Low-Temperature Solution Crystallization of Nanostructured Oxides and Thin Films

As an introduction to this themed issue, a critically selected overview of recent progress on the topic of solution methods for the low-temperature crystallization of nanoscale oxide materials is presented. It is focused on the low-temperature solution processing of oxide nanostructures and thin films. Benefits derived from these methods span from minimizing the environmental impact to reducing the fabrication costs. In addition, this topic is regarded as a key objective in the area because it offers a unique opportunity for the use of these materials in areas like flexible electronics, energy conversion and storage, environmental sciences, catalysis, or biomedicine.     

Supramolecular Coordination of Pb2+ Defects in Hybrid Lead Halide Perovskite Films Using Truxene Derivatives as Lewis Base Interlayers

Truxene derivatives, due to their molecular structure and properties, are good candidates for the passivation of defects when deposited onto hybrid lead halide perovskite thin films. Moreover, their semiconductor characteristics can be tailored through the modification of their chemical structure, which allows-upon light irradiation- the interfacial charge transfer between the perovskite film and the truxene molecules. In this work, we analysed the use of the molecules as surface passivation agents and their use in complete functional solar cells. We observed that these molecules reduce the non-radiative carrier recombination dynamics in the perovskite thin film through the supramolecular complex formation between the Truxene molecule and the Pb²⁺ defects at the perovskite surface. Interestingly, this supramolecular complexation neither affect the carrier recombination kinetics nor the carriers collection but induced noticeable hysteresis on the photocurrent vs voltage curves of the solar cells under 1 sun illumination.     

金属铝诱导法低温制备多晶硅薄膜

以氢气稀释的硅烷(SiH₄)和硼烷(B₂H₆)为气源,利用等离子体增强化学气相沉积法(PECVD)制备出p型a-Si薄膜.采用铝诱导晶化技术对不同厚度的铝膜对a-Si薄膜晶化的影响进行了研究.实验中发现,铝膜溅射为10 s的非晶硅薄膜样品在450℃下退火10 min后,p型a-Si结构仍为非晶态,铝膜溅射为20 s的非晶硅薄膜在450℃下退火20 min后,p型a-Si薄膜开始晶化为poly-Si薄膜,并且铝膜厚度越厚,则a-Si薄膜晶化程度越强.     

铅卤钙钛矿敏化型太阳能电池的研究进展

铅卤钙钛矿太阳能电池由于其低廉的成本, 简易的制备工艺和具有商业化潜力的效率等优点, 在最近两年里成为太阳能领域广受关注的新星. 铅卤钙钛矿太阳能电池的结构, 材料合成和制作工业在短时期内发生多项革命性的变化. 铅卤钙钛矿敏化型太阳能电池从最初使用液体电解液的敏化电池, 演变为固态敏化电池. 铅卤钙钛矿也从最初沉积在介孔膜的空隙的传统敏化结构, 演变为介孔空隙填充和致密覆盖层结合的混合型敏化结构. 通过这些结构的演化和材料制备的进步, 敏化型铅卤钙钛矿太阳能电池具备了较高的稳定性和高效率的两大优点. 对铅卤钙钛矿敏化型太阳能电池的研究进展进行简要综述.     

聚对苯二甲酰十碳二胺的制备和非等温结晶动力学研究

以对苯二甲酸和癸二胺为原料,经成盐,预聚合和固相聚合三个步骤合成了新型长碳链和较高相对分子质量的半芳香尼龙聚对苯二甲酰十碳二胺,由红外光谱和核磁共振对其结构进行了确认。用DSC方法研究了聚对苯二甲酰十碳二胺的非等温结晶动力学,用莫志深提出的R～f法对非等温结晶动力学进行了分析,由R～t法得到α值在0.70～0．81之间。利用Kissinger方法求得了半芳香尼龙的非等温结晶活化能,△E=-297．08kJ／mol。     

Aqueous Synthesis of Methylammonium Lead Halide Perovskite Nanocrystals

Methylammonium lead halide perovskite nanocrystals offer attractive optoelectronic properties but suffer from fast degradation in the presence of water. In contradiction to this observation, we demonstrate the possibility of a direct aqueous synthesis of CH₃NH₃PbX₃ (X=Br or Cl/Br) nanocrystals through the reaction between the lead halide complex and methylamine when the pH is maintained in the range of 0–5. Under these synthetic conditions, the positively charged surface of the perovskite nanocrystals and the proper ionic balance help to prevent their decomposition in water. Additional surface capping with organic amine ligands further improves the photoluminescence quantum yield of the perovskite nanocrystals to values close to 40 %, ensures their stability under ambient conditions for several months, and their photoluminescence performance under continuous 0.1 W mm^?2 405 nm light irradiation for over 250 hours.     

Unveiling the Effect of Solvents on Crystallization and Morphology of 2D Perovskite in Solvent-Assisted Method

Controlling the crystallographic orientations of 2D perovskite is regarded as an effective way to improve the efficiency of PSCs based on 2D perovskite. In this paper, five different assistant solvents were selected to unveil the effect of solvents on crystallization and morphology of 2D perovskite in a solvent-assisted method. Results demonstrated that the effect of Lewis basicity on the crystallization process was the most important factor for preparing 2D perovskite. The stability of the intermediate, reacted between the solvent and the Pb²⁺, determined the quality of 2D film. The stronger the Lewis basicity was, the more obvious the accurate control effect on the top-down crystallization process of 2D perovskite would be. This could enhance the crystallographic orientation of 2D perovskite. The effect of Lewis basicity played a more important role than other properties of the solvent, such as boiling point and polarity.     

PEEK-PEDEK嵌段共聚物非等温结晶动力学研究

PEEK以其优异的热稳定性和耐溶剂性被广泛应用在航空航天和电子电气等领域^[1].经过增强后的PEEK长期使用温度(UL温度指数)可达523 K.但在温度高于523 K的情况下,模量下降较快,这在一定程度上限制了其应用.在PEEK的分子链上引入刚性较强地联苯基团,可以有效的提高分子链的刚性,使聚合物的玻璃化转变温度得以提高^[2,3].我们曾合成了一系列含有刚性单体联苯二酚的嵌段共聚物,并对其热性能进行了研究^[4],本文着重对这一系列共聚物的非等温结晶动力学进行研究.     

Completely Amine-Free Open-Atmospheric Synthesis of High-Quality Cesium Lead Bromide (CsPbBr3) Perovskite Nanocrystals

Cesium lead halide perovskite nanocrystals (NCs) CsPbX₃ (X=Cl, Br, and I) have been prominent materials in the last few years due to their high photoluminescence quantum yield (PLQY) for light-emitting diodes and other significant applications in photovoltaics and optoelectronics. In colloidal CsPbX₃ synthesis, the most commonly used ligands are oleic acid and oleylamine. The latter plays an important role in surface passivation but may also be responsible for poor colloidal stability as a result of facile proton exchange leading to the formation of labile oleylammonium halide, which pulls halide ions out of the NC surface. Herein, a facile, efficient, completely amine-free synthesis of cesium lead bromide perovskite nanocrystals using hydrobromic acid as halide source and tri-n-octylphosphane as ligand under open-atmospheric conditions is demonstrated. Hydrobromic acid serves as labile source of bromide ion, and thus this three-precursor approach (separate precursors for Cs, Pb, Br) gives more control than a conventional single-source precursor for Pb and Br (PbBr₂). The use of HBr paved the way to eliminate oleylamine, and thus the formation of labile oleylammonium halide can be completely excluded. Various Cs:Pb:Br molar ratios were studied and optimum conditions for making very stable CsPbBr₃ NCs with high PLQY were found. These completely amine-free CsPbBr₃ perovskite NCs synthesized under bromine-rich conditions exhibit good stability and durability for more than three months in the form of colloidal solutions and films, respectively. Furthermore, stable tunable emission across a wide spectral range through anion exchange was demonstrated. More importantly, this work reports open-atmosphere-stable CsPbBr₃ NCs films exhibiting strong PL, which can be further used for optoelectronic device applications.     

聚丙烯/纳米蒙脱土复合材料的结晶动力学研究

采用热分析方法，研究了聚丙烯／纳米蒙脱土复合材料（PP／CLAY）的等温结晶行为，并分别用Avrami方程和赵志英方法对所得数据进行了分析，研究结果表明，纳米蒙脱土微粒对聚丙烯等温和非等温结晶行为均有不同程度的影响，可提高聚丙烯的结晶速率并改善结晶结构。     

First-Principles Study of Aziridinium Lead Iodide Perovskite for Photovoltaics

The long-term stability remains one of the main challenges for the commercialization of the rapidly developing hybrid organic-inorganic perovskite solar cells. Herein, we investigate the electronic and optical properties of the recently reported hybrid halide perovskite (CH₂)₂NH₂PbI₃ (AZPbI₃), which exhibits a much better stability than the popular halide perovskites CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃, by using density functional theory (DFT). We find that AZPbI₃ possesses a band gap of 1.31 eV, ideal for single-junction solar cells, and its optical absorption is comparable with those of the popular CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃ materials in the whole visible-light region. In addition, the conductivity of AZPbI₃ can be tuned from efficient p-type to n-type, depending on the growth conditions. Besides, the charge-carrier mobilities and lifetimes are unlikely hampered by deep transition energy levels, which have higher formation energies in AZPbI₃ according to our calculations. Overall, we suggest that the perovskite AZPbI₃ is an excellent candidate as a stable high-performance photovoltaic absorber material.     

Ultraviolet-Laser-Induced Crystallization of Sol-Gel Derived Inorganic Oxide Films

Structural changes stimulated by ultraviolet (UV) laser irradiations of sol-gel derived inorganic oxide films were investigated. Dried gel films of TiO₂, Nb₂O₅, Ta₂O₅, SrTiO₃ and Pb(Zr _x Ti_1–x )O₃ (PZT) were found to be crystallized by the laser irradiation. On the other hand, the photo-induced change in gel films of BaTiO₃, LiNbO₃ and LiTaO₃ was not observed although the laser beams were absorbed in the films. These sol-gel films were thermally crystallized at almost the same temperature around 600–700°C except TiO₂. Thus, the UV-laser-induced crystallization is not directly ascribed to a simple thermal effect with the irradiation. Photochemical properties of the cations are assumed to be important for the change in sol-gel films.     

溶液法铝诱导晶化多晶硅薄膜

介绍了一种基于溶液的廉价制备Al诱导晶化多晶硅薄膜的方法. 先以低压化学气相沉积(LPCVD)方法制备50 nm厚的非晶硅(amorphous silicon, a-Si)薄膜作为前驱物, 通过旋涂的方法, 将含有Al的盐溶液涂覆在a-Si薄膜表面, 550-620 ℃下氮气氛围退火若干小时得到多晶硅薄膜. 文中针对化学诱导源的种类、前驱物表面状况对晶化效果的影响进行了研究. 发现只有反应生成物中含有偏铝酸根(AlO-2)的碱性溶液才能发生诱导晶化, 而若Al溶液浓度过低, 则不能得到连续的多晶硅薄膜. a-Si表面若附有薄氧化层会有利于Al盐溶液在表面上的粘附以及得到大尺寸的晶粒, 然而又会增高退火晶化所需要的温度. 同时溶液在薄膜表面的粘附状况还会受到溶液中存在的其它离子的影响. 因此必须选用合适的实验条件.     

钛硅沸石的结晶动力学研究

 在TPABr-正丁胺体系中合成了钛硅沸石TS-1, 研究了此体系中的结晶动力学,求出了不同温度下的成核速率、晶体生长速率及表观活化能. 还研究了晶种类型和用量对钛硅沸石晶化的影响. 结果表明,随着晶化温度的升高, TS-1成核诱导期缩短,成核速率及晶体生长速率加快; 加入晶种可明显缩短TS-1成核诱导期,并减小晶粒粒度; TS-1, M, ZSM-11和β沸石等均可作为晶种合成TS-1, 并存在一个最佳晶种用量; 不加晶种时TS-1成核活化能和晶体生长活化能分别为44.4和75.7 kJ/mol.     

聚丙烯/凹凸棒土纳米复合材料的非等温结晶动力学

聚丙烯/凹凸棒土纳米复合材料的非等温结晶动力学     

等规聚丙烯自成核的等温结晶动力学

近年来 ,有关等规聚丙烯 (i PP)的自成核研究已引起了人们的关注 [1 ] ,但有关其结晶动力学的报道并不多见 .Carfagna等 [2 ]用膨胀计法研究了 i PP在未完全熔融重结晶情况下的等温结晶动力学 ,得到的 Avrami指数远远小于 3 .张新远等[3 ] 研究了 i PP未完全熔融情况下的非等温结晶动力学 .到目前为止 ,i PP自成核的熔体降温等温结晶动力学尚未见报道 .本文在 i PP自成核研究的基础上 [4] ,用 DSC方法研究了 i PP自成核在较高温度下的等温结晶动力学 ,讨论了结晶机理 .结果表明 ,在本实验的自成核条件下 ,i PP依然是三维球晶生长 ,…     

苯乙烯-丙烯嵌段共聚物等温结晶动力学的研究

用DSC法研究苯乙烯-丙烯嵌段共聚物(iPS-b-iPP)的等温结晶动力学。结果表明,在所选择的结晶温度(127～132℃)范围内,共聚物很好地符合Avrami动力学方程;共聚物结晶温度、结晶速率、结晶成核和生长方式都与共聚物结构和组成比有关,随着嵌段共聚物中iPS段含量的增加,结晶速率和Avranu指数(n)明显降低。     

Chitosan‐Assisted Crystallization and Film Forming of Perovskite Crystals through Biomineralization

Biomimetic mineralization is a powerful approach for the synthesis of advanced composite materials with hierarchical organization and controlled structure. Herein, chitosan was introduced into a perovskite precursor solution as a biopolymer additive to control the crystallization and to improve the morphology and film‐forming properties of a perovskite film by way of biomineralization. The biopolymer additive was able to control the size and morphology of the perovskite crystals and helped to form smooth films. The mechanism of chitosan‐mediated nucleation and growth of the perovskite crystals was explored. As a possible application, the chitosan–perovskite composite film was introduced into a planar heterojunction solar cell and increased power conversion efficiency relative to that observed for the pristine perovskite film was achieved. The biomimetic mineralization method proposed in this study provides an alternative way of preparing perovskite crystals with well‐controlled morphology and properties and extends the applications of perovskite crystals in photoelectronic fields, including planar‐heterojunction solar cells.     

水性聚氨酯/功能化石墨烯纳米复合材料的非等温结晶动力学

采用差示扫描量热法DSC研究了水性聚氨酯/功能化石墨烯(WPU/FGNs)纳米复合材料的非等温结晶行为,分别采用Ozawa方程、莫志深方程研究复合材料的非等温结晶动力学,并通过Kissinger方程计算了结晶过程中的活化能。 结果表明,石墨烯在复合材料的结晶过程中起到异相成核剂的作用,提高了复合材料的结晶起始温度、峰值温度和结晶速率;增加石墨烯的质量分数,复合材料的结晶维数增加;石墨烯增加至0.3%,复合材料的活化能从-47.74 kJ/mol降低至-53.60 kJ/mol,继续增加石墨烯至1.0%,复合材料的活化能增加至-41.74 kJ/mol。     

薄膜结构及形貌对钙钛矿电池性能的影响

采用液相连续沉积法制备了有机/无机杂化钙钛矿太阳电池,并研究了不同形貌钙钛矿(CH3NH3PbI3)光活性层对太阳电池性能的影响.实验结果表明在连续沉积法中PbI2的结构对CH3NH3PbI3层的形貌具有重要的影响,PbI2薄膜中适当的孔洞结构有利于其与CH3NH3I充分反应形成CH3NH3PbI3层.致密的PbI2层造成PbI2的转化不完全,导致CH3NH3PbI3颗粒较小,吸收较弱,影响电池的短路电流.而CH3NH3PbI3颗粒过大会引起CH3NH3PbI3薄膜孔洞产生,造成电池的开路电压下降.通过对电池制备工艺的优化获得了13.5%的最佳光电转换效率.