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Brominated chemistry for chemical vapor deposition of electronic grade SiC
Linköping University, Department of Physics, Chemistry and Biology, Semiconductor Materials. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Semiconductor Materials. Linköping University, The Institute of Technology.ORCID iD: 0000-0001-8116-9980
Linköping University, Department of Physics, Chemistry and Biology, Semiconductor Materials. Linköping University, The Institute of Technology.
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2015 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 27, no 3, p. 793-801Article in journal (Refereed) Published
Abstract [en]

Chlorinated chemical vapor deposition (CVD) chemistry for growth of homoepitaxial layers of silicon carbide (SiC) has paved the way for very thick epitaxial layers in short deposition time as well as novel crystal growth processes for SiC. Here, we explore the possibility to also use a brominated chemistry for SiC CVD by using HBr as additive to the standard SiC CVD precursors. We find that brominated chemistry leads to the same high material quality and control of material properties during deposition as chlorinated chemistry and that the growth rate is on average 10 % higher for a brominated chemistry compared to chlorinated chemistry. Brominated and chlorinated SiC CVD also show very similar gas phase chemistries in thermochemical modelling. This study thus argues that brominated chemistry is a strong alternative for SiC CVD since the deposition rate can be increased with preserved material quality. The thermochemical modelling also suggest that the currently used chemical mechanism for halogenated SiC CVD might need to be revised.

Place, publisher, year, edition, pages
2015. Vol. 27, no 3, p. 793-801
National Category
Chemical Sciences Physical Sciences
Identifiers
URN: urn:nbn:se:liu:diva-111075DOI: 10.1021/acs.chemmater.5b00074ISI: 000349934500016OAI: oai:DiVA.org:liu-111075DiVA, id: diva2:753046
Available from: 2014-10-07 Created: 2014-10-07 Last updated: 2018-06-19Bibliographically approved
In thesis
1. Precursors and defect control for halogenated CVD of thick SiC epitaxial layers
Open this publication in new window or tab >>Precursors and defect control for halogenated CVD of thick SiC epitaxial layers
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Silicon carbide (SiC) is a very hard semiconductor material with wide band gap, high breakdown electric field strength, high thermal conductivity and high saturation electron drift velocity making it a promising material for high frequency and high power devices. The performance of electrical devices is strongly dependent on the quality, doping level and thickness of the grown epitaxial layers. The SiC epitaxial layers are usually grown by chemical vapor deposition (CVD), using silane (SiH4) and light hydrocarbons (C2H4 or C3H8) as precursors, diluted in a massive flow of hydrogen (H2), at growth temperatures and pressures of 1500-1600 °C and 100-300 mbar, respectively. A Silicon Carbide (SiC) device with a high breakdown voltage (> 10 kV) requires thick (> 100 μm) and low doped (1014cm-3) epitaxial layers. The typical growth rate is usually 5-10 μm/h, rendering very long growth times which result in a high cost for the final device. It is hard to increase the growth rate without running into problems with homogeneous gas phase nucleation, which badly affects the surface morphology and the usefulness of the epitaxial layers for devices. This problem can be avoided by lowering the growth pressure and/or increasing the carrier gas flow (H2) to minimize the homogeneous gas phase nucleation or by increasing the growth temperature to evaporate the silicon droplets. On the other hand introducing chlorine into the gas mixture, by adding HCl or using some chlorinated silicon precursor, such as trichlorosilane (SiHCl3) or tetrachlorosilane (SiCl4), or by methyltrichlorosilane (CH3SiCl3) as a single molecule will prevent nucleation in the gas phase. In this thesis a detailed study of the chloride-based processes and an investigation of a bromide-based CVD process is made using a horizontal hot wall reactor. Focus has been mainly on the study of various precursor molecules but also the effect of process parameters on the growth of thick epitaxial layers (100-200 μm). In paper 1 the growth of SiC epitaxial layers on 4° off-axis substrates manifesting very good morphology when using methane (CH4) as carbon precursor is demonstrated. A comparative study of SiCl4, SiHCl3, SiH4+HCl, C3H8, C2H4 and CH4 in an attempt to find the optimal precursor combination is presented in Paper 2 for growth of 4H-SiC epitaxial layers on 4° off-axis substrates with very good morphology. Paper 3 presents a direct comparison between chloride-based and bromide-based CVD chemistries for growth of SiC epitaxial layers using SiH4 and C2H4 as Si- respectively C-precursors with HCl or HBr as growth additives. The influence of temperature ramp up conditions on the carrot defect density on 8° off-axis 4H-SiC epitaxial layers using the single molecule precursor methyltrichlorosilane (MTS) as growth precursor is studied in Paper 4. In paper 5 growth of about 200 μm thick epitaxial layers with very good morphology at growth rates exceeding 100 μm/h using SiCl4+C2H4 and SiH4+HCl+C2H4 precursor approaches is reported. The effect of growth conditions on dislocation density by decorating the dislocations using KOH etching is reported in Paper 6. In Paper 7 the effect of varying parameters such as growth  temperature, C/Si ratio, Cl/Si ratio, Si/H2 ratio and in situ pre-growth surface etching time are studied in order to reduce the formation of step bunching and structural defects, mainly triangular defects for growth of about 100 μm thick epitaxial layers on 4° off-axis substrates with very good morphology at growth rates up to 115 μm/h.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. p. 61
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1625
National Category
Physical Sciences Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-111076 (URN)10.3384/diss.diva-111076 (DOI)978-91-7519-213-0 (ISBN)
Public defence
2014-10-31, Plank, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2014-10-07 Created: 2014-10-07 Last updated: 2019-11-19Bibliographically approved
2. Quantum chemical studies of deposition and catalytic surface reactions
Open this publication in new window or tab >>Quantum chemical studies of deposition and catalytic surface reactions
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Quantum chemical calculations have been used to model chemical reactions in epitaxial growth of silicon carbide by chemical vapor deposition (CVD) processes and to study heterogeneous catalytic reactions for methanol synthesis. CVD is a common method to produce high-quality materials and e.g. thin films in the semiconductor industry, and one of the many usages of methanol is as a promising future renewable and sustainable energy carrier. To optimize the chemical processes it is essential to understand the reaction mechanisms. A comprehensive theoretical model for the process is therefore desired in order to be able to explore various variables that are difficult to investigate in situ. In this thesis reaction paths and reaction energies are computed using quantum chemical calculations. The quantum-chemical results can subsequently be used as input for thermodynamic, kinetic and computational fluid dynamics modelling in order to obtain data directly comparable with the experimental observations.

For the CVD process, the effect of halogen addition to the gas mixture is studied by modelling the adsorption and diffusion of SiH2, SiCl2 and SiBr2 on the (0001̅) 4H-SiC surface. SiH2 was found to bind strongest to the surface and SiBr2 binds slightly stronger than the SiCl2 molecule. The diffusion barrier is shown to be lower for SiH2 than for SiBr2 and SiCl2 which have similar barriers. SiBr2 and SiCl2 are found to have similar physisorption energies and bind stronger than the SiH2 molecule. Gibbs free-energy calculations also indicate that the SiC surface is not fully hydrogen terminated at CVD conditions since missing-neighboring pair of surface hydrogens is found to be common. Calculations for the (0001) surface show that SiCl, SiCl2, SiHCl, SiH, and SiH2 likely adsorb on a methylene site, but the processes are thermodynamically less favorable than their reverse reactions. However, the adsorbed products may be stabilized by subsequent surface reactions to form a larger structure. The formation of these larger structures is found to be fast enough to compete with the desorption processes. Also the Gibbs free energies for adsorption of Si atoms, SiX, SiX2, and SiHX where X is F or Br are presented. Adsorption of Si atoms is shown to be the most thermodynamically favorable reaction followed by SiX, SiHX, and SiX2, X being a halide. The results in this study suggest that the major Si contributors in the SiC–CVD process are Si atoms, SiX and SiH.

Methanol can be synthesized from gaseous carbon dioxide and hydrogen using solid metal-metal oxide mixtures acting as heterogeneous catalysts. Since a large surface area of the catalyst enhances the speed of the heterogeneous reaction, the use of nanoparticles (NP) is expected to be advantageous due to the NPs’ large area to surface ratio. The plasma-induced creation of copper NPs is investigated. One important element during particle growth is the charging process where the variation of the work function (W) with particle size is a key quantity, and the variation becomes increasingly pronounced at smaller NP sizes. The work functions are computed for a set of NP charge numbers, sizes and shapes, using copper as a case study. A derived analytical expression for W is shown to give quite accurate estimates provided that the diameter of the NP is larger than about a nanometer and that the NP has relaxed to close to a spherical shape. For smaller sizes W deviates from the approximative expression, and also depends on the charge number. Some consequences of these results for NP charging process are outlined.

Key reaction steps in the methanol synthesis reaction mechanism using a Cu/ZrO2 nanoparticle catalyst is investigated. Two different reaction paths for conversion of CO2 to CO is studied. The two paths result in the same complete reaction 2 CO2 → 2 CO + O2 where ZrO2 (s) acts as a catalyst. The highest activation energies are significantly lower compared to that of the gas phase reaction. The presence of oxygen vacancies at the surface appear to be decisive for the catalytic process to be effective. Studies of the reaction kinetics show that when oxygen vacancies are present on the ZrO2 surface, carbon monoxide is produced within a microsecond. The IR spectra of CO2 and H2 interacting with ZrO2 and Cu under conditions that correspond to the catalyzed CH3OH production process is also studied experimentally and compared to results from the theoretical computations. Surface structures and gas-phase molecules are identified through the spectral lines by matching them to specific vibrational modes from the literature and from the new computational results. Several surface structures are verified and can be used to pin point surface structures in the reaction path. This gives important information that help decipher how the reaction mechanism of the CO2 conversion and ultimately may aid to improve the methanol synthesis process.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2018. p. 65
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1925
National Category
Theoretical Chemistry Nano Technology Physical Chemistry
Identifiers
urn:nbn:se:liu:diva-148757 (URN)10.3384/diss.diva-148757 (DOI)9789176853337 (ISBN)
Public defence
2018-08-30, Planck, Fysikhuset, Campus Valla, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2018-06-19 Created: 2018-06-19 Last updated: 2019-09-30Bibliographically approved

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