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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Use of Diffusion Bonded Cu Strap and Integrated MLI for Thermal Control of 100 K IR Detector on L’Ralph Instrument

Passive cooling of cryogenic instruments is one of the most challenging aspects of spaceflight thermal control systems. They are highly sensitive to parasitic heat leaks from their warmer environment, especially the spacecraft components. The L’Ralph instrument on the Lucy mission is an example of such a system, with its LEISA detector requiring passive cooling to temperatures below 112 K. MLI performance can be measured in terms of estar, and analysts apply bias between a high and low estar value. This approach works well for conventional MLI at room temperature, however, it can be dangerous when a mission goes through a wide range of temperatures during its lifetime, with estar values increasing exponentially as temperatures get colder. Various estar correlations are presented as well as how L’Ralph is approaching the MLI problem with the use of IMLI. IMLI uses discrete spacers to isolate each layer, and doesn’t require intermediate layers such as dacron netting. This results in estar performance that can be more precisely estimated, and yields valuesaround 0.004 at the 112K operating temperature. L’Ralph is using IMLI on the backside of the radiator, which permits a more effective use of increased radiator area, by minimizing the area dependent heat leak impact from the instrument backloading. The detector is thermally coupled to the radiator via a diffusion bonded Cu strap. The diffusion bonding process chemically bonds the Cu foil ends in order to maximize heat transfer effectiveness across the multiple foils used. Employing a pressure compensation design via the use of Ti blocks and a clamp at the strap ends ensures that as temperatures go colder, pre-load is maintained in order to minimize resistance at the strap ends. The use of both of these technologies, and how they work together are crucial to the success of the L’Ralph thermal control system.

Thermal↗
NASA NTRS1998

Substrate Effects for Atomic Chain Electronics

A substrate for future atomic chain electronics, where adatoms are placed at designated positions and form atomically precise device components, is studied theoretically. The substrate has to serve as a two-dimensional template for adatom mounting with a reasonable confinement barrier and also provide electronic isolation, preventing unwanted coupling between independent adatom structures. For excellent structural stability, we demand chemical bonding between the adatoms and substrate atoms, but then good electronic isolation may not be guaranteed. Conditions are clarified for good isolation. Because of the chemical bonding, fundamental adatom properties are strongly influenced: a chain with group IV adatoms having two chemical bonds, or a chain with group III adatoms having one chemical bond is semiconducting. Charge transfer from or to the substrate atoms brings about unintentional doping, and the electronic properties have to be considered for the entire combination of the adatom and substrate systems even if the adatom modes are well localized at the surface.

Yamada, Toshishige↗
NASA NTRS1999

Precise Nanoelectronics with Adatom Chains

Adatom chains on an atomically regulated substrate will be building components in future precise nanoelectronics. Adatoms need to be secured with chemical bonding, but then electronic isolation between the adatom and substrate systems is not guaranteed. A one-dimensional model shows that good isolation with existence of surface states is expected on an s-p crossing substrate such as Si, Ge, or GaAs, reflecting the bulk nature of the substrate. Isolation is better if adatoms are electronically similar to the substrate atoms, and can be manipulated by hydrogenation. Chain structures with group IV adatoms with two chemical bonds, or group III adatoms with one chemical bond, are semiconducting, reflecting the surface nature of the substrate. These structures are unintentionally doped due to the charge transfer across the chemical bonds. Physical properties of adatom chains have to be determined for the unified adatom-substrate system.

Yamada, Toshishige↗
NASA NTRS1996

Enhancing Adhesion: Relative Merits of Different Approaches

Adhesive performance is improved mainly by manipulation of the bimaterials interface zone, which is only a few molecules thick. There are three approaches to enhancement of interfacial adhesion at the molecular level. They are 1) changing the nonchemically bonded interactions across the interface from weak ones to strong ones, 2) making the true interfacial area much larger than the simple geometric area, and 3) inducing chemical bonding between the two materials forming the interface. Our goal this summer was to question some of the built-in assumptions contained within these approaches and to determine the most promising approach, both theoretically and practically, for enhancing adhesion in NASA structures. Our computations revealed that all three of these approaches have, in theory, the potential to enhance molecular adhesion approximately ten-fold. Experiments, however, revealed that this excellent level of enhancement is not likely to be reached in practice. Each approach was found to be severely limited by practical problems. In addition, some of the built-in assumptions associated with these approaches were found to be insufficient or inadequate. The first approach, changing the nonchemically bonded interactions from weak to strong, Is an example of one containing inadequate assumptions. The extensive literature on intermolecular interactions, based on solution studies, shows that certain functional group pairs interact much more strongly than others. It has always been assumed that these data can be reliably extended to systems where only one member of the pair is in solution and the other Is contained in a solid surface. Our experiments this summer demonstrated that solution data do not adequately predict the strength of functional group interaction at the solid-liquid interface. Furthermore, the strong solvents needed to dissolve the monomers or polymers to which the functional groups of interest are attached compete successfully with the solid surface for the functional group. As a result, functional groups in solution cannot pair with the complementary groups in the solid surface, and the expected enhancement of nonchemically bonded interactions is not realized. The second approach, increasing the true interfacial area, is an example of one containing inadequate assumptions and suffering from numerous practical problems. First, practitioners have assumed that material removal, such as bead blasting or etching, increases true surface area (and therefore interfacial area) in a meaningful way. Our geometric analysis demonstrated that removal methods increase area by a factor of two at most. To increase interfacial area by an order of magnitude or more. a thin layer of high porosity must be added to the substrate surface prior to application of the adhesive phase. Consistent with this finding, we attempted to create a thin layer of rigid, highly porous glass on the surface of our smooth glass substrate by means of sol-gel technology. We were unable to surmount a wide variety of practical problems and obtained only collapsed, nonporous layers. Thus this approach, appealing in principle, would require long term development and is not promising in the near term. The third approach, inducing chemical bonding at the interface, is an example of one having neither inadequate assumptions nor insurmountable practical problems. When silicate glass is the substrate, there are only a few chemical reactions that can be successfully conducted to create these chemical bonds, and these reactions usually involve silicon-containing reagents. We compared the silazane reagents to the silane reagents and found through experiment that the silazanes react with the glass surface much more readily, and under milder conditions, than the silanes. The functional groups attached to the glass surface by silazane reactions were not able to be removed by solvent extraction, elevated temperature exposure, or mechanical action. This clearly indicates that the formation of chemical bonds at the interface is the most effective approach for enhancing molecular adhesion.

Penn, L. S.↗
DOE OSTI2025

Potentials of mean force fail to describe chemical bond-breaking in solution

Many liquid phase studies assume that the potential energy surfaces of reacting molecules are the same as in the gas phase, neglecting complex solvent dynamics that can completely alter the nature of chemical reactivity. Even studies that include solvent effects typically only consider them in an average, equilibrium way as part of a potential of mean force (PMF). In this work, we use mixed quantum/classical simulations to compare how equilibrium and non-equilibrium solvent motions affect the photodissociation of a simple diatomic molecule, NaK + , in liquid tetrahydrofuran. A PMF analysis shows that as the excited-state molecule dissociates with the solvent at equilibrium, the bonding electron remains associated with K + at short bond distances but eventually localizes on Na + at the end of dissociation. When we examine non-equilibrium dynamical photodissociation trajectories, however, we find that they fall into three distinct categories: about a quarter of them have the bonding electron mainly associated with Na + , another quarter stay mainly associated with K + , and about half have the bonding electron shared roughly equally between the two ions. The results show that equilibrium PMFs cannot accurately describe the dynamics of bond-breaking chemical reactions in solution because there is insufficient time for the solvent to reach equilibrium on the time scale over which bond dissociation occurs. Furthermore, our analysis shows that the solvent coupling between the electronic energy surfaces is similar at and away from equilibrium, suggesting that other factors, such as solute velocity-driven solvent memory effects, play a more important role in explaining the failure of the equilibrium PMF to predict the non-equilibrium dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

On Substrate for Atomic Chain Electronics

A substrate for future atomic chain electronics, where adatoms are placed at designated positions and form atomically precise device components, is studied theoretically. The substrate has to serve as a two-dimensional template for adatom mounting with a reasonable confinement barrier and also provide electronic isolation, preventing unwanted coupling between independent adatom structures. However, the two requirements conflict. For excellent electronic isolation, we may seek adatom confinement via van der Waals interaction without chemical bonding to the substrate atoms, but the confinement turns out to be very weak and hence unsatisfactory. An alternative chemical bonding scheme with excellent structural strength is examined, but even fundamental adatom chain properties such as whether chains are semiconducting or metallic are strongly influenced by the nature of the chemical bonding, and electronic isolation is not always achieved. Conditions for obtaining semiconducting chains with well-localized surface-modes, leading to good isolation, are clarified and discussed.

Yamada, Toshishige↗
DOE OSTI2024

Observation of halogen-like behavior of gold in fluorinated bimetallic CoAuF 1-2 − and CuAuF 1-2 − clusters: Anion photoelectron spectroscopy and density functional theory

Using size-selected anion photoelectron spectroscopy and density functional theory, we investigated the structures and properties of fluorinated bimetallic clusters CoAuF 1-2 − and CuAuF 1-2 − and their neutrals. Both experimental and theoretical results show that in these cluster anions, Au behaves like a halogen atom. For example, the measured vertical detachment energies (VDEs) of CoAuF − (2.00 ± 0.08 eV) and CuAuF − (3.8 ± 0.1 eV) are close to those of CoF 2 − (2.12 ± 0.08 eV) and CuF 2 − (3.58 ± 0.08 eV), respectively. The theoretical results show that the geometries and electronic structures of CoAuF − and CuAuF − are similar to those of CoF 2 − and CuF 2 − . The natural population analysis and natural electron configuration analyses further confirm that the electronic properties of Au in MAuF − (M = Co, Cu) mimic those of MF 2 − . In addition, the electron localization function analyses show that the M-Au chemical bonds are similar to the corresponding M-F chemical bonds, providing evidence for the ionic nature of the interactions. When a second F atom is attached to the CoAuF − and CuAuF − clusters, the VDEs of the resulting CoAuF 2 − and CuAuF 2 − are 4.38 ± 0.08 eV and 3.71 ± 0.08 eV, respectively, indicating their superhalogen character as these values are higher than those of halogen anions. The results may be useful for understanding the properties of gold at the nanoscale that play an important role in catalysis and nanotechnology.

Ab-initio methods↗
NASA NTRS1998

The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under most astrophysical conditions, is catalyzed by iron, an abundant constituent of interstellar dust. At temperatures between 600 and 1000 K, which occur in the outflows from red giants and near luminous young stars, this reaction readily proceeds in the presence of an iron catalyst. Iron is one of the more abundant elements composing interstellar dust. Its abundance relative to hydrogen is almost that of silicon, and both of these heavy elements are primarily locked up in dust at all but the hottest regions of interstellar space.

Kress, M. E.↗
NASA NTRS1985

Bonding Solar-Cell Modules

Status of research program on chemical bonding for solar-cell arrays subject of 57-page report. Program aimed at identifying, developing, and validating weather-stable chemical bonding promoters. Materials key to ensuring long life in encapsulated photovoltaic modules for electric-power generation. To be cost-effective, modules must hold together for at least 20 years, reliably resisting delamination and separation of component materials

Coulter, D. R.↗
NASA NTRS2000

[Methods Used for Monitoring Cure Reactions in Real-time in an Autoclave]

The goal of the research was to investigate methods for monitoring cure reactions in real-time in an autoclave. This is of particular importance to NASA Langley Research Center because polyimides were proposed for use in the High Speed Civil Transport (HSCT) program. Understanding the cure chemistry behind the polyimides would allow for intelligent processing of the composites made from their use. This work has led to two publications in peer-reviewed journals and a patent. The journal articles are listed as Appendix A which is on the instrument design of the research and Appendix B which is on the cure chemistry. Also, a patent has been awarded for the instrumental design developed under this grant which is given as Appendix C. There has been a significant amount of research directed at developing methods for monitoring cure reactions in real-time within the autoclave. The various research efforts can be categorized as methods providing either direct chemical bonding information or methods that provide indirect chemical bonding information. Methods falling into the latter category are fluorescence, dielectric loss, ultrasonic and similar type methods. Correlation of such measurements with the underlying chemistry is often quite difficult since these techniques do not allow monitoring of the curing chemistry which is ultimately responsible for material properties. Direct methods such as vibrational spectroscopy, however, can often be easily correlated with the underlying chemistry of a reaction. Such methods include Raman spectroscopy, mid-IR absorbance, and near-IR absorbance. With the recent advances in fiber-optics, these spectroscopic techniques can be applied to remote on-line monitoring.

Cooper, John B.↗
DOE OSTI2023

First-principles study of interfaces in Al/SiC metal-matrix composite system

In this work, first-principles calculations were performed on the interfaces between Al and SiC, which is a widely used strengthening agent in aluminum metal-matrix-composites (Al/MMC). C-terminated interfaces have much larger work of adhesion than Si-terminated interfaces, indicating that the former has much stronger interfacial bonding. The electron localization function shows that the chemical bonding between Al and C has a strong covalent character, while the bonding between Al and Si is largely metallic. As a result of the vastly different chemical bonding, the work of adhesion for C-terminated interfaces increases with the number of dangling bonds at the interface, while the opposite trend was observed for Si-terminated interfaces. Additionally, the interface energy for Si-terminated interfaces is comparable to that for C-terminated interfaces, suggesting both types of terminations can coexist in the Al/SiC system.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Comprehensive Characterization of Multi-Phase Sulfurized Polyacrylonitrile Cathodes for Lithium-Sulfur Batteries

Sulfurized polyacrylonitrile (SPAN) is considered one of the most promising cathode materials to overcome the operational challenges that plague lithium-sulfur (Li-S) batteries. However, material properties and electrochemical performance implications of SPAN prepared under different synthesis conditions are not yet fully investigated. In this study, we show the impacts of different synthesis conditions on the formation of sulfur to PAN bonds and redox reaction mechanisms of multi-phase SPAN via comprehensive material and electrochemical characterizations. In-situ Raman analysis was first applied to study the multi-phase SPAN-based Li-S cells. We found that both elemental sulfur and chemically bonded sulfur are present under the synthesis condition of 300 degree C/3 h along with unreacted PAN. The incompletely sulfurized, multi-phase SPAN exhibited an unusually rapid capacity degradation in the resultant Li-S cells, which is attributed to polysulfide formation and continuously growing interfacial impedance in the Li-S cells. On the other hand, SPAN samples prepared under the synthesis condition of 350 degree C/3 h are found completely sulfurized with chemically bonded sulfur to the PAN backbone without the presence of free elemental sulfur. Complete sulfurization of SPAN led to exceptionally stable cycle performance due to excellent reversible redox processes of chemically bonded sulfur with Li+ in the Li-S cells.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗
DOE OSTI2024

Intrinsic Bonding and Reactivity of Actinide Clusters Poster

The effect of electronic structure on chemical bonding and reactivity is one of the most important questions in the field of chemistry. Insight into chemical bond formation involving elements that contain f electrons (i.e., the lanthanides and actinides) is critical for solving specific technical challenges, such as development of advanced nuclear fuel cycles and efficient rare earth separations, as well as a broader understanding of bonding across the entire periodic table. The primary technique for studying the fundamentals of lanthanide and actinide bonding is crystallization of metal-ligand compounds followed by structural determination with X-rays and comparison to theory with computational chemistry. While this procedure has yielded significant insights for a wide variety of elements, it is challenging to apply to the heavier trans-uranic actinides such as berkelium and californium because of limited material availability, significant radioactivity, and poorly understood chemical reactivity of these elements. We hypothesize that by forming actinide-ligand clusters in a mass spectrometer and probing their reactivity in the gas-phase, many of the challenges associated with studying the heavier trans-uranic elements can be circumvented. This project will develop a capability to address a wide range of actinide bonding and reactivity phenomena, increasing Idaho National Laboratory’s capability to address fundamental questions at the forefront of heavy element chemical and molecular science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

ASMS 2024 Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision Induced Dissociation

Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision Induced Dissociation Brittany D. M. Hodges, Christopher A. Zarzana, JungSoo Kim, Jonathan Martens, and W. C. M. Berden Introduction (120 words max) Effects of electronic structure on chemical bonding and reactivity play critical roles shaping the chemical bonding and reactivity behaviors of heavy elements. Understanding the role of f electrons in bond formation between the actinide-series elements like uranium with other ligands is critical for solving technical challenges associated with these heavy elements, important to nuclear fuel cycles, efficient separations of rare earth metals, and understanding the chemistry of stored nuclear fuels and related environmental management sites. In this study, we further examine the interactions between uranyl and the perchlorate ion in order to understand the structures of these ions through the use of IRMPD. Here we report the IRMPD spectra of [UO2(ClO4)3]-, [UO3(ClO4)2]-, and a proposed transition state. Methods (120 word max) IRMPD spectra and CID spectra were acquired using a Bruker amaZon QIT/MS instrument at the Free-Electron Lasers for Infrared eXperiments (FELIX) laboratory at Radboud University. The FELIX QIT/MS is modified to allow for the high-intensity tunable IR beam from FELIX to be directed into the ion packet, resulting in multiphoton dissociation that is measured only when the IR frequency is in resonance with an adequately high absorption vibrational mode of the mass-selected complex. DFT geometry optimizations and frequency calculations using the Gaussian suite of programs were performed using B3LYP, TPSSh, and PBE0 level of theory with 6-31+G(d) basis for the O, C, H, and N atoms and the SDD basis set for U. The SDD basis set employs the Stuttgart/Dresden effective core potential. Preliminary Data or Plenary Speakers Abstract (300 words max) Metal ion clusters of uranyl perchlorate were formed via direct electrospray ionization. For each metal ligand complex of interest, the parent ion was isolated and collision induced dissociation fragmentation and Infrared Multiphoton Dissociation (IRMPD) fragmentation spectra were acquired. Results presented here are the first look at the IRMPD spectra of [UO3(ClO4)2]-, [UO2(ClO4)3]-. Structures were examined using Gaussian at different levels of theory B3LYP level of theory, TPPSh and PBE0 levels, to reflect the behaviors of uranium metal ligand complexes most accurately. In these structures, we identified an overlap between each of these uranyl stretches resulting in their largely being obscured by a perchlorate mode. The CID product spectra agree with similar structures reported by Groenewold for uranyl nitrate in 2006 (10.1021/ja058106n).

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

Quantitative Account of the Bonding Properties of a Rubredoxin Model Complex [Fe(SCH3)4]q, q = -2, -1, +2, +3

Iron-sulfur clusters play important roles in biology as parts of electron transfer chains and catalytic cofactors. Here, we report a detailed computational analysis of a structural model of the simplest natural iron-sulfur cluster of rubredoxin and its cationic counterparts. Specifically, we report results for the ground and low-lying electronically excited states of the complex [Fe(SCH3)4]2-/1-/2+/3+, using Multi-Reference (CASSCF, MRCISD), and Coupled Cluster [CCSD(T)] methodology in order to provide accurate adiabatic reduction energies, dissociation energies and insights into the bonding analysis. The nature of the Fe-S chemical bond and the magnitude of the ionization potentials in the anionic and cationic [Fe(SCH3)4] complexes offer a physical rationale for the relative stabilization, structure and speciation of these complexes. Anionic and cationic complexes present different types of chemical bonds: prevalently ionic in [Fe(SCH3)4]2-/1- complexes and covalent in [Fe(SCH3)4]2+/3+ complexes. The ionic bonds result in an energy gain for the transition [Fe(SCH3)4]2-®[Fe(SCH3)4]- (i.e., FeII®FeIII) of 1.5 eV, while the covalent bonds result in an energy loss for the transition [Fe(SCH3)4]2+®[Fe(SCH3)4]3+ of 16.6 eV, almost half of the IP of Fe2+. The ionic vs covalent bond character influences the Fe-S bond strength and length, i.e., ionic Fe-S bonds are longer than covalent ones by about 0.2 Å (for FeII) and 0.04 Å (for FeII). Finally, the average Fe-S heterolytic bond strength is 6.7 eV (FeII) and 14.6 (FeIII) eV at the RCCSD(T) level of theory.

Tzeli, Demeter↗
DOE OSTI2022

Evidence for Dissociation and Ionization in Shock Compressed Nitrogen to 800 GPa

Triple bonding in the nitrogen molecule (N 2 ) is among the strongest chemical bonds with a dissociation enthalpy of 9.8 eV/molecule. Nitrogen is therefore an excellent test bed for theoretical and numerical methods aimed at understanding how bonding evolves under the influence of the extreme pressures and temperatures of the warm dense matter regime. Here, we report laser-driven shock experiments on fluid molecular nitrogen up to 800 GPa and 4.0 g/cm 3 . Line-imaging velocimetry measurements and impedance matching method with a quartz reference yield shock equation of state data of initially precompressed nitrogen. Comparison with numerical simulations using path integral Monte Carlo and density functional theory molecular dynamics reveals clear signatures of chemical dissociation and the onset of L-shell ionization. Furthermore, combining data along multiple shock Hugoniot curves starting from densities between 0.76 and 1.29 g/cm 3 , our study documents how pressure and density affect these changes in chemical bonding and provides benchmarks for future theoretical developments in this regime, with applications for planetary interior modeling, high energy density science, and inertial confinement fusion research.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Structure-thermal property relationships of aikinite PbCuBiS 3

Understanding the structural properties and chemical bonding in complex multinary chalcogenides is highly valuable, as it provides vital information for controlling their physical properties to suit various technological applications. Here, we report on the structural, thermal, and electronic properties of PbCuBiS 3 by incorporating an experimental and theoretical investigation of this material. Analysis of the experimental temperature-dependent heat capacity and thermal conductivity data show that weak bonding and strong lattice anharmonicity give rise to ultralow thermal conductivity. Chemical bonding information obtained from the density functional theory electronic calculations reveal significant antibonding interactions that underscore the dominant role of the Cu-S tetrahedra on occupied antibonding states, as well as a highly distorted Pb/Bi-S environment inducing weak bonding and strong lattice anharmonicity. This study broadens our understanding of the structure-property relationships for this material, and can be useful for developing this and similar chalcogenide materials for potential applications of interest.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effect of Thermal Oxidation on the Structure, Surface Texturing, and Microstructure Evolution in Nanocrystalline Ga-O-N Films

An extensive examination of the nanoscale, crystallographic growth dynamics of the system, which is impacted by the thermal energy given to the GaN, is carried out to derive a deeper understanding of the growth kinetics, morphology and microstructure evolution, chemical bonding, and optical properties of Ga-O-N films. Thermal annealing of GaN films is performed in the temperature range of 900–1200 °C. Crystal structure, phase formation, chemical composition, surface morphology, and microstructure evolution of Ga-O-N films are investigated as a function of temperature. Increasing temperature induces surface oxidation, which results in the formation of stable β-Ga2O3 phase in the GaN matrix, where the overall film composition evolves from nitride (GaN) to oxynitride (Ga-O-N). While GaN surfaces are smooth, planar, and featureless, oxidation induced granular-to-rod shaped morphology evolution is seen with increasing temperature to 1200 °C. The considerable texturing and stability of the nanocrystalline Ga-O-N on Si substrates can be attributed to the surface and interface driven modification because of thermal treatment. Corroborating with structure and chemical changes, Raman spectroscopic analyses also indicate that the chemical bonding evolution progresses from fully Ga-N bonds to Ga-O-N. While the GaN oxidation process starts with the formation of β-Ga 2 O 3 at an annealing temperature of 1000 °C, higher annealing temperatures induce structural distortion with the potential formation of Ga-O-N bonds. The structure-phase-chemical composition correlation, which will be useful for nanocrystalline materials for selective optoelectronic applications, is established in Ga-O-N films made by thermal treatment of GaN.

36 MATERIALS SCIENCE↗