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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

XRD and SEM/EDS characterization of two quaternary fuel alloys (U-2.5Mo-2.5Ti-5.0Zr and U-1.5Mo-1.5Ti-7.0Zr in wt. %) for fast reactors

The current study focuses on characterization of two potential fuel alloys for sodium-cooled fast reactors: U-2.5Mo-2.5Ti-5.0Zr (U-MT5Z) and U-1.5Mo-1.5Ti-7.0Zr (U-MT7Z) in wt. %. As-cast alloys and annealed (600°C, 500h) alloys are studied by X-ray powder diffraction (XRD) for their bulk structures, and scanning electron microscopy / energy dispersive X-Ray spectroscopy (SEM/EDS) for their microstructures and phase constituents. For as-cast alloys, the XRD results show that U-MT5Z mainly contains γ, while U-MT7Z alloy contains a. In both alloys, there are three phases indicated by EDS, a U-rich phase, secondary phase, and Zr-rich phase. Further, the elemental compositions varied in different phases and in different alloys. After annealing, both alloys exhibit the structures of α-U and U 2 Ti according to XRD. The EDS results suggest there are five phases found in both alloys.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Challenges in computationally designing high temperature Fe-based austenitic alloys: Addressing the role of Ni additions

Alumina-forming austenitic (AFA) alloys are relatively inexpensive high performance materials which combine the creep resistance of low-cost austenitic alloys and the oxidation resistance of expensive alumina forming alloys. However, a fundamental understanding of the role of key alloying elements such as Ni, Cr, Al, Nb, Ti, V, B and C in the experimentally observed oxidation behavior of these alloys is still lacking. The present work is a first in a series of studies aiming to quantitatively describe the role of Ni in promoting or disrupting protective Al 2 O 3 scale formation on AFA alloys. Here, ternary Fe-Al-xNi model alloys with three different Ni contents were isothermally exposed in an atmosphere with a low partial pressure of oxygen between 800–1000 °C for 24 h to evaluate the role of Ni in the observed internal oxidation behavior. Increasing Ni contents had no impact on the internal oxidation behavior of the alloys. The experimental and theoretical analyses in the present work suggested a negligible effect of the internal oxide precipitates on the inward diffusion of oxygen, typically expected in these systems, while simultaneously highlighting the barriers in the development of reliable models for computation-assisted design of these alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Chemical short-range order in derivative Cr–Ta–Ti–V–W high entropy alloys from the first-principles thermodynamic study

The development of high-entropy alloys (HEAs) focuses on exploring compositional regions in multi-component systems with all alloy elements in equal or near-equal atomic concentrations. Initially it was based on the main idea that high mixing configurational entropy contributions to the alloy free energy could promote the formation of a single solid solution phase. By using the ab-initio based Cluster Expansion (CE) Hamiltonian model constructed for the quinary bcc Cr–Ta–Ti–V–W system in combination with Monte Carlo (MC) simulations, we show that the phase stability and chemical short-range order (SRO) of the equiatomic quinary and five sub-quaternary systems, as well as their derivative alloys, can dramatically change the order–disorder transition temperatures (ODTT) as a function of alloy compositions. In particular, it has been found, that the equiatomic quaternary Ta–Ti–V–W and Cr–Ta–Ti–W alloys had the lowest order–disorder transition temperature (500 K) among all the analysed equiatomic compositions. In all investigated alloy systems, the strongest chemical ordering has been observed between Cr and V, which led to the conclusion that decreasing the concentration of either Cr or V might be beneficial in terms of decreasing the ODTT. It also predicts that increasing concentration of Ti significantly decreases the ODTT. Our analysis of chemical SRO as a function of alloy composition allows to understand the microstructure evolution of HEAs as a function of temperature in excellent agreement with available experimental observations. Importantly, our free energy of mixing and SRO calculations predict that the origin of precipitates formed by Cr- and V-rich in the sub-quaternary Cr–Ta–V–W system is driven by the thermodynamics. The modelling results are in an excellent agreement with experimental observation of Cr and V segregation in the W 0.38 Ta 0.36 Cr 0.15 V 0.11 alloy which in turns shows an exceptional radiation resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structural trends in the dehydrogenation selectivity of palladium alloys

Alloying is well-known to improve the dehydrogenation selectivity of pure metals, but there remains considerable debate about the structural and electronic features of alloy surfaces that give rise to this behavior. To provide molecular-level insights into these effects, a series of Pd intermetallic alloy catalysts with Zn, Ga, In, Fe and Mn promoter elements was synthesized, and the structures were determined using in situ X-ray absorption spectroscopy (XAS) and synchrotron X-ray diffraction (XRD). The alloys all showed propane dehydrogenation turnover rates 5–8 times higher than monometallic Pd and selectivity to propylene of over 90%. Moreover, among the synthesized alloys, Pd 3 M alloy structures were less olefin selective than PdM alloys which were, in turn, almost 100% selective to propylene. This selectivity improvement was interpreted by changes in the DFT-calculated binding energies and activation energies for C–C and C–H bond activation, which are ultimately influenced by perturbation of the most stable adsorption site and changes to the d-band density of states. Furthermore, transition state analysis showed that the C–C bond breaking reactions require 4-fold ensemble sites, which are suggested to be required for non-selective, alkane hydrogenolysis reactions. These sites, which are not present on alloys with PdM structures, could be formed in the Pd 3 M alloy through substitution of one M atom with Pd, and this effect is suggested to be partially responsible for their slightly lower selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electronic and catalytic engineering in two-dimensional vdW metal–organic frameworks through alloying

Bimetallic metal-organic framework (MOF s ) alloys, in which heterogeneous metal clusters are incorporated into their backbone, are capable of highly selective separations and catalysis. Due to limitations in our fundamental understanding of their alloying, however, established methods result in phase-separated or amorphous two-dimensional (2D) MOF s or lack precise control over alloy ratios. Here, our results demonstrate 2D MOF alloys where metal cation ratios (M 1 and M 2 ) in M 1 xM 2 1-x BDC (M 1 or M 2 = Zn, Cu, Ni, Co, Fe, Mn) can be engineered on demand by controlling the metal salt dissociation constants. Resulting MOF alloys exhibit a highly 2D nature with excellent crystallinity and minute control over metal cation ratios. Overall, our experimental and theoretical results show that their electronic bandgaps and photoexcited carrier lifetimes can be engineered by metal cation alloying. Interestingly, 2D alloyed MOF s enable high-efficiency photo-catalytic water reduction performance in Co/Ni MOF alloys owing to the spatially separated metal clusters in 2D MOF alloys.

2D materials↗
DOE OSTI2024

Influence of Nb alloying on Nb recrystallization and the upper critical field of Nb 3 ⁢Sn

Nb 3 Sn conductors are important candidates for high-field magnets for particle accelerators, and they continue to be widely used for many laboratory and NMR magnets. However, the critical current density, J c , of present Nb 3 Sn conductors declines swiftly above 12-15 T. State-of-the-art Ta- and Ti-doped strands exhibit upper critical field, H c2 , values of ~ 24-26.5 T (4.2 K) and do not reach the FCC target J c , which serves as the present stretch target for Nb 3 Sn development. As recently demonstrated, to meet this goal requires enhanced vortex pinning but an independent and supplementary approach is to significantly enhance H c2 . In this study, we have arc-melted multiple Nb alloys with added Hf, Zr, Ta and Ti and drawn them successfully into monofilament wires to investigate the possibilities of H c2 enhancement through alloying. H c2 (T) was measured for all samples in fields up to 16 T and some up to 31 T. We have found that all alloys show good agreement with the standard Werthamer, Helfand, and Hohenberg (WHH) fitting procedure without the need to adjust the paramagnetic limitation parameter (α) and spin-orbit scattering parameter (λ so ). The evaluation of dH c2 /dT near T c , which is proportional to the electronic specific heat coefficient γ and the normal state resistivity ρn, allows a better understanding of the induced disorder introduced by alloying in the A15 phase. So far, we have observed that Hf alloying of pure Nb can enhance H c2 (0) by 3-4 T to ~28 T, while adding just 1 at. %Hf or Zr into a Nb4Ta base alloy can raise H c2 (0) to ~31 T. Very importantly we find that Hf and Zr raise the alloy recrystallization temperature above the usual A15 reaction temperature range of 650°C – 750°C, thus ensuring denser A15 phase nucleation in the Nb alloy grain boundaries, possibly leading to a more homogeneous A15 phase Sn content and refined A15 grain size. Furthermore, the potential for further advancements in Nb 3 Sn properties is explored in relation to the recrystallization of the Nb alloy and the factors controlling the upper critical field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Fabrication and Characterization of Candidate Alloys for Advanced LEU Fuel Concepts

A set of novel uranium-based alloys has been proposed for use in advanced LEU fuel systems. This study seeks to develop methods to fabricate single-phase alloys and evaluate the compatibilities of the alloys for use in composite fuel systems. The as-cast microstructure of each alloy was characterized via scanning electron microscopy (SEM), and candidate alloys were further down-selected for homogenization and interaction testing. The U 22 Zr 20 Nb 58 alloy was successfully fabricated as a single-phase system, as demonstrated via X-ray diffraction (XRD) and SEM. The thermal and mechanical properties of the U-Nb-Zr alloy were further assessed via differential scanning calorimetry (DSC), laser flash analysis (LFA), and Vickers’ micro-hardness testing. This alloy also demonstrated improved compatibility with fuel candidate alloys from conventional matrix materials and may be a viable option for use in advanced fuel systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Development and Evaluation of Embrittlement Resistant Alloys for Advanced LWR Cladding

The primary challenge preventing the deployment of reactor designs that leverage wrought FeCrAl as an advanced light-water reactor (LWR) cladding is irradiation hardening and embrittlement. Wrought FeCrAl alloys experience a loss of post-irradiation ductility and fracture toughness under low-temperature neutron irradiation (< 350°C) resulting from the combined effects of dislocation loop formation and the irradiation-enhanced precipitation of Cr-rich alpha-prime precipitates throughout the microstructure. Over the past decade, significant improvements in our understanding regarding the effect of Cr and Al content have been enabled through neutron irradiations, but even optimized wrought alloys such as C26M remain vulnerable to brittle failure during storage, transportation, and handling following irradiation. This report summarizes multiple irradiation campaigns initiated over the past 7 years and provides recent insights into the effect of (1) minor alloying composition, (2) alloy processing strategy, (3) crystal structure, and (4) the use of advanced oxide dispersion strengthened (ODS) alloys. The first irradiation campaign irradiated body-centered cubic FeCrAl alloy C26M with and without elements such as Mo and Y. It also included face-centered cubic alumina-forming austenitic (AFA) alloys that have a steeper neutronic penalty but that have far superior high-temperature strength than wrought FeCrAl. Finally, this campaign compared conventional wrought C26M with the same material produced using modern powder metallurgical hotisostatic pressing (PM-HIP). The second irradiation campaign, initiated in 2018, irradiated wrought and FeCrAl-ODS materials up to 50 dpa to assess their irradiation resistance to high-doses. The results of this work indicate that wrought C26M suffers significant degradation following neutron irradiation at LWR-relevant temperatures regardless of Mo and Y content. The PM-HIP variant appears to be more resilient to irradiation-induced ductility loss in comparison with wrought variants but still loses almost all ductility by 8 dpa. Notably, the AFAs retained at least 5% total elongation after irradiation at the same dose and temperature condition, although additional deterioration may be expected at higher fluence levels. FeCrAl-ODS materials show the greatest promise as a transformative longer-term accident-tolerant fuel (LT-ATF) cladding material. The extruded 106ZY10C alloy retained 10% total elongation after 16 dpa irradiation and retained 8% total elongation after 50 dpa. Additional challenges with FeCrAl-ODS alloys also remain, including optimization of end cap joining methodologies, enhancement of fracture toughness, scaling production to prove economic viability, and optimizing post-pilger heat treatments to maximize ductility and irradiation resistance. This series of irradiations demonstrates the efficacy of the LWR testbed available within the United States for the rapid irradiation and down-selection of LT-ATF candidates. As the country rapidly accelerates its timeline for the deployment of advanced reactor concepts, the effective utilization of the High Flux Isotope Reactor for separate-effects style irradiations should continue to be prioritized to answer the final questions pertaining to LT-ATF candidates necessary for the deployment of advanced boiling water reactors and small modular reactors.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

A Quantitative Phase Analysis by Neutron Diffraction of Conventional and Advanced Aluminum Alloys Thermally Conditioned for Elevated-Temperature Applications

As the issue of climate change becomes more prevalent, engineers have focused on developing lightweight Al alloys capable of increasing the power density of powertrains. The characterization of these alloys has been focused on mechanical properties and less on the fundamental response of microstructures to achieve these properties. Therefore, this study assesses the quality of the microstructure of two high-temperature Al alloys (A356 + 3.5RE and Al-8Ce-10Mg), comparing them to T6 A356. These alloys underwent thermal conditioning at 250 and 300 °C for 200 h. Time-of-flight neutron diffraction experiments were performed before and after conditioning. The phase evolution was quantified using Rietveld refinement. It was found that the Si phase grows significantly (13–24%) in T6 A356, A356 + 3.5RE, and T6 A356 + 3.5RE alloys, which is typically correlated with a reduction in mechanical properties. Subjecting the A356 3.5RE alloy to a T6 heat treatment stabilizes the orthorhombic Al4Ce3Si6 and monoclinic β-Al5FeSi phases, making them resistant to thermal conditioning. These two phases are known for enhancing mechanical properties. Additionally, the T6 treatment reduced the vol.% of the cubic Al20CeTi2 and hexagonal ᴨ-Al9FeSi3Mg5 phases by 13% and 23%, respectively. These phases have detrimental mechanical properties. The Al-8Ce-10Mg alloy cubic β-Al3Mg2 phase showed significant growth (82–101%) in response to conditioning, while the orthorhombic Al11Ce3 phase remained stable. The growth of the beta phase is known to decrease the mechanical properties of this alloy. These efforts give valuable insight into how these alloys will perform and evolve in demanding high-temperature environments.

Chemistry↗
NASA NTRS1974

High temperature mechanical properties of a zirconium-modified, precipitation- strengthened nickel, 30 percent copper alloy

A precipitation-strengthened Monel-type alloy has been developed through minor alloying additions of zirconium to a base Ni-30Cu alloy. The results of this exploratory study indicate that thermomechanical processing of a solution-treated Ni-30Cu-0.2Zr alloy produced a dispersion of precipitates. The precipitates have been tentatively identified as a Ni5Zr compound. A comparison of the mechanical properties, as determined by testing in air, of the zirconium-modified alloy to those of a Ni-30Cu alloy reveals that the precipitation-strengthened alloy has improved tensile properties to 1200 K and improved stress-rupture properties to 1100 K. The oxidation characteristics of the modified alloy appeared to be equivalent to those of the base Ni-30Cu alloy.

Whittenberger, J. D.↗
NASA NTRS1977

Creep and tensile properties of several oxide-dispersion-strengthened nickel-base alloys at 1365 K

The tensile properties at room temperature and at 1365 K and the tensile creep properties at low strain rates at 1365 K were measured for several oxide-dispersion-strengthened (ODS) alloys. The alloys examined included ODS Ni, ODS Ni-20Cr, and ODS Ni-16Cr-Al. Metallography of creep tested, large grain size ODS alloys indicated that creep of these alloys is an inhomogeneous process. All alloys appear to possess a threshold stress for creep. This threshold stress is believed to be associated with diffusional creep in the large grain size ODS alloys and normal dislocation motion in perfect single crystal (without transverse low angle boundaries) ODS alloys. Threshold stresses for large grain size ODS Ni-20Cr and Ni-16Cr-Al type alloys are dependent on the grain aspect ratio. Because of the deleterious effect of prior creep on room temperature mechanical properties of large grain size ODS alloys, it is speculated that the threshold stress may be the design limiting creep strength property.

Wittenberger, J. D.↗
NASA NTRS1980

Evaluation of candidate Stirling engine heater tube alloys for 1000 hours at 760 C

Six tubing alloys were endurance tested in a diesel fired, Stirling engine simulator materials test rig for 1000 hours of 760 C while pressurized at 17 to 21 MPa with either hydrogen or helium. The alloys tested were N 155, A 286, Incoloy 800, 19 9DL, Nitronic 40 and 316 stainless steel. The alloys were in the form of thin wall tubing. Hydrogen permeated rapidly through the tube walls of all six alloys when they were heated to 760 C. Helium was readily contained. Creep rupture failures occurred in four of the six alloys pressurized with hydrogen. Only two alloys survived the 1000 hour endurance test with no failures. Simultaneous exposure to either hydrogen or helium and the combustion environment did not seriously degrade the tensile strength of the six alloys in room temperature or 760 C tests after exposure. Decreases in room temperature ductility were observed and are attributed to aging rather than to hydrogen embrittlement in three of the alloys. However, there may be a hydrogen embrittlement effect in the N 155, 19 9DL, and Nitronic 40 alloys.

Misencik, J. A.↗
NASA NTRS1989

Identification of a cast iron alloy containing nonstrategic elements

A program was performed to address the mechanical and environmental needs of Stirling engine heater head and regenerator housing components, while reducing the dependence on strategic materials. An alloy was developed which contained no strategic elemental additions per se. The base is iron with additions of manganese, molybdenum, carbon, silicon, niobium, and ferro-chromium. Such an alloy should be producible on a large scale at very low cost. The resulting alloy, designated as NASAUT 4G-Al, contained 15 Mn, 15 Cr, 2 Mo, 1.5 C, 1.0 Si, 1.0 Nb (in weight percent) with a balance of Fe. This alloy was optimized for chemistry, based upon tensile strength, creep-rupture strength, fracture behavior, and fatigue resistance up to 800 C. Alloys were also tested for environmental compatibility. The microstructure and mechanic properties (including hardness) were assessed in the as-cast condition and following several heat treatments, including one designed to simulate a required braze cycle. The alloy was fabricated and characterized in the form of both equiaxed and columnar-grained castings. The columnar grains were produced by directional solidification, and the properties were characterized in both the longitudinal and transverse orientations. The NASAUT 4G-Al alloy was found to be good in cyclic-oxidation resistance and excellent in both hydrogen and hot-corrosion resistance, especially in comparison to the baseline XF-818 alloy. The mechanical properties of yield strength, stress-rupture life, high-cycle-fatigue resistance, and low-cycle-fatigue resistance were good to excellent in comparison to the current alloy for this application, HS-31 (X-40), with precise results depending in a complex manner on grain orientation and temperature. If required, the ductility could be improved by lowering the carbon content.

Cooper, C. V.↗
NASA NTRS1990

Surface characterization of hydrogen charged and uncharged alpha-2 and gamma titanium aluminide alloys using AES and REELS

The surfaces of selected uncharged and hydrogen charged alpha-2 and gamma titanium aluminide alloys with Nb additions were characterized by Auger electron (AES) and reflected electron energy loss (REELS) spectroscopy. The alloy surfaces were cleaned before analysis at room temperature by ion sputtering. The low energy (500 eV) ion sputtering process preferentially sputtered the surface concentration. The surface concentrations were determined by comparing AES data from the alloys with corresponding data from elemental references. No differences were observed in the Ti or Nb Auger spectra for the uncharged and hydrogen charged alloys, even though the alpha-2 alloy had 33.4 atomic percent dissolved hydrogen. Also, no differences were observed in the AES spectra when hydrogen was adsorbed from the gas phase. Bulk plasmon energy shifts were observed in all alloys. The energy shifts were induced either by dissolved hydrogen (alpha-2 alloy) or hydrogen adsorbed from the gas phase (alpha-2 and gamma alloys). The adsorption induced plasmon energy shifts were greatest for the gamma alloy and cp-Ti metal.

Shanabarger, M. R.↗
NASA NTRS1993

Study on solidification of immisible alloys (M-10)

Alloying of immiscible alloys under microgravity is of interest in metallurgical processes. Several experiments investigating the alloying of immiscible alloys, such as Al-In, Al-Bi, Zn-Bi, and Zn-Pb, were done in space. Homogeneous distribution of small L2 particles in the matrix, such as an emulsion structure, was expected in the space-solidifed alloys. However, the alloys demonstrated an extremely segregated structure. To date insufficient information was obtained to explain these unexpected results. Our experiment was proposed to clarify the solidification manner of immiscible alloys and to obtain fundamental information concerning structural control of the alloys. In space, density differences between the two liquids separated in immiscible regions can be neglected, so that no sedimentation of L(sub 2) phase will take place. When the growth of the alloys is interrupted and this status is frozen by an adequate rapid cooling procedure, it will provide much information concerning decomposing homogeneous liquid and the interaction between the monotectic growth front morphology and the distribution of L(sub 2) phase. It is anticipated that the results will be useful for elucidating the monotectic solidification manner and it will be instructive to explain the segregated structures obtained in the past space experiments.

Kamio, Akihiko↗
NASA NTRS1998

Modeling of Substitutional Site Preference in Ordered Intermetallic Alloys

We investigate the site substitution scheme of specific alloying elements in ordered compounds and the dependence of site occupancy on compound stoichiometry, alloy concentration. This basic knowledge, and the interactions with other alloying additions are necessary in order to predict and understand the effect of various alloying schemes on the physical properties of a material, its response to various temperature treatments, and the resulting mechanical properties. Many theoretical methods can provide useful but limited insight in this area, since most techniques suffer from constraints in the type of elements and the crystallographic structures that can be modeled. With this in mind, the Bozzolo-Ferrante-Smith (BFS) method for alloys was designed to overcome these limitations, with the intent of providing an useful tool for the theoretical prediction of fundamental properties and structure of complex systems. After a brief description of the BFS method, its use for the determination of site substitution schemes for individual as well as collective alloying additions to intermetallic systems is described, including results for the concentration dependence of the lattice parameter. Focusing on B2 NiAl, FeAl and CoAl alloys, the energetics of Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Hf, Ta and W alloying additions are surveyed. The effect of single additions as well as the result of two simultaneous additions, discussing the interaction between additions and their influence on site preference schemes is considered. Finally, the BFS analysis is extended to ternary L1(sub 2) (Heusler phase) alloys. A comparison between experimental and theoretical results for the limited number of cases for which experimental data is available is also included.

Bozzolo, Guillermo↗
NASA NTRS2001

Dendritic Alloy Solidification Experiment (DASE)

A space experiment, and supporting ground-based research, is proposed to study the microstructural evolution in free dendritic growth from a supercooled melt of the transparent model alloy succinonitrile-acetone (SCN-ACE). The research is relevant to equiaxed solidification of metal alloy castings. The microgravity experiment will establish a benchmark for testing of equiaxed dendritic growth theories, scaling laws, and models in the presence of purely diffusive, coupled heat and solute transport, without the complicating influences of melt convection. The specific objectives are to: determine the selection of the dendrite tip operating state, i.e. the growth velocity and tip radius, for free dendritic growth of succinonitrile-acetone alloys; determine the growth morphology and sidebranching behavior for freely grown alloy dendrites; determine the effects of the thermal/solutal interactions in the growth of an assemblage of equiaxed alloy crystals; determine the effects of melt convection on the free growth of alloy dendrites; measure the surface tension anisotropy strength of succinon itrile -acetone alloys establish a theoretical and modeling framework for the experiments. Microgravity experiments on equiaxed dendritic growth of alloy dendrites have not been performed in the past. The proposed experiment builds on the Isothermal Dendritic Growth Experiment (IDGE) of Glicksman and coworkers, which focused on the steady growth of a single crystal from pure supercooled melts (succinonitrile and pivalic acid). It also extends the Equiaxed Dendritic Solidification Experiment (EDSE) of the present investigators, which is concerned with the interactions and transients arising in the growth of an assemblage of equiaxed crystals (succinonitrile). However, these experiments with pure substances are not able to address the issues related to coupled heat and solute transport in growth of alloy dendrites.

Beckermann, C.↗
NASA NTRS2001

Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(x)V(1-x), alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(x),V(1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(x)Te(l-x) and ZnSe(Y)Te(1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(y)Te(1-y) alloys in the entire composition range, 0 less than or equal to y less than or equal to 1. The samples used in this study are bulk ZnSe(y)Te(1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the interaction between localized Se states and the conduction band. On the other hand we show that the large band gap reduction observed on the Se-rich side of the alloy system is a result of an interaction between the localized Te level and the valence bands. This interaction leads to the formation of a Te-like valence band edge that strongly interacts with the light hole valence band. Calculations based on a modified k p model account for the reduction of the band gap and the large increase of the spin-orbit splitting observed in Se-rich ZnSe(y)Te(l-y) alloys. We will also discuss the importance of these new results for understanding of the electronic structure and band offsets in other highly mismatched alloy systems.

Yu, Kin Man↗