Effects of Mn substitution on the structure and properties of chalcopyrite-type CuInSe2

Mn-doped CuInSe₂ compounds (CuIn_1−xMn_xSe₂, x=0.0125–0.20 and Cu_1−yIn_1−yMn_2ySe₂, 2y=0.0125–0.60) were synthesized by high-temperature solid-state reactions. Single phase materials with chalcopyrite structure persist up to 0.10 and 0.20 doping for CuIn_1−xMn_xSe₂ and Cu_1−yIn_1−yMn_2ySe₂, respectively. The chalcopyrite and sphalerite phases co-exist in the Cu_1−yIn_1−yMn_2ySe₂ system for 2y=0.25–0.50. Attempts to introduce greater manganese content, x=0.15–0.20 for CuIn_1−xMn_xSe₂ and 2y=0.60 for Cu_1−yIn_1−yMn_2ySe₂, result in partial phase segregation. For the single-phase samples, the lattice parameters of both systems increase linearly with manganese concentration and thus follow Vegard's law. The temperature of the chalcopyrite–sphalerite phase transition is decreased by manganese substitution for all single-phase samples. The bandgap of the materials remains around 0.9 eV. Additionally, the Mn-doped CuInSe₂ compounds display paramagnetic behavior, whereas pure CuInSe₂ is diamagnetic at 5–300 K. All the CuIn_1−xMn_xSe₂ and Cu_1−yIn_1−yMn_2ySe₂ compounds with chalcopyrite structure show antiferromagnetic coupling and measured effective magnetic moments up to 5.8 μ_B/Mn.     

β-苄基苯乙酮吸收与发射光谱的密度泛函研究

β-苯基羰基化合物的光化学特征历来受到重视,是n,π*羰基三线态猝灭机理的典型代表。研究了气相和甲醇中β-苄基苯乙酮的基态结构和激发态结构,模拟了其吸收和发射光谱,并从分子轨道角度阐明了其发光机制。研究发现:(1)在甲醇中,β-苄基苯乙酮的基态结构与气相结构非常接近,只是在羰基官能团附近键长有差别;(2)在甲醇中,β-苄基苯乙酮的S1态无法维持平面构型,且αC—C键显著拉长;(3)在气相中,β-苄基苯乙酮的吸收光谱很弱,而在甲醇中很强;(4)气相中,β-苄基苯乙酮的荧光光谱的发光机制与甲醇中不同;(5)在气相中,β-苄基苯乙酮荧光光谱的最大发射峰蓝移到228.67nm处,发射强度(f=0.306 1)比吸收光谱大幅增加;(6)从分子轨道角度看,荧光光谱是吸收光谱的逆过程;(7)在气相中,β-苄基苯乙酮的磷光光谱在252.58和246.04nm处有两个较强的发射峰,而甲醇中只在258.88nm处有一个很强的发射峰。     

城市CIS物理关联脆弱性的动态分析方法

本文以城市关键基础设施系统(Critical Infrastructure System, CIS)为研究对象,将关键基础设施之间组成的复杂物理网络划分为个体层面、中观层面和系统层面三种类型,从物理关联势差的角度分析了城市CIS内部物理关联机理。根据城市CIS物理关联特性,引入元胞自动机(Cellular Automata, CA),以一种物理资源为主导建立模型,采用“自底向上”的方法,从微观关键基础设施活动推出宏观城市CIS表现。选取元胞连通性、元胞正常状态变化率和传输效率作为脆弱性评估指标,估算不同时间点城市CIS脆弱性的动态变化,实现物理关联脆弱性的动态分析,并运用加权平均值作为一段时间内城市CIS脆弱值。最后,以S城市为例,对物理关联脆弱性动态分析方法的合理性和有效性进行验证,评估结果为城市CIS保护提供支持。     

CuInSe2电子结构与光学性质的第一性原理计算

从头计算了CuInSe₂(CIS)体相的性质，参数设定和性质计算都基于密度泛函理论，交换相关能采用GGA，泛函形式为PBE，原子间相互作用的描述采用超软赝势.计算发现CIS中存在共价键，是一种非典型的离子型晶体，在整个晶体内存在共用电子对，Cu原子和Se原子的作用大于Se原子和In原子.CIS是一种典型的直接带隙半导体，计算得到了光学性质的各项参数，包括折射指数和反射率，吸收系数以及介电函数与光子能量的关系，发现CIS的主要光吸收峰有6个，分别为：3.1，7.6，10.0，16.1，19.0，21.0eV，理论上最强吸收峰在紫外光区.     

Biomimetic synthesis of CuInS2 nanoparticles: Characterization,cytotoxicity, and application in quantum dots sensitized solar cells

CuInS₂ (CIS) nanoparticles have unique chemical, toxicological and optoelectronic properties that favor their technological applications. In the present work we report a novel one step biomimetic method for the aqueous synthesis of CIS nanoparticles, that is also low cost and environmentally friendly. This biomimetic method uses only CuSO₄ and InCl₃ as precursor salts, and the biological molecule glutathione as sulfur donor and stabilizer of the nanoparticles (NPs). The reaction is performed at low temperatures, under aerobic conditions and atmospheric pressure. CIS nanoparticles produced by our biomimetic method exhibit fluorescence emission between 650 and 700 nm when excited at 500 nm. A size between 10 and 15 nm was determined by Dynamic light scattering (DLS) and corroborated by electron transmission microscopy. X-ray diffraction analysis (XRD) confirmed the crystalline structure of the CIS NPs produced. Energy Dispersive X-Ray Spectroscopy (EDX) analyses revealed the presence of Cu, In, and S in a 0.6: 1.4: 2 ratio, which has been reported for other CIS NPs in literature. No cytotoxicity of CIS NPs was observed in human OKT6/TERT2 cells and bacteria. Besides, the potential application of biomimetic CIS NPs as photosensitizers in quantum dots sensitized solar cells (QDSSCs) was confirmed. The biocompatibility, spectroscopic properties, and energy harvesting performance in solar cells of the CIS NPs produced by our biomimetic method make them suitable for their use in different biotechnological applications.     

硒化共溅射Cu—In合金法制备CuInSe2多晶薄膜

用共溅射方法和固态源硒化方法,分别合成了Cu-In合金膜和CuIn(CIS）多晶薄膜,并用XRD,SEM和霍尔效应测量技术,分别测量了两种薄膜的结构、表面形貌春电学性质,分析结果,Cu-In合金膜仅有单峰,晶面间距约2．13A,CIS薄膜的几个主峰与PDF卡中的数据对应得好,并且（112）峰有择优取向,CIS样品的电学参数随着Cu/In比例和基片种类的不同而变化,而电阻从几个到几十个Ω／□,面载流子浓度达10^18/cm^2数量级,迁移率在0．1－3．0cm^2/V.s之间,并讨论了Cu/In比例对两种薄膜性质的影响,分析结果显示,In占总溅射面积的3％是Cu/In比例的转折点,此时,CIS薄膜的结构、PN导电类型都有明显变化,而且用扫描电镜形貌分析也证明了这一点。     

Luminescent Properties of Mercury-taining Diethynylfluorene Derivatives

IntroductionThere has been an ongoing interestin the design ofalkynylmetal complexes over the past few decades be-cause of the potential applications of these compoundsto the diverse areas, such as organic and organometallicsyntheses[1], homo- and hetero …     

1π→1π* Ultraviolet Absorption Bands and Electronic Charge Transfers in Singlet Excited States of Sulfur Aromatic Heterocycles

Abstract

Indoline‐2‐thione (BC), benzimidazole‐2‐thione (BN), benzoxazole‐2‐thione (BO), and benzothiazole‐2‐thione (BS) define an interesting series of aromatic compounds containing a NCS synthonic unit in a heterocyclic ring of five centers, substituted by atomic centers of the type C, N, O, or S, where the main electronic absorption bands are localized in the spectral range of ultraviolet A or B.

The first two singlet electronic transitions of this series, ¹S₀→¹S₁(n,π*) and ¹S₀ → ¹S₂(π,π*), determine the main spectroscopic characteristic of these compounds in order to be used as potential photochemical actinometers of solar ultraviolet radiation. Furthermore, the second electronic transition, localized in the 270–360 nm ultraviolet spectral range, presents a hipsochromic spectral shift as function of the electronic nature of the heteroatomic centers in the heterocyclic ring.

In order to determine a spectroscopic assignment of the main absorption bands in aqueous solution and analyze the effect of the substituent on the electronic charge distributions in the ground and the first two singlet excited electronic states, we have used a semiempirical molecular orbital calculation in the INDO/S‐CIS approach. On the other hand, we have carried out a molecular orbital calculation in the AM1 framework, in order to determine the energetic stability of the thiones with respect to the thiol compounds.     

Absorption and emission properties of phenylene ethynylene oligomers: effect of substitution and π-conjugation length

The optical properties of a series of π-conjugated phenylene-ethynylene oligomers (OPEs) have been studied by advanced quantum chemical methods. The ground state and lowest singlet excited state geometries of unsubstituted and different electron donor and acceptor groups substituted OPEs are optimized by density functional theory and configuration interaction singles methods. The absorption and emission spectra of unsubstituted and substituted OPEs have been calculated using the time-dependent density functional theory (TDDFT) method. The results of theoretical calculations are in good agreement with the available experimental results. It has been found that the substitution of electron donating and withdrawing groups in the phenyl ring and conjugation length of the OPEs has significantly affect both the absorption and emission spectra