Gap states at organic-metal interfaces: A combined spectroscopic and theoretical study

A systematic understanding and controlling of gap states formed at the organic-metal interfaces is a key factor for fabricating functional organic-metal systems, as in case of heterojunctions in semiconductor devices. We report here the characterization of gap states near the Fermi level of metal substrate by metastable atom electron spectroscopy and first-principles density functional calculations. The gap states in organic-metal systems are classified into two types, i.e., chemisorption-induced gap states (CIGSs) and complex-based gap states (CBGSs). CIGSs can be further classified whether the metal wave function tails a short distance into the chemisorbed species with the exponential decay (damping type) or is exposed sufficiently to the chemisorbed species by mixing with the organic orbitals (propagating type). CIGSs observed in alkanethiolate and C₆₀ on Pt(1 1 1) are their typical examples, respectively. As a consequence, alkanethiolate serves as a poor mediator of metal wave function, whereas C₆₀ acts as a good mediator, which is responsible for tunneling mechanism and eventually electric conductivity in the relevant metal-organic-metal junctions. CBGSs are identified in bathocuproine films deposited on K-covered Au, where the K atoms migrate into the film to form an organic-metal complex. The CBGSs are distributed over the multilayer film, in contrast to the case of CIGS. With increasing film thickness, the CBGSs exhibit incommensurate energy shifts with the valence band top of the film, indicating that the Schottky-Mott model breaks down as evaluating charge transport in organic-metal systems.     

Photoelectron injection at metal-semiconductor interfaces

A modelling of the photoinjection process is developed which permits fitting of the spectral photoresponse of Schottky barriers including the electric field dependence of barrier height and photoresponse by means of two adjustable parameters: the zero field barrier qφ_BO and λ₀ the zero temperature mean free path for optical phonon scattering of high energy electrons. The model assumes an image force potential barrier with Thomas-Fermi screening in the metal. Effects of optical phonon scattering and quantum mechanical transmission are convoluted on the Fowler photoelectron supply function. The effects of phonon scattering are frequently large because the ranges in energies associated with the transverse momentum and normal momentum are approximately the amount by which the quantum energy hv exceeds the barrier energy qφ_B. At high fields, quantum mechanical tunneling dominates the response when hv < qφ_B. At low fields, phonon assisted transmission is appreciable for the same quantum energy range. The calculation of the collection probability includes effects of multiple scattering even for electrons that do not lie initially within the cone of acceptance at the barrier maximum. An approach that considers the probability of collection the same as that of reaching the potential maximum without scattering is found to be acceptable only at high fields. Experimental results are reported from oxide-passivated epitaxial Pt_xSi-〈111〉 n-type Si Schottky barrier diodes with annular Schottky barrier guard rings measured at temperatures of 90 and 298 K for an electric field range from 5 × 10³ to 9 × 10⁴$\text{V}\text{cm}$. The field, spectral and temperature dependences of the photoresponse data are in excellent agreement with theoretical predictions with λ₀ = 110 Å at both 90 and 298 K. The zero field barrier height obtained from fitting photoresponse curves at a number of electric fields is also in excellent agreement with I-V and C-V measurements.     

Spin-polarized two-dimensional electron gas at oxide interfaces

The possibility of formation of a fully spin-polarized 2D electron gas at the SrMnO_3/(LaMnO_3)_1/SrMnO_3 heterostructure is predicted from density-functional calculations. The La(d) electrons become confined in the direction normal to the interface in the electrostatic potential well of the positively charged layer of La atoms, acting as electron donors. These electrons mediate a ferromagnetic alignment of the Mn t_2g spins near the interface via Zener double exchange and become, in turn, spin-polarized due to the internal magnetic fields of the Mn moments.     

Evidence for the changes in hole injection mechanism with a CoPc hole injection layer

The hole injection in hole-only devices with the structures of Al/N,N′-bis(1-naphthyle)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB)/ITO and Al/NPB/cobalt phthalocyanine (CoPc)/ITO were analyzed. With the combined analysis of current density–voltage and impedance measurement, the charge injection mechanism based on the injection limited current model was investigated. The NPB single layer device shows Richardson–Schottky type thermionic emission in the entire applied bias range. On the other hand, the device with the CoPc hole injection layer shows thermionic emission until the applied bias reaches 3.7 V. Increasing the bias further, Fowler–Nordheim tunneling dominates the charge injection. The changes of hole injection mechanism were discussed by evaluating the energy level changes with internal field distributions.     

Gate-controlled spin injection at LaAlO3/SrTiO3 interfaces

We report results of electrical spin injection at the high-mobility quasi-two-dimensional electron system (2-DES) that forms at the LaAlO3/SrTiO3 interface. In a nonlocal, three-terminal measurement geometry, we analyze the voltage variation associated with the precession of the injected spin accumulation driven by perpendicular or transverse magnetic fields (Hanle and inverted Hanle effect). The influence of bias and back-gate voltages reveals that the spin accumulation signal is amplified by resonant tunneling through localized states in the LaAlO3 strongly coupled to the 2-DES by tunneling transfer.     

Carrier injection at silicide/silicon interfaces in nanowire based-nanocontacts

In this article, we investigate the silicide/Si nanowire (Si NW) interface properties based on a detailed characterization of PtSi/NW nanocontacts. For that purpose, we fabricate two-terminal structures implemented on vertical Si NWs arrays defined by a top-down approach with an ultra-high density. Each termination of Si NWs is silicided and contacted to an external metal line. The temperature dependence and the non-linearity of current–voltage (I–V) characteristics are identified as a clear signature indicating that contacts dominate the overall resistance of the Si NW arrays. It is demonstrated that this trend remains valid in the limit of extremely small NW radii and that trap-induced surface depletion also reduces the contact injection cross-section. In this context, the electrostatic landscape at the vicinity of the silicide-to-semiconductor contact interface is dominated by the field effect imposed by peripheral surface states and not by the Schottky barrier height.     

Stopping of ions and local electron densities at strong coupling

We employ molecular dynamics (MD) computer simulations to investigate ions in electron plasmas at strong coupling. We observed in this regime a stopping power of highly charged ions at low velocities which scales with the charge like Z^1.5. This clearly deviates from the Z² ln(const./Z) scaling of the conventional weak coupling theories and is connected with a strongly enhanced local density of electrons around the ions which is caused by the trapping of electrons in high Rydberg states due to multi-particle collisions occurring at strong coupling. For the parameters corresponding to the less strongly coupled situation in an electron cooler we find a moderate enhancement of the local electron density created under the influence of the external magnetic field. This revised version was published online in August 2006 with corrections to the Cover Date.     

Competitive segregation of gallium and indium at heterophase Cu-MnO interfaces studied with transmission electron microscopy

This paper concentrates on the possible segregation of indium and gallium and competitive segregation of gallium and indium at atomically flat parallel {111}-oriented Cu-MnO interfaces. The segregation of gallium at Cu-MnO interfaces after introduction of gallium in the copper matrix of internally oxidized Cu-1 at.% Mn could be hardly detected with energy-dispersive spectrometry in a field emission gun transmission electron microscope. After a heat treatment to dissolve indium in the copper matrix, gallium has a weak tendency to segregate, that is 2.5 at.% Ga per monolayer at the interface compared with 2 at.% in the copper matrix. The striking result is that this gallium segregation is observable because it does not occur at the metal side of the interface but in the first two monolayers at the oxide side. Using the same heat treatment as for introducing indium in the sample, but without indium present, gallium segregates strongly at the oxide side of the Cu-MnO interface with a concentration of about 14.3 at.% in each monolayer of the two. In contrast, the presence of gallium has no influence on the segregation of indium towards Cu-MnO interfaces, because the outermost monolayer at the metal side of the interface contains 17.6 at.% In, that is similar to previously found results. This leads to the intriguing conclusions, firstly, that, in contrast with antimony and indium, gallium segregates at the oxide side of the interface and, secondly, that the presence of indium strongly hampers gallium segregation. The results from analytical transmission electron microscopy on gallium segregation are supported by high-resolution transmission electron microscopy observations.     

Andreev reflection at the edge of a two-dimensional electron system with strong spin-orbit coupling

We experimentally investigate transport properties of a single planar junction between the niobium superconductor and the edge of a two-dimensional electron system in a narrow In_0.75Ga_0.25As quantum well with strong Rashba-type spin-orbit coupling. We experimentally demonstrate suppression of Andreev reflection at low biases at ultralow temperatures. From the analysis of temperature and magnetic field behavior, we interpret the observed suppression as a result of a spin-orbit coupling. There is also an experimental sign of the topological superconductivity realization in the present structure.     

Elementary processes at semiconductor/electrolyte interfaces: perspectives and limits of electron spectroscopy

Semiconductor device properties based on electrolyte contacts or modified by electrochemical reactions are dominated by the electronic structure of the interface. Electron spectroscopy as e.g. photoemission is the most appropriate surface science techniques to investigate elementary processes at semiconductor/electrolyte interfaces. For such investigations a specific experimental set-up (SoLiAS) has been built-up which allows performing model experiments as well as surface analysis after emersion under different experimental conditions. The experimental approach is presented by a number of experiments performed during the last years with GaAs as substrate material. Model experiments by adsorption and coadsorption of electrolyte species give information on fundamental aspects of semiconductor/electrolyte interactions. Emersion experiments give information on a final composition and the related electronic structure of electrodes after electrochemical reactions. The use of frozen electrolytes will help to bridge the gap between these two approaches. With the combination of the experimental procedures one may expect a detailed analysis of electrolyte (modified) interfaces covering chemical composition, electronic structure of surfaces/interfaces as well as surface/interface potentials.     

Chemisorption at interfaces between organic semiconductors and metals: role of the electron affinity

Chemisorption is a well-known phenomenon for many interfaces between organic semiconductors and metals. It is shown that many published data indicate that the occurrence of chemisorption can be rationalized upon the consideration of the metal work function versus the electron affinity of the organic semiconductor.     

Ring of C60 polymers formed by electron or hole injection from a scanning tunneling microscope tip

Carrier (electron or hole) injection from a scanning tunneling microscope tip causes various surface modifications on the molecular scale. We report that injection into C60 close-packed layers forms a ring-shaped distribution of C60 polymers. This can be explained on the basis of the radial propagation and energy dissipation of carriers. Subsequent electron or hole injections enlarge the ring, showing that both carriers can induce both polymerization and depolymerization. Furthermore, we demonstrate visualization of carrier scattering by injecting carriers into C60 layers with grain boundaries.     

Study of electron bremsstrahlung in strong Coulomb fields at the ESR storage ring

Electron bremsstrahlung has been investigated for collisions of 223.2 MeV/amu He-like uranium ions with N₂ and Ar gaseous targets. The doubly differential cross-sections for bremsstrahlung are compared to the predictions of relativistic first order Born calculations (Bethe-Heitler formula with Elwert correction factor) and to the calculations based on the exact wavefunctions for electrons moving in the external point-Coulomb potential of the projectile. Whereas the “exact” IPA calculations give an improved agreement with experimental data, as compared to the Bethe-Heitler theory, in particular at the end-point region of the bremsstrahlung spectra, discrepancies still remain at lower photon energies. This revised version was published online in July 2006 with corrections to the Cover Date.     

Affect of the electrical characteristics depending on the hole and electron injection materials of red organic light-emitting diodes

This study examined the electrical and optical properties of red OLEDs (organic light-emitting diodes) with a four-layer structure, ITO/amorphous fluoropolymer (AF)/N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1-biphenyl-4,4′-diamine (TPD)/R-H:R-D/lithium fluoride (LiF)/Al, containing a hole injection material, AF (amorphous fluoropolymer) and an electron injection layer material, LiF. Compared to the basic structure (two-layer structure), the brightness and luminous efficiency of the four-layer structure, ITO/TPD/R-H:R-D/Al, increased approximately 100 times (30,000 lm/m²) and 150 times (51 lm/W), respectively, with an applied voltage. The excellent efficiency of the external proton was also increased 150 times (0.51%). That is, the hole and electron injection layers improved the surface roughness of ITO and Al, and the interfacial physical properties. In addition, these layers allowed the smooth injection of holes and electrons. The luminance, luminous efficiency and external quantum efficiency were attributed to an increase in the recombination rates.