Metallic conduction at organic charge-transfer interfaces

The electronic properties of interfaces between two different solids can differ strikingly from those of the constituent materials. For instance, metallic conductivity-and even superconductivity-have recently been discovered at interfaces formed by insulating transition-metal oxides. Here, we investigate interfaces between crystals of conjugated organic molecules, which are large-gap undoped semiconductors, that is, essentially insulators. We find that highly conducting interfaces can be realized with resistivity ranging from 1 to 30 kohms per square, and that, for the best samples, the temperature dependence of the conductivity is metallic. The observed electrical conduction originates from a large transfer of charge between the two crystals that takes place at the interface, on a molecular scale. As the interface assembly process is simple and can be applied to crystals of virtually any conjugated molecule, the conducting interfaces described here represent the first examples of a new class of electronic systems.     

Sandwich Structured Metal oxide/Reduced Graphene Oxide/Metal Oxide-Based Polymer Electrolyte Enables Continuous Inorganic–Organic Interphase for Fast Lithium-Ion Transportation

Introducing inorganic fillers into organic poly(ethylene oxide)(PEO)-based electrolyte has attracted substantial attention to enhance its ionic conductivity and mechanical strength, but limited inorganic–organic interphases are always caused by isolated particles agglomeration. Herein, a variety of sandwich structured metal oxide/reduced graphene oxide(rGO)/metal oxide nanocomposites to optimize lithium-ion conduction by interconnected amorphous organic–inorganic interphases in lithium metal batteries, are proposed. With the support of high surface area rGO, the agglomeration of metal oxide particles is precluded, forming continuous amorphous organic–inorganic interphases with stacked layer-by-layer structure, thus creating 3D interconnected lithium-ion transportation channels vertically and laterally. Besides, metal oxide nanoparticles with hydroxyls possess high affinity toward bis(tri-fluoromethanesulfonyl)imide anions by hydrogen bindings between hydroxyls and fluorine and metal-oxygen bonds, releasing more free lithium ions. Consequently, PEO-ZnO/rGO/ZnO electrolyte delivers superior ionic conductivity of 1.02 × 10⁻⁴ S cm⁻¹ at 25 °C and lithium-ion transference number of 0.38 at 60 °C. Furthermore, ZnO/rGO/ZnO insertion promotes the formation of LiF-rich stable solid electrolyte interface, endowing Li symmetric cells with long-term cycling stability over 900 hours. The corresponding LiFePO₄ cathode possesses a high reversible specific capacity of 130 mAh g⁻¹ at 0.5C after cycling 300 cycles with a poor capacity fading of 0.05% per cycle.     

Effect of interfacial features on the mechanical and electrical properties of rGO/Al composites

This study investigates the effect of interfacial features on the mechanical and electrical properties of reduced graphene oxide (rGO)/aluminum (Al) composites. The composites were fabricated using a hybrid process that includes chemical and mechanical methods. First, GO was uniformly dispersed on the surface of Al powder via a solution process. A strong interface was formed between GO and Al via several chemical bonds by using polyvinyl alcohol (PVA) as an organic binder during the solution process. Then, GO was thermally reduced to rGO, wherein the interfacial features were varied according to the atmosphere (vacuum or H₂(10%)/N₂(90%) mixed gas). Subsequently, rGO was mechanically embedded and further dispersed within soft Al powder through the plastic deformation of Al. Vacuum was found to be more effective than the mixed gas at removing functional groups containing oxygen in GO and therefore generated a tighter interface. As a result, the composites containing rGO that were reduced under vacuum showed higher strength and lower ductility compared with those reduced under the mixed gas. Conversely, the interfacial features rarely affected the electrical conductivity of the composites because the electrical conductivity of rGO was considerably lower than that of Al. Consequently, compared with their monolithic counterparts, the composites containing only 0.2 vol% rGO showed a 374-MPa yield strength without a significant loss of electrical conductivity, thereby demonstrating their potential feasibility in electrical and electronic applications.     

Realizing the Accurate Measurements of Thermal Conductivity over a Wide Range by Scanning Thermal Microscopy Combined with Quantitative Prediction of Thermal Contact Resistance

Quantitative thermal performance measurements and thermal management at the micro-/nano scale are becoming increasingly important as the size of electronic components shrinks. Scanning thermal microscopy (SThM) is an emerging method with high spatial resolution that accurately reflects changes in local thermal signals based on a thermally sensitive probe. However, because of the unclear thermal resistance at the probe-sample interface, quantitative characterization of thermal conductivity for different kinds of materials still remains limited. In this paper, the heat transfer process considering the thermal contact resistance between the probe and sample surface is analyzed using finite element simulation and thermal resistance network model. On this basis, a mathematical empirical function is developed applicable to a variety of material systems, which depicts the relationship between the thermal conductivity of the sample and the probe temperature. The proposed model is verified by measuring ten materials with a wide thermal conductivity range, and then further validated by two materials with unknown thermal conductivity. In conclusion, this work provides the prospect of achieving quantitative characterization of thermal conductivity over a wide range and further enables the mapping of local thermal conductivity to microstructures or phases of materials.     

Effects of high temperature mechanical damage on physical properties of unidirectional Ti/SiC metal matrix composite

Abstract

A miniaturised test system was used to investigate how the thermal and electrical properties of a unidirectionally reinforced titanium alloy (Ti–6Al–4V)/SiC (SM1140+)metal matrix composite change with mechanical damage at elevated temperature. Thermal conductivity and expansion measurements were obtained in the longitudinal and transverse direction both before and after short term strength and creep tests and at intervals during tests to assess changes in interface characteristics as functions of mechanical or thermal damage. The mechanical tests included monotonic stress–strain and ramp creep at temperatures between 500 and 650°C. The changes in thermal properties were compared with model predictions for the dependence of thermal properties on interface characteristics. The agreement was good for thermal expansion changes but not for thermal conductivity. This was ascribed to the nature of the damage at the interface that probably still allowed thermal transport but not mechanical load transfer.     

Interfacial polymerization to high-quality polyacrylamide/polyaniline composite hydrogels

Conducting polymer hydrogels composed of polyacrylamide (PAAm) and polyaniline (PAn) have been successfully synthesized through the interfacial polymerization. Compared to the conventional preparation methods, the interfacial polymerization is much more economical and effective because the PAn formed at the water/organic-solvent interface assembles spontaneously and exclusively into the PAAm hydrogel. In contrast to conventional materials, the resulting PAAm/PAn composite hydrogel exhibits high qualities including homogeneous structure, enhanced mechanical toughness, high electrical conductivity and the ability to reversibly interconvert between the doped and dedoped states. As-described interfacial polymerization for the fabrication of conducting polymer hydrogels does not depend on specific kinds of organic solvents or acid dopants.     

Phase orientation, interface structure, and properties of aged Cu-6 wt.% Ag

The crystallographic orientation and interface structure of Ag precipitates were investigated for aged Cu-6 wt.% Ag. The hardness and resistivity were determined for the aged alloy for different times. Ag secondary particles form in the Cu matrix from a discontinuous precipitation and the precipitated cells extend with the increase in aging time. There are the cube-on-cube relationship and semi-coherent interface between the Ag precipitate and the Cu matrix. Some dislocations are regularly arranged at the interface. The improvements of the hardness and conductivity can mainly be attributed to the increase in interface strengthening and the decrease in solute scattering in the Cu matrix during aging treatment. The high lattice-matching level and regular dislocation arrangement at the interface produce high strain resistance and low electron scattering.     

Structural Defects Control the Energy Level Alignment at Organic/Organic Interfaces

The dependence of the energy level alignment (ELA) on structural defects at an organic/organic heterojunction (OOH) of perfluoropentacene (PFP)‐on‐diindenoperylene (DIP) was investigated using X‐ray scattering and ultraviolet photoelectron spectroscopy. The density of structural defects near the interface between the PFP and DIP layers was varied by changing the growth temperature of the DIP film. A direct relationship was found between the defect density and the ELA at the OOH; the ELA together with the change in the electrostatic potential (quasi‐interface dipole layer) at the OOH varies systematically with the defect density near the interface. This indicates that a key factor affecting the ELA is the electrostatic potential change across the OOH interface, which is produced by electron transfer from DIP occupied gap states to PFP unoccupied gap states. These gap states originate from the defects and are effectively controlled by adjusting the growth conditions of the organic films. As a result, the ELA at OOH interfaces can be controlled by the density of structural defect, which is important for organic devices employing OOHs, such as organic photovoltaic cells.     

Bounds on the effective thermal conductivity of composites with imperfect interface

A new model is developed to bound the effective thermal conductivity of composites with thermal contact resistance between spherical inclusions and matrix. To construct the trial temperature and heat flux fields which satisfy the necessary interface conditions, the transition layer for each spherical inclusion is introduced. For the upper bound, the trial temperature field needs to satisfy the thermal contact resistance conditions between spherical inclusions and transition layers and the continuous interface conditions between transition layers and remnant matrix. For the lower bound, the trial heat flux field needs to satisfy the continuous interface conditions between different regions. It should be pointed out that the continuous interface conditions mentioned above are absolutely necessary for the application of variational principles, and the thermal contact resistance conditions between spherical inclusions and transition layers are suggested by the author. According to the principles of minimum potential energy and minimum complementary energy, the bounds of the effective thermal conductivity of composites with imperfect interfaces are rigorously derived. The effects of the size and distribution of spherical inclusions on the bounds of the effective thermal conductivity of composites are analyzed. It should be shown that the present method is simple and does not need to calculate the complex integrals of multi-point correlation functions. Meanwhile, the present method provides an entirely different way to bound the effective thermal conductivity of composites with imperfect interface, which can be developed to obtain a series of bounds by taking different trial temperature and heat flux fields. In addition, the present upper and lower bounds are finite when the thermal conductivity of spherical inclusions tends to ∞ and 0, respectively.     

固态电池中的正极/电解质界面性质研究进展EI北大核心CSCD

锂离子电池是便携式电子产品、电动汽车和智能电网的理想电源。目前使用有机液体电解质的锂离子电池仍然存在安全问题和寿命不足的问题,而使用不燃的固态电解质的固态电池有望解决这些问题。从原理上讲,不燃的固体电解质可以从根本上防止电池的燃烧和爆炸,并且只允许锂离子在固体电解质中传输,可以减少副反应的发生。近年来,随着几种高离子电导率的固态电解质的出现,锂离子在固态电解质中的传输不再是瓶颈。然而,固态电池中各种固态成分具有不同的化学/物理/力学性能,因此在固态电池中存在多种类型的界面,包括松散的物理接触、晶界、化学和电化学反应界面等,这些都可能增加界面离子传输阻力。而正极材料与电解质之间的界面反应尤其复杂,深入理解这些复杂的正极侧界面及其反应特点是实现实用高比能固态电池的必要条件。因此,本文主要回顾了近年来在探索和理解正极/电解质界面上的工作,总结了固态电池中典型的正极侧界面类型及其各自独特的反应特征。     

Thermal conductivity of organic liquid binary mixtures: Measurements and prediction method

A correlation presented in previous papers for the prediction of organic liquid thermal conductivity, , is generalized in order to estimate the thermal conductivity of the binary mixtures of organic liquids. The proposed equation contains the reduced temperature, the molar fractions, and two factors characteristic of the components. The comparison between predicted and experimental A values is developed at atmospheric pressure, taking into account data present in the literature and experimental values obtained at the Department of Energy of Ancona University, using the steady-state hot-wire method. Fifty binary mixtures are considered (28 of them are investigated by the authors at 25 and 50°C), and the mean general deviation between predicted and experimental thermal conductivity values (621 data points) is 2.5%.     

Effect of the incorporation of interfacial elements on the thermophysical properties of Cu/VGCNFs composites

Vapour grown carbon nanofibres exhibit high mechanical properties and thermal conductivities. Therefore they are potential reinforcements in composites materials for high strength and high thermal conductivity applications. A problem not yet solved is the promotion of an improved copper/carbon interface. Several strategies have been envisaged for the incorporation of alloying elements (Ni, Co, B and Ti) at the interface. These techniques are based on duplex electroless plating coatings (combination of Cu and Ni or Cu and Co), electroless plating of alloys (Cu-B) and addition of metal nanoparticles (Ti) to Cu matrix deposited by electroless plating. The effect of the incorporation of these metallic elements on the microstructure and thermophysical properties is discussed. B and Ti lead to higher interaction at the Cu/C interface over Ni and Co. This allows the reduction of the coefficient of thermal expansion but regarding the thermal conductivity it was not possible to obtain a value higher than that of copper.     

Electrical conductivity of polycrystalline semiconductors

A phenomenological model for the electrical conductivity in polycrystalline semiconductors is presented, using the assumption that an isotype heterojunction with a certain interface state density exists at the grain-intergrain domain interface. Tunnelling, thermionic emission of carriers through the intergrain barriers and ohmic conductivity of the heterojunction are all considered as possible charge transfer mechanisms. Explicit calculations are performed for wide-gap n-type semiconductors and a general expression is derived for the electrical conductivity. It is shown that the known models of Petritz and van den Broek, and also the expression for the conductivity of monocrystalline semiconductors, are special limiting cases of the theory presented.     

Effect of homogeneous Al(OH)3 covered MWCNT addition on the thermal conductivity of Al2O3/epoxy-terminated poly(dimethylsiloxane) composites

Aluminum hydroxide covered multiwalled carbon nanotubes (A-MWCNTs) were synthesized as a conducting additive to alumina-epoxy-terminated poly(dimethylsiloxane). The measured diffusivity and calculated conductivity exhibited dissimilar behavior between several Al₂O₃ concentrations as a function of A-MWCNT loading, which correlated with the interface density and interconnectivity of the structures. The fabricated heterostructured A-MWCNT did not have a significant effect on the thermal conductivity of the composite because of phonon scattering at the interface. A small amount of A-MWCNT was feasible for establishment of a heat conductive percolating network with the greatest enhancement of thermal conductivity and diffusivity at an A-MWCNT loading of 1.0 and 2.0 wt%. Continuously increasing thermal transport properties were observed with the 49.1 vol.% Al₂O₃ loading which derived from a lower interface density nanowire and polymer matrix with enhanced interconnectivity.     

Superfluid-Normal Interface of 4He Near a Wall

We observed a profile of nonequilibrium superfluid-normal (SN) interface of ⁴He near a vertical wall. A glass, brass or copper wall was used. The SN interface was produced by cooling liquid ⁴He in a bath from the bottom, where liquid ⁴He was pumped through a flow impedance in order to cool down the liquid. Superfluid (Normal fluid) occupied the lower (upper) part of the bath. The SN interface was visualized by three methods: simple visualization, shadowgraphy and schlieren method. The interface touched a vertical glass wall at almost 90°. A large hollow was observed near a brass wall which had intermediate thermal conductivity. Downward flow was observed on a copper wall due to the very good thermal conductivity of the wall. Various types of interface profile were observed depending on the thermal conductivity of the wall used.      

Electronic functionalization of the surface of organic semiconductors with self-assembled monolayers

Self-assembled monolayers (SAMs) are widely used in a variety of emerging applications for surface modification of metals and oxides. Here, we demonstrate a new type of molecular self-assembly: the growth of organosilane SAMs at the surface of organic semiconductors. Remarkably, SAM growth results in a pronounced increase of the surface conductivity of organic materials, which can be very large for SAMs with a strong electron-withdrawing ability. For example, the conductivity induced by perfluorinated alkyl silanes in organic molecular crystals approaches 10(-5) S per square, two orders of magnitude greater than the maximum conductivity typically achieved in organic field-effect transistors. The observed large electronic effect opens new opportunities for nanoscale surface functionalization of organic semiconductors with molecular self-assembly. In particular, SAM-induced conductivity shows sensitivity to different molecular species present in the environment, which makes this system very attractive for chemical sensing applications.     

Magnetic effects at the interface between non-magnetic oxides

The electronic reconstruction at the interface between two insulating oxides can give rise to a highly conductive interface. Here we show how, in analogy to this remarkable interface-induced conductivity, magnetism can be induced at the interface between the otherwise non-magnetic insulating perovskites SrTiO3 and LaAlO3. A large negative magnetoresistance of the interface is found, together with a logarithmic temperature dependence of the sheet resistance. At low temperatures, the sheet resistance reveals magnetic hysteresis. Magnetic ordering is a key issue in solid-state science and its underlying mechanisms are still the subject of intense research. In particular, the interplay between localized magnetic moments and the spin of itinerant conduction electrons in a solid gives rise to intriguing many-body effects such as Ruderman-Kittel-Kasuya-Yosida interactions, the Kondo effect and carrier-induced ferromagnetism in diluted magnetic semiconductors. The conducting oxide interface now provides a versatile system to induce and manipulate magnetic moments in otherwise non-magnetic materials.     

Effect of coating on the microstructure and thermal conductivities of diamond-Cu composites prepared by powder metallurgy

Diamond-Cu composites from the direct combination of diamond and Cu show low thermal conductivities due to weak interface and high thermal resistance as a result of chemical incompatibility. In this paper, a new method is proposed to strengthen interfacial binding between diamond and Cu by coating strong carbide-forming elements, e.g., Ti or Cr on the surface of the diamond through vacuum micro-deposition. Interfacial thermal resistance of diamond-Cu composites is greatly decreased when diamond particles are coated by a Cr or Ti layer of a certain thickness before combining with Cu. Thermal conductivity is also increased several times. Cr coating can reduce more effectively interface thermal resistance between diamond and Cu than Ti coating. Moreover, it has a smaller negative impact on the thermal conductivity of the Cu matrix, resulting in higher thermal conductivity of Cr-coated diamond-Cu composites. Through the vacuum micro-deposition technology, Cr on the diamond particle surface is present in the form Cr₇C₃ near diamond and a pure Cr outer layer at 2:1. The optimum thickness is within 0.6-0.9 μm; at this depth, the thermal conductivities of 70 vol% diamond-Cu composites can be increased four times and reach as high as 657 W/m K. In this work, an original theoretical model is proposed to estimate the thermal conductivities of composite materials with an interlayer of a certain thickness. The predicted values from this model are in good agreement with the experimental values.     

Numerical evaluation on heat transport characteristics between Al2O3 and ZnO materials in nanoscale situation

The aim of this article is to provide a systematic method to perform numerical evaluation on the cross-plane thermal conductivity of Al(2)O(3)/ZnO film interface. The Equilibrium Molecular Dynamics (EMD) simulations method is used to investigate the cross-plane thermal conductivity of Al(2)O(3)/ZnO film interface along the direction of Z axis at different equilibrium temperature and film interface thickness. The Buckingham two-body potential function and Green-Kubo linear response theory are used for modeling and calculation. The results show that the size effect is obvious. It implies the film interface thickness is 23.4-52 ? and the equilibrium temperature is 300-600 K. The cross section thermal conductivity of Al(2)O(3)/ZnO film interface increases with the increase of interface thickness, and decreases with the increase in equilibrium temperature.     

离子液体在有机光电转换器件中的应用研究进展

近年来,离子液体因具有不易挥发、性质稳定、透光性好、导电率高、可设计性,以及易于在界面处形成双电层等物理化学性质,而展现出广阔的应用潜力和前景,逐渐成为国际科学研究的前沿和热点之一。其中,将离子液体应用于染料敏化太阳能电池(Dye-sensitized solar cells,DSSCs)、钙钛矿太阳能电池和有机光电探测器等有机光电转换器件的研究备受关注。 在有机光电转换器件中,离子液体在染料敏化太阳能电池方面的应用最为广泛且完善。高效DSSCs主要是基于有机溶剂的液态电解质结,但有机溶剂在带来较高光电转换效率的同时,其本身存在的易挥发汽化、光热稳定性差等缺点,导致DSSCs的器件寿命与长期稳定性受到影响,离子液体的引入能有效解决以上问题。此外,离子液体还以电子传输层以及界面修饰层的形式引入,具有高电荷迁移率、低功函数以及高稳定性等优点,能在一定程度上改善器件的短路电流、填充因子和光电转换效率等。因此,离子液体成为在DSSCs的实际应用中兼具性价比高、封装难度低、性能好、稳定性高四大优点的辅助材料。在钙钛矿太阳能电池方面,离子液体的低功函数和高电子迁移率以及一些特殊性质如钝化反应、黏度效应等,都能够实现对电子萃取率、电荷转移电阻、钙钛矿结晶情况等方面的控制以满足实际设计要求,进而有助于钙钛矿太阳能电池的光电转换效率、填充因子等性能指标不同程度的提升。在有机光电探测器方面,引入的离子液体能促使在与之接触的界面处形成双电层,双电层的形成及离子液体的高导电率使得入射光不必照射有机光电探测器上下电极的重叠区域仍旧可以产生较大的光电流输出,从而可以有效摆脱有机光电探测器对电极材料透光性要求的局限性。同时双电层的形成还将促进有机光电探测器工作层中的电荷分离,进一步提高有机光电探测器的响应率。 本文主要从染料敏化太阳能电池、钙钛矿太阳能电池、有机光电探测器三个方面,综述了离子液体在有机光电转换器件中的国内外应用研究进展,就离子液体对提升有机光电转换效率及其实现器件新功能的工作机理进行了详细分析,并对其未来的应用研究方向进行了展望,为今后进一步设计出更适合有机光电转换领域应用的离子液体提供参考。