氢键诱导液晶的DSC和变温红外光谱研究

制备了两个分别基于4,4’-联吡啶(BPy)和丙基反式环己基苯甲酸(PCBA)以及BPy和丙基反式双环己基甲酸(PCCA)的氢键液晶复合物(PCBA-BPy和PCCA-BPy),结合使用偏光显微镜(POM),用差示扫描量热(DSC)和变温傅里叶变换红外光谱对它们的中间相性能和分子间氢键的热稳定性进行了表征。结果表明,这两个氢键复合物都具有由于分子间氢键作用而导致的近晶相,但它们中存在的氢键作用却不相同,在PCBA-BPy中,温度变化时,发生氢键结合的羰基的吸收峰的位置仅在发生晶型转变时有突变,而在PCCA-BPy中,温度变化时,其羰基的吸收峰的位置则基本不发生突变。另外,当温度高于它们的清亮点时,这两个氢键液晶复合物的分子间氢键都发生部分分解。     

Colossal dielectric constant in high entropy oxides

Entropic contributions to the stability of solids are very well understood and the mixing entropy has been used for forming various solids, for instance such as inverse spinels, see Nawrotsky et al., J. Inorg. Nucl. Chem. 29 , 2701 (1967) [1]. A particular development was related to high entropy alloys by Yeh et al., Adv. Eng. Mater. 6 , 299 (2004) [2] and Cantor et al., Mater. Sci. Eng. A 375–377 , 213 (2004) [3] (for recent reviews see Zhang et al., Prog. Mater. Sci. 61 , 1 (2014) [4] and Tsai et al., Mater. Res. Lett. 2 , 107 (2014) [5]) in which the configurational disorder is responsible for forming simple solid solutions and which are thoroughly studied for various applications especially due to their mechanical properties, e.g. Gludovatz et al., Science 345 , 1153 (2014) [6] and Lu et al., Sci. Rep. 4 , 6200 (2014) [7], but also electrical properties, Kozelj et al., Phys. Rev. Lett. 113 , 107001 (2014) [8], hydrogen storage, Kao et al., Int. J. Hydrogen Energy 35 , 9046 (2010) [9], magnetic properties, Zhang et al., Sci. Rep. 3 , 1455 (2013) [10]. Many unexplored compositions and properties still remain for this class of materials due to their large phase space. In a recent report it has been shown that the configurational disorder can be used for stabilizing simple solid solutions of oxides, which should normally not form solid solutions, see Rost et al., Nature Commun. 6 , 8485 (2015) [11] these new materials were called ”entropy‐stabilized oxides”. In this pioneering report, it was shown that mixing five equimolar binary oxides yielded, after heating at high temperature and quenching, an unexpected rock salt structure compound with statistical distribution of the cations in a face centered cubic lattice. Following this seminal study, we show here that these high entropy oxides (named HEOx hereafter) can be substituted by aliovalent elements with a charge compensation mechanism. This possibility largely increases the potential development of new materials by widening their (already complex) phase space. As a first example, we report here that at least one HEOx composition exhibits colossal dielectric constants, which could make it very promising for applications as large‐k dielectric materials. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Nuclear relaxation and motional anisotropy of liquid s-triazine

The dynamic structure of liquid s-triazine has been studied by analysing the deuterium and nitrogen-14 quadrupolar relaxation data of d ₃-s-triazine.

The molecular motions are markedly anisotropic with: (a) fast, large angle jump, inertial type in-plane motions of almost zero activation enthalpy and large negative activation entropy; (b) comparatively slow, small angle jump, rotational diffusion type, out of plane motions of higher activation enthalpy and small activation entropy. Comparison of the data on the dynamic behaviour of pyridine [3] and benzene [4] with the present ones on s-triazine leads to a general picture of molecular motions of planar hexagonal rotors in the liquid state (at atmospheric pressure). The behaviour of pyridine, which has a dipole moment departs somewhat from the more similar (and more anisotropic) behaviour of benzene and s-triazine. These results also support our previous finding of motional anisotropy in liquid pyridine [3].

A pictorial representation of the motional anisotropy in benzene, pyridine and s-triazine is giving using motional ellipsoids whose axes lengths are proportional to the diffusion constants.     

Orientational order parameters of nematogenic trans-4-propyl cyclohexyl-4 (trans-4-alkyl cyclohexyl) benzoates

The refractive indices and densities of three members of trans-4-propyl cyclohexyl-4 (trans-4-alkyl cyclohexyl) benzoates are reported as functions of temperature in the nematic and isotropic phases. The principal molecular polarizabilities and order parameters (S) have been evaluated using the anisotropic internal field model (Neugebauer’s approach). Also order parameters have been estimated by studying the dipole-dipole splittings in the wide line proton magnetic resonance (PMR) spectra. The results obtained are in close agreement with those obtained from refractive index measurements.     

三苯胺衍生物分子非线性光学性质的理论研究

在密度泛函理论水平上,利用响应函数方法,研究了1-{(1E)-2-[4-(二苯胺基)苯基]乙烯基}-4-[4-N,N-二甲胺]苯(PVMB)和1-[(1E)-2-(4-(1E)-2-{4-[4-N,N-二甲胺]苯基}乙烯基)苯基]苯胺}苯基)乙烯基]-4-[4-N,N-二甲胺]苯(DPVMB)两分子的双光子吸收特性.计算结果表明,这两个化合物都具有较好的双光子吸收特性,且具有两分支结构的DPVMB分子比具有单支结构的PVMB分子有更强的双光子吸收强度.计算数值结果和实验结果符合地较好.     

不同应变对Ge的光学性质影响的第一性原理研究

研究了不同方向、不同强度的应变对Ge光学性质的影响。结果表明,Ge在单轴张应变和双轴张应变的调控下,均可由间接带隙转向直接带隙,其中,单轴应变有更低的转变点。Ge在常用波段处(0.4 eV)的介电函数实部和虚部在张应变作用下,均急速上升而后在一定应变范围内下降。对Ge进行[111]单轴应变调控能表现出更好的光学性能以及更便捷的器件设计(较低的应变量)。     

Effect of substitution group on dielectric properties of 4H-pyrano [3,2-c] quinoline derivatives thin films

The AC electrical conductivity and dielectrical properties of 2-amino-6-ethyl-5-oxo-4-(3-phenoxyphenyl)-5,6-dihydro-4H-pyrano[3, 2-c]quinoline-3-carbonitrile(Ph-HPQ) and 2-amino-4-(2-chlorophenyl)-6-ethyl-5-oxo-5,6-dihydro-4H-pyrano [3, 2-c] quinoline-3-carbonitrile(Ch-HPQ) thin films were determined in the frequency range of 0.5 k Hz–5 MHz and the temperature range of 290–443 K. The AC electrical conduction of both compounds in thin film form is governed by the correlated barrier hopping(CBH) mechanism. Some parameters such as the barrier height, the maximum barrier height, the density of charges, and the hopping distance were determined as functions of temperature and frequency. The phenoxyphenyl group has a greater influence on those parameters than the chlorophenyl group. The AC activation energies were determined at different frequencies and temperatures. The dielectric behaviors of Ph-HPQ and Ch-HPQ were investigated using the impedance spectroscopy technique. The impedance data are presented in Nyquist diagrams for different temperatures. The Ch-HPQ films have higher impedance than the Ph-HPQ films. The real dielectric constant and dielectric loss show a remarkable dependence on the frequency and temperature. The Ph-HPQ has higher dielectric constants than the Ch-HPQ.     

Dielectric constants of binary mixtures of propylene carbonate with dimethyl carbonate and ethylene carbonate from molecular dynamics simulation: comparison between non-polarizable and polarizable force fields

Using non-polarizable and polarizable molecular dynamics simulations, binary mixtures of propylene carbonate?+?dimethyl carbonate and propylene carbonate?+?ethylene carbonate with various compositions were investigated. The polarizable model produces more reasonable estimation of dielectric constants than the non-polarizable model; however, combining the electronic continuum model with the non-polarizable MD improves the comparison between the two models. Fair agreement was found between the results from these simulations and available experimental data. In addition, for a better understanding of the mixing behaviour, the excess dielectric constants over the entire composition were calculated. By comparison of the two mixtures in various mole fractions, distinctive mixing behaviours of propylene carbonate?+?dimethyl carbonate (poorly symmetric mixture) and propylene carbonate?+?ethylene carbonate (highly symmetric mixture) were observed.     

Thermodielectric bistability in dual frequency nematic liquid crystal

We report on a thermodielectric bistability in dual frequency nematic liquid crystals (LCs) caused by the anisotropic nature of dielectric heating and director reorientation in an electric field. The bistability is a result of the positive feedback loop: director reorientation --> anisotropic dielectric heating --> dielectric anisotrophy --> director reorientation. We demonstrate both experimentally and theoretically that two states with different temperature and director orientation, namely, a cold planar state and a hot homeotropic state coexist in a LC cell for a certain frequency and amplitude range of the applied voltage.     

Optical characterization of bromo-alkoxyl-substituted copper phthalocyanine derivative thin films

A series of thin films of copper phthalocyanine derivatives with bromine and alkoxyl substituents [CuPc(OC₈H₁₇)₄Br_m, m=0,1,2,4] were prepared on single-crystal silicon substrates by spin coating. The ellipsometric spectra of the films have been studied on a rotating analyzer–polarizer type of scanning ellipsometer. The optical, dielectric constants and absorption coefficients of the films in 500–800 nm wavelength region were obtained. The results show that the complex refractive index, dielectric constants and absorption coefficient of these thin films are influenced regularly by bromine substituent on conjugated macrocycle. It was found that there are approximately linear relationships between the resonance absorption wavelengths of the films and the average number of bromine atoms substituted on the phthalocyanine ring.     

Abnormal switching behavior of nanoparticle composite systems

We have investigated the properties of liquid crystals (LCs) doped with ZnO (8% Cu doped) nanoparticles. The electro-optic properties of LCs have changed with varying concentration of ZnO nanoparticles. The dielectric anisotropy obtained from the values of dielectric permittivity at 5 kHz in the nematic and smectic phases was found to increase with increasing concentration of nanoparticles in LCs. It has been established that the effect of nanoparticles on the dielectric anisotropy depends on the physical properties of LCs; the nanoparticle disturbs the orientation ordering of LC molecules. The nanoparticle also influences the switching behavior, splay elastic constant, rotational viscosity and threshold voltage of pure LCs. A small quantity of nanoparticles causes slight reduction of the splay elastic constant and rotational viscosity of LC cells.     

Mesomorphic and dielectric properties of esters useful for formulation of nematic mixtures for dual frequency addressing system

Mesomorphic and dielectric properties of three homologous series of two and three ring fluorosubstituted esters are described. They are 4-cyano-3-fluorophenyl 4-alkyloxy-2-fluorobenzoates, 4-cyano-3-fluorophenyl 4-(4-alkylbenzoyloxy)-2-fluorobenzoates and 3-fluoro-4-cyanophenyl, or 3-fluoro-4-isothiocyanatophenyl or 3,4-difluorophenyl 4′-alkyl-2,3-difluoro-biphenyl-4-carboxylates. The compounds exhibit the nematic mesophase accompanied by the smectic A or smectic C mesophase in some cases. Most of them show strong dependence of the dielectric anisotropy Δε upon frequency, at low frequencies Δε reaches a value ∼200, while at high frequencies a small negative dielectric anisotropy appears.     

席夫碱修饰的α-氰基二苯乙烯荧光液晶材料的合成与发光性质

为获得高效的发光液晶材料,将席夫碱结构单元引入α-氰基二苯乙烯体系,合成了(Z)-2-(4-((E)-4-丁氧基-2-羟基苯乙烯氨基)苯基)-3-(4-丁氧基苯基)丙烯腈(BHPA)。通过紫外-可见吸收光谱和荧光光谱,研究其聚集诱导发光增强(AIEE)性质;利用热重分析(TGA)、差示量热扫描(DSC)、偏光显微镜(POM)研究其热力学性质和液晶性质。结果表明,BHPA是具有AIEE特性的发光液晶材料,取向的BHPA膜具有发光各向异性,其线偏振度约为0.41。     

Dispersion of fluorescent dye in the nematic liquid crystal: Enhanced photoluminescence and high birefringence

In the present investigation optical, electro-optical and dielectric properties have been measured for nematic liquid crystal (NLC) material 1550C which consists of 4’-(trans, trans-4-alkylbicyclohexyl) carbonates and 4’-(4-(trans,trans-4-alkyl)-4-cyanobicyclohexane, dispersed with fluorescent dye (Benzo 2,1,3 Thiadiazole) in two different concentrations. Photoluminescence has been enhanced for a dye dispersed system which is the key finding of this investigation. UV absorbance study has also been performed and found to be increased for composite system. Enhanced birefringence after dispersion of dye into pure NLC is also a prominent result of this investigation. Relative permittivity, threshold voltage and dielectric anisotropy have also been measured and found to be increased. The outcome of the present work may be very useful in the construction of liquid crystal displays (LCDs).     

用两端对称缺陷复合光子晶体实现多通道滤波和光开关

用传输矩阵法计算了两端对称缺陷复合光子晶体结构的光传输特性。计算结果表明:两端对称缺陷复合光子晶体[D(AB)mD]2结构中的禁带出现两个完全共振透射峰。通过控制入射光强来微调光子晶体材料的介电常数,使得完全共振透射峰移动,且介电常数变化越大,共振透射峰偏移越大,从而形成高效率的双通道光开关。当光子晶体为[D(AB)mD]N结构时,每个完全共振透射峰都分裂为N-1条,这样可通过调节N同时实现所需要通道数目的高效多通道光开关和多通道滤波器。     

Transient response of blue organic electroluminescence devices with short fluorescence lifetime of substituted phenyl/vinyl compound as an emissive layer

We have demonstrated a short fluorescence lifetime of the substituted phenyl/vinyl compound, 1,4-bis[2-[4-[N,N-di(p-tolyl)amino]phenyl]vinyl]benzene (DSB). The fluorescence lifetime of the 0.5 mol.% DSB-doped 4,4'-bis(9-carbazolyl)biphenyl film is 1.2 ns, which is desirable for organic light-emitting diode (OLED) light sources for optical interconnect applications. We have also examined frequency dependences on the electroluminescence (EL) intensity of the OLED and the photoluminescence (PL) intensity of the DSB film. The -3 dB cutoff frequency of the EL intensity is about 3 MHz for the optimized device, and the -3dB cutoff frequency of the PL intensity is about 160 MHz for the optically pumping DSB film.     

Solvatochromic and Preferential Solvation Studies on Schiff Base 1,4-Bis(((2-Methylthio)Phenylimino)Methyl) Benzene in Binary Liquid Mixtures

The solvatochromic behavior of the 1,4-bis(((2-methylthio) phenylimino)methyl) benzene [BMTPMB] in single solvents and binary mixtures were investigated. Fluorescence spectra show the dual emission due to twisted intramolecular charge transfer (TICT) state. The preferential solvation parameters: local mole fraction, X₂^L, solvation index δ_s2, exchange constant K₁₂ were calculated for the binary mixtures, ACN+MEOH, DMSO+CCl₄ and CCl₄+1,2 DCE. The dipole moment ratios between ground and excited states were deduced using the solvatochromic shifts of absorption and fluorescence spectra as a function of dielectric constant (ε), refractive index (n) and it was found to be 1.25.     

Ellipsometry of anisotropic graphene-like two-dimensional materials on transparent substrates

New possibilities for determining anisotropic properties of the dielectric constants of two-dimensional materials by ellipsometry are developed. Graphene-like 2D materials are considered within the framework of macroscopic electrodynamics as ultrathin absorbing anisotropic films where the optical axis is perpendicular to the film surface. The ellipsometric inversion problem is resolved analytically. The resulting inversion formulas are very fast because they allow you to directly calculate the complex anisotropic dielectric constants without the use of sophisticated regression analysis or iterative root-finding procedures. In particular, the method offers an interest in graphene and related 2D materials because the anisotropic properties of such materials have not been studied to date.     

Electro-optical characteristics of photoinduced isomerization in 2,2′-azobis[5,6-bis(dodecyloxy)quinoxaline]-azo-dye-doped nematic liquid crystals

The formation of photoinduced gratings was realized and dielectric properties were investigated in a nematic liquid crystal (LC) doped by 2,2′-azobis[5,6-bis(dodecyloxy)quinoxaline] azo dye (AD). The enhancement of the optical and electrical properties of the system was studied by dielectric spectroscopy and diffraction grating measurements. We report the electro-optical properties of LC cells containing pure LC (E7) and its doped form with 1% (wt/wt) 2,2′-azobis[5,6-bis(dodecyloxy)quinoxaline] AD. Diffraction efficiencies, η, of 441 nm pump and 632 nm probe beams were measured in two-wave-mixing experiment. Diffraction efficiency has a noteworthy increase in AD-doped nematic liquid crytals. A maximum diffraction efficiency of 14% was found for cell doped with AD, while cells without AD had a maximum efficiency of 1%. Photoinduced refractive index change Δn and nonlinear index coefficient n₂ were also determined by the two-wave-mixing method. The dielectric parameters of AD-doped E7 and pure E7 LC have been investigated in the frequency range 1 kHz-1 MHz by the dielectric-spectroscopy method. Dielectric anisotropy (Δε) property of the LCs changes from the positive type to negative type and dielectric anisotropy values decrease with AD.     

不同方法制备的CO2-3替换磷灰石固溶体晶体化学的FTIR研究

采用不同方法制备了CO2-3替换的磷灰石固溶体,利用FTIR结合XRD对其进行了晶体化学研究,结果表明均相沉淀法制备的碳羟磷灰石(CHAP)属B型替换且替换方式是[CO3·OH]四面体替换[PO4]四面体;固相离子交换法制备的CHAP属A型替换且替换方式是[CO3]三角形配位体替换通道位置的OH-;固相反应法制备的碳氟磷灰石(CFAP)属B型替换,其替换方式是[CO3·F]四面体替换[PO4]四面体;sol-gel法制备的CHAP属AB混合型替换,其Ψ3分裂为Ψ3-1,Ψ3F,Ψ3-4.高斯函数法拟合表明Ψ3F峰是A型替换的Ψ3-2与B型替换的Ψ3-3的叠合.当WCO2-3＜3.34%时,随CO2-3含量增加,A型替换量增大,且当WCO2-3=3.34%时达最大值,当3.34%＜WCO2-3＜7.52%时,随CO2-3含量增加,B型替换量增大,且当WCO2-3= 7.52%时亦到饱和.