钙钛矿/银电极界面降解和离子迁移的原位研究（英文）

本文对CH_3NH_3PbI_3钙钛矿层与Ag电极之间的界面降解和离子迁移过程进行了全面地研究.利用原位光电子能谱检测于段,发现了Ag电极会诱导钙钛矿层的降解,导致PbI_2和AgI物种的形成以及Pb~(2+)离子在界面处还原成金属Pb物种.I 3d谱峰强度的反常增强为碘离子从CH_3NH_3PbI_3下表面迁移到Ag电极提供了直接的实验证据.此外,Ag电极和钙钛矿层接触会在CH_3NH_3PbI_3/Ag界面处诱导0.3 eV的界面偶极,这可能进一步促进碘离子扩散迁移,导致钙钛矿层的分解和Ag电极的侵蚀.     

α-P/GaAs(100)界面的光电子能谱研究

本文采用X射线光电子能谱、紫外光电子能谱和低能电子衍射对室温下P在GaAs(100)表面上的生长进行了研究。结果表明,在生长初期P是成团吸附的,随着淀积量的增加而生长成α-P薄膜,该薄膜的价带结构与等离子体淀积的α-P:H薄膜的价带结构相似。在界面处有约一单层的P与衬底表面的Ga成键。α-P覆盖层使GaAs表面势垒下降约0.2eV。 关键词：     

基于界面的钙钛矿氧化物电子学

文章介绍了基于钙钛矿过渡金属氧化物LaAlO₃/SrTiO₃界面的研究进展,其中特别关注了LaAlO₃/SrTiO₃界面上二维电子气的起源、超导和磁学性质的最新成果, 以及与氧化物界面相关的器件应用等。此外,文章还对相关的氧化物薄膜制备技术、表征技术和理论研究手段等也作了简单的介绍。     

原位电子显微学探索固体中的离子迁移行为

离子在固体材料中的迁移是很多应用的基础,包括锂离子电池、存取器件及催化剂等。研究固体材料中的离子迁移行为是固态离子学的核心内容。微观上,固体中离子迁移的行为取决于材料微观结构所确定的局域势垒特征。因此,研究离子迁移行为与微观结构的关联至为重要。文章讲述了具有高空间分辨率的原位透射电子显微镜技术用于锂离子电池材料、阻变存储材料等体系中离子迁移行为的研究现状与发展趋势。     

Si/ZnS极性界面能带偏移的同步辐射光电子能谱研究

用同步辐射光电子能谱测量了Si/ZnS（111）及（100）异质结的价带偏移ΔE_v．对于Si/ZnS（111）及（100）两界面，ΔE_v的实验结果均为（1.9±0.1）eV，与已有理论预期值相当符合，但与Maierhofer所报告的ZnS/Si（111）异质结测量结果之间则存在明显差别．该实验结果表明对于Si/ZnS极性界面，互逆性规则（commutativity rule）可能不成立，就此进行了讨论． 关键词：     

Fe/ZnO (0001)体系界面相互作用中薄膜厚度效应的光电子能谱研究

利用同步辐射光电子能谱(SRPES)和X射线光电子能谱(XPS)技术,系统研究了室温下Fe/ZnO界面形成过程中Fe薄膜与氧结尾的ZnO(000 1 )衬底之间的相互作用,结果显示初始沉积的Fe明显被表面氧氧化为Fe²⁺离子,在Fe覆盖度为0—3 nm的范围内,分别观察到与界面电荷传输、化学反应以及薄膜磁性相关的三个有意义的临界厚度,这一结果将有助于基于Fe/ZnO界面的相关器件的设计和研发. 关键词： Fe/ZnO 界面作用 同步辐射光电子能谱 X射线光电子能谱     

材料设计以及界面与器件工程最适化以实现高性能聚合物和钙钛矿太阳能电池

有机聚合物和钙钛矿杂化物在合成控制、加工及属性调控的进展显著地增强了其太阳能电池性能。聚合物和杂化太阳能电池的性能十分依赖材料吸收光子、激子离解、电荷传输以及在金属/有机/金属氧化物或金属/钙钛矿/金属氧化物界面的电荷收集的效率。介绍了如何通过有效地整合材料设计以及界面与器件工程以显著提高聚合物和杂化钙钛矿型太阳能电池性能(转换效率>18%)。还介绍了一些关于制备串联和半透明太阳能电池的新型器件结构和光学工程策略,以发挥聚合物和钙钛矿太阳能电池的最大潜能。     

阳极界面修饰对钙钛矿太阳能电池性能的影响

采用在聚(3,4-乙撑二氧噻吩)∶聚苯乙烯磺酸(Poly(3,4-ethylenedioxythiophene)∶Poly(styrenesulfonate),PEDOT∶PSS)阳极界面层上直接旋涂二甲基亚砜(Dimethyl Sulfoxide,DMSO)的方法,对PEDOT∶PSS薄膜进行修饰,以提高所制得的钙钛矿太阳能电池器件性能.在5000rpm转速条件下旋涂DMSO后,器件的能量转换效率达到11.43%,与PEDOT∶PSS阳极界面层未做任何修饰的器件相比,效率提高了29.15%.测试表征了修饰前后PEDOT∶PSS薄膜的透光性、表面形貌、电导率、器件的外量子效率曲线以及器件在光照和暗态下的J-V特性曲线,分析了器件性能提高的原因.结果表明:经过修饰的PEDOT∶PSS薄膜导电性显著增强,从而更加有利于器件阳极对空穴的抽取和收集;较未修饰时,器件的短路电流密度得到了大幅度提升,进而使得器件获得更高的能量转换效率.     

NaTFSI界面修饰对平面TiO2基钙钛矿太阳能电池的影响

在钙钛矿太阳能电池(PSCs)中,光吸收钙钛矿层夹在电子传输层(ETL)和空穴传输层(HTL)之间.钙钛矿层与电荷传输层之间的界面复合被认为是诱发器件电压损失的主要原因.通过对电荷传输层的修饰,不仅可以提高其电荷传输性能,而且还可以钝化界面缺陷,从而提高电池的光电转换效率(PCE)和稳定性.通过在平面二氧化钛层上引入一...     

苯乙胺钝化钙钛矿埋底界面提高太阳能电池性能EI北大核心CSCD

采用有机小分子钝化钙钛矿下表面(埋底界面)可以有效抑制钙钛矿埋底界面缺陷形成,降低载流子复合几率。本工作通过预先沉积钝化分子苯乙胺(PEA)的方法来钝化钙钛矿埋底界面。钝化后的钙钛矿晶粒大小与表面形貌无明显变化,吸收边和发光波长稍有红移,最高分子占据轨道能级略有提高。“Pb”元素结合能向高能级移动,而“N”元素结合能向低能级移动,并且钙钛矿中PbI2的残留量明显减少,表明钝化分子PEA通过“N”原子与钙钛矿下表面悬挂的“Pb”以及残留PbI2相互作用。基于PEA钝化的钙钛矿电池的开路电压、短路电流密度、填充因子和转换效率分别从1.041 V、21.29 mA/cm2、74.09%和16.41%提高到1.102 V、22.44 mA/cm2、79.28%和19.6%。器件性能的显著提高主要由于载流子的复合降低,归因于:(1)PEA钝化未饱和配位“Pb”引起的缺陷;(2)PEA钝化卤化铅微晶组成的复杂相引起的缺陷;(3)钙钛矿与空穴传输层之间的电荷转移速率的提高。钝化的钙钛矿电池器件稳定性明显增强。这种简便、有效的埋底界面钝化策略可以应用于未来大面积钙钛矿太阳能电池的制备。     

Optical properties of CH3NH3PbI3 crystal grown using inverse temperature crystallization

Perovskite CH₃NH₃PbI₃ (MAPbI₃) single crystal was grown using inverse temperature crystallization method. Crystallinity of the perovskite was confirmed by X-ray diffraction. Photoluminescence (PL) spectra revealed abnormal behavior due to a temperature-induced orthorhombic to the tetragonal phase transition. Four PL emission peaks, A, B, C, and D, were observed in the low temperature regime. Peaks A and B were observed at 756 and 776?nm?at 12?K, and were blue-shifted and disappeared at 130 and 70?K, respectively. Peaks C and D were observed at 789 and 807?nm?at 40?K and were also blue-shifted to 780 and 794?nm?at 100?K. On the other hand, the peak C red-shifted to 799?nm from 100 to 140?K because of an orthorhombic to the tetragonal phase change and was also blue-shifted above 140?K. From the excitation intensity- and temperature-dependent PL results, peaks A and B were assigned to the free-exciton and bound-exciton of the orthorhombic phase crystal, respectively. In addition, peaks C and D were associated with the free-exciton and bound-exciton of the tetragonal phase crystal, respectively. The activation energy of peak C was calculated to be 98?meV from temperature dependence of the PL intensity.     

Blocking of interfacial diffusion at Ag/Alq3 by LiF

X-ray photoelectron spectroscopy has been applied to interface studies of Ag/tris-(8-hydroxyquinoline) aluminum (Alq₃) and Ag/LiF/Alq₃. For Ag/Alq₃, diffusion of Ag atoms into the Alq₃ layer occurs immediately after the adhesion of the metal onto the organic layer and the process lasts several hours. Insertion of a monolayer-thick LiF buffer at the interface can effectively block the diffusion process. This is quite different from what is observed from Al/LiF/Alq₃, where Al penetrates into the LiF layer as deep as several nanometers. It is thus concluded that the LiF buffer may play different roles in Ag/LiF/Alq₃ and Al/LiF/Alq₃ and hence different mechanisms may dominate in the two cases for the enhanced carrier injection observed.     

K-shell excitation of CH4, NH3, H2O,CH3OH,CH3OCH3 and CH3NH2 by 2.5 keV electron impact

The regions around the respective carbon, nitrogen and oxygen K-edges of CH₄, NH₃, H₂O, CH₃OH, CH₃OCH₃ and CH₃NH₂ have been investigated by electron energy loss spectroscopy using a beam of 2.5 keV electrons. All spectra show a number of discrete peaks just below the K-shell ionization threshold. These discrete structures have been interpreted as being associated with the promotion of a K-shell electron to Rydberg orbitals which converge to the K-shell ionization threshold.     

Birefringence,X-ray and neutron diffraction measurements on the structural phase transitions of (CH3NH3)2 MnCl4 and (CH3NH3)2FeCl4

We used optical birefringence, X-ray and neutron diffraction methods with single crystals to study the structural phase transitions of the perowskite-type layer structures of (CH₃NH₃)₂MeCl₄ with Me=Mn, Fe. The Mn-compound shows the following structural transitions at 394 K — a continuous order-disorder phase transition from tetragonal symmetry $\text{I4}\text{mmm}$ to orthorhombic space group Abma (Cmca in reference 10); at 257 K — a discontinuous transition to a second tetragonal modification; at 95 K — a discontinuous transition to a monoclinic phase. For the Fe-compound the corresponding transition temperatures are 328 K and 231 K, respectively. A low temperature monoclinic phase could not be observed. The lattice parameters of the different modifications were determined as a function of temperature. The temperature dependent course of the order parameter has been investigated for the order—disorder transition. For both compounds, all the methods used gave the same value for the critical exponent of β = 0.315.     

钙钛矿(C6H5CH2NH3)2PbBr4拉曼光谱研究

运用激光拉曼光谱实验和密度泛函理论计算研究了450～1 700 cm-1光谱范围内有机-无机杂化钙钛矿材料(C₆H₅CH₂NH₃)₂PbBr₄的振动模式特性。对比实验所得拉曼光谱和理论计算所得拉曼光谱,发现密度泛函理论计算可以很好的模拟(C₆H₅CH₂NH₃)₂PbBr₄有机部分的分子振动模式。同时通过比较分析密度泛函理论计算和参考文献,对450～1 700 cm-1光谱范围内的拉曼峰的分子振动模式进行了初步的归属,并发现该光谱范围内的拉曼峰主要是由(C₆H₅CH₂NH₃)₂PbBr₄分子中有机部分振动所产生的。     

Dichroism of (CH3NH3)2CdCl4 in the farinfrared

The dielectric constant of (CH₃NH₃)₂ CdCl₄ has been measured as a function of temperature in the submillimeter range. Freshly grown samples with a wide domain structure at room temperature show a pronounced dichroism in this spectral range which is caused by the orientation of the molecules in the room temperature orthorhombic phase and their response to the electromagnetic wave.     

Structural characterization,thermal, vibrational properties and molecular motions in perovskite-type diaminopropanetetrachlorocadmate NH3(CH2)3NH3CdCl4 crystal

The work presents a detailed analysis of the sequencing of the structural phase transitions in NH₃(CH₂)₃NH₃CdCl₄ crystal by differential scanning calorimetry (DSC), X-ray, infrared, far infrared and Raman spectroscopy. DSC studies have shown that in analyzed crystal occurring one reversible continuous phase transition at 375/374 K (on heating/cooling). Observed in Nujol and Fluorolube mulls in the wide temperature range between 296 K and 413 K spectral changes through the structural phase transition can be attributed to an onset of motion of cations. An assignment of some bands due to internal modes has been also proposed.     

Synthesis and characterization of a new monophosphate [2,5-(CH3)2C6H3NH3]H2PO4

Chemical preparation, calorimetric studies, crystal structure and spectroscopic investigations are given for a new noncentrosymmetric organic cation monophosphate [2,5-(CH₃)₂C₆H₃NH₃]H₂PO₄. This compound is orthorhombic P2₁2₁2₁ with the following unit-cell parameters: a=5.872(4), b=20.984(3), c=8.465(1) Å, Z=4, V=1043.0(5) Å³ and D_x=1.396 g cm⁻³. Crystal structure has been solved and refined to R=0.048 using 2526 independent reflections. Structure can be described as an inorganic layer parallel to (a,b) planes between which organic groups [2,5-(CH₃)₂C₆H₃NH₃]⁺ are located. Multiple hydrogen bonds connecting the different entities of compound thrust upon three-dimensional network a noncentrosymmetric configuration.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Synthesis and crystal structure of [3,5-(CH3)2C6H3NH3]4P4O12·3H2O

Chemical preparation and crystal structure are given for a new cyclotetraphosphate: [3,5-(CH₃)₂C₆H₃NH₃]₄P₄O₁₂·3H₂O. This compound is triclinic P with the following unit-cell parameters: a=8.298(3), b=8.299(3), c=17.242(7)Å, α=97.13(3), β=102.72(3), γ=64.55(3)°, Z=1 and V=1045.2(8)ų. The crystal structure has been solved and refined to R=0.040 using 6086 independent reflections. The atomic arrangement can be described as layers organization. Layers built by P₄O₁₂ ring anions, ammonium groups and water molecules parallel to the plan (001), between which the organic groups are located. Characterization by X-ray diffraction, IR absorption, and thermal analysis are described.