| 1. |
- Aidas, Kestutis, et al.
(författare)
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The Dalton quantum chemistry program system
- 2014
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Ingår i: WIREs Computational Molecular Science. - : Wiley. - 1759-0876 .- 1759-0884. ; 4:3, s. 269-284
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Tidskriftsartikel (refereegranskat)abstract
- Dalton is a powerful general-purpose program system for the study of molecular electronic structure at the Hartree-Fock, Kohn-Sham, multiconfigurational self-consistent-field, MOller-Plesset, configuration-interaction, and coupled-cluster levels of theory. Apart from the total energy, a wide variety of molecular properties may be calculated using these electronic-structure models. Molecular gradients and Hessians are available for geometry optimizations, molecular dynamics, and vibrational studies, whereas magnetic resonance and optical activity can be studied in a gauge-origin-invariant manner. Frequency-dependent molecular properties can be calculated using linear, quadratic, and cubic response theory. A large number of singlet and triplet perturbation operators are available for the study of one-, two-, and three-photon processes. Environmental effects may be included using various dielectric-medium and quantum-mechanics/molecular-mechanics models. Large molecules may be studied using linear-scaling and massively parallel algorithms. Dalton is distributed at no cost from for a number of UNIX platforms.
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| 2. |
- Aquilante, Francesco, et al.
(författare)
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Cholesky decomposition techniques in electronic structure theory
- 2011
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Ingår i: Linear-Scaling Techniques in Computational Chemistry and Physics. - Dordrecht : Springer. - 9789048128525 ; , s. 301-304
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Bokkapitel (övrigt vetenskapligt/konstnärligt)abstract
- We review recently developed methods to efficiently utilize the Cholesky decomposition technique in electronic structure calculations. The review starts with a brief introduction to the basics of the Cholesky decomposition technique. Subsequently, examples of applications of the technique to ab inito procedures are presented. The technique is demonstrated to be a special type of a resolution-of-identity or density-fitting scheme. This is followed by explicit examples of the Cholesky techniques used in orbital localization, computation of the exchange contributionto the Fock matrix, in MP2, gradient calculations, and so-called method specific Cholesky decomposition. Subsequently, examples of calibration of the method with respect to computed total energies, excitation energies, and auxiliary basis set pruning are presented. In particular, it is demonstrated that the Cholesky method is an unbiased method to derive auxiliary basis sets. Furthermore, details of the implementational considerations are put forward and examples from a parallel Cholesky decomposition scheme is presented. Finally, an outlook and perspectives are presented, followed by a summary and conclusions section. We are of the opinion that the Cholesky decomposition method is a technique that has been overlooked for too long. We have just recently started to understand how to efficiently incorporate the method in existing ab initio programs. The full potential of the Cholesky technique has not yet been fully explored.
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| 3. |
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| 4. |
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| 5. |
- Böör, Katalin, et al.
(författare)
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On the growth kinetics, texture, microstructure, and mechanical properties of tungsten carbonitride deposited by chemical vapor deposition
- 2022
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Ingår i: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : American Institute of Physics (AIP). - 0734-2101 .- 1520-8559. ; 40:5
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Tidskriftsartikel (refereegranskat)abstract
- Tungsten carbonitride [W(C,N)] was deposited on cemented carbide substrates by chemical vapor deposition (CVD) in a hot-wall reactor using tungsten hexafluoride (WF6), acetonitrile (CH3CN), and hydrogen (H-2) as precursors. Tungsten carbides and nitrides with a hexagonal 6-WC type structure are generally difficult to obtain by CVD. Here, it was found that the combination of WF6 and CH3CN precursors enabled the deposition of W(C,N) coatings with a delta-WC type structure and columnar grains. A process window as a function of the deposition temperature and precursor partial pressures was determined to establish the conditions for the deposition of such coatings. Scanning electron microscopy, x-ray diffraction, electron backscatter diffraction, and elastic recoil detection analysis were used for the investigation of the coating thickness, microstructure, texture, and composition. From the investigation of the kinetics, it was concluded that the growth was mainly controlled by surface kinetics with an apparent activation energy of 77 kJ/mol, yielding an excellent step coverage. The partial reaction orders of the reactants together with their influence on the microstructure and coating composition was further used to gain a deeper understanding of the growth mechanism. Within the process window, the microstructure and the texture of the W(C,N) coatings could be tailored by the process parameters, enabling microstructural engineering with tuning of the mechanical properties of the W(C,N) coatings. The nanoindentation hardness (36.6-45.7 GPa) and elastic modulus (564-761 GPa) were found to be closely related to the microstructure.
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| 6. |
- Fondell, Mattis, 1984-, et al.
(författare)
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Phase control of iron oxides grown in nano-scale cauliflower structures: hematite, maghemite and magnetite
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- We demonstrate that iron oxide in the form of hematite, suitable as absorber in photoelectrochemical cells, can be produced by pulsed chemical vapour deposition. By choosing carbon monoxide or nitrogen as carrier gases in the process the phase and granularity of the grown material can be controlled. The choice of carrier gas a ect the decomposition rate of iron pentacarbonyl used as iron precursor. The iron oxide phase is also dependent on the chosen substrate, here fluorine doped tin oxide and crystalline silicon have been used. Regardless of the substrate nitrogen yields hematite, whereas carbon monoxide gives magnetite on Si and maghemite on fluorine doped tin oxide. A combination of Raman spectroscopy, X-ray di raction, and hard X-ray photoelectron spectroscopy were used for characterization of the crystalline phase and chemical composition in the films. Scanning electron microscopy were used to visualise the deposited films’ nano-structure reminiscent of a cauliflower.
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| 7. |
- Fondell, Mattis, et al.
(författare)
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Phase control of iron oxides grown in nano-scale structures on FTO and Si(100) : Hematite, maghemite and magnetite
- 2015
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Ingår i: Vacuum. - : Elsevier BV. - 0042-207X .- 1879-2715. ; 117, s. 85-90
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate that iron oxide in the form of hematite, suitable as absorption material in photo-electrochemical cells, can be produced by pulsed chemical vapour deposition. By choosing carbon monoxide or nitrogen as carrier gases in the process the phase and granularity of the grown material can be controlled. The choice of carrier gas affect the decomposition rate of iron pentacarbonyl used as iron precursor. The iron oxide phase is also dependent on the chosen substrate, here fluorine doped tin oxide and crystalline silicon have been used. Regardless of the substrate nitrogen yields hematite, whereas carbon monoxide gives, magnetite on Si and maghemite on fluorine doped tin oxide. A combination of Raman spectroscopy, X-ray diffraction, and hard X-ray photoelectron spectroscopy were used for characterization of the crystalline phase and chemical composition in the films. Scanning electron microscopy were used to visualise the deposited films' nano-structure.
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| 8. |
- Fondell, Mattis, 1984-, et al.
(författare)
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Temperature Induced Diffusion of Sn and Si in Hematite and Implications for Photocatalytic Water Splitting Applications
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The performance of Hematite (α-Fe2O3) for the water oxidation step in solar hydrogen production is dependent upon annealing of the material. In this study, these effects are investigated in terms of temperature induced diffusion of Sn and Si from the substrate into thin films of hematite by using hard X-ray photoelectron spectroscopy (HAXPES). Here, HAXPES is used for the first time to characterize a buried interface between a conducting substrate and a nanostructured thin film overlayer by diffusion upon annealing. This process is prototypical for the large class of photoelectrochemical devices that uses indium and fluorine doped tin oxide as substrates where the device is subsequently annealed. Indeed, we observe that: diffusion of Sn and Si is significant, already at 550 °C; the photocatalytic efficiency of the hematite films increased, from low values to 0.23 mA/cm2; annealing in air preserves the hematite phase, while annealing in vacuum induces a phase transition into magnetite, which impairs the photocatalytic performance. The increase in efficiency is explained in terms of an improvement of the quantum efficiency of the oxygen evolution reaction accompanied by a slight improvement in charge carrier transport.
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| 9. |
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| 10. |
- von Fieandt, Linus, et al.
(författare)
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Chemical vapor deposition of TiN on transition metal substrates
- 2018
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Ingår i: Surface and Coatings Technology. - : Elsevier BV. - 0257-8972 .- 1879-3347. ; 334, s. 373-383
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Tidskriftsartikel (refereegranskat)abstract
- The growth of chemical vapor deposited TiN from a reaction gas mixture of TiCl 4 , N 2 and H 2 was investigated on three different transition metal substrates: Fe, Co and Ni at deposition temperatures ranging from 850 °C to 950 °C. The interactions between the substrate metals and the gas phase were investigated using thermodynamic calculations. The TiN coatings were characterized by scanning electron microscopy, scanning transmission electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy and transmission Kikuchi diffraction. Chemical vapor deposition (CVD) of TiN on Co substrates resulted in dense, columnar coatings of single phase TiN. The activation energy for TiN deposition on Co was determined to be 90 kJ/mol. CVD of TiN on Fe substrates caused severe substrate corrosion by the formation of gaseous FeCl x . Due to the substrate corrosion, the activation energy could not be determined. Furthermore, it was found that CVD of TiN on Ni substrates produced a phase mixture of TiN and Ni 3 Ti. Formation of Ni 3 Ti could be minimized by decreasing the H 2 partial pressure and increasing the N 2 partial pressure. Deposition on Ni yielded two different activation energies, 40 kJ/mol in the temperature interval 850 °C to 900 °C and 165 kJ/mol in the interval 900 °C to 950 °C. This is an indication of two different types of process control, which were identified as Ni diffusion into the growing film and a gas phase processes. The results of the present study showed that CVD of TiN on a cemented carbide using Fe and Ni in the binder phase, must be optimized in order to avoid corrosion or unwanted phases. Methods to achieve this are presented in this paper.
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| 11. |
- von Fieandt, Linus, et al.
(författare)
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Corrosion properties of CVD grown Ti(C,N) coatings in 3.5 wt-% NaCl environment
- 2018
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Ingår i: Corrosion Engineering, Science and Technology. - 1478-422X .- 1743-2782. ; 53:4, s. 316-320
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Tidskriftsartikel (refereegranskat)abstract
- The corrosion behaviour of Titanium carbonitride (Ti(C,N)) films grown by chemical vapour deposition was analysed in artificial sea water environment. From potentiodynamic polarisation curves, two passivation zones were detected, which originated from an initial oxidation of TiC and TiN to TiO2 followed by growth of the TiO2 layer upon increased polarisation. X-ray photoelectron spectroscopy analyses verified the mechanism by detecting a gradual decrease in Ti(C,N) peaks accompanied by a gradual increase of oxidised Ti (e.g. TiO2). It was likewise found that carbon in TiC mainly decomposes into carbonate species while the nitrogen in TiN remains elemental and likely escapes as nitrogen gas. Accordingly, Ti(C,N) behaves like a superposition of TiC and TiN with their individual oxidation behaviour, resulting in a highly corrosion resistant material.
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| 12. |
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| 13. |
- von Fieandt, Linus
(författare)
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Cutting Edge Titanium-based CVD Hard Coatings
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Modern tools for metal cutting applications, such as turning or milling, are typically improved with a thin protective coating. Despite being only a few microns thick, the coating can increase the lifetime of the tool by more than 100 times compared to an uncoated tool. Two different types of techniques are normally used to deposit the coatings, i.e. chemical vapor deposition (CVD) or physical vapor deposition (PVD). A CVD coated tool often includes several different layers. TiN-Ti(C,N)-Al2O3-TiN is a common combination. The research in this thesis has focused on deposition, characterization, and optimization of TiN and Ti(C,N) layers. CVD has been used to deposit all coatings studied in this thesis. They were characterized with a variety of techniques such as: X-ray diffraction, electron microscopy and X-ray photoelectron spectroscopy.TiN was deposited on three different substrates, Co, Fe and Ni. It was found that the TiN coating was strongly affected by the substrate. TiN deposited on Fe substrates resulted in a porous interface caused by substrate etching by the reaction gas mixture. CVD of TiN on Ni substrates resulted in an unwanted intermetallic phase (Ni3Ti) in addition to TiN. Etching or corrosion of the Fe substrates could be reduced by lowering the deposition temperature. In addition, the formation of (Ni3Ti) could be significantly reduced by adjusting the partial pressure of the reactant gases. This shows that CVD of TiN on cutting tools with Fe or Ni as a binder phase needs to be optimized with respect to the process parameters.Thermodynamic calculations of the Ti(C,N) CVD process indicates that the major growth species using CH3CN, TiCl4 and H2 as precursors, was HCN and TiCl3. They were formed in the gas phase by homogeneous reactions. Furthermore, it was found that by adjusting the composition of the reaction gas mixture, the preferred orientation, morphology, and micro-structure of the Ti(C,N) coatings could be tailored. As a result, the tribological/mechanical properties of the Ti(C,N) coatings could be significantly improved. A hardness of 40 GPa, i.e. close to super hard could for instance be achieved. The origin of the mechanical improvements was attributed to a more ordered crystallographic orientation in the <111> direction as well as a high defect density close to the coating surface. In addition to the excellent mechanical properties, the Ti(C,N) coatings were also found to have a high corrosion resistance in sea water, thanks to a formation of a passivating surface layer (TiO2).
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| 14. |
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| 15. |
- von Fieandt, Linus, et al.
(författare)
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On the growth, orientation and hardness of chemical vapor deposited Ti(C,N)
- 2018
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Ingår i: Thin Solid Films. - : Elsevier BV. - 0040-6090 .- 1879-2731. ; 645, s. 19-26
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Tidskriftsartikel (refereegranskat)abstract
- Chemical vapor deposition (CVD) of Ti(C,N) from a reaction gas mixture of TiCl4, CH3CN, H2 and N2 was investigated with respect to gas phase composition and kinetics. The gas phase composition was modelled by thermodynamic calculations and the growth rate of the CVD process was measured when replacing H2 for N2 while the sum of partial pressures H2+N2 was kept constant. The N2/H2 molar ratio was varied from 0 to 19. Single crystal c-sapphire was used as substrates. It was found that low molar ratios (N2/H2 molar ratio below 0.6) lead to an increased Ti(C,N) growth rate with up to 22%, compared to deposition without added N2. The mechanism responsible for the increased growth rate was attributed to the formation and increased gas phase concentration of one major growth species, HCN, in the gas phase. The texture of the Ti(C,N) films were also studied. ⟨211⟩ textured layers were deposited at N2/H2 molar ratios below 9. At higher molar ratios, ⟨111⟩ oriented Ti(C,N) layers were deposited and the grain size increased considerably. The films deposited at a N2/H2 ratio above 9 exhibited superior hardness, reaching 37GPa. The increased hardness is attributed to an almost epitaxial orientation between the layer and the substrate. The absence of grain twinning in the ⟨111⟩ oriented layer also contributed to the increased hardness.The Ti(C,N) layers were characterized by elastic recoil detection analysis, X-ray photo electron spectroscopy, scanning electron microscopy, X-ray diffraction and nanoindentation.
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| 16. |
- von Fieandt, Linus, et al.
(författare)
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Texture formation in chemical vapor deposition of Ti(C,N)
- 2019
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Ingår i: Journal of Crystal Growth. - : Elsevier BV. - 0022-0248 .- 1873-5002. ; 508, s. 90-95
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Tidskriftsartikel (refereegranskat)abstract
- The growth mechanism of Ti(C,N) coatings produced by chemical vapor deposition was investigated as a function of the TiCl4/CH3CN molar ratio in excess of H-2. The depositions were carried out at a total pressure of 8 kPa, using single crystalline (0 0 l) alpha-Al2O3 substrates. The Ti(C,N) coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The investigated coatings were between 6 and 13 mu m thick. The reaction orders of TiCl4 CH3CN were determined to 0 and 1, respectively, showing that CH3CN is the rate-determining reactant. The preferred orientation of the deposited Ti(C,N) was investigated, showing that molar ratios TiCl4 /CH3CN higher than 2.5 lead to < 2 1 1 >/< 3 1 1 > oriented coatings. A formation mechanism for the < 2 1 1 >/< 3 1 1 > orientations is suggested. Such high ratios lead to the formation of Ti {1 1 1} twinning planes, which provide surface sites that can facilitate fast dissociation of the strong cyanide bond, and thereby cause faster growth in the < 2 1 1 >/< 3 1 1 > directions. Coatings deposited at lower molar ratios show a pronounced < 1 1 1 > out-of-plane orientation, characterized by a {1 1 1} rocking curve yielding values for full width at half maximum (FWHM) below 0.5 degrees.
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| 17. |
- von Fieandt, Linus, et al.
(författare)
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Tribological properties of highly oriented Ti(C,N) deposited by chemical vapor deposition
- 2018
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Ingår i: Tribology International. - : Elsevier BV. - 0301-679X .- 1879-2464. ; 119, s. 593-599
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Tidskriftsartikel (refereegranskat)abstract
- Two Ti(C,N) coatings were tested by means of micro abrasion and scratch testing. The coatings differed in grain size, orientation (<111> and <111>, <311> and <211> respectively) and hardness (36 GPa and 23 GPa respectively). The <111> oriented coating had a 20% higher wear resistance compared to the reference coating when abraded with 1 pm diamonds. When abraded with 6 pm diamonds the abrasion resistance of the reference coating was superior compared to the <111> oriented coating by 36%. Furthermore, it was found that the <111> oriented coating had 35% better adhesion compared to the reference. The improved mechanical properties of the <111> oriented coating was attributed to a high degree of orientation and the higher hardness.
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