Surface and near-surface passivation, chemical reaction, and Schottky barrier formation at ZnO surfaces and interfaces

Using a combination of depth-resolved cathodoluminescence spectroscopy, electronic transport, and surface science techniques, we have demonstrated the primary role of native defects within ZnO single crystals as well as native defects created by metallization on metal-ZnO Schottky barrier heights and their ideality factors. Native defects and impurities resident within the ZnO depletion region as well as defects extending into the bulk from the intimate metal-ZnO interface contribute to barrier thinning of, carrier hopping across, and tunneling through these Schottky barriers. Chemical reactions at clean ZnO-metal interfaces lead to metal-specific eutectic or oxide formation with pronounced transport effects. These results highlight the importance of bulk crystal quality, surface cleaning, metal interaction, and post-metallization annealing for controlling Schottky barriers.     

Single Metal Ohmic and Rectifying Contacts to ZnO Nanowires: A Defect Based Approach

Ohmic and rectifying metal contacts to semiconductor nanowires are integral to electronic device structures and typically require different metals and different process techniques to form. Here we show how a noble metal ion beam of Pt commonly used to pattern conducting contacts in electron microscopes can form both ohmic and Schottky/blocking contacts on ZnO nanowires by controlling native point defects at the intimate metal‐semiconductor interface. Spatially‐resolved cathodoluminescence spectroscopy on a nanoscale both laterally and in depth gauges the nature, density, and spatial distribution of specific native point defects inside the nanowires and at their metal interfaces. Combinations of electron and ion beam deposition, annealing, and sculpting of the same nanowire provide either low contact resistivity ohmic contacts or a high Schottky/blocking barrier with a single metal source. These results highlight the importance of native point defects distributed inside nanowires and their variation near interfaces with sculpting and annealing.     

Enhancement of zinc interstitials in ZnO nanotubes grown on glass substrate by the hydrothermal method

In this study, high density well aligned ZnO nanotubes were grown on glass via a two-step growth-then-etching by simple and template-free hydrothermal method. We used etching procedure to introduce additional zinc interstitial defects in the ZnO nanotubes. The optical properties of the ZnO nanotubes have been investigated by depth-resolved cathodluminescence spectroscopy (DRCLS) which provides information about the physical origin and growth dependence of optically active defects together with their spatial distribution. The DRCLS study gives clear evidence about the enhancement of zinc interstitial defects which are responsible for the violet and decrease of the DL emission in ZnO nanotubes when compared to the as grown ZnO nanorods. We observed a variation in the zinc interstitials along the nanotube depth.     

Low-energy electron-excited nanoluminescence studies of GaN and related materials

We have used low-energy electron-excited nanoluminescence (LEEN) spectroscopy combined with ultrahigh vacuum surface analysis techniques to obtain electronic bandgap, confined state and deep-level trap information from III nitride compound semiconductor surfaces and their buried interfaces on a nanometer scale. Localized states are evident at GaN/InGaN quantum wells, GaN ultrathin films, AlGaN/GaN pseudomorphic heterostructures, and GaN/Al₂O₃ interfaces that are sensitive to the chemical composition, bonding and atomic structure near interfaces, and in turn to the specifics of the epitaxial growth process. Identification of electrically active defects in these multilayer nanostructures provides information to optimize interface growth and control local electronic properties.     

Hydrothermal growth of ZnO microstructures on Ar plasma treated graphite

We have investigated the effect of argon (Ar) plasma treatment on the surface of graphite and the hydrothermal growth of zinc oxide (ZnO) microstructures. With the plasma treatment, the growth behavior of ZnO microrods on the graphite substrates changed drastically. After the graphite surface was exposed to the Ar plasma, the number density of ZnO was one order of magnitude higher than that on the pristine graphite without plasma treatment. Raman spectroscopy revealed that Ar plasma treatment created the structural defects on the graphite surfaces and decreased the mean distance of defects. Surface characterization through atomic force microscopy and X-ray photoelectron spectroscopy showed that the graphite surface was roughened and that oxygen–carbon bonding was formed. The enhanced nucleation of ZnO can be explained by the generation of structural defects, surface roughness, and surface functional groups on the graphite substrate. Therefore, Ar plasma treatment can be used as a simple method to engineer the surface properties of graphite substrates and to control the crystal nucleation and growth of inorganic materials on their surface.     

Hard X-ray photoemission spectroscopy: Variable depth analysis of bulk,surface and interface electronic properties

The electronic properties of surfaces and buried interfaces can vary considerably in comparison to the bulk. In turn, analyzing bulk properties, without including those of the surface, is understandably challenging. Hard X-ray photoelectron spectroscopy (HAXPES) allows the well known ability of photoemission to interrogate the electronic structure of material systems with bulk volume sensitivity. This is achieved by tuning the kinetic energy range of the analyzed photoelectrons in the multi-keV regime. This unique ability to probe truly bulk properties strongly compliments normal photoemission, which generally probes surface electronic structure that is different than the bulk selected examples of HAXPES and possible implications towards the study of complex oxide-based interfaces and highly correlated systems are discussed.     

Nanostructure growth-induced defect formation and band bending at ZnO surfaces

Morphological, electrostatic, and optical techniques reveal spontaneous growth of nano-“mounds” on ZnO polar surfaces in air creating native point defects at and under the surface that increase work function locally by hundreds of meV. Nanoscale surface photovoltage spectroscopy reveals Zn vacancies with gap states whose density grows with nano-mound proximity over hundreds of nanometers. The low activation energy for ZnO nano-mound growth with oxygen indicates interstitial Zn diffusion that feeds nanostructure growth, generating deep level acceptors that increase n-type band bending and impact Schottky barrier formation.     

Forced Air Plasma Treatment (FAPT) of Hybrid Wood Plastic Composite (WPC)–Fiber Reinforced Plastic (FRP) Surfaces

Forced atmospheric (air) plasma treatment (FAPT) was applied to wood plastic composite (WPC) and continuous glass fiber reinforced plastic (FRP) surfaces to improve their adhesive bonding properties. The FRP was composed of oriented continuous E-glass fibers in a polypropylene matrix, while the WPC was fabricated using wood flour, polypropylene and additives. The FAPT was applied using two levels of discharge length projected from the discharge head (2.5″ and 1″) to ionize the air, oxidize the surfaces and improve wettability. The treatment was performed by passing the electrode over either surface, five or ten times. Surface characterization consisted of thermodynamic (surface energy determination), chemical (X-ray photoelectron spectroscopy), mechanical (shear strength) and microscopic (atomic force microscopy (AFM)) analysis. The results indicate that the acid–base component of the surface energy for both WPC and FRP after FAPT correlates with an increase in wettability. X-ray photoelectron spectroscopy was performed on wood regions and non-wood regions of the WPC surfaces; the oxygen concentration increased to a larger extent in the non-wood regions. Bonding shear strength measurements indicated increases of 50% after FAPT on WPC surfaces (2.5″ discharge length, 1 pass) and up to 200% for the hybrid WPC–FRP. Atomic force microscopy measurements using a silicon tip probe showed increases in adhesive force interactions up to 56% on WPC surfaces post-FAPT.     

Growth mechanism and characterization of zinc oxide microcages

We report the growth mechanism and structural properties of micrometer sized ZnO cages which were synthesized directly from Zn vapor deposition and oxidation. The ZnO microcages exhibit a hexagonal or spherical shape with partly or completely open surfaces and hollow interiors. The growth process of the microcages includes the deposition of Zn polyhedral particles, top face breaking of the Zn particles and Zn sublimation, and subsequent reaction to ZnO. By controlling the various growth stages, we obtained information on the growth mechanism of the ZnO cages, which appears to be different from a mechanism reported previously. The chemical composition and crystalline structure were studied using energy dispersive X-ray spectroscopy and transmission electron microscopy, respectively. The room-temperature photoluminescence spectrum indicates a large quantity of oxygen-vacancy related defects within the wall of the ZnO cages.     

Surface state control of III–V semiconductors using molecular modification

An attempt to control surface electronics of III–V semiconductor using wet chemical processes has been performed. Here, we report results on the use of self-assembled monolayers (SAMs) of organic molecules on (0 0 1) GaAs surface. Octadecanethiol (ODT) and benzenethiol (BT) have been the choice in the present study.GaAs wafers were modified by thiol molecules on the flat surface after the native oxide layers are removed by chemical etching under optimized conditions. The change in the electronic properties was measured in terms of transport properties via the SAM layer by conductive probe atomic force microscopy. The current–voltage characteristics thus obtained show that ODT functions as a tunnel barrier while BT is conductive due to the presence of π-electrons. As a result, we can control the electronic states of GaAs–molecule interface for realizing novel device structures by the selection of functional molecules.     

Effects of sapphire substrates surface treatment on the ZnO thin films grown by magnetron sputtering

The surface treatment effects of sapphire substrate on the ZnO thin films grown by magnetron sputtering were studied. The sapphire substrates properties have been investigated by means of atomic force microscopy (AFM) and X-ray diffraction rocking curves (XRCs). The results show that sapphire substrate surfaces have the best quality by CMP with subsequent chemical etching. The surface treatment effects of sapphire substrate on the ZnO thin films were examined by X-ray diffraction (XRD) and photoluminescence (PL) measurements. Results show that the intensity of (0 0 2) diffraction peak of ZnO thin films on sapphire substrates treated by CMP with subsequent chemical etching was strongest, FWHM of (0 0 2) diffraction peak is the narrowest and the intensity of UV peak of PL spectrum is strongest, indicating surface treatment on sapphire substrate preparation may improve ZnO thin films crystal quality and photoluminescent property.     

Wet-chemical passivation of atomically flat and structured silicon substrates for solar cell application

Special sequences of wet-chemical oxidation and etching steps were optimised with respect to the etching behaviour of differently oriented silicon to prepare very smooth silicon interfaces with excellent electronic properties on mono- and poly-crystalline substrates. Surface photovoltage (SPV) and photoluminescence (PL) measurements, atomic force microscopy (AFM) and scanning electron microscopy (SEM) investigations were utilised to develop wet-chemical smoothing procedures for atomically flat and structured surfaces, respectively. Hydrogen-termination as well as passivation by wet-chemical oxides were used to inhibit surface contamination and native oxidation during the technological processing. Compared to conventional pre-treatments, significantly lower micro-roughness and densities of surface states were achieved on mono-crystalline Si(100), on evenly distributed atomic steps, such as on vicinal Si(111), on silicon wafers with randomly distributed upside pyramids, and on poly-crystalline EFG (Edge-defined Film-fed-Growth) silicon substrates.The recombination loss at a-Si:H/c-Si interfaces prepared on c-Si substrates with randomly distributed upside pyramids was markedly reduced by an optimised wet-chemical smoothing procedure, as determined by PL measurements. For amorphous-crystalline hetero-junction solar cells (ZnO/a-Si:H(n)/c-Si(p)/Al) with textured c-Si substrates the smoothening procedure results in a significant increase of short circuit current I_sc, fill factor and efficiency η. The scatter in the cell parameters for measurements on different cells is much narrower, as compared to conventional pre-treatments, indicating more well-defined and reproducible surface conditions prior to a-Si:H emitter deposition and/or a higher stability of the c-Si surface against variations in the a-Si:H deposition conditions.     

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.     

Modifying the physicochemical and electrical properties of tantalite and columbite surfaces under conditions of electrochemical treatment and high-voltage nanosecond pulses

Structural and chemical modifications of tantalite and columbite surfaces, induced by treating the minerals with anolyte—a product derived via the electrolysis of aqueous solutions—and high-voltage electromagnetic pulses, are studied by means of X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive spectroscopy, atomic force microscopy, and electrophoretic light scattering. The mechanical properties of the surfaces are characterized via Vickers microhardness testing. Treating the minerals with anolyte removes iron-containing surface films and leads to considerable conversion of surface-confined Fe(II) species into Fe(III), increasing the differences between the physicochemical and electrical properties of these rare earth minerals. The nonthermal impact of high-voltage pulses results in effective surface softening, a reduction in microhardness, and the disintegration of mineral particles, yielding surface micro- and nanosized phases enriched with iron and oxygen.     

Structure and electronic properties of imperfect oxides and nanooxides

Results of studies of the structure and physicochemical properties of perfect (defectless) and imperfect (containing point defects) nanoparticles of metal oxides by the methods of scanning tunnel microscopy (STM) and spectroscopy (STS) are summarized and reviewed. Using nanooxides of various metals (Al, Pt, W, and Ti), as examples, it was demonstrated that the modern STM and STS methods make it possible to measure the electronic spectra of perfect nanoparticles, detect individual and associated point defects, determine spatial distributions of defects, derive spatial and energetic distributions of electrons trapped on point defects (anionic vacancies, intercalation atoms, and adatoms), detect single electron spins (paramagnetic surface complexes), measure phonon and vibration spectra of individual nanoparticles and surface complexes, determine (from measured electronic and phonon spectra) the chemical composition and atomic structure of individual nanoparticles. It was emphasized that modern versions of the STM-STS methods can constitute the foundation of new analytical methods needed in nanometrology and nanodefectoscopy.     

Electrostatic investigation into the bonding of poly(phenylene) thiols to gold

The advancement of nanotechnology relies on the understanding of electrical connection to individual molecules. Electrostatic surface potential measurements of self-assembled monolayers can provide insight into the structural and electronic properties of molecules attached to surfaces. In this paper we report on the electrostatic potential of poly(phenylene) thiol molecules bound to gold surfaces. Kelvin force microscopy is used to probe self-assembled monolayers of a series of phenyl, biphenyl, and triphenyl thiol molecules. The dipole moments of the isolated molecules have been determined and show similar electronic trends. A difference in polarity between the isolated molecules and the electrostatic surface potential of a monolayer attached to gold reflects the electron transfer on to the bound molecule.     

Chemical and electronic properties of sulfur-passivated InAs surfaces

Treatment with ammonium sulfide ((NH₄)₂S_x) solutions is used to produce model passivated InAs(0 0 1) surfaces with well-defined chemical and electronic properties. The passivation effectively removes oxides and contaminants, with minimal surface etching, and creates a covalently bonded sulfur layer with good short-term stability in ambient air and a variety of aqueous solutions, as characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and Hall measurements. The sulfur passivation also preserves the surface charge accumulation layer, increasing the associated downward band bending.     

纳米级光滑石墨表面的拉曼光谱表征

石墨微结构的表面一般为原子级光滑或纳米级光滑,是研究表面、界面物理性质的重要基础,对结构超润滑、微机电器件的研究和应用非常重要。为了解石墨微结构表面的状态和性质,其无损表征具有重要意义。通过微加工方法制备出石墨微结构,使用微纳机械手上的针尖推动石墨微结构上部可以得到原子级光滑或纳米级光滑的石墨表面。使用拉曼光谱对获得的石墨表面进行表征。通过与原子力显微镜和电子显微镜的表征结果进行对比发现,拉曼光谱能够准确反映石墨表面的缺陷程度,同时具有非接触、无损和快速的优点。这表明拉曼光谱在纳米级光滑石墨表面的表征中能够提供可靠表征信息,并且检测快速、不破坏样品,为石墨结构超润滑和MEMS器件的后续研究和应用奠定了基础。     

Reflection anisotropy spectroscopy: A new probe for the solid-liquid interface

Introducing reflection anisotropy spectroscopy (RAS) as a new probe for solid-liquid interfaces, we present results for the Au(110)/electrolyte interface which serves as a model system. We demonstrate that RAS is sensitive to surface phase transitions, step morphology, and electronic surface states. Using an empirical approach, the RA spectra are reproduced and features are identified which reflect the known character of the bias voltage driven (2x1) to (1x1) phase transition. RAS is established as an experimental technique to probe the electronic structure of solid-liquid interfaces in real time to study a wide range of interface properties.     

Influence of the substrate properties on the electronic structure of organic film-inorganic substrate interfaces

The structure of electronic states at the interfaces between perylene tetracarboxyldianhydride films and ZnO, Cu, GaAs, and InAs substrates is studied by the method of total current spectroscopy. It is found that the physicochemical properties of the substrate have a strong effect on the electronic state configuration in the substrate and film. On the basis of the experimental data, potential diagrams of the interfaces are constructed, which illustrate the formation of sharp and extended dipole layers, change in the charge state of surface levels, and modification of the electronic structure of the film.