The band alignment of SiO2 and GaN is important for passivation of high voltage devices and for gate insulator applications. In this study XPS and UPS techniques are employed to determine the electronic states as SiO2 is deposited onto a clean GaN surface. The substrate was epitaxially grown n-type GaN on 6H-SiC (0001) substrates with an AlN (0001) buffer layer. The GaN surface was atomically cleaned via a 860°C anneal in an NH3 atmosphere. For the clean GaN surface, upward band bending of ~0.3 ±0.1 eV was measured, and the electron affinity was measured to be ~2.9 eV. Layers of Si were deposited on the GaN surface via Molecular Beam Epitaxy (MBE), and the Si was oxidized by a remote O2 plasma. The oxidation of the Si occurred without oxidizing the GaN. Densification of the created SiO2 film was achieved by annealing the substrate at 650°C. Surface analysis techniques were performed after each process, and yielded a valence band offset of ~2.0 eV, and a conduction band offset of ~3.6 eV for the GaN-SiO2 interface.

Thin a-Si:H films, with a thickness of 1 µm, with different hydrogen concentrations, prepared by hot wire deposition were crystallized by 514.5 nm cw Ar ion laser radiation, with a power density between 150 and 270 kW/cm2. The crystallization was continuously monitored by Raman spectroscopy for exposures up to hours. The analysis of crystallization process using Johnson-Mehl phenomenological equations showed an apparent crystallization energy of around 0.5 eV and low dimensional crystal growth. The mean value of the crystal size decreases with increasing irradiation energy and initial hydrogen content and varies between 3 and 6 nm.

Imaging of field emission and photoemission from diamond surfaces is accomplished with a high resolution photo-electron emission microscope (PEEM). Measurements obtained as a function of sample temperature up to 1000°C display thermionic field emission images (TFEEM). The system can also record the emission current versus applied voltage. N-doped diamond films have been produced by MPCVD with a N/C gas phase ratio of 48. The surfaces display uniform emission in PEEM at all temperatures. No FEEM images are detectable below 500°C. At ∼680°C the T-FEEM and PEEM images are nearly identical in intensity and uniformity. This is to be contrasted with other carbon based cold cathodes in which the emission is observed from only a low density of highly emitting sites. The I/V measurements obtained from the N-doped films in the T-FEEM configuration show a component that depends linearly on voltage at low fields. At higher fields, an approximately exponential dependence is observed. At low temperatures employed (<700°C), the results indicate a thermionic component to the emitted current.

The technique of photo-electron emission microscopy (PEEM) is based on imaging of photo excited electrons from a surface. Typically ultra violet (UV) light above the work function of a metal will cause electrons to be emitted from a surface. Since photo excited electrons originate very near to the surface, they essentially reflect the electronic structure of the surface. These electrons may be accelerated and imaged, and the image will reflect the properties of the surface.

While the PEEM technique has been understood in a basic sense for many years, it has been limited by the lack of high intensity UV light sources. The most crucial part of the electron imaging system for PEEM, the objective lens, is essentially the same as for the sister technique of low energy electron microscopy (LEEM), and advances in electron optics capabilities have been exploited both for LEEM and for PEEM.

This study explores the field emission properties of nitrogen doped diamond grown by microwave plasma CVD. Several diamond samples were grown on silicon under varying conditions. With certain process parameters, films can be grown which exhibit photoluminescence bands at 1.945eV and 2.154eV that are attributed to single substitutional nitrogen. Field emission characteristics were measured in ultrahigh vacuum with a position variable anode. For samples grown with gas phase [N]/[C] ratios less than 16, damage from micro-arcs occurred during the field emission measurements. Samples grown at higher [N]/[C] content could be measured without damage. These measurements indicate relatively high threshold fields (>100V/νm) for electron emission. From the data, two possible field emission mechanisms are presented. Conducting defect states in the bandgap of diamond may provide a source of electrons to the emitting diamond surface.

This study explores the field emission properties of nitrogen doped diamond grown by microwave plasma CVD. Several diamond samples were grown on silicon under varying conditions. With certain process parameters, films can be grown which exhibit photoluminescence bands at 1.945eV and 2.154eV that are attributed to single substitutional nitrogen. Field emission characteristics were measured in ultrahigh vacuum with a position variable anode. For samples grown with gas phase [N]/[C] ratios less than 16, damage from micro-arcs occurred during the field emission measurements. Samples grown at higher [N]/[C] content could be measured without damage. These measurements indicate relatively high threshold fields (>100V/µm) for electron emission. From the data, two possible field emission mechanisms are presented. Conducting defect states in the bandgap of diamond may provide a source of electrons to the emitting diamond surface.

The morphologies of nanoscale epitaxial islands of TISi2 are studied. The islands are prepared by deposition of ultrathin Ti (3-20Å) on both smooth and roughened.Si(001) substrates. The island formation is initiated by annealing to 800-1000°C. The roughened substrates are prepared by etching with atomic H produced in a plasma. The morphologies of the substrate before and after island formation are examined by atomic force microscopy (AFM). In particular, the influence of surface-roughness on both the formation of islands and the size distribution of islands is investigated. On a rough substrate islands with a lateral dimension of ~350Å and a vertical dimension of ~25Å were observed with size uniformity of ~20%. Also it was observed that the roughness of the surface reduced the island size and affected the island distribution. The results are discussed in terms of surface energy and the strain field around the islands.

The effects of Si1−xGex alloy composition on the Ti-Si1−xGex solid phase reaction have been examined. Specifically, effects on the titanium gcrmanosilicide phase formation sequence. C54 Ti(Si1−yGey)2 nucleation temperature, and C54 Ti(Si1−yGey)2 morphology were examined. It was determined that the Ti-Si1−xGex reaction follows a “Ti-Si-like” reaction path for Si-rich Si1−xGex alloys and follows a “Ti-Ge-like” reaction path for Ge-rich Si1−xGex alloys. The coexistence of multiple titanium germanosilicide phases was observed during Ti-Si1−xGex reactions for Si1−xGex alloys in an intermediate composition range. The morphology and stability of the resulting C54 germanosilicides were directly correlated to the Ti-Si1−xGex reaction path. Smooth continuous C54 titanium germanosilicide was formed for samples with Si1−xGex compositions in the “Ti-Si-like” regime. Discontinuous islanded C54 germanosilicides were formed for samples with Si1−xGex compositions in the mixed phase and “Ti-Ge-like” regimes. Using rapid thermal annealing techniques, it was found that the C54 titanium germanosilicides were stable to higher temperatures. This indicated that the morphological degradation occurs after C54 phase formation. The C54 Ti(Si1−xGex)2 formation temperature was examined as a function of alloy composition and was found to decrease by ≍ 70 °C as the composition approached x ≍ 0.5. An optimum Si1−xGex alloy composition range of 0 ⋚ x ⋚ 0.36 was determined for the formation of stable-continuous-low-resistivity-C54 titanium germanosilicide films from the solid phase reaction of Ti and Si1−xGex alloy. The results were described in terms of the relevant nucleation processes.

The structural transformation of polycrystalline Si induced by high energy ball milling has been studied. The structure and property characteristics of the milled powder have been investigated by x-ray diffraction, scanning electron microscopy, high-resolution electron microscopy, differential scanning calorimetry, Raman scattering, and infrared absorption spectroscopy. Two phase amorphous and nanocrystalline Si has been produced by ball milling of polycrystalline elemental Si. The nanocrystalline components contain some defects such as dislocations, twins, and stacking faults which are typical of defects existing in conventional coarse-grained polycrystalline materials. The volume fraction of amorphous Si is about 15% while the average size of nanocrystalline grains is about 8 nm. Amorphous elemental Si without combined oxygen can be obtained by ball milling. The distribution of amorphous Si and the size of nanocrystalline Si crystallites is not homogeneous in the milled powder. The amorphous Si formed is concentrated near the surface of milled particles while the grain size of nanocrystalline Si ranges from 3 to 20 nm. Structurally, the amorphous silicon component prepared by ball milling is similar to that obtained by ion implantation or chemical vapor deposition. The amorphous Si formed exhibits a crystallization temperature of about 660 °C at a heating rate of 40 K/min and crystallization activation energy of about 268 kJ/mol. Two possible amorphization mechanisms, i.e., pressure-induced amorphization and crystallite-refinement-induced amorphization, are proposed for the amorphization of Si induced by ball milling.

The electron affinity of a semiconductor defines the relationship of the vacuum level and the semiconductor band structure. It is dependent on the atomic orbitals of the material and the surface termination. We report experimental and theoretical results that support the presence of a negative electron affinity on AlN and the Al rich AlGaN alloys. The GaN surface is found to exhibit a (positive) electron affinity of 3.3eV. The experimental measurements employ UV-photoemission spectroscopy on in situ gas-source MBE samples and on CVD samples. Theoretical results indicate that the (negative) electron affinity of AlN depends sensitively on the surface reconstruction and adatom termination. The experimental dependence of the electron affinity on alloy concentration is presented. The results indicate that AlGaN alloys with band gap similar or greater than that of diamond will exhibit a negative electron affinity. Field emission results are reported, and the characteristics are similar to those obtained from a diamond film. Issues related to cold cathode electronic devices based on NEA surfaces are noted.

“Morphology of TiSi2 and ZrSi2 on Si(100) and (111) surfaces” [J. Mater. Res. 9, 1214–1227 (1994)]

The morphologies of ZrSi2 on Si(111) and TiSi2 on Si(111) and (100) have been investigated, and the results compared and contrasted. Films were prepared by UHV deposition of Ti or Zr onto clean, reconstructed Si(100) or (111) substrates, and reacted by in situ annealing. The sheet resistivity of the ZrSi2 was measured and found to be 33-42 μΩ-cm. The morphologies were examined by transmission and scanning electron microscopy. In particular, the islanding properties were studied; both the temperature of the onset of islanding and the island characteristics were measured. The surface and interface energies have been determined from the contact angles of the silicide islands, according to a solid-state capillarity model. The system of ZrSi2 on Si(111) was found to have surface and interface energies lower than those of the system of TiSi2 on Si(100), but higher than those of the system TiSi2 on Si(111). ZrSi2 on Si(111) was found to island at a higher temperature than TiSi2 on either substrate, a result attributed to kinetic effects. Areal coverage of the islands was measured, and the results were consistent with the solid-state capillarity model. For both TiSi2 and ZrSi2, increasing faceted structure was observed with increasing anneal temperature. Preferred faceting planes were found to be of Si(111) and (100) type for TiSi2 islands and of Si(111) type for ZrSi2. Faceted islands were apparently epitaxial. As the solid-state capillarity model does not directly apply to islands with a faceted structure, an observation of the percentage of faceted islands produced by different annealing temperatures was used to suggest the processing conditions in which the model is applicable.

Samples of diamond crystals produced under various high pressure, high temperature conditions were studied using both micro photoluminescence and Raman spectroscopy. The 0.3 - 0.6 mm sized samples exhibited various levels of inclusion content, impurity content and strain. Photoluminescence studies revealed the presence of nitrogen in three forms. The 1.945 eV, 2.15 eV and 2.46 eV zero phonon lines and their associated sidebands were detected. The ratios between forms of impurities and their integrated intensities varied between samples. Variations in the distribution of the nitrogen forms were seen between regions of high and low strain birefringence patterns.

The high temperature solid phase reaction of Ti with SixGe1−x produces a low resistivity titanium germanosilicide which is isomorphic with the C54 phase of TiSi2 and TiGe2. The composition of the final C54 Ti(SiyGe1−y)2 film is dependent on the composition of the initial Si-Ge alloy and on the annealing conditions. The intermediate phases of the Ti-Si and Ti-Ge reactions are C49 TiSi2 and Ti6Ge5 respectively. The reaction path of Ti - SixGe1−x shifts from that of Ti-Si to that of Ti-Ge as the SixGe1−x alloy composition changes (×=1→0). Phase separations were observed at low temperatures for Ti reactions with Si-Ge alloys and the C54 formation temperature was observed to decrease as the Si-Ge alloy composition approached Si.5Ge.5. Surface and interface morphologies were examined using SEM and TEM. The formation of smooth, large grain, low resistivity films has been observed for the reaction of Ti with low Ge content alloys (x≥0.7). As germanium content is increased the formation of faceted islands is observed. Reactions with high Ge content alloys (x≤0.3) produce films with morphologies similar to those of the Ti-Ge reaction.

This study explores the local structures of TiSi2 and ZrSi2 films on Si. The strain effect on the surface morphologies and phase stability of the films is investigated. Titanium silicide and zirconium silicide films were fabricated on atomically clean Si(111) substrates in UHV using electron gun evaporation followed by in situ annealing. A quantitative X-ray absorption spectroscopy analysis was performed to study the formation of epitaxial TiSi2 and ZrSi2 films on the Si surfaces, as well as the phase transition of TiSi2 from the metastable C49 structure to the stable C54 structure. The surface morphologies and the surface roughness of the films were studied using atomic force microscopy (AFM). The strains of these films were determined by comparing the calculated bond lengths with the measured bond lengths using the extended X-ray absorption fine structure (EXAFS) technique. The final stable C54 structure of TiSi2 has less strain than the initially formed metastable C49 phase. While the surface and interface free energies and the bulk free energy are critical to the structural formations and phase changes of the films, the energy associated with the lattice strain is another important factor.

The surfaces of Si(100) and Ge(100), cleaned at low temperatures by H-plasma, were studied by Angle Resolved UV-Photoemission Spectroscopy(ARUPS). In the case of Si(100), H-plasma exposure produced ordered H-terminated crystallographic structures with either a 2×1 or 1×1 LEED pattern while for Ge(100) a weak H-terminated 2x1 pattern was obtained. The hydride phases, found on the surfaces of the cleaned Si(100), were shown to depend on the temperature of the surface during H-plasma cleaning. The electronic states for the monohydride and dihydride phases were identified by ARUPS. When the plasma cleaned surface was annealed, the phase transition from the dihydride to monohydride was observed. For the Ge(100) surface, an ordered 2x1 monohydride phase was obtained from the surface cleaned at 180°C. After plasma exposure at ≤170°C a 1×1 surface was observed, but the ARUPS indicated that the surface was predominantly composed of disordered monohydride structures. After annealing above the H-dissociation temperatures, the dangling bond surface states were identified for both Si and Ge. The Si(100) and Ge(100) ARUPS spectra shifted after annealing, indicating that the H-terminated surfaces were unpinned.

An investigation of the parameters in H-plasma cleaning influencing H-diffusion and surface etching is described. The Si surface and subsurface regions were characterized with Raman spectroscopy and high resolution transmission electron microscopy (HRTEM), and the plasma parameters were monitored with a double Langmuir probe and optical emission spectroscopy. The parameters varied in the rf plasma cleaning were the substrate temperature, the rf power, and the plasma exposure time. It was found that low pressure and low power H-plasma exposure was effective in terms of cleaning the surface. In the 300°C, 20 Watts, 2 min. H-plasma exposure case, the Raman spectra indicated that there was no detectable H incorporation into the Si bulk and HRTEM showed no obvious defect microstructure in the near surface region and that the surface was smooth. In contrast, in the 150°C, 50 Watts, 60 min. H-plasma exposure case, HRTEM indicated that H-induced platelet defects formed in the Si(100) subsurface region and that the surface morphology was rough. Raman scattering revealed Si-H features at ∼2100 cm−1.

The reactions of titanium on germanium were studied using Raman spectroscopy and X-ray Absorption Spectroscopy (XAS). Samples used in this study were produced in a custom MBE system with dual E-gun sources, two filament sources, and base pressure <1x10−10 Torr. Ge(100) substrates were prepared by chemical cleaning and homoepitaxial deposition of 500Å - 1000Å Ge at 550°C. Ti was deposited and subsequently annealed at 50°C intervals from 500°C to 700°C. Raman and XANES spectra of the titanium germanides were obtained and used to examine the.evolution of the crystalline structures which form by the interface reactions of Ti on Ge. A low-order phase formed by diffusion controlled growth prior to the formation of TiGe2 (isomorphous with TiSi2 [C54]) by nucleation controlled growth.

In the present study we report the first results pertaining to the heteroepitaxial growth of Ti films on 6H-SiC (0001). The Ti epitaxial films of typically 400–1000 Å thickness have been deposited at room temperature in ultra-high vacuum (< 10−9 torr) using both thermal and electron beam evaporation sources. In-vacuo techniques of low energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS) have been used to monitor the surface structure and interface chemistry during growth. An unreconstructed (1×1) ordered LEED pattern corresponding to that of the SiC (0001) surface was observed for all Ti coverages. Epitaxial growth of Ti has been confirmed from cross-sectional TEM diffraction patterns and images, which indicate the presence of threading dislocations to relieve a 4% lattice mismatch strain. Rutherford backscattering (RBS) with channeling of 2 MeV He+ ions gave X = 0.71 for Ti deposited at room temperature. Current-voltage measurement for both un-annealed and annealed Ti contacts displayed rectifying characteristics with low leakage currents (≈, 6 nA at −10V) and low ideality factors (1.02–1.08).

This study details low pressure and low temperature cleaning of Si(100) surfaces. The properties of Si surfaces exposed to variations in plasma generated H are described. The diagnostic techniques used to study the processing conditions are residual gas analysis (RGA) and emission spectroscopy. The surface is characterized by low energy electron diffraction (LEED) and angle resolved uv-photoemission spectroscopy (ARUPS). During the cleaning, Si complexes are formed which indicates the removal of species from the Si(100) surface. Plasma cleaning at 300°C results in a Si(100) surface with 2×1 surface diffraction patterns as detected by LEED. Measurements by ARUPS with He I radiation show the absence of Si surface states on the Hpassivated surface. The ARUPS measurements also indicate that the H begins to desorb from the Si(100) H-passivated surface at ∼500°C.