| 1. |
- Araujo, C. Moysés, et al.
(författare)
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Room temperature ferromagnetism in pristine MgO thin films
- 2010
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Ingår i: Applied Physics Letters. - : AIP Publishing. - 0003-6951 .- 1077-3118. ; 96:23
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Tidskriftsartikel (refereegranskat)abstract
- Robust ferromagnetic ordering at, and well above room temperature is observed in pure transparent MgO thin films (<170 nm thick) deposited by three different techniques. Careful study of the wide scan x-ray photoelectron spectroscopy rule out the possible presence of any magnetic contaminants. In the magnetron sputtered films, we observe magnetic phase transitions as a function of film thickness. The maximum saturation magnetization of 5.7 emu/cm(3) is measured on a 170 nm thick film. The films above 500 nm are found to be diamagnetic. Ab initio calculations suggest that the ferromagnetism is mediated by cation vacancies.
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| 2. |
- Blomqvist, A., et al.
(författare)
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Understanding the catalytic effects of H(2)S on CVD-growth of alpha-alumina : Thermodynamic gas-phase simulations and density functional theory
- 2011
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Ingår i: Surface & Coatings Technology. - : Elsevier BV. - 0257-8972 .- 1879-3347. ; 206:7, s. 1771-1779
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Tidskriftsartikel (refereegranskat)abstract
- The catalytic effect of H(2)S on the AlCl(3)/H(2)/CO(2)/HCl chemical vapor deposition (CVD) process has been investigated on an atomistic scale. We apply a combined approach with thermodynamic modeling and density functional theory and show that H(2)S acts as mediator for the oxygenation of the AI-surface which will in turn increase the growth rate of Al(2)O(3). Furthermore we suggest surface terminations for the three investigated surfaces. The oxygen surface is found to be hydrogenated, in agreement with a number of previous works. The aluminum surfaces are Cl-terminated in the studied CVD-process. Furthermore, we find that the AlClO molecule is a reactive transition state molecule which interacts strongly with the aluminum and oxygen surfaces.
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| 3. |
- Blomqvist, A., et al.
(författare)
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Understanding the catalytic effects of H2S on CVD-growth of α-alumina : Thermodynamic gas-phase simulations and density functional theory
- 2011
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Ingår i: Proceedings of the 38th International Conference on Metallurgical Coatings and Thin Films (ICMCTF) — ICMCTF 2011. - : Elsevier BV. ; 206:7, s. 1771-1779
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Konferensbidrag (refereegranskat)abstract
- The catalytic effect of H2S on the AlCl3/H2/CO2/HCl chemical vapor deposition (CVD) process has been investigated on an atomistic scale. We apply a combined approach with thermodynamic modeling and density functional theory and show that H2S acts as mediator for the oxygenation of the Al-surface which will in turn increase the growth rate of Al2O3. Furthermore we suggest surface terminations for the three investigated surfaces. The oxygen surface is found to be hydrogenated, in agreement with a number of previous works. The aluminum surfaces are Cl-terminated in the studied CVD-process. Furthermore, we find that the AlClO molecule is a reactive transition state molecule which interacts strongly with the aluminum and oxygen surfaces.
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| 4. |
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| 5. |
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| 6. |
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| 7. |
- Huang, L. M., et al.
(författare)
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Tuning magnetic properties of In2O3 by control of intrinsic defects
- 2010
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Ingår i: Europhysics letters. - : IOP Publishing. - 0295-5075 .- 1286-4854. ; 89:4
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Tidskriftsartikel (refereegranskat)abstract
- The electronic structure and magnetic properties of In2O3 with four kinds of intrinsic point defects (O vacancy, In interstitial, O interstitial, and In vacancy) have been theoretically studied using the density functional theory. The defect energy states of the O vacancy and In interstitial are close to the bottom of conduction band and act as shallow donors, while the defect energy states of the In vacancy and O interstitial are just above the top of the valence band and act as shallow acceptors. Without addition of any magnetic ions, all the hole states are completely spin polarized, while the electron states display no spin polarization. This implies that semiconducting In2O3 can display magnetic ordering, purely due to the intrinsic defects. However, the formation energies for neutral p-type defects are too high to be thermodynamically stable at reasonable temperatures. Nevertheless, it is shown that negative charging can greatly decrease the formation energies of p-type defects, simultaneously removing the local magnetic moments. We conlcude that V-In''' and O-I '' will be the dominant compensating defects as In2O3 is doped with TM ions, such as Sn, Mo, V and Cr. This result is consistent with the general view that the p-type defect is a key feature to mediate ferromagnetic coupling between transition metal ions of dilute concentration in metal oxides.
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| 8. |
- Kaplan, Bartek, et al.
(författare)
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Structural Determination of (Cr,Co)7C3
- 2013
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Konferensbidrag (refereegranskat)abstract
- Chromium is one of the most well-known WC grain growth inhibitors in cemented carbides. It is thus vital to understand and to be able to thermodynamically model the prevailing phase equilibria in the WC-Co-Cr system. To do this it is important that the lower order systems, such as the Co-Cr-C system, are correctly described. Previous investigations have shown that the M7C3 (M=Cr,Co,W) phase is the first carbide to form when Cr is added in excess to the WC+fcc-Co/liquid+graphite phase field. However, the exact structure of this phase has not been investigated and there are many proposed structures already for the binary Cr7C3 carbide, ranging from trigonal, via hexagonal to orthorhombic symmetry. Recent investigations show that the hexagonal structure belonging to the P63mc space group is the stable structure at 0 K. In the present study the binary Cr7C3 carbide and a mixed M7C3 carbide are investigated. The structures of both carbides and preferential positions for Co atoms in the mixed carbide are determined by XRD measurements in combination with ab initio calculations and Rietveld refinement.
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| 9. |
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| 10. |
- Niklasson, Gunnar A., 1953-, et al.
(författare)
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Optics of sunscreen lotions : Preliminary results on scattering and absorption coefficients
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Sunscreen lotions are used to protect the skin from damage due to solar ultraviolet (UV) radiation. The active UV-blocking components can be organic molecules or inorganic particles, for example TiO2. While both in-vivo and in-vitro methods exist for assessing the protective capacity of sunscreens, their basic optical properties have received little attention. In this paper we take the first steps to address this issue by presenting a method to obtain spectra of absorption and scattering coefficients of a sunscreen by analysis of experimental transmittance and reflectance spectra. We model the optical properties of the sunscreen by two-flux theory, develop approximate expressions for interface reflection coefficients and obtain the remaining optical parameters by fitting the two-flux theory to measurements. We analyze spectrophotometric reflectance and transmittance spectra of experimental narrow band UV blocking materials based on mesoporous magnesium carbonate – TiO2 mixtures, as well as some commercial sunscreens. Our method is demonstrated in vitro using quartz substrates and is further used to model in vivo measurements on the upside of the hand of one of the authors. The obtained absorption and scattering coefficient spectra give information on the relative contributions of these processes to the UV-blocking effect as well as the scattering of visible light responsible for the whitening of the skin upon application of a sunscreen lotion. Our analysis method may be useful for computational optimization of novel sunscreen formulations as well as for the development of in-vivo test methods.
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| 11. |
- Niklasson, Gunnar, 1953-, et al.
(författare)
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Light Scattering Parameters by Inversion of Experimental Data: The Case of Sunscreen Lotions
- 2021
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Ingår i: Proceedings of the Bremen Zoom Workshop on Light Scattering 2021. - Bremen : Leibniz Institute for Materials Engineering IWT. ; , s. 16-19
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Konferensbidrag (refereegranskat)abstract
- We present a method to obtain absorption and backscattering coefficients of a light scattering material and apply it to the technologically important case of sunscreen lotions. While both in-vivo and in-vitro methods exist for assessing the ultraviolet (UV) protective capacity of sun-screens, their basic optical properties have previously received little attention. We model the light scattering properties by two-flux theory and invert spectrophotometric total transmittance and reflectance measurements to obtain backscattering and absorption coefficient spectra.
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| 12. |
- Nisar, Jawad, et al.
(författare)
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Optical gap and native point defects in kaolinite studied by the GGA-PBE, HSE functional, and GW approaches
- 2011
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 84:7, s. 075120-
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Tidskriftsartikel (refereegranskat)abstract
- The electronic structure of kaolinite with and without intrinsic defects has been studied by the Perdew-Burke-Ernzerhof (PBE) and Heyd-Scuseria-Ernzerhof (HSE) functionals and by the G0W0 approach. The band gap of defect-free kaolinite was estimated to between 6.2 and 8.2 eV. Analysis of the formation energy of native point defects in kaolinite was carried out under different growth conditions. When the PBE defect formation energy as a function of temperature is considered, the hydroxyl vacancy is compensated by a hydrogen vacancy at a formation energy of 0.45 eV at oxygen-rich and hydrogen-poor conditions. The hydroxyl vacancy acts as a donor whereas the hydrogenvacancy acts as an acceptor, both inducing states in the band gap. The HSE03 hybrid functional increases the defect formation energy and tends to localize and move these states away from the band edges, as compared to the other two methods. Our results imply that intrinsic defects will tune the band gap of kaolinite and influence properties related to its band structure such as the cation retention capability and drug release.
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| 13. |
- von Fieandt, Linus, et al.
(författare)
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Chemical Interactions Between Cemented Carbide and Difficult-to-Machine Materials by Diffusion Couple Method and Simulations
- 2018
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Ingår i: Journal of phase equilibria and diffusion. - : SPRINGER. - 1863-7345 .- 1547-7037. ; 39:4, s. 369-376
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Tidskriftsartikel (refereegranskat)abstract
- A simple and efficient diffusion couple method is utilized to study the chemical interactions between cemented carbide cutting tools and difficult-to-machine materials (Ti, Ti-6Al-4V, Ni, Inconel 718, Fe, and AISI 316L). The experimental results and simulations probe different chemical interactions between the cemented carbide and work materials. In particular, the formation of a thick TiC layer is observed at the cemented carbide/Ti and Ti-6Al-4V interface while eta-phase is formed at the interface between the cemented carbide and work materials Inconel 718, Fe and AISI 316L. Pure titanium and Ti-6Al-4V both interact strongly with the tool causing formation of TiC and dissolution of WC-grains. Experiments and diffusion simulations confirm bcc-W formation and progressive diffusion of W into bcc-Ti. For both Ti and Fe work materials a dense band of carbides (WC + eta or WC + TiC) forms at the interface, effectively inhibiting further diffusion. Ni does not form any stable carbide and lowers the eta-phase limit in terms of carbon content, wherefore diffusion can occur freely. The diffusion couple method used in this work, corroborated by DICTRA simulations should serve as a useful tool in the detailed analysis of worn tools where chemical wear is dominant.
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| 14. |
- Wang, Baochang, et al.
(författare)
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A Comparison Between Hybrid Functional, GW Approach and the Bethe Salpether Equation : Optical Properties of High Pressure Phases of TiO2
- 2014
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Ingår i: Science of Advanced Materials. - : American Scientific Publishers. - 1947-2935 .- 1947-2943. ; 6:6, s. 1170-1178
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Tidskriftsartikel (refereegranskat)abstract
- Titanium dioxide has good corrosion resistance in aqueous solutions and is a good candidate for photoelectrodes. The limitation of the anatase phase of TiO2 is its large band gap. High pressure phases of TiO2 like fluorite, pyrite and cotunnite may possess a more suitable band gap than the well known atmospheric phases. In this paper, the electronic properties of high pressure phases of TuO(2), fluorite, pyrite and cotunnite, have been investigated by hybrid functional and GW methods. Our calculations suggest that the band gap of fluorite and pyrite phases have optimal band gaps to absorb visible light for photocatalysis to decompose water. The imaginary part of the dielectric function has also been calculated for fluorite, pyrite, cotunnite and anatase phases using the Bethe-Salpether (BSE) method. The dielectric function calculated by BSE for the anatase phase agrees well with experiment and with previous studies, using the same level of theory. Therefore we expect that we are also able to predict the optical properties of the high pressure phases of TiO2 by the BSE method. The spatial properties and the localization character of excitons in these high pressure phases were investigated and discussed in terms of photoconversion efficiency.
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| 15. |
- Århammar, Cecilia, et al.
(författare)
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A theoretical study of point defects incorporated into CVD-grown α-alumina
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The energetics and electronic structure of a number of defects; C, Cl, H and S in alpha-Al2O3 is investigated. These species are present in the gas phase during the Chemical Vapor Deposition (CVD) and little is known of their solubility in alpha-Al2O3. It is found that not only the hydrogen interstitial, which is already wellknown for its dual action as a donor and acceptor defect will be amphotheric, but also the carbon and sulfur interstitial may gain both negative and positive charge states. However, at the CVD equilibrium conditions, charge compensation between the different defects will most likely not take place. For this a non equilibrium method such as Plasma Enhanced CVD or Physical Vapor Deposition (PVD) is needed.
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| 16. |
- Århammar, Cecilia, 1981-
(författare)
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Atomistic modelling of functional solid oxides for industrial applications : Density Functional Theory, hybrid functional and GW-based studies
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this Thesis a set of functional solid oxides for industrial applications have been addressed by first principles and thermodynamical modelling. More specificially, measurable quantities such as Gibbs free energy, geometry and electronic structure have been calculated and compared when possible with experimental data. These are crystalline and amorphous aluminum oxide (Al2O3), Zirconia (ZrO2), magnesium oxide (MgO), indiumoxide (In2O3) and Kaolinite clay (Al2Si2O5(OH)4). The reader is provided a computation tool box, which contains a set of methods to calculate properties of oxides that are measurable in an experiment. There are three goals which we would like to reach when trying to calculate experimental quantities. The first is verification. Without verification of the theory we are utilizing, we cannot reach the second goal -prediction. Ultimately, this may be (and to some extent already is) the future of first principles methods, since their basis lies within the fundamental quantum mechanics and since they require no experimental input apart from what is known from the periodic table. Examples of the techniques which may provide verification are X-Ray Diffraction (XRD), X-ray Absorption and Emission Spectroscopy (XAS and XES), Electron Energy Loss Spectroscopy and Photo-Emission Spectroscopy (PES). These techniques involve a number of complex phenomena which puts high demands on the chosen computational method/s. Together, theory and experiment may enhance the understanding of materials properties compared to the standalone methods. This is the final goal which we are trying to reach -understanding. When used correctly, first principles theory may play the role of a highly resolved analysis method, which provides details of structural and electronic properties on an atomiclevel. One example is the use of first principles to resolve spectra of multicomponentsamples. Another is the analysis of low concentrations of defects. Thorough analysis of the nanoscale properties of products might not be possible in industry due to time and cost limitations. This leads to limited control of for example low concentrations of defects, which may still impact the final performance of the product. On example within cutting tool industry is the impact of defect contents on the melting point and stability of protective coatings. Such defects could be hardening elements such as Si, Mn, S, Ca which diffuse from a steel workpiece into the protective coating during high temperature machining. Other problems are the solving of Fe from the workpiece into the coating and reactions between iron oxide, formed as the workpiece surface is oxidized, and the protective coating. The second part of the computational toolbox which is provided to the reader is the simulation of solid oxide synthesis. Here, a formation energy formalism, most often applied to materials intended in electronics devices is applied. The simulation of Chemical Vapour Deposition (CVD) and Physical Vapor Deposition (PVD) requires good knowledge of the experimental conditions, which can then be applied in the theoretical simulations. Effects of temperature, chemical and electron potential, modelled concentration and choice of theoretical method on the heat of formation of different solid oxides with and without dopants are addressed in this work. A considerable part of this Thesis is based upon first principles calculations, more specifically, Density Functional Theory (DFT) After Kohn and Pople received the Nobel Prize in chemistry in 1998, the use of DFT for computational modelling has increased strikingly (see Fig. 1). The use of other first principles methods such as hybrid functionals and the GW approach (see abbreviations for short explanations and chapter 4.5 and 5.3.) have also become increasingly popular, due to the improved computational resources. These methods are also employed in this Thesis.
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| 17. |
- Århammar, Cecilia, et al.
(författare)
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Energetics and magnetic properties of V-doped MgO bulk and (001) surface : A GGA, GGA+U, and hybrid density functional study
- 2010
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 82:13, s. 134406-
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Tidskriftsartikel (refereegranskat)abstract
- In this work, a first-principles study of the energetic and magnetic properties of V-doped MgO is presented, where both the bulk and (001) surface were investigated. It is found that V assumes a high-spin state with a local moment of about 3 mu(B). In the bulk, the interaction between these local moments is very short ranged and the antiferromagnetic (AFM) ordering is energetically more favorable. The formation of V-V-Mg-V defect clusters is found to weaken the antiferromagnetic coupling in bulk MgO, degenerating the AFM and ferro-magnetic state. However, these clusters are high in energy and will not form at equilibrium conditions. By employing the GGA+U approach, with U=5 eV, the V 3d states on the (001) surface are shifted below the Fermi level, and a reasonable surface geometry was achieved. A calculation with the hybrid HSE03 functional, contradicts the GGA+U results, indicating that the V-MgO surface should be metallic at this concentration. From the energetics it is concluded that, at the modeled concentration, VxOy phases will limit the solubility of V in MgO at equilibrium conditions, which is in agreement with previous experimental findings. In order to achieve higher concentrations of V, an off-equilibrium synthesis method is needed. Finally, we find that the formation energy of V at the surface is considerably higher than in the bulk and V is thus expected to diffuse from the surface into the bulk of MgO.
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| 18. |
- Århammar, Cecilia, et al.
(författare)
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Energetics of Al doping and intrinsic defects in monoclinic and cubic zirconia : First-principles calculations
- 2009
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 80:11, s. 115208-
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Tidskriftsartikel (refereegranskat)abstract
- First-principles theory within the supercell approach has been employed to investigate Al doping and intrinsic defects in monoclinic and cubic zirconia. The effect of oxygen chemical potential and Fermi level on the formation energy and on the defect concentration have been taken into account. The formation of oxygen vacancies is found to be energetically more favorable in the cubic than in the monoclinic phase under the same oxygen chemical potential and Fermi energy. In both phases, substitutional Al decays from neutral charge state into the charge state -1, with the transition energy just above to the top of the valence band. Our findings indicate that by confining the Fermi energy to the region between the middle of the band gap and the bottom of the conduction band, high Al solubility could be achieved, although formation of Al is likely followed by the formation of interstitial oxygen. Furthermore, the concentration of Al with charge state -1 along with the equilibrium Fermi energy have been calculated in a self-consistent procedure. Here, the possible compensating defects with the relevant charge states have been considered. The obtained concentrations of Al and oxygen vacancies follow the experimental trend but underestimates experimental data. When the formation of defect clusters, composed by two substitutional Al and one oxygen vacancy, are considered, good quantitative agreement with experimental values of both Al and oxygen vacancy concentration is achieved. The results suggest that defect clusters will be formed as a result of Al doping in cubic phase of ZrO2, whereas the concentration of defect clusters is negligible in the monoclinic phase, both in accordance with experiment.
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| 19. |
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| 20. |
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| 21. |
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| 22. |
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| 23. |
- Århammar, Cecilia, et al.
(författare)
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Unveiling the complex electronic structure of amorphous metal oxides
- 2011
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Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 108:16, s. 6355-6360
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Tidskriftsartikel (refereegranskat)abstract
- Amorphous materials represent a large and important emerging area of material's science. Amorphous oxides are key technological oxides in applications such as a gate dielectric in Complementary metal-oxide semiconductor devices and in Silicon-Oxide-Nitride-Oxide-Silicon and TANOS (TaN-Al2O3-Si3N4-SiO2-Silicon) flash memories. These technologies are required for the high packing density of today's integrated circuits. Therefore the investigation of defect states in these structures is crucial. In this work we present X-ray synchrotron measurements, with an energy resolution which is about 5-10 times higher than is attainable with standard spectrometers, of amorphous alumina. We demonstrate that our experimental results are in agreement with calculated spectra of amorphous alumina which we have generated by stochastic quenching. This first principles method, which we have recently developed, is found to be superior to molecular dynamics in simulating the rapid gas to solid transition that takes place as this material is deposited for thin film applications. We detect and analyze in detail states in the band gap that originate from oxygen pairs. Similar states were previously found in amorphous alumina by other spectroscopic methods and were assigned to oxygen vacancies claimed to act mutually as electron and hole traps. The oxygen pairs which we probe in this work act as hole traps only and will influence the information retention in electronic devices. In amorphous silica oxygen pairs have already been found, thus they may be a feature which is characteristic also of other amorphous metal oxides.
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