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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Advancing Heteroanionicity in Zintl Phases: Crystal Structures, Thermoelectric and Magnetic Properties of Two Quaternary Semiconducting Arsenide Oxides, Eu 8 Zn 2 As 6 O and Eu 14 Zn 5 As 12 O

Two novel quaternary oxyarsenides, Eu 8 Zn 2 As 6 O and Eu 14 Zn 5 As 12 O, were synthesized through metal flux reactions, and their crystal structures were established by single-crystal X-ray diffraction methods. Eu 8 Zn 2 As 6 O crystallizes in the orthorhombic space group Pbca, featuring polyanionic ribbons composed of corner-shared triangular [ZnAs 3 ] units, running along the [100] direction. The structure of Eu 14 Zn 5 As 12 O crystallizes in the monoclinic space group P2/m and its anionic substructure can be described as an infinite “ribbonlike” chain comprised of [ZnAs 3 ] trigonal-planar units, although the structural complexity here is greater and also amplified by disorder on multiple crystallographic positions. In both structures, the O 2– anion occupies an octahedral void with six neighboring Eu 2+ cations. Formal electron counting, electronic structure calculations, and transport properties reveal the charge-balanced semiconducting nature of these heteroanionic Zintl phases. High-temperature thermoelectric transport properties measurements on Eu 14 Zn 5 As 12 O reveal relatively high resistivity (ρ 500K = 8 Ω·cm) and Seebeck coefficient values (S 500K = 220 μV K –1 ), along with a low concentration and mobility of holes as the dominant charge-carriers (n 500K = 8.0 × 10 17 cm –3 , μ 500K = 6.4 cm 2 /V s). Magnetic studies indicate the presence of divalent Eu 2+ species in Eu 14 Zn 5 As 12 O and complex magnetic ordering, with two transitions observed at T 1 = 21.6 K and T 2 = 9 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Tunable Semiconducting Behavior and Linear-Nonlinear Optical Properties of Ag–Sn Dual-Doped Nanocrystalline CdO Thin Films for Optoelectronics

Semiconductor-based thin films have a great impact on determining the anticipated optoelectronic device construction and the advancement of cutting-edge applications. Herein, Ag and Sn dual-doped nanocrystalline transparent conducting CdO thin films were prepared on glass substrates using a cost-effective spray coating method, and their structural, morphological, optical, and semiconducting behaviors were investigated. The successful incorporation of Ag and Sn resulted in the polycrystalline nature of the deposited films without the additional peaks, as verified by X-ray diffraction (XRD) analysis. The XRD report also revealed the enhanced crystallinity (65%) at the higher doping level (3 wt % Ag and Sn-doped CdO film). All the deposited CdO films exhibited homogeneous, spherical, or round-shaped grains, with agglomeration revealed by scanning electron microscopy analysis. UV–visible spectroscopy was utilized to determine the linear and nonlinear optical properties of the deposited CdO thin films, and a reduction in the band gap from 3.891 to 3.772 eV was observed. A significant enhancement in the first- and third-order nonlinear susceptibility and nonlinear refractive index of the doped CdO films was also observed with increasing doping concentration. Hall effect data were collected at room temperature to investigate the electrical properties of all of the CdO films. The charge carrier concentration of CdO thin films was increased from 142.08 × 10 18 to 169.10 × 10 18 cm –3 , and the highest conductivity was found to be 192 s/cm on doping 3 wt % Ag–Sn. All the CdO thin films exhibited n-type conductivity, while an incredible n-type to p-type charge carrier transition was noticed at a higher doping level (3 wt % Ag–Sn). The findings of the current work are expected to advance the synthesis of semiconductor thin films through cost-effective spray coating methods for optoelectronic device applications.

deposition↗
DOE OSTI2024

Remote-Contact Catalysis for Target-Diameter Semiconducting Carbon Nanotube Arrays

Electrostatic catalysis has been an exciting development in chemical synthesis (beyond enzymes catalysis1 ) in recent years, boosting reaction rates and selectively producing certain reaction products2 . Most of the studies to date have been focused on using external electric field (EEF) to rearrange the charge distribution in small molecule reactions such as Diels-Alder addition3 , carbene reaction4 , etc. However, in order for these EEFs to be effective, a field on the order of 1 V/nm (10 MV/cm) is required, and the direction of the EEF has to be aligned with the reaction axis5 . Such a large and oriented EEF will be challenging for large-scale implementation, or materials growth with multiple reaction axis or steps. Here, we demonstrate that the energy band at the tip of an individual single-walled carbon nanotube6 (SWCNT) can be spontaneously shifted in a high-permittivity growth environment, with its other end in contact with a low-work function electrode (e.g., hafnium carbide or titanium carbide7 ). By adjusting the Fermi level at a point where there is a substantial disparity in the density of states (DOS) between semiconducting (s-) and metallic (m-) SWCNTs8 , we achieve effective electrostatic catalysis for s-SWCNT growth assisted by a weak EEF perturbation (200V/cm). This approach enables the production of high-purity (99.92%) s-SWCNT horizontal arrays with narrow diameter distribution (0.95±0.04 nm), targeting the requirement of advanced SWCNT-based electronics for future computing9-11. These findings highlight the potential of electrostatic catalysis in precise materials growth, especially for s-SWCNTs, and pave the way for the development of advanced SWCNT-based electronics12.

Wang, Jiangtao↗
DOE OSTI2025

Intrinsic Defect-Induced Local Semiconducting-to-Metallic Regions Within Monolayer 1T-TiS2 Displayed by First-Principles Calculations and Scanning Tunneling Microscopy

Using density functional theory (DFT) and scanning tunneling microscopy (STM), the intrinsic point defects, formation energy, and electronic structure of 1T-TiS2 were investigated. Defect systems include single-atom vacancies, interstitial and adatom additions, and direct atomic substitution. Using a collective approach for analyzing realistic systems for point defect investigation, we provide a more straightforward comparison to the experimental measurements, reproducing more realistic environmental conditions related to thin film growth. STM images are compared to computationally simulated electron density images to identify specific geometries that result from favorable point defects. DFT suggests that titanium interstitials are the most energetically favorable intrinsic defect, and sulfur vacancies are more likely to form than titanium vacancies within this realistic analysis, which is in agreement with STM data. A pristine, stoichiometric monolayer system is calculated to have a direct band gap of 0.422 eV, which varies based on local point defects. Local semiconducting-to-metallic electronic transitions are predicted to occur based on the presence of Ti interstitials.

Keeney, P. J.↗
NASA NTRS1981

Photoproduction of I2, Br2, and Cl2 on n-semiconducting powder

The photosynthetic production of Br2 and Cl2 and the photocatalytic production of I2 from aqueous solutions of the respective halide ions in the presence of platinized semiconducting n-TiO2 powder are reported. Reactions were produced in 2-3 M oxygen-saturated aqueous solutions of KI, KBr or NaCl containing Pt-TiO2 powder which were irradiated by a high-pressure mercury lamp at a power of 400 mW/sq cm. Halogens are found to be produced in greater quantities when platinized TiO2 powders are used rather than pure TiO2, and rates of halogen production are observed to increase from Cl2 to Br2 to I2. The presence of the synthetic reactions producing Br2 and Cl2 with a net influx of energy indicates that an effective separation of the photoproduced electron-hole pair occurs in the semiconductor. Quantum efficiencies of the reaction, which increase with decreasing solution pH, are found to be as high as 30%, implying a solar-to-chemical energy conversion efficiency between 0.03% and 3% for the case of chlorine production. It is concluded that the photoproduction of halogens may be of practical value if product halogens are efficiently removed from the reaction cell.

Reichman, B.↗
NASA NTRS1982

Investigation of compositional segregation during unidirectional solidification of solid solution semiconducting alloys

Compositional segregation of solid solution semiconducting alloys in the radial direction during unidirectional solidification was investigated by calculating the effect of a curved solid liquid interface on solute concentration at the interface on the solid. The formulation is similar to that given by Coriell, Boisvert, Rehm, and Sekerka except that a more realistic cylindrical coordinate system which is moving with the interface is used. Analytical results were obtained for very small and very large values of beta with beta = VR/D, where V is the velocity of solidification, R the radius of the specimen, and D the diffusivity of solute in the liquid. For both very small and very large beta, the solute concentration at the interface in the solid C(si) approaches C(o) (original solute concentration) i.e., the deviation is minimal. The maximum deviation of C(si) from C(o) occurs for some intermediate value of beta.

Wang, J. C.↗
NASA NTRS1984

Solidification and crystal growth of solid solution semiconducting alloys

Problems associated with the solidification and crytal growth of solid-solution semiconducting alloy crystals in a terrestrial environment are described. A detailed description is given of the results for the growth of mercury cadmium telluride (HgCdTe) alloy crystals by directional solidification, because of their considerable technological importance. A series of HgCdTe alloy crystals are grown from pseudobinary melts by a vertical Bridgman method using a wide range of growth rates and thermal conditions. Precision measurements are performed to establish compositional profiles for the crystals. The compositional variations are related to compositional variations in the melts that can result from two-dimensional diffusion or density gradient driven flow effects ahead of the growth interface. These effects are discussed in terms of the alloy phase equilibrium properties, the recent high temperature thermophysical data for the alloys and the highly unusual heat transfer characteristics of the alloy/ampule/furnace system that may readily lead to double diffusive convective flows in a gravitational environment.

Lehoczky, S. L.↗
NASA NTRS1989

Narrow bandgap semiconducting silicides: Intrinsic infrared detectors on a silicon chip

Polycrystalline thin films of CrSi2, LaSi2, and ReSi2 were grown on silicon substrates. Normal incidence optical transmittance and reflectance measurements were made as a function of wavelength. It was demonstrated that LaSi2 is a metallic conductor, but that CrSi2 and ReSi2 are, in fact, narrow bandgap semiconductors. For CrSi2, the complex index of refraction was determined by computer analysis of the optical data. From the imaginary part, the optical absorption coefficient was determined as a function of photon energy. It was shown that CrSi2 possesses an indirect forbidden energy gap of slightly less than 0.31 eV, and yet it is a very strong absorber of light above the absorption edge. On the other hand, the ReSi2 films exhibit an absorption edge in the vicinity of 0.2 eV. Measurements of the thermal activation energy of resistivity for ReSi2 indicate a bandgap of 0.18 eV. It is concluded that the semiconducting silicides merit further investigation for development as new silicon-compatible infrared detector materials.

Mahan, John E.↗
NASA NTRS1992

The effect of induced charges on low-energy particle trajectories near conducting and semiconducting plates

The effect of the induced charge was found on particles less than 1 eV as they passed through simulated parallel, grounded channels that are comparable in dimension to those that are presently in space plasma instruments which measure the flux of low-energy ions. Applications were made to both conducting and semiconducting channels that ranged in length from 0.1 to 50 mm and in aspect ratio from 1 to 100. The effect of the induced charge on particle trajectories from simple straight lines. Several configurations of channel aspect ratio and detector locations are considered. The effect is important only at very low energies with small dimensions.

Coffey, Victoria N.↗
NASA NTRS1993

Ultraviolet optical absorptions of semiconducting copper phosphate glasses

Results are presented of a quantitative investigation of the change in UV optical absorption in semiconducting copper phosphate glasses with batch compositions of 40, 50, and 55 percent CuO, as a function of the Cu(2+)/Cu(total) ratio in the glasses for each glass composition. It was found that optical energy gap, E(opt), of copper phosphate glass is a function of both glass composition and Cu(2+)/Cu(total) ratio in the glass. E(opt) increases as the CuO content for fixed Cu(2+)/Cu(total) ratio and the Cu(2+)/Cu(total) ratio for fixed glass composition are reduced.

Bae, Byeong-Soo↗
NASA NTRS1996

Effect of melt-solid interface shape on lateral compositional distribution of unidirectionally solidified 2-6 semiconducting alloys

A computer code developed previously has been used to simulate lateral compositional distributions for several 2-6 semiconducting systems. The code is based on analytical results obtained previously. The system under study is an azimuthal symmetric cylindrical system with a curved melt-solid interface shape during an unidirectional solidification process. It is assumed that the system is under a steady state diffusion limited growth condition.

Wang, Jai-Ching↗
NASA NTRS1998

Doping Scheme of Semiconducting Atomic Chains

Atomic chains, precise structures of atomic scale created on an atomically regulated substrate surface, are candidates for future electronics. A doping scheme for intrinsic semiconducting Mg chains is considered. In order to suppress the unwanted Anderson localization and minimize the deformation of the original band shape, atomic modulation doping is considered, which is to place dopant atoms beside the chain periodically. Group I atoms are donors, and group VI or VII atoms are acceptors. As long as the lattice constant is long so that the s-p band crossing has not occurred, whether dopant atoms behave as donors or acceptors is closely related to the energy level alignment of isolated atomic levels. Band structures are calculated for Br-doped (p-type) and Cs-doped (n-type) Mg chains using the tight-binding theory with universal parameters, and it is shown that the band deformation is minimized and only the Fermi energy position is modified.

Toshishige, Yamada↗
NASA NTRS2002

Transient Torque Technique for Viscosity and Electrical Conductivity Determination of Semiconducting Liquids

A novel apparatus based on transient torque technique is constructed in MSFC/NASA. The apparatus uses a 125um diameter quartz fiber as torsion wire. A high sensitive angular detector is implemented to measure the deflection angle of the crucible containing the liquid. A rotating magnetic field (RMF) is used to induce a rotating flow of a conducting or semiconducting melts. By measuring the magnitude and transient behavior of the induced deflection angle, the electrical conductivity and viscosity of the melt can be measured simultaneously. High purity elements namely Hg, Ga, Zn and Te are tested at room temperature and high temperature up to 900 C.

Li, C.↗
NASA NTRS2003

Modeling of Schottky Barrier Modulation due to Oxidation at Metallic Electrode and Semiconducting Carbon Nanotube Junction

A model is proposed for the previously reported lower Schottky barrier for holes PHI (sub bH) in air than in vacuum at a metallic electrode - semiconducting carbon nanotube (CNT) junction. We assume that there is a transition region between the electrode and the CNT, and an appreciable potential can drop there. The role of the oxidation is to increase this potential drop with negatively charged oxygen molecules on the CNT, leading to lower PHI(sub Bh) after oxidation. The mechanism prevails in both p- and n-CNTs, and the model consistently explains the key experimental findings.

Yamada, Toshishige↗