Search

The high-angular-resolution electron backscatter diffraction (HR-EBSD) technique has been utilized to evaluate the elastic strain distribution of grinding-induced damage layers in silicon carbide wafers. HR-EBSD analysis, along with transmission electron microscopy observation, revealed that the damage layers formed beneath the wafer surface when the surface was ground by diamond abrasives; the layers were classified hierarchically based on the distribution of elastic strain and lattice defects. In particular, very large elastic strain formed in a defective region of roughly 0.6 μm in thickness, just beneath the ground wafer surface, where lattice defects such as dislocations, stacking faults, and microcracks were introduced inhomogeneously by abrasive interaction and related plastic deformation and fracture. Based on this inhomogeneity, the defective region was itself classified into two types: one, a highly defective region with very large, complicated strain and high defect density; and the other, a basal plane dislocation (BPD)-glide region, with small strain and few BPDs or stacking faults. Beneath the defective region, a strain gradient region of roughly 1.8 μm in thickness, which was unambiguously identified by HR-EBSD strain analysis alone, revealed a monotonic gradient in the dominant compressive strain component, with no grinding-induced defects. Overall, HR-EBSD analysis revealed a nanometer-scale, hierarchical elastic strain distribution in the grinding-induced damage layers.

Evaluation of surface damage layers formed by mechanical grinding processes is indispensable in epi-ready SiC wafer preparation. As well as microstructure, the analysis of local strain distribution in the damage layers gives a clue on control of the wafer quality. Advanced electron backscatter diffraction (EBSD) technique is applied to evaluate the strain distribution of the damage layers. It is revealed that the elastic strain distribution can be classified into a hierarchy of three regions with respect to depth from the surface. Combining EBSD analysis with TEM observation, large compressive elastic strain and misorientation are introduced in the highly-defective region underneath the ground wafer surface. In addition, the gradient distribution of the strain is observed clearly below the highly-defective region. The knowledge of correlating between strain distribution and microstructure is promising to control the damage layer for the wafer preparation.

Ultrafine cerium oxide nanorods are produced from rapidly liquid quenched Ce-Al alloy precursors by a corrosion method through the selective leaching of Al and the oxidation of Ce in an alkaline medium under mild conditions. The obtained nanorods, having 5-7 nm diameter, exhibit unprecedented low-temperature oxygen-storage capacity (OSC) performance.

Nickel (Ni) is expected to be an attractive anode material for protonic ceramic fuel cells using Y-doped BaZrO_3 (BZY) as an electrolyte, since Ni shows good catalytic properties for the anode reaction, and NiO is a sintering aid for BZY. In this work, a systematic investigation has been performed to reveal the influence of Ni incorporation on structural and electrochemical properties of BZY. Then, some new knowledge was obtained; the important point is that Ni cations occupy the interstitial position of (1/2, 0, 0) in the lattice of BZY, with a greatly Ba-deficient environment. As a result, Ba cations were possibly driven to the grain boundary and induced the formation of a liquid phase, which promoted the sintering process. However, the occupation of Ni on this (1/2, 0, 0) position also resulted in a negative influence on conductivity. A careful processing is required to apply Ni as the electrode in BZY based fuel cells.

Damaged layers, which are introduced during chemo-mechanical polishing (CMP) underneath the 4°off-cut 4H-SiC wafer surface and cause surface defects formations after epitaxial films growth, are investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM observations show presence of small scratches on wafer surfaces after CMP process. The widths of such scratches are submicron meters, thus it is hard to detect them by optical microscopy. TEM observations show that high-density regions of dislocation loops exist below scratches and the widths of such dislocation loops are much wider than the morphological width. Details of the dislocation structure are also analyzed. It is shown that the high-density dislocation loops cause local surface roughening on the surface of the epitaxial film.

We report a synthesis of two types of CeO 2 nano-rods via the facile and efficient hydrothermal process free from any surfactant and template. The synthesized nano-rods are chemically identified as CeO 2 with the standard fluorite structure but their morphologies are different. The nano-rods prepared with cerium nitrate hexahydrate and sodium phosphate are thicker and shorter with diameter of ∼30 nm and length of ∼100 nm, and those prepared with cerium acetate hydrate and dibasic sodium phosphate are thinner and longer with ∼10 nm in diameter and ∼400 nm in length. Microstructural analyses reveal that the two species of nano-rods have low-energy {111} surfaces and grow along the 〈112〉 direction. As a consequence of their morphologies, the two types of synthesized nano-rods exhibit excellent UV-absorption ability in comparison to the irregular CeO 2 nanoparticles.

Clear understanding of the structure–property relation in polycrystalline materials requires atomic-resolution imaging of grain boundary (GB) structures especially for the GBs with misalignments. In this study, we apply a bicrystal technique to fabricate the Σ5 and near-Σ5 GBs of MgO with tunable bonding angle and demonstrate that the misalignments in GBs could be compensated by a periodic displacement shift complete dislocation array. The atomic-resolution images reveal that the near-Σ5 GB is composed of an array of normal Σ5 GB structural units intercalated by deformed Σ17 GB units. The atomic-scale characterization presented is applicable to other GB species in a range of polycrystalline materials.

We report the synthesis of three kinds of hybrid architectures with two different types of ceria nanoparticles, the nano-rods and nano-octahedrons, within one step via a facile yet efficient hydrothermal process. We demonstrate that morphology of the synthesized CeO2 nanomaterials can be manipulated via tuning the type and concentration of the mineralizer. The synthesis mechanism and chemical evolution of the harvested nanomaterials are also discussed in light of the role played by the mineralizer. Such a simple method to synthesize the functional nano-crystallites with tunable morphology by tailoring the concentration of mineralizer alone should be applicable to other types of nanomaterials and significant for a wide range of applications.

a Department of Chemistry, University of Tokyo, Tokyo 113-0033, Japan b PRESTO, Japan Science and Technology Agency, Kawaguchi 332-0012, Japan c Quantum-Phase Electronics Center and Department of Applied Physics, University of Tokyo, Tokyo 113-8656, Japan d Department of Basic Science, University of Tokyo, Tokyo 153-8902, Japan e Department of Physics, Tohoku University, Sendai, Japan f WPI-AIM Research, Tohoku University, Sendai 980-8577, Japan g Institute of Engineering Innovation, University of Tokyo, Tokyo 113-8656, Japan h Nanostructures Research Laboratory, Japan Fine Ceramics Center, Nagoya 456-8587, Japan

A hybrid architecture comprising two types of cerium compound nanoparticles is synthesized via a facile surfactant- and template-free hydrothermal process. The prepared hybrid materials show an unusual morphology with small hexagonal nano-disks dispersed on relatively larger frustum pyramids. Microscopic analyses identify the chemical composition of the nano-disks as CeF3 and the frustum pyramids as CeO2. Apart from absorption on the CeO2 supports, the CeF3 nano-disks are self-assembled as well to form ordered one-dimensional chain nanostructure. Such unique hybrid architecture may open an avenue for the scientific and technological application in the rapidly emerging catalytic field.

We report the preparation of cerium-containing nanoparticles by a simple yet efficient hydrothermal synthesis process using cerium resource and NaF mineralizer with no surfactant or template. We demonstrate that morphology and chemistry of the synthesized CeO2 and CeF3 nanomaterials can be manipulated via tuning concentration of the mineralizer NaF alone. The synthesis mechanism, chemical evolution, and optical properties of the harvested nanomaterials have also been investigated. The ceria and its hybrid system are found to exhibit an excellent UV-shielding capability, which provides further evidence that the mineralizer NaF is critical for governing the morphology and properties of the cerium-containing nanomaterials. Such a facile method to synthesize the functional nano-crystallites with tunable morphology and chemistry by tailoring the concentration of mineralizer alone should be applicable to other types of nanomaterials and relevant for a wide range of applications.

Oxide heterointerfaces often trigger unusual electronic properties that are absent in respective bulks. Here, direct evidence is offered for spontaneously assembled local structural distortions in a single-phase bulk, which confine electrons to within an atomic layer with notable orbital reconstruction and coupling, close the forbidden band, induce a ferromagnetic ordering, and give rise to a strongly anisotropic, spin-polarized quasi-one-dimensional electron gas.

Direct observation of delithiated structures of LiCoO2 at atomic scale has been achieved using spherical aberration-corrected scanning transmission electron microscopy (STEM) with high-angle annular-dark-field (HAADF) and annular-bright-field (ABF) techniques. The ordered Li, Co, and O columns for LiCoO2 nanoparticles are clearly identified in ABF micrographs. Upon the Li ions extraction from LiCoO2, the Co-contained (003) planes distort from the bulk to the surface region and the c-axis is expanded significantly. Ordering of lithium ions and lithium vacancies has been observed directly and explained by first-principles simulation. On the basis of HAADF micrographs, it is found that the phase irreversibly changes from O3-type in pristine LiCoO2 to O1-type LixCoO2 (x ≈ 0.50) after the first electrochemical Li extraction and back to O2-type LixCoO2 (x ≈ 0.93) rather than to O3-stacking after the first electrochemical lithiation. This is the first report of finding O2-LixCoO2 in the phase diagram of O3-LiCoO...

High-resolution transmission electron microscopy was used to analyze basal-plane dislocations, which display very characteristic contrasts in grazing incidence monochromatic X-ray topographic images, on the Si-face of 4H–SiC. Grazing incidence monochromatic synchrotron X-ray topography, which is a lattice defect observational technique, has been used in power devices made from 4H–SiC. This technique is useful in analyzing lattice defects near the surface but without the contrast of high-density lattice defects inside the wafer. Basal-plane dislocations exhibit several distinct types of contrast: dark, bright, asymmetric dark/bright and intermediate contrast. Dark and bright contrast areas have been reported to be the edge dislocation regions of basal-plane dislocations. Nevertheless, it remains unclear whether the dark contrast regions are edge dislocations with extra half-planes on the surface side, i.e. Si-core edge dislocations, or those with extra half planes on the deeper crystal side, namely C-core ...

We demonstrate that the atomic structures, electronic states, and bonding nature of the interface between SrTiO3 substrate and anatase TiO2 thin films could be related and technologically manipulated at the atomic level. Applying advanced transmission electron microscopy, the grown anatase TiO2 thin films are found to make a clean and direct contact to the SrTiO3 substrates in an epitaxial, coherent, and atomically abrupt way. The atomic-resolution microscopic images reveal that the interface comprises SrO-terminated SrTiO3 and Ti-terminated TiO2 with the interfacial Ti of TiO2 sitting above the hollow site, which is confirmed theoretically to be the most energetically favorable. Quantitatively, the first-principles calculations predict that the oxygen sublattice at the interface undergoes a notable reconstruction, i.e., the interfacial O atoms of TiO2 are displaced largely toward the SrO plane of the SrTiO3, flattening the originally zigzag TiO2 atomic chains. Consequently, the interfacial layers suffer a remarkable modification in the charge accumulation and also a deviation in the density of states from their bulk counterparts, indicating that the substrate can have an impact on the deposited thin films electronically. Using several analytic methods, the SrTiO3/TiO2 interface is found to take on a metallic nature, and the interfacial bonding is determined to be of a mixed covalent and ionic character. This combined experimental and theoretical investigation gains insight into the complex atomic and electronic structures of the buried interface, which are fundamental for relating the atomic-scale structures to their properties on a quantum level.

The ability to resolve spatially and identify chemically atoms in defects would greatly advance our understanding of the correlation between structure and property in materials. This is particularly important in polycrystalline materials, in which the grain boundaries have profound implications for the properties and applications of the final material. However, such atomic resolution is still extremely difficult to achieve, partly because grain boundaries are effective sinks for atomic defects and impurities, which may drive structural transformation of grain boundaries and consequently modify material properties. Regardless of the origin of these sinks, the interplay between defects and grain boundaries complicates our efforts to pinpoint the exact sites and chemistries of the entities present in the defective regions, thereby limiting our understanding of how specific defects mediate property changes. Here we show that the combination of advanced electron microscopy, spectroscopy and first-principles calculations can provide three-dimensional images of complex, multicomponent grain boundaries with both atomic resolution and chemical sensitivity. The high resolution of these techniques allows us to demonstrate that even for magnesium oxide, which has a simple rock-salt structure, grain boundaries can accommodate complex ordered defect superstructures that induce significant electron trapping in the bandgap of the oxide. These results offer insights into interactions between defects and grain boundaries in ceramics and demonstrate that atomic-scale analysis of complex multicomponent structures in materials is now becoming possible.

A fluoride-based cathode (FeF3·0.33H2O) for lithium batteries, the synthesis of which has been reported recently (C. L. Li et al. Adv. Mater.2010, 22, 3650), is described in terms of structure, morphology, and performance. A self-assembled mesoporous morphology connected with a high specific surface area is obtained through the soft template role of the ionic liquid. The fluoride exhibits a one-dimensional tunnel structure produced by continuous hexagonal cavities, in which hydration water molecules are located. The high Li-intercalation activity of carbon-free FeF3·0.33H2O is expected to be associated with various factors, including electrolyte-infiltratable mesoporosity, wide Li+-insertable channels, and medium conductivities. A single solid-solution reaction mechanism is indicated by potentiostatic intermittent titration technique and ex situ X-ray diffraction at different reactive potentials.

We grew 3 inch thick 4H-SiC epitaxial layers on the substrate Si-face, and attempted warpage reduction. The substrates were coved by grinding their C-face before the epitaxial growth to cancel out the increase in convex warpage due to the epitaxial growth. We found that the amount of convex warpage change was approximately 26 μm, when the thickness of the epitaxial layer was 200 μm. To reduce warpage, we prepared the substrate with concave warpage of about 27 μm by grinding the C-face, whose roughness was 60 nm. Then, we grew an epitaxial layer of 200 μm thickness on this and we succeeded in reducing the warpage to 5 μm. We concluded that the warpage of thick epitaxial layers on the substrates can be reduced by controlling the roughness of the ground back side, in accordance with the estimated amount of warpage change from the objective thickness of the epitaxial layers.

Recent breakthroughs in transmission electron microscopy enable a direct quantitative determination of the technologically significant heterointerfaces, yet a direct interpretation is not always possible. Here, we review the general processes to introduce the high-precision first-principles calculations into the microscopy in order to obtain an atomistic understanding of effects of buried interfaces on a wide range of properties. We demonstrate the possibility and important advance of this combined method in relating interface structures to device physics even for the complex heterointerfaces, SiC/Ti3SiC2, LaxSr1−xO/(SrTiO3)n, and Pd/ZnO presented here. We therefore believe that this approach should be widely applicable to many other interfaces and a range of materials, providing new insights into many long-standing unresolved issues regarding interfaces.

The increase in threading dislocation during the initial stage of physical vapor transport growth of n-type 4H-SiC crystals was evaluated by cross-sectional X-ray topography. Crystals were grown under two different temperature conditions. A significant increase in threading dislocation was observed in crystals grown at a high, not low, temperature. The local strain distribution in the vicinity of the grown/seed crystal interface was evaluated using the electron backscatter diffraction technique. The local nitrogen concentration distribution was also evaluated by time-of-flight secondary ion mass spectrometry. We discuss the relationship between the increase in threading dislocation and the local strain due to thermal stress and nitrogen concentration.

The structural, adsorptive, and electronic properties of oxygen adsorption on anatase TiO 2 are investigated by first-principles calculations with special focus on two experimentally confirmed surfaces. We find that compared with (101) surface, the (001) surface exhibits lower oxygen adsorption energy, reduced band gap, and larger charge transfer, thereby holding the potential for the improvement of sensitivity to reductive gases. Moreover, the (001) surface is found to be more active in oxygen adsorption. These findings render a careful synthesis of anatase TiO 2 crystals so as to form, to the largest extent, the (001) surface primarily important for further improving gas-sensing properties of TiO 2 -based sensors.

Growth and microstructure of ternary Ti3SiC2 compound layers on 4H-SiC, which play am important role in formation of TiAl-based ohmic contacts to p-type SiC, were investigated in this study. The Ti3SiC2 layer was fabricated by deposition of Ti/Al contacts (where a slash ‘‘/’’ indicates the deposition sequence) on the 4H-SiC(0001) substrate and subsequent rapid thermal anneal at 1000 � C in ultra high vacuum. After annealing, reaction products and microstructure of the Ti3SiC2 layer were investigated by X ray diffraction analysis and transmission electron microscopy observations in order to understand the growth processes of the Ti3SiC2 layer and determination of the Ti3SiC2/4H-SiC interface structure. The Ti3SiC2 layers with hexagonal plate shape were observed to grow epitaxially on the SiC(0001) surface by anisotropic lateral growth process. The interface was found to have a hetero-epitaxial orientation relationship of ð0001ÞTSC== ð0001ÞS and ½0� 1� TSC== ½0� 1� S where TSC and S represent Ti3SiC2 and 4H-SiC, respectively, and have well-defined ledge-terrace structures with low density of misfit dislocations due to an extremely low lattice mismatch of 0.4% between Ti3SiC2 and 4H-SiC. [doi:10.2320/matertrans.MC200831]

Smooth GaN layers were successfully grown on metallic TiN buffer layers by metalorganic chemical vapor deposition (MOCVD). One important factor in controlling GaN layer smoothness was the TiN layer thickness. We investigated systematically the effects of this thickness, and found an optimal thickness of 5 nm, at which the smallest average grain size (20 nm) and smoothest surface were obtained. The TiN layers increased surface coverage with GaN hexagons at an early stage of GaN growth, indicating that enhancing the GaN nucleation is essential for smooth GaN layer growth, and small grain size and smooth surface are needed to enhance GaN nucleation. Further reduction in TiN layer thickness to 2 nm decreased the surface coverage with GaN hexagons, and a high density of grooves and holes were observed in the surface of the 2-μm-thick GaN layers. Defect structures in the GaN layers grown on the TiN layers were remarkably changed on reduction of TiN layer thickness from 5 nm to 2 nm. GaN growth was found to be sensitive to the TiN layer thickness between 2 nm and 5 nm.

The fabrication procedure for silicon carbide power metal oxide semiconductor field-effect transistors can be improved through simultaneous formation (i.e., using the same contact materials and a one-step annealing process) of ohmic contacts on both the n-source and p-well regions. We have succeeded in the simultaneous formation of Ni/Al ohmic contacts to n- and p-type SiC after annealing at 1000°C for 5 min in an ultrahigh vacuum. Ohmic contacts to n-type SiC were found when the Al-layer thickness was less than about 6 nm, while ohmic contacts to p-type SiC were observed for an Al-layer thickness greater than about 5 nm. Only the contacts with an Al-layer thickness in the range of 5 nm to 6 nm exhibited ohmic behavior to both n- and p-type SiC, with a specific contact resistance of 1.8 × 10−4 Ω cm2 and 1.2 × 10−2 Ω cm2 for n- and p-type SiC, respectively. An about 100-nm-thick contact layer was uniformly formed on the SiC substrate, and polycrystalline δ-Ni2Si(Al) grains were formed at the contact/SiC interface. In the samples that exhibited ohmic behavior to both n- and p-type SiC, the distribution of the Al/Ni ratios in the δ-Ni2Si(Al) grains was larger than that observed for any of the samples that showed ohmic behavior to either n- or p-type SiC. Furthermore, the grain size of the δ-Ni2Si(Al) grains in the samples showing ohmic behavior to both n- and p-type SiC was smaller than the grains in any of the samples that showed ohmic behavior to either n- or p-type SiC. Thus, the large distribution in the Al/Ni ratios and a fine microstructure were found to be characteristic of the ohmic contacts to both n- and p-type SiC. Grains with a low Al concentration correspond to ohmic contacts to n-type SiC, while grains with a high Al concentration correspond to ohmic contacts to p-type SiC.

In our previous studies, thin Ti-rich diffusion barrier layers were found to be formed at the interface between Cu(Ti) films and SiO2/Si substrates after annealing at elevated temperatures. This technique was called self-formation of the diffusion barrier, and is attractive for fabrication of ultralarge-scale integrated (ULSI) interconnects. In the present study, we investigated the applicability of this technique to Cu(Ti) alloy films which were deposited on low dielectric constant (low-k) materials (SiOxCy), SiCO, and SiCN dielectric layers, which are potential dielectric layers for future ULSI Si devices. The microstructures were analyzed by transmission electron microscopy (TEM) and secondary-ion mass spectrometry (SIMS), and correlated with the electrical properties of the Cu(Ti) films. It was concluded that the Ti-rich interface layers were formed in all the Cu(Ti)/dielectric-layer samples. The primary factor to control the composition of the self-formed Ti-rich interface layers was the C concentration in the dielectric layers rather than the enthalpy of formation of the Ti compounds (TiC, TiSi, and TiN). Crystalline TiC was formed on the dielectric layers with a C concentration higher than 17 at.%.

In our previous studies, Ti atoms in Cu(Ti) alloy films were found to segregate at the film surface and the interface between Cu(Ti) alloy films and dielectric layers after annealing in Ar atmosphere at elevated temperatures. Such self-formed Ti-rich interface layers can act as a diffusion barrier layer. This technique was called ‘‘self-formation of the diffusion barrier,’’ which is attractive for the fabrication of ultra-large scale integrated interconnects. In the present study, we investigated the growth of Ti-rich barrier layers in Cu(Ti)/dielectric-layer samples wit ha low Ti content (1 at%) after annealing in ultra high vacuum (UHV). Ti atoms were found to segregate only to the Cu(Ti)/dielectric-layer interface under annealing in UHV. The microstructures were analyzed by transmission electron microscopy and Rutherford backscattering spectrometry, and correlated with the electrical properties of the Cu(Ti) films. It was concluded that Ti-rich interface layers were formed in all the Cu(Ti)/dielectric-layer samples. The Ti-rich interface layers were identified to consist of TiC or TiSi in addition to Ti oxides. The growth of the Ti-rich interface layers consisting of TiC was faster than those consisting of TiSi. Similarly, the resistivities of Cu(Ti)/dielectric-layer samples in which the TiC formation was observed were quickly reduced and those in which the TiSi formation was observed were gradually reduced. Compositions of the self-formed Ti-rich interface layers were concluded to be determined by the C concentration in the dielectric layers rather than by the enthalpy of formation. The growth of the self-formed Ti-rich interface layers consisting of TiC may be controlled by C diffusion in the Ti-rich interface layer. The composition of the dielectric layers was concluded to play an important role on the growth of the Ti-rich interface layers. [doi:10.2320/matertrans.MAW200809]

The electrical and optical properties, and microstructures of 100 nm-thick Ga2O3 films fabricated on Al2O3(0001) substrates by a sputtering deposition were investigated. The partial pressure of oxygen was controlled and the substrate temperature was kept to be 500 °C during deposition. With increasing the oxygen partial pressure, the structures of the Ga2O3 films deposited on the substrates were observed to change from amorphous to crystalline (monoclinic β-type Ga2O3). The transmittance of the Ga2O3 films was measured to be more than 80 % at the visible and ultraviolet regions although the electrical resistivity was high. In order to obtain both low electrical resistivity and high transmittance at the ultraviolet regions, the addition of active dopant elements such as Sn into the Ga2O3 films would be required.

We investigated effect of reducing thickness of TiN buffer layers on growth of the smooth GaN layers. The sputtered TiN layers with thicknesses in the range of 2 to 100 nm were deposited on sapphire substrates. The sputtered TiN layers were exposed NH3 + H2 mixed gas atmosphere at about 1000°C to enrich nitrogen concentration of the layers. GaN layers were deposited on the nitrogen-enriched TiN layer using a MOCVD method. Average grain size of the nitrogen-enriched TiN layer was minimized at the thickness of 5 nm. In the initial stages of GaN growth, density of GaN hexagons grown on the 5nm-thick TiN layers was the highest. The 2μm-thick GaN layers grown on the 5nm-thick TiN layers exhibited the smoothest surface. Thus, the 5nm thickness is believed to be the best thickness for the smooth GaN growth on the sapphire/TiN substrates.

Copper interconnects with self-formed thin TiSixOy barrier layers were successfully fabricated by sequentially depositing Cu(7 at.%Ti) alloys and pure Cu films on SiO2-based substrates with 0.1-μm-wide trenches, and embedding the samples using a high-pressure annealing technique at 550°C and 195 MPa. Microstructural analyses revealed that the self-formed Ti-rich layers with thicknesses of about 5 nm were uniformly formed on the trench bottom and sidewall. In addition, these layers were thermally stable against Cu diffusion into the SiO2-based interlayers. The present study suggests that the Cu-Ti alloy is one of the best candidates among possible interconnect and/or seed layer materials.

Copper (titanium) [Cu(Ti)] films with low titanium (Ti) concentration were found to form thin Ti-rich barrier layers at the film/substrate interfaces after annealing, which is referred to as self-formation of the barrier layers. This Cu(Ti) alloy was one of the best candidates for interconnect materials used in next-generation ultra-large-scale integrated (ULSI) devices that require both very thin barrier layers and low-resistance interconnects. In the present paper, in order to investigate the influences of annealing ambient on resistivity and microstructure of the Cu alloys, the Cu(7.3at.%Ti) films were prepared on the SiO2 substrates and annealed at 500°C in ultra-high vacuum (UHV) or argon (Ar) with a small amount of impurity oxygen. After annealing the film at 500°C in UHV, the resistivity was not reduced below 16 μΩ-cm. Intermetallic compounds of Cu4Ti were observed to form in the films and believed to cause the high resistivity. However, after subsequently annealing in Ar, these compounds were found to decompose to form surface TiO x and interfacial barrier layers, and the resistivity was reduced to 3.0 μΩ-cm. The present experiment suggested that oxygen reactive to titanium during annealing played an important role for both self-formation of the interfacial barrier layers and reduction of the interconnect resistivity.

In our previous studies, thin Ti-rich layers were found to uniformly cover SiO2/Si substrate surfaces at the interface with Cu(Ti) alloy films after annealing at elevated temperature. These Ti-rich layers were also found to prevent intermixing between the Cu(Ti) alloy films and the substrate, resulting in a simple barrier formation technique, called “self-formation of the diffusion barrier,” which is attractive for fabrication of ultra-large scale integrated (ULSI) interconnect structures. In the present study, to understand the mechanism of self-formation of the Ti-rich barrier layers on the substrate surface, the effects of SiO2/Si, SiN/SiO2/Si and NaCl substrate materials on the interfacial microstructure were investigated. The microstructures were analyzed by transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS), and correlated with the electrical properties of the Cu(Ti) interconnects. It was concluded that the chemical reaction of Ti with the substrate materials was essential for the self-formation of the Ti-rich layers.

We have investigated the roles of interfacial reaction, work function variation, and localized states of annealed Ti/Al ohmic contacts to p-type 4H-SiC. The Al was found to be absent in the near interface region. The possibility of additional p-doping by Al indiffusion in the top SiC layer was ruled out. The work function of Ti3SiC2, the direct contact layer to SiC, was determined to be intermediate between Ti and p-SiC, leading to a considerably lowered Schottky barrier height. Reaction-induced interfacial states were observed in the near-interface SiC, which may further reduce the barrier height and cause the formation of ohmic contact.

To study the self-formation mechanism of Ti-rich layers in Cu(Ti) alloy films, the microstructures and electrical resistivities of the Cu(Ti) alloy films were investigated by changing the annealing atmosphere and substrate materials. Oxygen contained in Ar facilitated Ti segregation at the surface, reduced the Ti content in the alloy films, and formed relatively large grains in the alloy films, which are essential for low-resistivity Cu alloy films. For the self-formation of the Ti-rich barrier layer, it was found that the selection of a substrate that is reactive to Ti atoms (forming Ti compounds) was essential. Although a strong reaction of the Ti atoms in the alloy films with SiN compared with that with SiO2 was expected, the resistivities in the annealed Cu(Ti) alloy films on the SiN/Si substrates were higher than those on the SiO2/Si substrates. Further reduction of the resistivities is required for application of the fabrication process to devices.

Ultrafine sodium titanate nanowires are produced from TiAl alloy precursors via a nonthermal process where Al leaching and Ti oxidation occur simultaneously in an alkaline medium. The obtained nanowires demonstrate a layered crystal structure with a diameter of a few nanometers and exhibit remarkable Sr ion-exchange properties.

We have used depth-resolved cathodoluminescence and Auger electron spectroscopies, DRCLS and AES, respectively, to probe the electronic structure and the composition of Ti/Al ohmic contacts to p-type SiC on a nanometer scale. A continuous Ti-Si-C compound layer was observed using the Auger depth profile. No interfacial Al segregation was found. The secondary electron threshold technique showed a continuous decrease in work function from the p-type SiC to the Ti-Si-C compound layer. Our results support an ohmic contact mechanism by an intermediate semiconductor layer which reduces the otherwise large interfacial Schottky barrier height. DRCLS revealed a ~2.78 eV sub-band gap transition enhanced by interfacial reaction in the near-interface SiC, suggesting the formation of additional C or Si vacancies.

To improve GaN light-emitting diode light emission, we produced metal organic chemical vapor deposition (MOCVD)-grown, continuous, flat GaN layers on metallic TiN buffer layers deposited on sapphire substrates. Three important conditions were found: (a) the sapphire substrate surface plane should be (1120), (b) the TiN layer surface plane should be (111), and (c) the TiN buffer layer nitrogen content should be higher than that of stoichiometric TiN. Reduction of TiN layer thickness reduced TiN buffer layer surface roughness. Threading dislocation density in GaN layers grown on TiN buffer layers was much lower than that in GaN layers grown on AlN.

To realize high-performance silicon carbide (SiC) power devices, low-resistance ohmic contacts to p-type SiC must be developed. To reduce the ohmic contact resistance, reduction of the barrier height at metal/SiC interfaces or increase in the doping concentration in the SiC substrates is needed. Since the reduction of barrier height is extremely difficult, the increase in the Al doping concentration in 4H-SiC by an ion-implantation technique was challenged. The Ti/Al and Ni/Ti/Al metals (where a slash “/” sign indicates the deposition sequence) were deposited on the Al ion-implanted SiC substrates. By comparing the experimental and theoretical contact resistances, the current transport mechanism through the metal/SiC interfaces was concluded to be thermionic field emission and the barrier height was determined to be ∼0.4 eV. Although the hole concentration increased with increasing the Al doping concentration in 4H-SiC, the barrier height at metal/SiC interfaces increased due to high density of dislocation loops observed in the implanted SiC layers by transmission electron microscopy. The present experiments suggested that the low-resistance ohmic contacts would be formed when a technique to eliminate the crystal defects formed in the 4H-SiC substrates after ion implantation was developed.

The maximum electrical conductivities in polycrystalline Cu interconnects with sub-100nm linewidth were extrapolated from the measured resistivities of the Cu interconnects with various linewidths (100–1000nm) using a Mayadas–Shatzkes (MS) model. These polycrystalline Cu interconnects with TiN cap layers were fabricated by the focused ion beam technique. The scattering parameters by the surface and grain boundary, which were needed to extrapolate the resistivities of the sub-100nm Cu interconnects (using the MS model), were determined to be zero and 0.5, respectively. The result suggested that the grain boundary scattering primarily increased the resistivity of the polycrystalline Cu interconnects. We concluded that large grained Cu interconnects and ultrathin barrier layers were essential to realize low resistance nano-scale Cu interconnects in the future ultralarge scale integration devices.

In order to study a formation mechanism of thin Ti-rich layers formed on the surfaces of Cu(Ti) wires after annealing at elevated temperatures, the 300-nm-thick Cu(Ti) alloy films with Ti concentration of 1.3 at.% or 2.9 at.% were prepared on the SiO2/Si substrates by a co-sputter deposition technique. The electrical resistivity and microstructural analysis of these alloy films were carried out before and after annealing at 400°C. The Ti-rich layers with thickness of ∼15 nm were observed to form uniformly both at the film surface and the substrate interfaces in the Cu(2.9at.%Ti) films after annealing (which we call the self-formation of the layers) using Rutherford backscattering spectrometry (RBS) and transmission electron microscopy (TEM). Both the resistivities and the microstructures of these Cu(Ti) films were found to depend strongly on the Ti concentrations. The resistivities of the films decreased upon annealing due to segregation of the supersaturated Ti solutes in the alloy films to both the top and bottom of the films. These Ti layers had excellent thermal stability and would be applicable to the self-formed diffusion barrier in Cu interconnects of highly integrated devices. The selection rules of the alloy elements for the barrier self-formation were proposed based on the present results.

Grain growth rates in sputtered Cu thin films were found to be influenced by impurity levels of the sputtering targets. The Cu thin films with thickness of 100 nm or 1 μm were deposited on the rigid substrates by a sputter-deposition technique using the Cu target with purity of 99.99% (4N) or 99.9999% (6N), then subsequently annealed at room temperatures. The microstructures of the Cu films were analyzed by scanning-ion microscopy and the sheet resistivities was measured by a four-point probe method. Significant grain growth and reduction of the electrical resistivities was observed during room-temperature storage in these sputtered Cu films. For the Cu films with a thickness of 1 μm, the grain growth rates of the Cu films were not influenced by the impurity levels of the targets. However, for the films with a thickness of 100 nm, the rate of the grain growth in the 6N-Cu films was found to be slower than that in the 4N-Cu films. This was contradictory to the grain growth mechanism of bulk Cu. The grain growth rates of the Cu films at room temperature, which were strongly influenced by the existence of a small amount of impurities in the Cu films, were well explained by the difference of the strain relaxation mechanisms in the films.

Recent strong demands for optoelectronic communication and portable telephones have encouraged engineers to develop optoelectronic devices, microwave devices, and high-speed devices using heterostructural compound semiconductors. Although the compound crystal growth techniques had reached at a level to control the compositional stoichiometry and crystal defects on a nearly atomic scale by the advanced techniques such as molecular beam epitaxy and metal organic chemical vapor deposition techniques, development of ohmic contact materials (which play a key role to inject external electric current from the metals to the semiconductors) was still on a trial-and-error basis. Our research efforts have been focused to develop, low resistance, refractory ohmic contact materials using the deposition and annealing techniques for n-GaAs, p-ZnSe, InP, p-SiC p-CdTe etc. It was found the growth of homo- or hetero–epitaxial intermediate semiconductor layers (ISL) was essential for low resistance contact formation. The importance of hetero-structural ISL was given taking an example of n-type ohmic contact for GaAs.

Since Cu was found to be attractive as interconnect materials for ultra-large scale integrated (ULSI) Si devices, the electrical properties of Cu films have been extensively studied to prepare low resistance films. It was found in our previous papers that reduction of the electrical resistance of the Cu films was achieved by increasing grain sizes of the Cu films and large-grained Cu films were essential for the low resistance Cu interconnects. The primary factor to increase the grain sizes was also found to be intrinsic and/or extrinsic strain (or stress) introduced into the films. The present paper addresses the driving force of the grain growth of the Cu thin films based on the strain energy criterion model.

The high-power SiC devices require ohmic contact materials, which are prepared by annealing at temperatures lower than 800°C. Recently, we demonstrated in our previous paper [J. Appl. Phys. 95, 2187 (2004)] that an addition of a small amount of Ge to the conventional binary Ti∕Al contacts reduced the ohmic contact formation temperature by about 500°C, and this ternary contacts yielded a specific contact resistance of approximately 1×10−4Ωcm2 after annealing at a temperature as low as 600°C. In this paper, the electrical properties and the microstructures of the Ge∕Ti∕Al contacts (where a slash “/” indicates the deposition sequence) were investigated by current-voltage measurements and transmission electron microscopy observations, respectively, in order to understand the ohmic contact formation mechanism. Ti3SiC2 compound layers (which were previously observed at the metal/SiC interface in the Ti∕Al ohmic contacts after annealing at temperatures higher than 1000°C) were observed to grow epitaxially on the...

The main purpose of the present microstructural analysis by transmission electron microscopy (TEM) and X-ray diffraction was to investigate whether amorphous TaN films are a potential candidate as diffusion barrier for Cu wiring used in Si devices. The TaN thin films were prepared by a sputter-deposition technique using Ar and N2 mixed gas, and the film structure was found to be sensitive to the gas flow ratio of N2 vs. Ar during sputtering. Polycrystalline TaN films were obtained when the N2/(Ar+N2) ratio was smaller than 0.10 and amorphous TaN films were obtained when the ratio was larger than 0.15. Cross-sectional TEM observations revealed that the amorphous films had columnar structure with fine grains and that nano-scaled voids segregated at the boundaries. In addition, two-layered structures were observed in the amorphous TaN films and high density of the grain boundaries was formed close to the substrate. The present results suggested that the amorphous TaN films would not have high resistance against interdiffusion between two different materials because the density of grain boundaries with small voids was extremely high.

The effect of intrinsic strain on grain growth in Cu thin films was studied by both plan-view and cross-sectional scanning ion microscope in a focused ion beam system. Significant grain growth with bimodal grain size distribution was observed during room temperature storage in the Cu films which were deposited on the Si 3 N 4 substrates by a sputter-deposition technique. In the thick Cu films, a non-uniform grain size distribution was observed along a direction normal to the film surface: the large grains were observed at the location close to the substrate surface. This grain size distribution coincided with inhomogeneous strain distribution normal to the film surface. We concluded that the grain growth in the Cu thin films was facilitated by the strain intrinsic in the Cu films deposited on the rigid substrates, and that strain (or stress) introduced in the films was a primary factor to induce the grain growth in the Cu films at room temperature.