An experimental study of cadmium substitution into AgXS2 phases (X = As, Bi, Sb) indicates significant amounts of cadmium can be incorporated in the structure by the mechanism 2Cd ⇌ Ag + X. The limit of substitution of Cd in the high-temperature polymorph of miargyrite, β-AgSbS2 is 6.2 at.%, whereas the low-temperature polymorph, α-AgSbS2, can accommodate at least 12 at.% cadmium. Substitution of Cd into the cubic β-AgSbS2 induces a small monoclinic distortion and the unit cell becomes pseudo-cubic. The α ⇌ β transition in Cd-substituted miargyrites is modified by the solute ions, with both a reduction of Tc and transition smearing evident. Similar effects are also recorded in Cd-substituted AgAsS2 and AgBiS2.

The weathering and oxidation of mine tailings has the potential to contaminate water and soil with toxic elements. To understand the mechanisms, extent and products of the long-term weathering of complex Bolivian tailings from the Cerro Rico de Potosí, and their effects on As, Pb, P and Sb cycling, three-year long laboratory column experiments were carried out to model 20 years of dry- and wet-season conditions in the Pilcomayo basin. Chemical analysis of the leachate and column solids, optical mineralogy, X-ray diffraction, scanning electron microscopy, electron probe microanalysis, microscale X-ray absorption near edge structure spectroscopy, Bureau Commun de Référence sequential extraction and water-soluble chemical extractions, and speciation modelling have shown that the weathering of As-bearing pyrite and arsenopyrite, resulted in a loss of 13–29% of the original mass of As. By contrast, Pb and Sb showed much lower mass losses (0.1–1.1% and 0.6–1.9%, respectively) due to the formation of insoluble Pb- and Sb(V)-rich phases, which were stable at the low pH (~2) conditions that prevailed by the end of the experiment. The experiment also demonstrated a link between the cycling of As, Sb, and the oxidation of Fe(II)-bearing sphalerite, which acted as a nucleation point for an Fe-As-Sb-O phase. Phosphorus was relatively immobile in the tailings columns (up to 0.3% mass loss) but was more mobile in the soil-bearing columns (up to 10% mass loss), due to the formation of soluble P-bearing minerals or mobilization by organic matter. These results demonstrate the influence of mine tailings on the mobility of P from soils and on the potential contamination of ecosystems with As, and strongly suggest that these materials should be isolated from fluvial environments.

GeTe/Sb2Te3 superlattices, also known as interfacial phase-change memory (iPCM), exhibit significantly faster switching and are characterized by much lower power consumption and longer data retention compared to devices based on alloyed materials. In early work, the superior performance of iPCM was linked to a crystal-crystal transition between the SET and RESET states. As the primary mechanism, a change in the stacking order of Ge and Te planes within a GeTe block was suggested. Subsequent STEM studies on epitaxial GeTe/Sb2Te3 superlattices demonstrated that the GeTe blocks were not located between Sb2Te3 quintuple layers but, were incorporated inside the latter, providing a serious challenge to the early explanation. In this work, we demonstrate that changes associated with the reconstruction of the SbTe terminating layers nearest to van der Waals gap leads to a pronounced change in the density of states and can serve as an alternative explanation for a large property contrast between the SET and RESET states in GeTe/Sb2Te3 superlattices.

GaSb/GaAs and InSb/GaAs material systems can create type-II quantum nanostructures which provide interesting electronic and optical properties such as having long carrier life time, low carriers-recombination rate, and emitting/absorbing low photon energy. These characteristics of type-II nanostructures can be applied for infrared or gas detection devices, for memory devices and even for novel intermediate band solar cells. In contrast, lattice mismatches of GaSb/GaAs and InSb/GaAs material system are 7.8% and 14.6%, respectively, which need some specific molecular beam epitaxial (MBE) growth conditions for quantum nanostructure formation via Stranski–Krastanov growth mode.

In this paper, the growth of self-assembled GaSb and InSb quantum nanostructures on (001) GaAs substrate by using MBE was reported. The surface morphology of these two quantum nanostructures and their optical properties were characterized by atomic force microscopy and photoluminescence (PL). The experimental results were compared between these two quantum nanostructures. Due to the lattice mismatch in each material system and the difference in sticking coefficient of Ga- and In-atoms during epitaxial growth, we obtain GaSb/GaAs quantum dots (QDs) with a density ∼1010 dots/cm2 and InSb/GaAs QDs with a density of ∼108 dots/cm2. The facet analysis of individual quantum nanostructure in each material system reveals that GaSb/GaAs QD has a dome-like shape with nearly isotropic property while InSb QDs form a rectangular-like shape with elongation along [110]-direction showing a strong anisotropic property.

Low temperature PL spectra from capped GaSb and InSb quantum nanostructures show the energy peaks at 1.08-1.11 and 1.16-1.17 eV, respectively. The variations of PL peaks as a function of both temperature and excitation power are investigated. PL peak shows clear blue shift when excitation power is increased. This work manifests a possibility to use both GaSb and InSb quantum nanostructures for nanoelectronic and nanophotonic applications.

We report the dry etch of GaSb(001) by inductively coupled plasma reactive ion etcher. Silicon Oxide, deposited by PECVD, was used as a mask. The oxide layer proved to be almost unaffected compared to the GaSb, when using chlorine compound gases as etchants (Cl2, BCl3, and SiCl4) as well as argon. This provides high selectivity for GaSb to the mask layer. The sample holder has no silicon that may contribute to the etching process. Etching using Cl2 + Ar showed increase in the etching rate as the chlorine ratio increases; however, the process led to grassy surface and chemical like reaction. The use of SiCl4+Cl2+Ar mixture with low chlorine ratio resulted in anisotropic etch with smooth sides. It has been found for this case that the increase of the chlorine ratio led to an increased etching rate as well. The repeat of previously reported result by Swaminathan et al. [Thin Solid Films 516 (2008) 8712.] yet with a sample holder not having silicon, proved the effect of Si-contribution in producing vertical profile etch with smooth surfaces.

Recent trends in composite research include the development of structural materials with multiple functionalities. In new studies, novel materials are being designed, developed, modified, and implemented into composite designs. Typically, an increase in functionality requires additional material phases within one system. The presence of excessive phases can result in deterioration of individual or overall properties. True multi-functional materials must maintain all properties at or above the minimum operating limit. In this project, samples of Sb-doped SnO2(ATO) sol-gel solutions are used to coat carbon fibers and are heat treated at a temperature range of 200 – 500 °C. Results from this research are used to model the implementation of sol-gel coatings into carbon fiber reinforced multifunctional composite systems. This research presents a novel thermo-responsive sol-gel/ (dopant) combination and evaluation of the actuating responses due to various heat treatment temperatures. While ATO is a well-known transparent conductive material, the implementation of ATO on carbon fibers for infrared thermal reflectivity has not been examined. These coatings serve as actuators capable of reflecting thermal infrared radiation in mid-range and near-range wavelengths (λ). By altering the ATO sol gel thickness and heat treatment temperatures, optimal optical properties are obtained. While scanning electron microscopy (SEM) is used for imaging, electron diffraction spectroscopy (EDS) is used to verify the compounds present in the coatings. Fourier transform infrared (FT-IR) spectroscopy was performed to analyze the reflectivity in the infrared spectra and analyze the crystal structures after heat treatments.

High resolution transmission electron microscopy in combination with geometric phase analysis is used to investigate the interface misfit dislocations, strain relaxation, and dislocation core behavior versus the surface treatment of the GaAs for the heteroepitaxial growth of GaSb. It is pointed out that Sb-rich growth initiation promotes the formation of a high quality network of Lomer misfit dislocations that are more efficient for strain relaxation.

We demonstrate low-resistivity Ohmic contacts for n-Ge with ultra-shallow junction. Using the impurity δ-doping techniques with Ge homoepitaxy on Ge(111) below 400 ºC, we can achieve a very abrupt doping profile within a nanometer-scale width. By introducing the δ-doping to atomically controlled metal/Ge contacts, the current-voltage characteristics clearly show Ohmic conductions owing to the effective tunneling through the Schottky barrier. This approach is promising for a formation technology of ultra-shallow source/drain contacts for scaled Ge devices.

The crystallization kinetics of nano-structured amorphous Ge2Sb2Te5 (GST) regions (20-100 nm in diameter) obtained by Electron Beam Lithography (EBL) and 40 KeV Ge+ 1014/cm2 ion irradiation of crystalline 20 nm thick films was investigated. The amorphous regions, surrounded by crystalline cubic (fcc) or hexagonal (hcp) phase, were recrystallized by isothermal annealing in the temperature range 80°C - 120°C and by focused electron beam irradiation. The process was followed in situ by transmission electron microscope (TEM). The recrystallization is governed by the growth of the surrounding f.c.c. crystalline interface with a velocity of 2×10-2 nm/s at 110°C. The interface velocity is higher in the h.c.p. substrate less than a factor ten. Local focused electron beam irradiation induces instead crystalline nucleation inside the nano amorphous regions. Similar experiments have been performed on planar ion amorphized thin films lying on both GST crystalline phases. In both cases the recrystallization is mainly associated to the movement of the amorphous-crystalline interface. These results indicate that the stability of the amorphous region, generated by ion irradiation, is severely affected by the adjacent crystalline structure and by the size of the amorphous area, critically involved in the scaling of the PCM-based devices.

The crystallization behavior of Ge-Sb phase change materials with variable Ge:Sb ratio X between 0.079 and 4.3 was studied using time-resolved x-ray diffraction, differential scanning calorimetry, x-ray reflectivity, optical reflectivity and resistivity vs. temperature measurements. It was found that the crystallization temperature increases with Ge content from about 130 °C for X = 0.079 to about 450 °C for X = 4.3. For low X, Sb x-ray diffraction peaks occurred during a heating ramp at lower temperature than Ge diffraction peaks. For X = 1.44 and higher, Sb and Ge peaks occurred at the same temperature. Mass density change upon crystallization and optical and electrical contrast between the phases show a maximum for the eutectic alloy with X = 0.17. The large change in materials properties with composition allows tailoring of the crystallization properties for specific application requirements.

The thermoelectric (TE) properties, such as the Seebeck coefficient, the electrical and thermal conductivities, and the output power, of Sb-doped n-type Mg2Si were studied. A commercial polycrystalline source was used for the source material for the Mg2Si. TE elements with Ni electrodes were fabricated by using a monobloc plasma-activated sintering (PAS) technique. Compared with undoped samples, the ZT values of the Sb-doped samples were higher over the whole temperature range in which measurements were made; the maximum value for the Sb doped Mg2Si was 0.72 at 864 K. The TE characteristics of Sb-doped samples were found to be comparable to those of Bi-doped ones, and no significant difference in ZT value was observed between them. Provisional results showed that the maximum value of the output power was 6.75 mW for the undoped sample, 4.55 mW for a 0.5 at% Sb doped sample, and 5.25 mW for a 1 at% Sb doped sample with ΔT = 500 K (between 873 K and 373 K).

We have measured the 121Sb NMR spectra, which are highly sensitive to the electric field gradients at the nuclear site, for crystalline Sb2Te3, Ge1Sb2Te4, Ge2Sb2Te4, and Ge2Sb2Te5. Estimates of the coupling constants, which are a measure of the field gradient, based on these spectra compare well with compounds containing Sb sites that are approximately 6-fold coordinated. The coupling constants of amorphous phase counterparts are roughly an order of magnitude larger and compare favorably with compounds where the Sb sites are 3-fold coordinated. We argue that the difference in the coupling constants arises primarily from a change in the local coordination, as opposed to the slight differences in the Sb-Te bond lengths and bond angles. The NMR data agree best with a structural model of amorphous phase based upon the “8-N” rule.

Phase Change Random Access Memory [PRAM] is one of the candidates for next generation memory due to its non-volatility, high speed, high density and compatibility with Si-based semiconductor process. Ge2Sb2Te5 [GST] thin film, an active layer in this device, is utilized because it has the well-known property of rapid crystallization without phase separation in erasable compact discs industry.

In order to integrate PRAM to beyond 512Mbit, a high writing current and degradation of cell transition at small cell size become a problem. To resolve these problem, Confined Cell structure PRAM was suggested. However, it was difficult to fill GST layer in a small hole with a conventional sputtering tool because a big overhang occurred.

In this work, we prepared GST films on the small hole patterned wafer by a new concept sputtering tool which designed developed a new concept sputtering tool. The structure of GST film was observed with cross section SEM and the film composition was measured with XRF.

It was observed an overhang was suppressed and a GST film was filled in a small hole with a new concept tool. In addition, the uniformity of the GST film composition was good at less than 1% in 200mm φ substrate.

Three different materials crystallizing in the cubic Ir3Ge7 type are under investigation in our group, namely Mo3(Sb,Te)7, Nb3(Sb,Te)7, and Re3(E,As)7 (with E = Si, Ge, Sn). Our electronic structure calculations reveal a band gap to occur at 55 valence-electrons in all three cases, namely Mo3Sb5Te2, Nb3Sb2Te5, and Re3EAs6. Cubic holes exist in these structures that may be filled with small cations such as 3d transition metal atoms. Ni0.06Mo3Sb5.4Te1.6 is a degenerate p-type semiconductor that reaches ZT = 0.96 at 750°C, while Re3Ge0.6As6.4 is a degenerate n- type semiconductor with slightly lower ZT values. Preliminary results indicate that the Re3(Sn,As)7 system may be the most promising of the rhenium arsenides.

We have characterized the in-film stress and the mechanical constants of a growth-dominated phase-change SbTe-alloy, a material beneficially used in the line-cell phase change memory architecture. The influence of the thickness of the films (5-120 nm) and of the substrate used for its deposition (Si, SiO2 and SiC) was studied. The characterizations were carried out on both amorphous and crystalline films. The crystallization temperature was determined by the resistance changes as a function of the temperature. The mechanical characteristics of the films were measured by the wafer curvature method. We observed that the mechanical behavior of these films was strongly dependent on their thicknesses and on the substrate material. For the thinnest amorphous films, the in-film stress was highly compressive (with the largest compressive stress for films on SiC), while it tended to be very low (fully relaxed films) for films thicker than 20 nm. The amorphous films furthermore did not reveal any stress relaxation in time-dependent stress measurements. Therefore, it was not possible to quantify the viscosity of the SbTe-alloy. This result maybe related to a lower defect state in the very thin films used, or to a blocking of the defects by enhanced reactivity of these thin SbTe-alloy films with their surroundings, both resulting in the absence of relaxation in the amorphous state. Finally, the coefficients of thermal expansion (CTE) of the amorphous and crystalline SbTe-alloys were similar, 1–3×10−6 K−1. These values were comparable to the CTE's of the substrates, clearly indicating that for thin films the substrates dominate their thermal expansion behavior.

Sheet resistance (Rs) reductions are presented for antimony and arsenic doped layers produced in strained Si. Results re-emphasise the Rs reduction for As comes purely as a result of mobility improvement whereas for Sb, a superior lowering is observed from improvements in both mobility and activation. For the first time, strain is shown to enhance the activation of dopant atoms whilst Sb is seen to create stable ultra-shallow junctions. Our results propose Sb as a viable alternative to As for the creation of highly activated, low resistance ultra-shallow junctions for use with strain-engineered CMOS devices.

We present analytical models and experimental results to describe low-defect density growth (∼ 6 × 105/cm2) of highly mismatched antimonides on Si and GaAs substrates, with strain relief achieved at the growth interface through periodic, 90° interfacial misfit dislocations (IMF). We use molecular mechanics (MM) based modeling techniques to understand, at the atomic level, the spontaneous formation and energetics of these IMF. We have modeled, grown and characterized two systems extensively, these are - AlSb on Si with ∼ 13% mismatch and GaSb on GaAs with 7.83% lattice mismatch. Growth of these materials by molecular beam epitaxy (MBE) and subsequent High-Resolution Transmission Electron Microscopy (HR-TEM) has indicated that there is no tetragonal distortion in these two systems despite the high lattice mismatch. Instead, the mismatched epi-layers spontaneously form periodic IMF arrays that run along both [110] and [1-10] directions and relieve almost 100% of the strain in a few monolayers of deposition. To model this form of strain relief, we use existing theories of strain relief adapted for very high strain conditions and we also use bond energetics to model the strain-relieving interface. The IMFs in these systems are periodic and so is the deviation in bond lengths and bond angles, which restricts our calculation space to a finite number of elements. We shall also demonstrate extensive growth and characterization results of the materials grown with a particular emphasis on the strain-relieving interface to show excellent agreement of the experimental data with the proposed models. The high quality and low-defect density in AlSb grown on Si, has helped us demonstrate optically pumped IR VCSELs and edge emitters monolithically on Si (001) and this data will also be presented.

Phase Change Random Access Memory [PRAM] is one of the candidate for next generation memory due to its non-volitality, high speed, high density and compatibility with Si-based semiconductor process. Ge2Sb2Te5 [GST] thin film , an active layer in this device, is utilized because it has the well-known property of rapid crystallization without phase separation in erasable compact discs industry.

We investigated the difference of the character of the GST thin film with various sputtering methods. 100nm thick GST films were prepared with DC magnetron sputtering and RF magnetron sputtering for this experiment. XRF, XRD,SEM and four point probe measurement are used to analyze the electrical properties of these films.

As for the composition of the DC sputtered GST films, Te was insufficient from target composition, while the composition of RF sputtered GST films were almost same as target composition. The RF sputtered GST films were composed of hcp by 400°C annealing. On the other hand, the DC sputtered films were mixed-phase of fcc and hcp. The resistivity of DC Sputtered GST films was higher than RF sputtered film cause of poor crystallinity. The uniformity of RF sputtered film was better than DC sputtered film.

We present first principles electronic structure calculations of oxygen substitutional defects in the Sb2Te3 layered crystalline system and a model of amorphous Sb2Te3 using density functional theory (DFT). Our calculated formation energies for oxygen substitutional defects at Sb sites are above 2 eV, so most of our results are on the Sb2Te3-xOx [x = .0074 - .20] system, where one of two inequivalent Te sites are instead occupied by a single oxygen atom with formation energies between -1.2 eV and .2 eV. Defect formation energies for the system show a preference for oxygen atoms on the Te1 site at low concentrations that switches to the Te2 site at high concentrations at approximately 6 atomic percent. In agreement with experiment, we find that oxygen does widen the band gap, even at relatively low concentrations.

The adsorption of Sb on the high index Si (5 5 12) has been studied at higher substrate temperature (HT) (800°C), using in situ surface characterization techniques like Auger Electron Spectroscopy (AES), Low Energy Electron Diffraction (LEED), and Electron Energy Loss Spectroscopy (EELS). The surface morphology of this high index Si (5 5 12) surface has row like trenches along (110) direction. We have performed the study of Sb adsorption and desorption on the Si (5 5 12) substrate held at different temperatures. The different pathways adopted during adsorption and desorption have suggested the dominant role of kinetics I forming various surface phases on the Si (5 5 12) substrate. The adsorption at room temperature resulted in the formation of (225) surface phase, while the adsorption at 680°C resulted in the (337) phase. The sequential thermal desorption of the room temperature and high temperature adsorbed surface resulted in the formation of (337) phases at 800°C, with anisotropic growth along one direction. While the adsorption at 800°C resulted in the formation of anisotropic (337) like phases, the further increase in the coverage formed a 2x Si (225) phase. Annealing this 2x Si (225) phase again resulted in the formation of anisotropic (337) phase. Thus formation of interface by controlling the growth kinetics can result in the formation of various tailored structures with desired properties.