Surfaces and interfaces in polymer-based electronics

Research on electronics applications such as light-emitting devices for flat-panel displays, transistors, sensors and even solid state lasers based on conducting polymers is presently under way and in some cases has reached the stage of prototype production. The mechanisms for charge injection and conduction in these materials are being studied, as are the physics of luminescence and its quenching. Lately, research into controlling film morphology through self-organizing techniques also has gained interest. Though the present interest in conducting polymers mainly concerns the pristine semiconducting state, doped conducting polymers are also studied for potential use in many applications.

In this paper, we present an overview of some of the central issues in surface and interface science in the field, as well as provide our view on what may lie ahead in the future. Specifically, the importance of metal/polymer, polymer/metal and polymer/polymer interfaces is addressed. We illustrate these using polymer-based light-emitting devices, though the same type of issues appear in other polymer-based applications such as transistors and solar cells.     

绝缘层LiF/Al电极对提高P-PPV发光器件发光性能的研究

为了提高聚合物电致发光器件中Ba（Ca）／Al阴极的稳定性,在该阴极与聚合物发光材料poly（2-（4-ethylexyl）phenyl-1,4-phenylene vinylene）（P-PPV）层之间插入一层7nm的LiF绝缘层,发光器件的发光性能在多项参数（发光器件的电压．电流特性、发光强度及外量子效率,以及电流效率等发光性能指标）上能够与工作性能优良但稳定性较差的Ba（Ca）／Al电极结构PLEDs器件的发光特性具有可比性。这对于研制高效率、高稳定的聚合物电致发光器件并最终将其用于商业目的,具有重大现实意义。     

Formation dynamics of bipolaron in a metal/polymer/metal structure

Charge injection process from metal electrode to a nondegenerate polymer in a metal/ polymer/ metal structure has been investigated by using a nonadiabatic dynamic method. We demonstrate that the dynamical formation of a bipolaron sensitively depends on the strength of applied electric field, the work function of metal electrode, and the contact between the polymer and the electrode. For a given bias applied to one of the electrode (V₀) and coupling between the electrode and the polymer (t^′), such as V₀=0.79 eV and t^′=1 eV, the charge injection process depending on the electric field can be divided into the following three cases: (1) in the absence of the electric field, only one electron tunnels into the polymer to form a polaron near the middle of the polymer chain; (2) at low electric fields, two electrons transfer into the polymer chain to form a bipolaron; (3) at higher electric fields, bipolaron can not be formed in the polymer chain, electrons are transferred from the left electrode to right electrode through the polymer one by one accompanying with small irregular lattice deformations.     

Wetting, Bonding and Interfacial Energy of Nanocrystalline Metal Particles on Crystalline DCH Polymer and Amorphous Carbon Substrates

Experimental results concerning the interaction between a variety of nanocrystalline metals (gold, silver, nickel and chromium) and both crystalline polymer [poly-DCH (1,6-di (N-carbazolyl)-2,4-hexadiene)] and amorphous carbon substrates, are presented and analyzed. Attention is focused on aspects of the interaction that concern interfacial bonding, its correlation with the cohesive energies of the various metals and the energy of the interfaces. Experimental contributions include qualitative estimates of the magnitude of interfacial energies for the crystalline polymer/metal and amorphous carbon/metal interfaces and a direct measurement of the interfacial energies for gold and silver nanocrystals deposited on the amorphous carbon substrate. The sequence of interfacial energy values for the polymer/metal and amorphous carbon/metal systems is also determined. The interfacial energies for both the poly-DCH and amorphous carbon substrates decreases in the order silver, gold, nickel, and chromium, as expected from cohesive energy, melting point and surface energy data for these elements. The crystalline polymer/metal interfaces were examined for the presence of orientation relationships using selected area diffraction and optical diffractometry of high-resolution TEM images. No orientation relationships were found for any of the polymer/metal combinations spanning a large range of metal reactivities. Lack of atomic matching or some as yet unknown surface condition on the polymer may be responsible for this effect.     

金属/掺杂聚合物/金属结构中载流子的注入与输运

基于紧束缚的Su-Schrieffer-Heeger模型,利用非绝热的动力学方法,研究了金属/聚合物/金属三明治结构中载流子注入与输运的动力学过程,其中,聚合物中含有一个掺杂离子. 电子波函数随时间的演化满足含时Schrdinger方程,晶格运动满足经典的牛顿运动方程. 研究发现,掺杂离子对注入到聚合物中的载流子的作用类似一个控制阀门,阀门的状态与电场的强度和偏压的大小密切相关. 关键词： 载流子输运 波包 非绝热动力学     

A method of determining the charge trapped at the interfaces of a metal/ferroelectric/metal thin-film structure

A method is developed for determining the trap density at the metal/ferroelectric interfaces in a completely depleted ferroelectric film with two Schottky barriers. The method is based on the recharging of traps induced by an external pulsed bias. The ranges of the bias fields and of the parameters of the metal/ferro-electric/metal structure for which analytical solution of the Poisson equation is possible are found. Using this method and measurements of the transient current, the density of the charge trapped at the upper and lower interfaces of Pt(Ir)/PZT/Ir(Ti/SiO₂/Si) capacitors is determined. The interface charge as estimated from the trap density proved to be much smaller than the residual polarization of the PZT film. The observed correlation between the symmetry of the interface trap charges and the symmetry of the hysteresis loops and switching currents indicates the reliability of the estimation of the trap density determined using the proposed method.     

Charge Injection and Transport in Metal/Polymer Chains/Metal Sandwich Structure

Using the tight-binding Su--Schrieffer--Heeger model and a nonadiabatic dynamic evolution method, we study the dynamic processes of the charge injection and transport in a metal/two coupled conjugated polymer chains/metal structure. It is found that the charge interchain transport is determined by the strength of the electric field and the magnitude of the voltage bias applied on the metal electrode. The stronger electric field and the larger voltage bias are both in favour of the charge interchain transport.     

Progress in Modification of Indium-Tin Oxide/Organic Interfaces for Organic Light-Emitting Diodes

The oxide/organic interfaces play crucial roles in the hole injection from the anode electrodes to the emitting organics in organic light-emitting diodes (OLEDs), and hence have strong impacts on the efficiencies and other properties of the devices. Indium-tin oxide (ITO) is currently the most popular anode material used in OLEDs due to several merits, such as good etch ability, good adherence, high transparency, low resistivity, and high work function. Interfacial engineering between the ITO electrode and the overlying organic layers is an important process to obtain the high performance of the diode devices. In this article, recent progress in modification of the ITO/organic interfaces is reviewed, as these interfaces are important to the development of the technologies aiming at improving the electroluminescence, and efficiencies as well as reducing the operation voltages of OLEDs. ITO/Organic interfacial properties can be controlled or modified by simply changing the surface properties of ITO using chemical or physical treatments, and by adding a buffer layer (e.g., metal, oxide, or organic thin films) between the ITO and hole transport or emitting organic layers. The literature data showed that the electroluminescence, efficiencies, and lifetimes of the OLEDs could be greatly increased and the operation voltage considerably decreased when the ITO/organic interfaces have been properly improved.     

Injection of holes at indium tin oxide/dendrimer interface: An explanation with new theory of thermionic emission at metal/organic interfaces

The traditional theory of thermionic emission at metal/inorganic crystalline semiconductor interfaces is no longer applicable for the interface between a metal and an organic semiconductor. Under the assumption of thermalization of hot carriers in the organic semiconductor near the interface, a theory for thermionic emission of charge carriers at metal/organic semiconductor interfaces is developed. This theory is used to explain the experimental result from Samuel group [J.P.J. Markham, D.W. Samuel, S.-C. Lo, P.L. Burn, M. Weiter, H. Baessler, J. Appl. Phys. 95 (2004) 438] for the injection of holes from indium tin oxide into the dendrimer based on fac-tris(2-phenylpyridyl) iridium(III).     

Superconductivity of polymers with charge injection doping

We show that conductivity measurements on sandwiches of a polymer between normal‐metal and superconducting‐metal electrodes can be interpreted in terms of intrinsic superconductivity due to injection of charge into the polymer.     

Dynamical study on charge injection and transport in a metal/polythiophene/metal structure

The dynamical process of charge injection from metal electrode to a nondegenerate polymer in a metal/polythiophene （PT）/metal structure has been investigated by using a nonadiabatic dynamic approach. It is found that the injected charges form wave packets due to the strong electron-lattice interaction in PT. We demonstrate that the dynamical formation of the wave packet sensitively depends on the strength of applied voltage, the electric field, and the contact between PT and electrode. At a strength of the electric field more than 3.0 × 10^4 V/cm, the carriers can be ejected from the PT into the right electrode. At an electric field more than 3.0 × 10^5 V/cm, the wave packet cannot form while it moves rapidly to the right PT/metal interface. It is shown that the ejected quantity of charge is noninteger.     

Chemical and physical interactions at metal/self-assembled organic monolayer interfaces

The purpose of research on metals (M) deposited onto self-assembled monolayers (SAMs) is to understand the interactions between metal (M) and eventually metal oxide overlayers on well-ordered organic substrates. Application of M/SAM and inorganic/SAM research results to the understanding of real inorganic/ organic interfaces in vacuum and under environmental conditions can potentially play a key role in the development of advanced devices with stable interfacial properties. The M/SAM approach to interface research is delineated as a new subfield in surface science in the context of other approaches to inorganic/organic interface research. Current issues in M/SAM research are outlined, including chemical compound formation, the morphology (spreading, clustering, or penetration) of the metal species, the kinetics of the metal morphology, the effect of the metal on the degree of order in the SAM, and the rate of metal penetration into the SAM. Probes are recommended that are suitable for M/SAM research. The results of M/SAM studies to date are reviewed, and M/SAM combinations are ranked according to reactivity and penetration. Key probes for addressing gaps in the research results are identified. The effects of defects, disordering, air exposure, and X-ray and electron beam exposure on the experimental results to date are evaluated. Thus far, the results have successfully revealed qualitative relationships of M/SAM chemistry, temperature, and penetration. The chemical interactions that have been found are applicable to real M/polymer interfaces as formed in vacuum. It has yet to be shown that M/SAM research will yield quantitative understanding of interface formation or that M/SAM interfaces are entirely analogous to M/polymer interfaces in the details of interface formation. The future of this subfield of surface science lies in its expansion from M/SAM interfaces in vacuum to other inorganic/SAM interfaces in vacuum and, eventually, under environmental conditions.     

EFM phase investigation of the metal-organic film interface

Phase sensitive electrostatic force microscopy (EFM phase) investigations of semiconducting polymers, poly(3-hexylthiophene) (P3HT) and poly(9,9-dioctylfluorene) (F8), are described, aimed at understanding the metal/polymer interfaces. The electrostatic behaviour and potential distributions of the Au/polymer/Au structure under various biases with emphasis on top and bottom Au contacts are presented. We observe, by analysing EFM phase data, that the top and bottom contacts of Au can have drastic effects on the device performance. Moreover, differences in conductivity of conjugated polymers (P3HT > F8) are also reflected in EFM phase measurements, which correlate well with I-V measurements. Detailed analysis indicates that the influence of metal/film interfaces depends strongly on both the ability of charge transport properties of the organic films and the type of surface modification.     

Electronic structure of organic interfaces – a case study on perylene derivatives

Organic semiconductors have attracted increasing interest owing to their potential application in various electronic and opto-electronic devices. Here, interfaces play an important role since they are responsible for the accumulation of charge carriers at and the efficiency of charge injection across interfaces. Both mechanisms are determined by the alignment of energy levels at the interface. This report is divided into two parts and presents some of the major physical mechanisms which determine the energy level alignment at interface of thin films of low molecular weight organic semiconductors. In the first part, the origin of interface dipoles, interface states, and surface band bending is discussed. In the second part, investigations on the properties of metal/perylene derivatives/inorganic semiconductor structures give further insight into the mechanisms at work, especially under non-thermal equilibrium conditions. PACS 73.20.-r; 73.40.-c; 79.60.Jv; 79.60.Fr     

载流子在金属/聚对苯乙炔/金属结构中注入及输运的动力学研究

采用紧束缚的Su-Schrieffer-Heeger模型,利用非绝热动力学方法研究了载流子在金属/聚对苯乙炔(poly(p-phenylene vinylene,简记为PPV))/金属三明治结构中注入与输运的动力学过程.发现由于强的电子-晶格相互作用,注入的电荷在PPV链中形成波包,波包的形成与施加在金属电极上的偏压、PPV链上的电场强度及金属电极与PPV之间的界面耦合强度密切相关.在无外电场的情况下,当偏压达到临界值时电荷能够从金属电极注入到PPV链中并形成波包.随着电场强度的增大,波包能 关键词： 金属/聚对苯乙炔/金属结构 载流子输运 波包     

Efficiency of injection of charge carriers with a definite spin into a ferromagnet

The efficiency of injection of charge carriers with a definite spin into a ferromagnetic material in the ferromagnet/nonmagnetic metal/ferromagnet three-layer structure is analyzed taking into account the contribution from the nonmagnetic layer. It is shown that in the Co/Cu/Fe structure, the efficiency of spin injection is several times higher than in the Co/Cu/Co symmetric structure. Optimal conditions of injection of charge carriers with a definite spin depending on the parameters of used material are established.     

Electric Field Analysis of Space Charge Injection from a Conductive Nano-Filler Electrode

A simulation on the electric field distribution near the electrode is proposed to explain the reason for using nanosized carbon black mixed with ethylene vinyl acetate, as the electrode could lead to more charge injection into the polymer than using a deposited metal electrode. The electrode is simplified to a layer of conductive semi-spheres with fixed size and constant electric potential. By using the finite element method, it is found that both the size of the semi-spheres and the distance between adjacent semi-spheres could dramatically influence the electric field near the surface of the spheres; these are considered to be the two decisive factors for the charge injecting rate at electrodes of various materials.     

On interface dipole layers between C60 and Ag or Au

C₆₀ layers on polycrystalline Ag and Au are studied by photoelectron spectroscopy. At these metal/C₆₀ interfaces an electron transfer occurs from the metal to the lowest unoccupied orbital of C₆₀. We found in the case of the polycrystalline Ag/C₆₀ interface a dipolar layer with its associated electric field in the direction corresponding to the charge transfer, so pointing from the substrate to the adsorbent. Yet, at the Au/C₆₀ interface we observed an overall electric field pointing from C₆₀ towards the metal. We discuss our observations in terms of charge transfer, screening and hybridization effects and propose the occurrence of a hybridization mechanism similar to back-bonding at the Au/C₆₀ interface. We show that the alignment of energy levels at the metal/C₆₀ interface cannot simply be deduced using the metal workfunction and the frontier orbitals of C₆₀, including screening effects, since hybridization effects may strongly alter the interfacial energy level structure. Our experimental findings on the polycrystalline metal/C₆₀ interfaces indicate an at-most weak dependence of the Fermi level of the C₆₀ overlayer on the workfunction of the polycrystalline metal substrate. These interfaces are found in donor–acceptor-based organic photovoltaic devices and our results may help to understand the electrical characteristics of these devices. Received: 26 September 2001 / Accepted: 15 January 2002 / Published online: 3 June 2002     

一种具有交互穿插界面结构的有机电致发光器件

报道了一种具有交互穿插界面结构的有机电致发光器件(OELD：organic electroluminescent devices), 器件以双层结构ITO/NPB/Alq₃/Al为基础,通过改变NPB与Alq₃、Alq₃与Al的界面接触形状,在这两个界面处构造了交互穿插层,从而改变了界面处的电荷分布和有机层中的电场分布,提高了阴极电子注入,平衡了空穴和电子在界面处的数量,增加了激子的形成和复合概率,减小了漏电流。与传统双层结构器件相比,交互穿插界面结构有效地降低了启亮电压,提高了发光效率,而且随着凸凹穿插数量的增加,呈现启亮电压降低,发光效率提高的趋势,同时随着电流密度的增加,交互穿插界面结构器件表现出更稳定的光电性能。利用三缝模板制备的器件e,启亮电压为3 V,在电流密度为54 mA·cm-2下,流明效率达到最大值,较传统结构器件a提高34%。     

理论计算中电势能零点的选取对电荷注入的影响

基于紧束缚的Su-Schrieffer-Heeger(SSH)模型,利用非绝热的动力学方法,研究了金属/聚合物结构中电势能零点的选取对电荷注入的影响.理论计算发现,电场越强,电势能零点的选取对电荷注入的影响就越大. 关键词： 电势能 电荷注入 非绝热动力学