Nature of a high-conductivity state of poly(diphenylene phthalide)

For thin films prepared from non-conjugated polymer, including poly(diphenylene phthalide) (PDP), a rather enigmatic transition to a metal-like high-conductivity state is observed. The existing models of the HCS in wide-band polymers were examined. The main feature of these models is a significant (often highly improbable) rearrangement of the electronic structure of part of the macromolecules under the action of external factors (an electric field, light, injected electrons, etc.). The model of the HCS in PDP proposed in the current work is based on the results of studying the electron-acceptor properties of fragments of PDP macromolecules and the concepts of molecular electronics. Electron-acceptor unoccupied orbitals of the fragments of macromolecules and the corresponding energy levels are assumed to act as transport nodes for the resonance coherent tunneling of electrons. Since PDP has no intrinsic charge carriers, the key role in the formation of the HCS is played by the injection of electrons from the electrodes and, hence, the processes occurring in the interface. The resonance injection of electrons from the Fermi level of the electrode immediately onto the transport levels of the polymer is achieved due to the applied electric field, chemical connection of macromolecules to the electrodes, and ensuing modification of the interface dipole. The connection of PDP macromolecules to the electrodes occurs via defective hydroxyl and carboxyl groups. Carboxylate ions, which interact with the electrode metal, can also be formed because of the dissociative capture of injected electrons by phthalide cycles adjacent to the electrode. Since a conducting channel in a 1-μm-thick film should be composed of at least ten PDP macromolecules, it is necessary to assume that an efficient electron transfer occurs between macromolecules. The proposed concept was additionally substantiated by invoking the published data on the conductivity of DNA molecules and the field emission of electrons from metals coated with a PDP film.     

Interface energetics and level alignment at covalent metal-molecule junctions: pi-conjugated thiols on gold

The energetics at the interfaces between metal and monolayers of covalently bound organic molecules is studied theoretically. Despite the molecules under consideration displaying very different frontier orbital energies, the highest occupied molecular levels are found to be pinned at a constant energy offset with respect to the metal Fermi level. In contrast, the molecular properties strongly impact the metal work function. These interfacial phenomena are rationalized in terms of charge fluctuations and electrostatics at the atomic length scale as determined by first-principles calculations.     

First-principles study on the electronic transport properties of M/SiC Schottky junctions (M=Ag,Au and Pd)

In this work, we investigate the electronic transport properties of M/SiC Schottky junctions (M=Ag, Au and Pd). The results show that the band structures of hydrogenated zigzag SiC nanoribbons (ZSiCNRs) and hydrogenated armchair SiC nanoribbons (ASiCNRs) are almost unaffected by their width changes. When the hydrogenated 7-ASiCNR is directly connected to the Ag, Au and Pd electrode, the transmission spectra of three metal-semiconductor junctions show that the Fermi level of metal is pinned to a fixed position in the semiconductor band gap of hydrogenated 7-ASiCNR. The nearly same rectifying current-voltage characteristics are found in three metal-semiconductor junctions. The average rectification ratios of three M/SiC Schottky junctions are all in the neighborhood of 10⁶. In other word, the M/SiC Schottky junction has remarkable application prospect as the candidate for Schottky Diode.     

Energy band alignment at ferroelectric/electrode interface determined by photoelectron spectroscopy

The most important interface-related quantities determined by band alignment are the barrier heights for charge transport, given by the Fermi level position at the interface. Taking Pb(Zr,Ti)O3(PZT) as a typical ferroelectric material and applying X-ray photoelectron spectroscopy(XPS), we briefly review the interface formation and barrier heights at the interfaces between PZT and electrodes made of various metals or conductive oxides. Polarization dependence of the Schottky barrier height at a ferroelectric/electrode interface is also directly observed using XPS.     

Effect of graphene tunnel barrier on Schottky barrier height of Heusler alloy Co_2MnSi/graphene/n-Ge junction

We demonstrate that the insertion of a graphene tunnel barrier between Heusler alloy Co_2MnSi and the germanium(Ge) channel modulates the Schottky barrier height and the resistance–area product of the spin diode. We confirm that the Fermi level is depinned and a reduction in the electron Schottky barrier height(SBH) occurs following the insertion of the graphene layer between Co_2MnSi and Ge. The electron SBH is modulated in the 0.34 eV–0.61 eV range. Furthermore,the transport mechanism changes from rectifying to symmetric tunneling following the insertion. This behavior provides a pathway for highly efficient spin injection from a Heusler alloy into a Ge channel with high electron and hole mobility.     

Back-to-back Schottky diodes: the generalization of the diode theory in analysis and extraction of electrical parameters of nanodevices

We report on the analysis of nonlinear current-voltage characteristics exhibited by a set of blocking metal/SnO(2)/metal. Schottky barrier heights in both interfaces were independently extracted and their dependence on the metal work function was analyzed. The disorder-induced interface states effectively pinned the Fermi level at the SnO(2) surface, leading to the observed Schottky barriers. The model is useful for any two-terminal device which cannot be described by a conventional diode configuration.     

Impact of coupling geometry on thermoelectric properties of oligophenyl-base transistor

Thermal and electron transport through organic molecules attached to three-dimensional gold electrodes in two different configurations, namely para and meta with thiol-terminated junctions is studied theoretically in the linear response regime using Green's function formalism. We used thiol-terminated(–SH bond) benzene units and found a positive thermopower because the highest occupied molecular orbital(HOMO) is near the Fermi energy level. We investigated the influence of molecular length and molecular junction geometry on the thermoelectric properties. Our results show that the thermoelectric properties are highly sensitive to the coupling geometry and the molecular length. In addition, we observed that the interference effects and increasing molecular length can increase the thermoelectric efficiency of device in a specific configuration.     

掺杂对金属-MoS_2界面性质调制的第一性原理研究

采用基于密度泛函理论的第一性原理赝势平面波方法,计算了卤族元素掺杂对金属-MoS_2界面性质的影响,包括缺陷形成能、电子能带结构、差分电荷密度以及电荷布居分布.计算结果表明:卤族元素原子倾向于占据单层MoS_2表面的S原子位置;对于单层MoS_2而言,卤族元素的掺杂将在禁带中引入杂质能级以及导致费米能级位置的移动.对于金属-MoS_2界面体系,结合Schottky-Mott模型,证明了卤族元素的掺杂可以有效地调制金属-MoS_2界面间的肖特基势垒高度.发现F和Cl原子的掺杂将会降低体系的肖特基势垒高度.相比之下,Br和I原子的掺杂却增大了体系的肖特基势垒高度.通过差分电荷密度和布居分布的分析,阐明了肖特基势垒高度的被调制是因为电荷转移形成的界面偶极矩的作用导致.研究结果解释了相关实验现象,并给二维材料的器件化应用提供了调节手段.     

Investigation of carrier injection mechanism in small molecular organic light emitting device with a mixed single organic layer

Injection properties of electrons and holes in a mixed single layer organic light emitting device with mixed small molecules tris-(8-hydroxy-quinoline) aluminum (Alq₃), 2,5-bis(6′-(2′,2″-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), 4′-bis[N-(1-napthyl)-N-phenyl-amino]biphenyl (α-NPD), and 5,6,11,12-tetraphenylnaphthacene (rubrene) were investigated using Au/MoO₃ as hole and Al alloy as electron injection electrodes. On the basis of measuring the temperature dependence of currents through the interface between the electrodes and the mixed single organic layer, the carrier injection mechanism was primarily ascribed to the Schottky thermionic emission with the barrier height of 0.25 eV for holes and 0.67 eV for electrons. By adding the dopant material rubrene and the electron transport material PyPySPyPy into the mixed single layer, the barrier height of electrons could be reduced. The interfacial state analysis demonstrated that the electron barrier height was also dependent on the interfacial conditions of the device.     

First-principles study on current through a single π conjugate molecule for analysis of carrier injection through an organic/metal interface

We have studied current flow through a single π conjugate molecule weakly adsorbed to, and sandwiched between, two electrodes, focusing specifically on carrier injection through an organic/metal interface. This is the first calculation to investigate the effects of the orientation of the molecule and the electrode material on current using a first-principles method: in the past, most calculations of current were based on the assumption of covalent bonding of a molecule to electrodes. We modeled two systems in which a naphthalene molecule is sandwiched between gold (Au) or aluminum (Al) electrodes. First, in both systems, the current through the molecule depends on the orientation of the molecule. This indicates that electrons mainly transfer through the π channel, which is the overlap between the molecular π orbital and the electrode orbital. Next, the current in the Au-naphthalene-Au system is higher than that in the Al-naphthalene-Al system. This shows that Au is more suitable as an electrode material than Al. Therefore, the orientation of the molecule at an organic/metal interface and the materials comprising the electrodes play a key role in carrier injection through the interface.     

Electrofluorescence polarity in a molecular diode

The kinetic equations describing the transmission of an electron in the molecular compound “electrode 1–molecule–electrode 2” (1M2 system) are derived using the method of a nonequilibrium density matrix. The steady-state transmission regime is considered, for which detailed analysis of the kinetics of electrofluorescence formation in systems with symmetric and asymmetric couplings between the molecule and the electrodes is carried out. It is shown that the optically active state of the molecule is formed as a result of electron hops between the molecule and each of the electrodes, as well as due to inelastic interelectrode tunneling of the electron. The electrofluorescence power for a molecular diode (asymmetric 1M2 system) depends on the polarity of the voltage bias applied to the electrodes. The polarity is explained using a model in which the optically active part of the molecule (chromophore group) is represented by the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). Two mechanisms of the emergence of polarity are revealed. One mechanism is associated with nonidentical Stark shifts of the HOMO and LUMO levels relative to the Fermi levels of the electrodes. The second mechanism is associated with the fact that the rates of an electron hopping between HOMO (LUMO) and one of the electrodes are much higher than the rates of such a hopping with the other electrode. The conditions in which each mechanism can be implemented experimentally are indicated.     

使用不同阴极缓冲层提升性能的反型有机太阳能电池

使用含Al_q3、Bphen、BCP、HATNA和Cs₂CO₃作为阴极缓冲层,制备了基于SubPc和C₆₀的反型平面异质结有机太阳能电池. 比较了有机阴极缓冲层的最低未占有分子轨道和电子迁移率对有机太阳能电池性能的影响. 结果显示,Al_q3、Bphen和HATNA能够大幅度提升器件的性能. 使用退火过后的HATNA作为阴极缓冲层获得了最高的效率,比没有阴极缓冲层的器件提升了7倍. 另外,使用空间电荷限制电流理论进行仿真的结果表明,通过加入HATNA作阴极缓冲层,反型有机太阳能电池结构中处于有机/电极界面处的肖特基势垒降低了27%.     

Role of fermi-level pinning in nanotube schottky diodes

At semiconductor-metal junctions, the Schottky barrier height is generally fixed by "Fermi-level pinning." We find that when a semiconducting carbon nanotube is end contacted to a metal (the optimal geometry for nanodevices), the behavior is radically different. Even when the Fermi level is fully "pinned" at the interface, the turn-on voltage is that expected for an unpinned junction. Thus the threshold may be adjusted for optimal device performance, which is not possible in planar contacts. Similar behavior is expected at heterojunctions between nanotubes and semiconductors.     

An Anomalous Gain Mechanism in GaN Schottky Barrier Ultraviolet Photodetectors

The gain mechanism in GaN Schottky barrier ultraviolet photodetectors is investigated by focused light beam. When the incident light illuminates the central region of the Schottky contact electrode, the responsiyity changes very little with the increase of reverse bias voltage. However, when the incident light illuminates the edge region of the electrode, the responsivity increases remarkably with the increase of reverse bias voltage, and the corresponding quantum efficiency could be even higher than 100%. It is proposed that the surface states near the edge of the electrode may lead to a reduction of effective Schottky barrier height and an enhancement of electron injection, resulting in the anomalous gain.     

Interface Fermi level pinning in a Cu/p-CuGaS2 Schottky diode

A Schottky contact to p-type CuGaS₂ that showed the highest rectification ratio of approximately 500 ever reported was realized using a Cu electrode on a HF/HNO₃-treated surface, as well as an excellent Au ohmic contact on a HF-etched surface. The effective Schottky barrier height of 0.9 eV was obtained from the current–voltage and capacitance–voltage characteristics. The value was smaller by 1.1 eV than that calculated from the values of the work function of Cu and electron affinity of CuGaS₂. The results indicated a surface pinning of the Fermi level to certain acceptor-type gap states below the midgap.     

肖特基势垒对铁磁/有机半导体结构自旋注入性质的影响

理论研究了铁磁/有机半导体肖特基接触时的电流自旋极化注入,并讨论了电流自旋极化率随界面处肖特基势垒高度、有机半导体层中特殊载流子及其迁移率、界面附近掺杂浓度的变化关系.通过计算发现,寻找在势垒区中载流子迁移率比较大的有机半导体材料对实现有效的自旋注入是必要的;同时还发现,由于铁磁/有机半导体接触而形成的肖特基势垒不利于自旋注入.因此要想实现有效的自旋注入,界面附近必须采用重掺杂来有效减少势垒区的宽度,且势垒的高度要限制在一定的范围内.     

Conduction in magnesium phthalocyanine thin films with aluminium electrodes

The various electrical properties and the nature of conduction mechanisms of magnesium phthalocyanine thin film devices with top and bottom aluminium electrodes have been investigated. The conduction mechanism was identified as injection limited essentially due to the electrode material. Even with the same electrode materials, the device showed asymmetric conduction behavior in the forward and reverse bias. In general the conduction was interpreted as a Schottky emission with barrier height Φ_s=1.07 eV for the forward bias and Φ_s=1.09 eV in the reverse bias. The effect of oxygen on the conductivity of the device has also been investigated. In the oxygen doped samples the conductivity is decreased which may be attributed to an interfacial layer between the electrode and the organic layer. Further in the oxygen doped sample while a Schottky emission is observed at lower voltages Poole-Frenkel conductivity was identified in the higher voltage region.     

Electronic properties of single-molecule junction: Effect of the molecular distortion

For a model system consisting of a benzenedithio (BDT) molecule sandwiched between two Au plates, the electronic properties as a function of different BDT geometry are investigated using density functional theory. The distorted BDT structures are got through stretching the electrode distance. The corresponding electronic properties, including the spatial distribution of the frontier orbits, the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital levels and density of states at the Fermi energy are determined. It reveals that the molecular distortion essentially determines electronic structures. The result should be beneficial to understand the stress-dependent or structure-dependent transport mechanism of electrons of the BDT junction.     

磁场增强的La2/3 Sr1/3 MnO3有机半导体界面载流子注入

文章作者制备了以多种π-共轭有机半导体（orgnanic semincondutor,简称OSEC）为中间层,La2/3Sr1/3MnO3（LSMO）和另一铁磁或非磁性金属为电极的有机二极管,测量了器件的磁致电阻和磁电致发光效应.器件显示了与LSMO电极类似的负磁电阻效应,但是它的电阻变化比LSMO电极本身的变化大3个数量级,而且器件还有正的磁电致发光效应.文章作者认为,这些磁场效应源于磁场作用下LSMO费米能级的异常移动,导致载流子在LSMO-OSEC界面注入的增强。