高质量钙钛矿单晶CH3NH3PbI3研究进展

有机-无机钙钛矿材料因为具有光谱吸收范围宽、缺陷密度低、载流子复合率低等非常优良的光电性能吸引了广泛关注, 掀起了钙钛矿材料研究热潮。近年来杂化钙钛矿型太阳能电池发展迅速, 光电转化效率目前已达到22.1%, 展现出极大的应用潜力。与多晶薄膜相比, 单晶具有极低的缺陷密度和极少的界面缺陷。多个课题组成功培养出大尺寸钙钛矿单晶, 发现钙钛矿单晶材料具有比其他薄膜多晶材料更好的光响应特性, 是设计制备光伏器件的理想材料。在各类钙钛矿材料中, CH₃NH₃PbI₃是研究和应用最广泛的一类钙钛矿材料。本文主要针对近年来CH₃NH₃PbI₃单晶材料的研究制备进行综述, 介绍了CH₃NH₃PbI₃单晶材料的结构及性能, 重点总结了CH₃NH₃PbI₃单晶材料生长制备方法和应用, 并对其发展趋势进行了展望。     

3D视像和3D音像

我们日常生活的空间是一个三维（3D,threedimensional）世界,人们是用两只眼睛观察周围具有空间立体感的外界景物的,即具有长、宽、高三种度量,因此以3D的形式展现我们所看、所听的世界是与生俱来的所见皆是。但是由于种种原因,人们以前对音、像的再现都是二维的,随着人类科技的发展,3D是未来发展的必然趋势,而这些都是源于人们不断地进取与追求。     

3 Cr3 Mo3 VNb 在热冲孔中的应用研究

高合金钢热冲孔冲头寿命关系到模具与产品成本、生产效率、自动化设备的使用,因此,应注重冲头的选材、材料制备与冲头制造工艺。 用 3 Cr3Mo3 VNb 作为高合金钢热冲孔冲头,为提高模具寿命,在材料制备上,优化了成分,采用电渣重熔冶炼,减少杂质,毛坯锻造两次,用大锻造比锻造,冲头热处理用真空炉,三次回火,热处理硬度取 HRC42 ~ 46 ,冲头表面处理采用镀铬工艺,开展了热冲孔工艺试验。 结果表明,用3 Cr3Mo3 VNb 可使冲孔冲头寿命平均达到 800 件以上。     

基于机器学习的BiFeO3-PbTiO3-BaTiO3固溶体居里温度预测

钙钛矿(ABO₃)型压电陶瓷的发展已有几十年历史, 现存有大量数据, 从这些数据中寻找出材料结构与性能之间的关系很有意义。本工作收集了BiFeO₃-PbTiO₃-BaTiO₃钙钛矿型压电陶瓷居里温度(T_c)实验数据, 通过机器学习,构建钙钛矿型压电陶瓷T_c的预测模型。热力学角度, T_c与约合质量符合二次多项式关系, 但偏差较大。选择元素信息、物理量、空间群编号等基础描述符, 利用基于压缩感知原理的SISSO(Sure Independence Screening and Sparsifying Operator)方法进行机器学习, 找出了T_c与成分之间的相关性。比较不同描述符在不同维度上的均方根误差RMSE (Root Mean Square Error), 发现描述符越多、越基础, 维数越大、RMSE越小。同时比较相同个数描述符在同一维度下的RMSE, 用约合质量、A位和B位的离子半径比、A位和B位的未填充电子数比和Ba、Pb、Bi的元素含量等六个描述符构建出最优的四维模型, 其RMSE为0.59 ℃, 最大绝对误差(MaxAE)为1.38 ℃, 外部测试的平均相对误差MRE (Mean Relative Error)为1.00%。结果表明,利用SISSO可以进行有限样本钙钛矿型压电陶瓷T_c的机器学习预测。     

水热法制备固态电解质Li3xLa2/3-xTiO3粉末

具有钙钛矿结构的固态电解质钛酸镧锂(Li3x La2/3-x TiO3,LLTO)因在室温下具有较高的电导率,是目前固态电解质领域重要的研究热点.探究可以制备出含杂相少、微观应变小、粒度分布均匀适宜、尺寸均一、形貌优良的LLTO固态电解质粉末的条件十分必要.通过水热法在900℃及1050℃两种不同煅烧保温温度下制备固态电解质LLTO,研究了在这两种不同保温条件下制备的LLTO的合成情况、形貌、粒度、微观应变等.结果表明在900℃和1050℃的保温温度下都能成功合成LLTO,但两种保温温度下合成的粉末均为不规则形状颗粒,且均存在一定程度的团聚;从最终合成的物质的相组成来看,900℃保温条件下合成的LLTO含杂相更少.结合激光粒度仪测量的颗粒尺寸与X射线衍射测量的晶粒尺寸,从宏观的激光粒度测量看,在900℃保温2 h,合成的粉末粒径分布在1.7～3μm和33～57μm范围,在1050℃保温2 h,合成的粉末粒径分布在2.5～7μm和24～48μm;而利用X射线衍射从微观角度分析,平均晶粒尺寸分别为217.3 nm(900℃)、314.3 nm(1050℃),与激光粒度仪分析的平均颗粒尺寸存在差异;从制备的颗粒的微观应变来看,在两种保温温度下均存在微观应变导致的晶格参数变化,在更高的保温温度(1050℃)下,微观应变更大.综合实验结果可知,煅烧保温温度900℃是制备LLTO粉末更适宜的保温条件.     

4+3不等于3+4

<正>有一位耍猴人养了很多只猴子。因为长期相处,猴子能听懂耍猴人的每句话,耍猴人对猴子的生活习性、性格特点和心理状态也完全了解。由于生意不景气,耍猴人想对猴子的粮食实行限量供应。在连续三天对每只     

(La2/3Ca1/3)(Mn(3-x)/3)Fex/3)O3体系磁电阻行为的研究

通过系统地测量（La_2/3Ca_1/3）（Mn_{（3-x）／3}Fe_x／3）O₃（x＝0、0.1、0．2、0．3的体系样品的电阻率-温度关系以及一定温度下磁电阻率与磁场的关系,发现随x的变化其磁电阻率峰和电阻率峰均发生位移,磁电阻率峰值增大,并伴生磁电阻率峰展宽效应．作者认为由于Fe的替代,引起体系中Mn³⁺／Mn⁴⁺比率及磁矩的变化,加之外场对磁有序结构的调制作用,从而影响了Mn³⁺－O^－Mn⁴⁺的双交换作用,最终导致磁电阻行为发生变化．     

Pb（Ni_（1／3）Nb_（2／3））O_3－PbZrO_3－PbTiO_3三

对Ｐｂ（Ｎｉ１／３Ｎｂ２／３Ｏ３－ＰｂＺｒＯ３－ＰｂＴｉＯ３，即ｘＰｂ（Ｎｉ１／３Ｎｂ２／３）Ｏ３－（１－ｘ）Ｐｂ（ＺｒδＴｉ１－δ）Ｏ３（０．２≤ｘ≤０．６，０．２≤δ≤０．５）三元系固溶体的压电性能进行了研究，结果表明材料压电活性较高的配方位于准同型相界（ＭＰＢ）附近，压电常数ｄ３１值可达２６０×１０－１２Ｃ／Ｎ．讨论了结构相变对压电性能的影响．     

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。     

三元体系LiNO_3-NaNO_3-KNO_3相图预测及其热性能研究

采用对称的Kohler模型对LiNO3-NaNO3-KNO3三元体系的相图进行预测,得到三元共晶点为395.50 K,摩尔分数组成为x(LiNO3)=0.388,x(NaNO3)=0.102,x(KNO3)=0.510。对该共晶点组成材料进行DSC实验测定,其熔点为397.32K,而热重TG测试表明热稳定温度为868.62K,表明该材料有可能作为高温蓄热传热材料应用于太阳能热电厂及核能发电厂,工作温度范围为397.32~868.62K。     

Photostriction of CH3NH3PbBr3 Perovskite Crystals

Organic–inorganic hybrid perovskite materials exhibit a variety of physical properties. Pronounced coupling between phonon, organic cations, and the inorganic framework suggest that these materials exhibit strong light–matter interactions. The photoinduced strain of CH₃NH₃PbBr₃ is investigated using high‐resolution and contactless in situ Raman spectroscopy. Under illumination, the material exhibits large blue shifts in its Raman spectra that indicate significant structural deformations (i.e., photostriction). From these shifts, the photostrictive coefficient of CH₃NH₃PbBr₃ is calculated as 2.08 × 10^?8 m² W^?1 at room temperature under visible light illumination. The significant photostriction of CH₃NH₃PbBr₃ is attributed to a combination of the photovoltaic effect and translational symmetry loss of the molecular configuration via strong translation–rotation coupling. Unlike CH₃NH₃PbI₃, it is noted that the photostriction of CH₃NH₃PbBr₃ is extremely stable, demonstrating no signs of optical decay for at least 30 d. These results suggest the potential of CH₃NH₃PbBr₃ for applications in next‐generation optical micro‐electromechanical devices.     

Constitution of the Ni3Cr-Ni3Al-Ni3W system

Isothermal sections of the Ni-Cr-Al-W system have been investigated at 75 at % Ni and temperatures of 1523 and 1273 K, by means of phase compositional analysis, X-ray diffraction and microscopical examination. The alloys studied lay in the range 2.5 to 10 at % Cr, 12.5 to 20 at% Al, 2.5 to 6.25 at % W, The phases formed were, and the bcc solid solution based on tungsten (designated ₂). The maximum extent of the region was found to be 3 at % each of chromium and tungsten. Preferential partitioning of tungsten to occurred. Study of an Ni-10Cr-12.5Al-2.5W alloy aged at 1273 and 1073 K, after quenching from 1573 K, showed that changes in and compositions and lattice parameters occur as a function of ageing time.     

PbZrO3-CdTiO3 solid solutions

The structural, nonlinear optical, and dielectric properties of (1-x)PbZrO₃ ·xtCdTiO₃ solid solutions were studied. The phase relations in the composition rangesx = 0–0.3 and 0.85-1.0 were established. The results suggest that the ferrielectric ordering in CdTiO₃ persists up to 730 K.     

Multicolor up-conversion emissions of Tm3+/Er3+/Yb3+ tri-doped YF3 phosphors

Tm3+/Er3+/Yb3+ tri-doped yttrium fluoride (YF3) phosphors were prepared by a facile hydrothermal method. X-ray topographic analysis found that the phosphors were crystallized products. Their sizes and morphologies were characterized by scanning electron microscopy (SEM, Hitachi S-4800), which indicated that most of the YF3 phosphors were hundreds of nanometers in size. Up-conversion (UC) spectra were recorded under 980-nm diode laser excitation at room temperature with a fluorescence spectrometer (Hitachi F-4500). Plenty of UC emissions of Tm3+ and Er3+ were observed from ultraviolet to red. For Tm3+ ions, a five-photon process (approximately 291 nm and approximately 347 nm), a four-photon process (approximately 362 nm and approximately 452 nm), and a three-photon process (approximately 475 nm) were identified in the UC spectra. The UC emissions from the Er3+ were: approximately 380 nm, approximately 408 nm, approximately 521 nm, approximately 537 nm, and approximately 652 nm. Therefore, cyan-white light can be observed by the naked eye at 980-nm excitation, even under low excitation power density. By comparing the UC spectra of the phosphors annealed at different temperatures, we found that the intensity of the UC luminescence increased as annealing temperature increased. Furthermore, the spectral dependencies on Tm3+ doped concentrations were studied. The energy transfer processes and fluorescence dynamics in the tri-doped system are currently being investigated.     

Phase equilibria in the system LaMnO3 + δ-SrMnO3-LaFeO3-SrFeO3 − d

We have revealed the formation of a continuous series of orthorhombic LaMn_{1 ? y} Fe_yO₃ solid solutions (0<y<1); La_{1 ? x} Sr_xFeO₃ solid solutions in the composition range 0 < x ≤ 0.8, with an orthorhombic structure at 0 < x ≤ 0.6 and a cubic structure at 0.6 < x ≤ 0.8; and a tetragonal SrMn_{1 ? y} Fe_yO₃ phase in the range 0.6 ≤ y ≤ 1. The composition stability limits of the perovskite phase La_{1 ? x} Sr_xMn_{1 ? y} Fe_yO₃ have been determined, and the 1100°C isotherm of the La₂O₃-SrO-Mn₃O₄-Fe₂O₃ system in air has been constructed.     

Sintering and piezoelectric properties of Pb(Ni1/3Sb2/3)O3-PbZrO3-PbTiO3 ceramics

The sintering and piezoelectric properties of Pb(Ni_1/3Sb_2/3)O₃-PbZrO₃-PbTiO₃ ceramics have been investigated. When the powders contain 48 mol% PbTiO₃ and less than 10 mol% Pb(Ni_1/3Sb_2/3)O₃ followed by calcination at 850°C for 2 h, the calcine only contains the perovskite structure; but if the Pb(Ni_1/3Sb_2/3)O₃ content is between 12 mol% and 14 mol%, both tetragonal and rhombohedral phases are obtained. The composition of the morphotropic phase boundary(MPB) in the Pb(Ni_1/3Sb_2/3)O₃-PbZrO₃-PbTiO₃ system is Pb(Ni_1/3Sb_2/3)O₃ = 12 mol%, PbZrO₃ = 40 mol% and PbTiO₃ = 48 mol%. As the composition at the MPB is sintered at 1260°C and 1280°C for 2 h, respectively, the maximum density (7.8 g/cm³) is obtained. The SEM micrographs indicate that a decrease in porosity with increasing sintering temperature is attained at 1280°C, which is due to a decrease in the number and size of pores. When the sintering temperature is higher than 1280°C, the porosity increases due to PbO evaporation leading to an increase of the number of pore sites and in enlargement of the pore diameter. When the compact composition at MPB is sintered at 1280°C for 2 h, the planar coupling coefficient (K _p) and mechanical quality coefficient (Q _m) tend to approach the maximum (0.488) and minimum values (292.5), respectively.