute with a bimolecular rate constant of 2.3 × 10⁸ dm³ mol^-1 s^-1 with the formation of a transient optical absorption spectrum similar to that observed on reaction with e_aq^- and assigned to a solute radical anion. The ^•H and ^-OH radicals react with bimolecular rate constants of 3.2 × 10⁹ and 4.4 × 10⁹ dm³ mol^-1 s^-1, respectively, and form transient absorption bands at 440, 510, and 660 nm. Based on electron transfer studies with suitable electron donor/acceptor substrates, the ranges of the reduction and oxidation potentials of the solute an estimated.     

银纳米相吸收增强型钙钛矿太阳电池薄膜的制备及性能研究

分别将银纳米相溶胶(银纳米颗粒、Ag@SiO₂核壳结构、银纳米线)掺入氧化铝异丙醇溶液中制成具有蜂窝结构的介孔层材料, 然后在介孔层表面制备CH₃NH₃PbI₃钙钛矿吸收层得到Al₂O₃/CH₃NH₃PbI₃复合薄膜, 并对复合膜的微观结构、光吸收特性及太阳电池器件性能进行了测试和分析。研究表明, Al₂O₃/CH₃NH₃PbI₃复合膜与CH₃NH₃PbI₃在可见光区域吸收光谱基本相同, 含量极少的Al₂O₃对CH₃NH₃PbI₃吸光性能影响较小。而掺入银纳米相可明显改善CH₃NH₃PbI₃钙钛矿薄膜的吸收性能。当银纳米颗粒、Ag@SiO₂核壳结构和银纳米线相对浓度比分别为0.15、0.3及0.15时, CH₃NH₃PbI₃吸光性能分别达到最佳; 银纳米相浓度继续增大时, 薄膜的光吸收性能逐渐减弱。此外, 掺入Ag@SiO₂核壳结构可使钙钛矿薄膜太阳电池光电转换效率由6.28%增大到7.09%, 而银纳米颗粒和银纳米线由于会增大太阳电池内部载流子传输路径, 提高电子空穴对复合效率, 最终反而降低了太阳电池短路电流密度和光电转换效率。     

锐钛矿型TiO2纳米棒薄膜的溶胶-凝胶法制备研究

以钛酸丁酯Ti（OC₄H₉）₄、冰醋酸、去离子水和聚乙二醇（PEG）1000为原料,采用溶胶-凝胶法和旋转涂膜工艺,在玻璃衬底上制备出锐钛矿型TiO₂纳米棒。利用X射线衍射仪（XRD）、SEM和紫外可见光谱（UV/Vis）对TiO₂纳米棒薄膜进行了表征。结果表明,实验制备的TiO₂纳米棒为锐钛矿晶型,在TiO₂反应体系中,胶体粒子在加热过程中偶联在一起,1h后形成了TiO₂纳米棒,其直径为30～50nm,长度为100～200nm。同时,在42mL钛的胶体溶液中添加0.30g PEG（1000）后,纳米TiO₂薄膜的可见光透射峰值降低,TiO₂薄膜表面孔径为20～50nm。     

具有固-液转变的磁性Fe3O4纳米流体的制备、结构及性能

Fe3O4纳米粒子与离子型改性剂N,N-二癸基-N-甲基-N-三甲氧基硅正丙基氯化铵进行接枝反应,再采用反离子脂肪醇聚氧乙烯醚磺酸盐的长链阴离子交换Cl-,在Fe3O4纳米粒子表面得到具有阴、阳离子双电层结构的表面处理层,制备出了无溶剂Fe3O4纳米流体。分析结果表明,表面处理鏖已成功地接枝在Fe3O4纳米粒子表面,改...     

溶液法CH3NH3PbCl3单晶的生长与性能研究

分别采用蒸发结晶法和逆温结晶法生长尺寸约为4 mm×3 mm×3 mm的CH₃NH₃PbCl₃单晶。对两种方法生长的单晶粉体的XRD分析结果显示, 单晶具有立方晶系结构, 其晶格常数分别为0.56833、0.56891 nm。实验测量了CH₃NH₃PbCl₃单晶的红外光谱(FT-IR)和拉曼光谱, 并对谱峰进行了指认; 使用UV-VIS-NIR分光光度计、荧光光度计对CH₃NH₃PbCl₃单晶的光学性能进行了测试。结果表明: CH₃NH₃PbCl₃晶体的吸收边约为423 nm, 光致发光峰为433 nm, 带隙值为2.97 eV, 与CH₃NH₃PbCl₃薄膜的光学特性相比, CH₃NH₃PbCl₃单晶更具潜在的应用前景。最后, 结合第一性原理研究了CH₃NH₃PbCl₃晶体的能带结构, 计算得出带隙值2.428 eV, 与实验值吻合较好。     

Burning velocity measurements of nitrogen-containing compounds

Burning velocity measurements of nitrogen-containing compounds, i.e., ammonia (NH₃), methylamine (CH₃NH₂), ethylamine (C₂H₅NH₂), and propylamine (C₃H₇NH₂), were carried out to assess the flammability of potential natural refrigerants. The spherical-vessel (SV) method was used to measure the burning velocity over a wide range of sample and air concentrations. In addition, flame propagation was directly observed by the schlieren photography method, which showed that the spherical flame model was applicable to flames with a burning velocity higher than approximately 5 cm s⁻¹. For CH₃NH₂, the nozzle burner method was also used to confirm the validity of the results obtained by closed vessel methods. We obtained maximum burning velocities (S_u0,max) of 7.2, 24.7, 26.9, and 28.3 cm s⁻¹ for NH₃, CH₃NH₂, C₂H₅NH₂, and C₃H₇NH₂, respectively. It was noted that the burning velocities of NH₃ and CH₃NH₂ were as high as those of the typical hydrofluorocarbon refrigerants difluoromethane (HFC-32, S_u0,max = 6.7 cm s⁻¹) and 1,1-difluoroethane (HFC-152a, S_u0,max = 23.6 cm s⁻¹), respectively. The burning velocities were compared with those of the parent alkanes, and it was found that introducing an NH₂ group into hydrocarbon molecules decreases their burning velocity.     

Up-conversion dynamics in GdAlO3:Er single crystal fibre

Green fluorescence has been obtained under continuous laser excitation in the 780–860 nm range in GdAlO₃:Er³⁺. With the help of the Judd-Ofelt treatment we built a model based on population rate equations to describe its time evolution. We found the intensity parameters to be Ω₂ = 2.045 × 10⁻²⁰ cm², Ω₄ = 1.356 × 10⁻²⁰ cm² Ω₆ = 1. 125 × 10⁻²⁰ cm². Even if a two-photon absorption and a looping mechanism are necessary to well describe the dynamics, the main process responsible for up-conversion is energy transfer between erbium ions.