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At least 1,261 records · Page 70

A Permanently Porous Chalcogen-Bonded Organic Framework

The nature of connectivity between constituent atomic or molecular building blocks is fundamental in shaping the properties and functionality of materials. The extrapolation of emergent interatomic interactions to enable functional materials has driven transformative technological advancements. However, the bonding interactions used in material design have been largely static since the emergence of dynamic covalent chemistry ~30 years ago. Here we demonstrate that non-covalent chalcogen bonding (Ch-bonding) is a distinct mode of interatomic connectivity for constructing functional materials by design. This is established by leveraging self-complementary assembly of 1,2,5-telluradiazole moieties to construct a honeycomb-type permanently porous Ch-bonded organic framework, assembled and stabilized solely through non-covalent Te...N contacts. Empirical and computational studies of electronic structure, structural healing and lattice dynamics highlight the pi-type electronic communication, controlled assembly and modulated lattice dynamics in Trip3Tez-I arising directly from the unique nature of the Te...N Ch-bonding that holds substantial implications for next generation crystalline semiconductors. In addition to introducing a distinct class of permanently porous frameworks, this work establishes Ch-bonding as a programmable molecular tool for constructing functional materials with distinct properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mn-induced spin glass behavior in metallic Ir 3 Sn 7-x Mn x

Transition metal stannides are usually semiconductors with a narrow band gap. We report experimental investigation on metallic Ir 3 Sn 7– x Mn x ( x = 0 and 0.56). Single crystal x-ray diffraction refinement indicates that Ir 3 Sn 7– x Mn x crystals form a cubic structure (space group Im 3 - m ) with the lattice parameter a = 9.362(4) Å for x = 0 and 9.328(6) Å for x = 0.56. The electrical resistivity shows metallic behavior between 2 K and 300 K with T 2 dependence at T < 30 K for x = 0, reflecting the Fermi-liquid ground state. While Ir 3 Sn 7 exhibits weak diamagnetism, partial substitution of Sn by Mn results in spin glass behavior in Ir 3 Sn 7- x Mn x below T g ~ 13 K for x = 0.56. Remarkably, an upturn in the resistivity is observed in x = 0.56 below ~2 T g , suggesting strong spin fluctuation. This fluctuation is suppressed by the application of magnetic field, which is reflected in the observation of negative magnetoresistance. The unusual properties that emerge due to Mn doping are discussed.

Physics↗

Investigation of the cesium activation of Ga⁢N photocathodes by low-energy electron microscopy

Low-energy electron microscopy (LEEM) was performed on p-Ga⁢N samples during in situ cesium deposition. LEEM images of electron reflectivity recorded as a function of the incident electron energy at different Cs coverages allowed to spatially resolve the evolution of the local work function (WF) during the activation process. While the average WF drops by more than 3 eV, the local WF remains quite uniform across the surface throughout the activation process. Maximum fluctuations of less than 0.2 eV were observed in the WF maps for Cs coverage of a fraction of a monolayer. These fluctuations are mainly related to the surface topography, in particular, to the atomic steps’ structure, which replicates the substrate miscut. Apart from these weak spatial fluctuations, no Cs clusters that would induce strong local WF contrast were observed at the scale of the 20-nm resolution of the measurements. These observations agree with the simple model of semiconductor activation to negative electron affinity that describes the formation of a dipole layer as responsible for the lowering of the WF. Additionally, at complete Cs coverage, the WF becomes fully homogeneous over the surface, smoothing out features originating from defects and topography.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hydrogen Transport from Dielectrics to poly-Si/SiOx Passivating Contacts Measured by Mass Spectrometry and Vibrational Spectroscopy

We demonstrate the relationship between Si solar cell passivation and hydrogen content of various passivating films, including hydrogenated amorphous silicon (a-Si:H), aluminum oxide (Al2O3), silicon nitride (SiNx) and combinations thereof. Through isotopic studies using quadrupole mass spectrometry (QMS), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, we determine how hydrogen content and stability within each type of film relates to final passivation quality of solar cell test structures. Si solar cells using polycrystalline silicon on silicon oxide (poly-Si/SiOx) passivating contacts are at the forefront of Si solar cell research and emerging as top performers within industrial production. Performance of passivating contact Si solar cells is largely determined by a parameter known as the open-circuit voltage Voc, which directly relates to material quality within the bulk of the device and at surfaces. High Voc is achieved when defects within the bulk crystalline silicon (c-Si) and at interfaces are passivated, preventing them from acting as charge carrier recombination centers. One of the most important means of passivating defects within Si solar cells is via hydrogenation, injecting the cells with large amounts of H to satisfy dangling bonds in the bulk and at interfaces. Hydrogen is especially important in deactivating a prevalent defect in industrial p-type devices which leads to decreased device performance over long-term exposure to light, called light-induced degradation (LID). Some of the most common materials used to supply H to devices are a-Si:H, Al2O3, and SiNx, which can contain very large amounts of H. Upon annealing at elevated temperatures, the hydrogen becomes mobile enough to find and disable defect sites. However, too much hydrogen can also be problematic, sometimes leading to an effect called light and elevated temperature induced degradation (LeTID). It has been shown that these films passivate the interfaces of poly-Si passivating contacts differently, leading to differing performance. Though Al2O3 is a well-defined dielectric material, SiNx can have many different values of x depending on precursor gases and deposition conditions. We observe different FTIR and Raman spectra from different SiNx over a range of x values films to determine the bonding environments within them and further correlate the relative concentrations of Si, N, and H to the stability of H within SiNx and the passivation performance of each film. Because deuterium is chemically identical to hydrogen within these systems, but gives different signals in FTIR and Raman spectroscopy as well as in QMS, isotopic substitution can be used as an excellent tool to probe the H within films. In addition to measuring the H and D bonding within films using FTIR and Raman spectroscopy, we will use such isotopic experiments to observe H and D movement out of these hydrogenating films at elevated temperatures using QMS to determine the stability of H bonding within such systems. With these films characterized based on elemental composition, we will relate such measurements to passivation quality of these films and combinations thereof on poly-Si/SiOx contact structures using quasi-steady state photoconductance decay measurements to obtain implied open-circuit voltage (iVoc) and saturation current density J0 values. Such investigations into the performance of different passivating films and film stacks will lead to greater understanding of dielectrics in semiconductor devices, further improvements in passivated contact design, and eventually, greater proliferation of renewable solar energy worldwide.

Al2O3↗

Observation of Single-Electron Transport and Charging on Individual Point Defects in Atomically Thin WSe 2

Defects significantly impact the properties of 2D semiconductors, providing in-gap quantum states that can serve as a natural platform for single-electron operations, localization sites for excitons to serve as single-photon sources, and potentially quantum spin memories. To date, however, a microscopic observation of such a single-electron transport (SET) behavior has been rarely reported on single defects of 2D semiconductors. In this study, we report a SET and charge-state transition on individual point-defect states buried in the bilayer WSe 2 using scanning tunneling microscopy. SET characteristics of their states is evidenced by both the Coulomb staircase and the saturation behavior of the transport current, consistent with the SET model. Furthermore, we demonstrate that, through the local field of a scanning tunneling microscope tip, it is possible to successively charge the defects by single electrons, suggested by both the ring structures and charging peaks in dI/dV measurements. Our results provide new insights into the quantum nature of these defect-bound states, as well as the possibility of using their single-electron behavior and response for applications in quantum information and local-field sensing.

2D semiconductor↗

Characterization of Semiconductor Materials Using AOTF Instruments

A non-invasive characterization of silicon-on-insulator (SOI) wafers using white light interference measured by an AOTF polarimetric hyperspectral imaging instrument will be presented an an illustration of the technology potential. Experiments provided high resolution thickness maps of both silicon and oxide layers with accuracy and observed optically active imperfections and distributions in the structure.

polarimetric hyperspectral imaging silicon oxide↗

Complementary MOS transistors.

MOS transistor structures with enhancement mode of operation, discussing fabrication processes via V-C characteristics, temperature effects on performance, etc

CRYSTAL GROWTH↗

Polaronic Conductivity in Cr 2 Ge 2 Te 6 Single Crystals

We report that intrinsic 2D ferromagnetic semiconductors are an important class of materials for spin-charge conversion applications. Cr 2 Ge 2 Te 6 retains long-range magnetic order in the bilayer at cryogenic temperatures and shows complex magnetic interactions with considerable magnetic anisotropy. Here, a series of structural, magnetic, X-ray scattering, electronic, thermal transport and first-principles calculation studies are performed, which reveal that localized electronic charge carriers in Cr 2 Ge 2 Te 6 are dressed by the surrounding lattice and are involved in polaronic transport via hopping that is observed via magnetocrystalline anisotropy. This opens the possibility for manipulation of charge transport in Cr 2 Ge 2 Te 6 —based devices by electron–phonon- and spin–orbit coupling-based tailoring of polaron properties.

2D materials↗

Control of polarization in bulk ferroelectrics by mechanical dislocation imprint

Defects are essential to engineering the properties of functional materials ranging from semiconductors and superconductors to ferroics. Whereas point defects have been widely exploited, dislocations are commonly viewed as problematic for functional materials and not as a microstructural tool. In this work, we developed a method for mechanically imprinting dislocation networks that favorably skew the domain structure in bulk ferroelectrics and thereby tame the large switching polarization and make it available for functional harvesting. The resulting microstructure yields a strong mechanical restoring force to revert electric field–induced domain wall displacement on the macroscopic level and high pinning force on the local level. This induces a giant increase of the dielectric and electromechanical response at intermediate electric fields in barium titanate [electric field–dependent permittivity (ε 33 ) ≈ 5800 and large-signal piezoelectric coefficient ( d 33 *) ≈ 1890 picometers/volt]. Dislocation-based anisotropy delivers a different suite of tools with which to tailor functional materials.

36 MATERIALS SCIENCE↗

Thermoelectric properties of Nb3SbxTe7-x compounds

Niobium antimony telluride, Nb3Sbx,Te7-x, was synthesized and tested for thermoelectric properties in the Thermoelectrics group at the Jet Propulsion Laboratory. The forty atoms per unit cell of Nb3Sb2Te5 and its varied mixture of atoms yield acomplicated structure, suggesting that Nb3Sb2Te5 and related compounds may exhibit low thermal conductivity and hence a higher ZT value. Nb3SbxTe7-x, compounds were synthesized and subsequently analyzed for their Seebeck voltage, heat conduction, and electrical resistivity. Results indicate that Nb3Sb2Te5 is a heavily doped semiconductor whose thermoelectric properties are compromised by compensating n-type and p-type carriers. Attempts to dope in favor of either carrier by varying the Sb:Te ratio yielded samples containing secondary metallic phases that dominated the transport properties of the resulting compounds.

thermoelectric power generation segmented↗

Inorganic Halide Perovskitoid TlPbI 3 for Ionizing Radiation Detection

Room temperature semiconductor detector (RTSD) materials for γ-ray and X-ray radiation are in great demand for the nonproliferation of nuclear materials as well as for biomedical imaging applications. Halide perovskites have attracted great attention as emerging and promising RTSD materials. In this contribution, the material synthesis, purification, crystal growth, crystal structure, photoluminescence properties, ionizing radiation detection performance, and electronic structure of the inorganic halide perovskitoid compound TlPbI 3 are reported on. This compound crystallizes in the ABX 3 non-perovskite crystal structure with a high density of d = 6.488 g·cm –3 , has a wide bandgap of 2.25 eV, and melts congruently at a low temperature of 360 °C without phase transitions, which allows for facile growth of high quality crystals with few thermally-activated defects. High-quality TlPbI 3 single crystals of centimeter-size are grown using the vertical Bridgman method using purified raw materials. A high electrical resistivity of ≈10 12 Ω·cm is readily obtainable, and detectors made of TlPbI 3 single crystals are highly photoresponsive to Ag K α X-rays (22.4 keV), and detects 122 keV γ-rays from 57 Co radiation source. The electron mobility-lifetime product µ e τ e was estimated at 1.8 × 10 –5 cm 2 ·V –1 . A high relative static dielectric constant of 35.0 indicates strong capability in screening carrier scattering and charged defects in TlPbI 3 .

36 MATERIALS SCIENCE↗

Studying the Recrystallization of Cu(InGa)Se 2 Semiconductor Thin Films by Silver Bromide In-situ Treatment

Cu(In,Ga)Se 2 samples were fabricated using a 3-stage thermal co-evaporation process on molybdenum back contact at low temperature. The process of recrystallization was carried out in between the 2 nd and 3 rd stages by flashing 25 mg of AgBr for 2 minutes. A change in morphological structure was observed as small grains transformed into large grains, as confirmed by XRD and SEM measurements. The decrease of the Ga gradient, seen in the SIMS depth profile, suggests Ga interdiffusion due to AgBr treatment. Altogether, the AgBr treatment contributes to a general improvement in device performance as compared to the as-deposited devices.

14 SOLAR ENERGY↗

Tunable Broad Light Emission from 3D “Hollow” Bromide Perovskites through Defect Engineering

We report hybrid halide perovskites consisting of corner-sharing metal halide octahedra and small cuboctahedral cages filled with counter cations have proven to be prominent candidates for many high-performance optoelectronic devices. The stability limits of their three-dimensional perovskite framework are defined by the size range of the cations present in the cages of the structure. In some cases, the stability of the perovskite-type structure can be extended even when the counterions violate the size and shape requirements, as is the case in the so-called "hollow" perovskites. In this work, we engineered a new family of 3D highly defective yet crystalline "hollow" bromide perovskites with general formula (FA) 1-x (en) x (Pb) 1-0.7x (Br) 3-0.4x (FA = formamidinium (FA + ), en = ethylenediammonium (en 2+ ), x = 0-0.44). Pair distribution function analysis shed light on the local structural coherence, revealing a wide distribution of Pb-Pb distances in the crystal structure as a consequence of the Pb/Br-deficient nature and en inclusion in the lattice. By manipulating the number of Pb/Br vacancies, we finely tune the optical properties of the pristine FAPbBr 3 by blue shifting the band gap from 2.20 to 2.60 eV for the x = 0.42 en sample. A most unexpected outcome was that at x > 0.33 en incorporation, the material exhibits strong broad light emission (1% photoluminescence quantum yield (PLQY)) that is maintained after exposure to air for more than a year. This is the first example of strong broad light emission from a 3D hybrid halide perovskite, demonstrating that meticulous defect engineering is an excellent tool for customizing the optical properties of these semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strong Magnetocrystalline Anisotropy Arising from Metal–Ligand Covalency in a Metal–Organic Candidate for 2D Magnetic Order

Layered metal–organic frameworks are promising candidates for new two-dimensional magnets, as their synthetic programmability of these materials can provide a route to diverse structural and electronic properties. However, such framework materials typically lack the heavy elements that engender magnetocrystalline anisotropy in the monolayer ferromagnets reported to date. Alternative sources of magnetic anisotropy are therefore needed in these materials. Here, we report the synthesis of single crystals of the framework material (NMe 4 ) 2 [Fe 2 L 3 ] (H 2 L = 3,6-dichloro-2,5-dihydroxybenzoquinone) and evaluate the angular dependence of its magnetic properties. Oriented-crystal magnetization measurements reveal strong uniaxial anisotropy, where the easy axis is aligned with the crystallographic c axis. While the spin carriers of this structure are isotropic $S = ^5/_2$ Fe III metal centers and $S = ^1/_2$ organic linkers, the anisotropy energy of the framework material is comparable to that of reported 2D ferromagnets. Density functional theory calculations indicate that the observed magnetocrystalline anisotropy arises from ligand-to-metal charge transfer that enhances the magnetic anisotropy of the otherwise isotropic Fe centers, suggesting that metal–ligand covalency can be utilized as a general additive for the development of 2D magnets. These results in this study show the possibility for (NMe 4 ) 2 [Fe 2 L 3 ] to retain magnetic order down to the 2D monolayer limit. In addition, the combination of large magnetic anisotropy and semiconducting character in (NMe 4 ) 2 [Fe 2 L 3 ] highlights its potential as a new 2D magnetic semiconductor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Change of Electrical and Transport Properties of Nickel Oxide by Carrier Concentration and Temperature through First-Principle Calculations

Abstract Nickel is typically used as one of the main components in electrical contact devices or connectors. Nickel oxide (NiO) is usually formed on the surfaces of electrodes and can negatively impact system performance by introducing electrical contact resistance. The thermal, electrical, and transport properties of NiO, as a Mott insulator or a p-type semiconductor, can be altered by operating and environmental conditions such as temperature and stress/strain by contact. In this study, we investigate the fundamental material properties of NiO through the first-principle calculations. First, we obtain and compare the lattice parameter, magnetic moment, and electronic structure for NiO via the WIEN2K simulations with four different potentials (i.e., GGA, GGA + U, LSDA, and LSDA + U). Then, using the WIEN2K simulation results with LSDA + U potential that produces a highly accurate bandgap for NiO, we calculate the electrical conductivity and electrical part of the thermal conductivity of nickel and NiO as a function of temperature and carrier concentration through the BoltzTraP simulations. Systematic simulation results revealed that the electrical conductivity relative to the relaxation time for NiO increases with the carrier concentration, while it shows a slightly decreasing trend with temperature under a fixed carrier concentration. By contrast, the electrical part of the thermal conductivity shows an increasing trend considering carrier concentration and temperature.

Shah, Nayem Md. Reza↗

Excited State Properties of Point Defects in Semiconductors and Insulators Investigated with Time-Dependent Density Functional Theory

Here, we present a formulation of spin-conserving and spin-flip hybrid time-dependent density functional theory (TDDFT), including the calculation of analytical forces, which allows for efficient calculations of excited state properties of solid-state systems with hundreds to thousands of atoms. We discuss an implementation on both GPU- and CPU-based architectures along with several acceleration techniques. We then apply our formulation to the study of several point defects in semiconductors and insulators, specifically the negatively charged nitrogen-vacancy and neutral silicon-vacancy centers in diamond, the neutral divacancy center in 4H silicon carbide, and the neutral oxygen-vacancy center in magnesium oxide. Our results highlight the importance of taking into account structural relaxations in excited states in order to interpret and predict optical absorption and emission mechanisms in spin defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FA x Cs 1–x PbI 3 Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition

Nanoscale semiconductors show remarkably tunable properties. For metal halide perovskite (MHP) nanocrystals (NCs), surface energy and lattice strain stabilize desirable MHP compositions and crystallographic phases that are unstable in the bulk. We report an X-ray scattering study of the average room-temperature crystal structure of ~15 nm FA x Cs 1–x PbI 3 (FA = formamidinium) NCs. All compositions crystallize in the perovskite structure; however, the average structure lowers in symmetry from the a (cubic) to ß (tetragonal) to γ (orthorhombic) perovskite phases with decreasing x (Cs addition). The corresponding a- to ß- and ß- to γ-phase transitions occur between x = 0.75–0.5 and x = 0.25–0.1, respectively. Furthermore, structural refinements also indicate large octahedral tilt angles (10–30°) in the ß- and γ-phases and an increase in (pseudo)cubic unit cell volume upon FA addition. This work establishes the composition–structure relationship for FA x Cs 1–x PbI 3 NCs and demonstrates the ability to target average crystal symmetry with facile synthetic control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boron Nitride Solid-State Neutron Detectors

The goal of this project is to build upon the work performed under the Texas Tech IDEAS project (DE-AR0000964 monitored by Dr. Isik Kizilyalli) to bring the developed B-10 enriched hexagonal boron nitride (h- 10 BN or 10 BN or BN) semiconductor neutron detector technology to the next level of maturity. In comparison to He-3 ( 3 He) gas detectors, BN neutron detectors possess all the intrinsic advantages of semiconductor devices: light weight, compact size, fast response speed, high spatial resolution, high temperature and low voltage operation capability, ease of mass production via existing semiconductor infrastructures, low cost of operation and maintenance, flexible form factors, and durability. The project will develop a prototype h- 10 BN neutron detector as a potential replacement for the 3 He gas neutron detectors (LND 25185 or equivalent) used in various neutron survey meters currently produced and commercialized by Ludlum Measurements, Inc. (LMI). To increase the overall detection efficiency, it is essential to maximize the collection efficiency of charge carriers (electrons and holes) generated by the nuclear reaction, which demands a further push to achieve 10 BN epilayers with improved material quality. The material growth processes will be guided by characterization of structural, optical, and electrical properties of h-BN. Selective devices will be calibrated at LMI. During ARPA-E supporting period, the key material parameters of h-BN produced by metal organic chemical vapor deposition (MOCVD), including the layer thickness, mobility-lifetime product, surface recombination field and detector size for maintaining a high charge collection efficiency all have been improved by several orders of magnitude. These improvements have enabled the realization of high-performance h 10BN semiconductor thermal neutron detectors. Presently, h- 10 BN thermal neutron detectors developed under ARPA-E’s support hold the record high detection efficiency among all solid-state detectors at 59%. With further development in manufacturing, there is no question that h-BN detectors will replace the traditional He-3 gas detectors in certain application areas by offering obvious advantages of semiconductor technologies over gas detectors and opportunities for users to dedicate the scarce and expensive supply of He-3 gas to other application areas where substitutes of He-3 gas are not possible.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗