Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Theoretical Routes for c-BN Thin Film Growth
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

c-BN has been in focus for several years due to its interesting properties. The possibility for large area CVD is a requirement for the realization of these different properties in various applications. Unfortunately, there are at present severe problems in the CVD growth of c-BN. The purpose with this research project has been to theoretically investigate, using DFT calculations, the possibility for a layer-by-layer CVD growth of c-BN. It could be established that, PEALD, using a BF3-H2-NH3-F2 pulse cycle and a diamond substrate, is a promising method for deposition of c-BN films. The gaseous species will decompose in the plasma and form BFx, H, NHx, and F species (x = 0, 1, 2, 3). The H and F radicals will uphold the cubic structure by completely hydrogenate, or fluorinate, the growing surface. However, surface radical sites will appear during the growth process as a result of atomic H, or F, abstraction reactions. The addition of NHx growth species (x = 0, 1, 2) to B radical sites, and BFx growth species (x = 0, 1, 2) to N radical sites, will then result in a continuous growth of c-BN.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2013. , 26 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1012
Keyword [en]
cubic boron nitride, chemical vapor deposition, density functional theory, adsorption, abstraction
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-191181ISBN: 978-91-554-8577-1 (print)OAI: oai:DiVA.org:uu-191181DiVA: diva2:586403
Public defence
2013-02-27, Häggsalen, Lägerhyddsvägen 1, 75121, Uppsala, 15:15 (English)
Opponent
Supervisors
Available from: 2013-02-06 Created: 2013-01-09 Last updated: 2013-04-02Bibliographically approved
List of papers
1. Hydrogen-Induced De/Reconstruction of the c-BN(100) Surface
Open this publication in new window or tab >>Hydrogen-Induced De/Reconstruction of the c-BN(100) Surface
2010 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 114, no 8, 3516-3521 p.Article in journal (Refereed) Published
Abstract [en]

The cubic phase of boron nitride (c-BN) is an extremely promising multifunctional material. However, to exploit all possible applications, large area chemical vapor deposition (CVD) of c-BN films is required. For a successful CVD growth of high-quality c-BN films one must obtain a deeper understanding about the structural and electronic properties of the dominant c-BN growth surfaces under CVD conditions, that is, the (100), (110), and (111) surfaces, and their modification in the presence of surface stabilizing atomic hydrogen (H). In the present study, the surface stabilizing effect of H on the B- and N-terminated (1 × 1), (2 × 1), (2 × 4), (2 × 4(3)), and c(2 × 2) surfaces of c-BN(100) has therefore been investigated using density functional theory (DFT) calculations. It was found that a 100% surface coverage of on-top H on the B-terminated c-BN(100) surfaces is not able to uphold an ideal bulk-like (1 × 1) structure. However, the H atoms were able to uphold a bulk-like bond angle and bond length for the surface B atoms on the 100% H-covered B-terminated c-BN(100)-(2 × 1) surface. For the N-terminated c-BN(100) surfaces opposite observations were made. The H atoms were found to chemisorb strongly to both the B-terminated c-BN(100)-(2 × 1) surface and the N-terminated c-BN(100)-(1 × 1) surface. The process of H abstraction, with gaseous atomic H, was found to be significantly more favorable for the B-terminated c-BN(100)-(2 × 1) surface than for the N-terminated c-BN(100)-(1 × 1) surface. It was also found that N radical sites are more stable toward radical surface site collapse than B radical sites.

Place, publisher, year, edition, pages
American Chemical Society, 2010
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-120724 (URN)10.1021/jp907186a (DOI)000274842700027 ()
Available from: 2010-03-16 Created: 2010-03-16 Last updated: 2017-12-12Bibliographically approved
2. Halogen-Induced Reconstruction of the c-BN(100) Surface
Open this publication in new window or tab >>Halogen-Induced Reconstruction of the c-BN(100) Surface
2011 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 46, 22910-22916 p.Article in journal (Refereed) Published
Abstract [en]

The cubic phase of boron nitride (c-BN) is an extremely promising multifunctional material. However, to exploit all possible applications, large area chemical vapor deposition (CVD) of c-BN films is required. To be successful in the CVD growth of high-quality c-BN films, one must be able to stabilize the sp(3) hybridization of the surface atoms; and in the present study, the surface stabilizing effect of F and Cl on the B- and N-terminated c-BN(100)-(1 x 1) surfaces has been investigated using density functional theory (DFT) calculations. It was found that Cl, most probably, will induce large sterical hindrance on both the B- and N-terminated c-BN(100) surface. F, on the other hand, was found to be a promising surface stabilizing agent for the B- and N-terminated c-BN(100) surface. However, the F atoms must be abstracted with H atoms. It can therefore be concluded that the optimal gas-phase composition for growth of c-BN consists of a mixture of H and F.

National Category
Chemical Sciences Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-163656 (URN)10.1021/jp205898w (DOI)000297001000028 ()
Available from: 2011-12-14 Created: 2011-12-13 Last updated: 2017-12-08Bibliographically approved
3. Adsorption of Growth Species on the c-BN(100) Surface
Open this publication in new window or tab >>Adsorption of Growth Species on the c-BN(100) Surface
2011 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 34, 16977-16983 p.Article in journal (Refereed) Published
Abstract [en]

The cubic phase of boron nitride (c-BN) is an extremely promising multifunctional material. However, to exploit all possible applications, a successful route for large area chemical vapor deposition (CVD) of c-BN films is required. Adsorption of gaseous growth species onto the c-BN surface is one of the key elementary reactions in CVD growth of c-BN. In the present work, the ability of BH(x), BF(x), and NH(x) species (x = 0, 1, 2, 3) to act as growth species for CVD of c-BN, in an H-, F-, or H/F-saturated gas-phase, has been investigated using density functional theory (DFT) calculations. It was found that the most optimal growth species for CVD growth of c-BN are B, BH, BH(2), BF, BF(2), N, NH, and NH(2) in an H/F-saturated gas-phase, i.e., decomposition of the incoming BH(3), BF(3), and NH(3) growth species is very crucial for CVD growth of c-BN. It was also found that it would be most preferable to use a CVD method where the incoming BH(3), BF(3), and NH(3) growth species are separately introduced into the reactor, e.g., by using an atomic layer deposition (ALD) type of method.

National Category
Chemical Sciences Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-158585 (URN)10.1021/jp203482v (DOI)000294146700032 ()
Available from: 2011-09-12 Created: 2011-09-12 Last updated: 2017-12-08Bibliographically approved
4. Kinetic Considerations of Gas-Phase Abstraction of H and F from the c-BN(100) Surface
Open this publication in new window or tab >>Kinetic Considerations of Gas-Phase Abstraction of H and F from the c-BN(100) Surface
2013 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 548, 280-287 p.Article in journal (Refereed) Published
Abstract [en]

The cubic phase of boron nitride (c-BN) is an extremely promising multifunctional material. To exploit all possible applications, large area chemical vapor deposition (CVD) of c-BN films is required. To maintain the cubic (sp(3)) structure of the surface atoms, the growing surface is covered with surface stabilizing species. However, the surface stabilizing species must also be able to undergo abstraction reactions with gaseous species and, hence, leave room for an incoming B-or N-containing growth species for a continuous c-BN growth to occur. The abstraction process is therefore a central elementary reaction step in CVD growth of c-BN. Hydrogen, H, and fluorine, F, have earlier been found to be promising as surface stabilizing species for both the B-and N-terminated c-BN(100) surfaces - the sp(2) structure is maintained and both H and F bind strongly to the surface. In addition, of highest importance is the chemical capability to remove these terminating species from the surface, leaving a highly reactive surface site (i.e., gas-phase abstraction). The present study has therefore focused on, by using density functional theory (DFT), the kinetics of the H-or F-abstraction processes from the B-or N-terminated c-BN(100) surface. The energetic and structural evolution for gaseous F approaching a surface-binding F species, show that F radicals are not able to abstract chemisorbed F atoms, i.e., a gas-phase containing only F is unfavorable for growth of c-BN(100). On the other hand, H radicals are able to abstract chemisorbed H atoms. However, a minor barrier of energy was observed for the N-terminated surface (+ 13 kJ/mol). The abstraction of F from the B-terminated surface, with gaseous H radicals, was found to be highly probable from both thermodynamic and kinetic considerations, being also the situation for the F-covered N-terminated surface (with a minor energy barrier of + 8 kJ/mol). In addition, the energy evolution for the approaching F to a surface H, clearly shows that any abstraction reaction will never take place. Hence, the results within the present study clearly show that at realistic deposition temperatures, it is only gaseous H that will have the capacity to remove H or F from the c-BN(100) surface.

Keyword
cubic boron nitride, chemical vapor deposition, density functional theory, adsorption, abstraction
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-191177 (URN)10.1016/j.tsf.2013.08.062 (DOI)000327530300045 ()
Available from: 2013-01-09 Created: 2013-01-09 Last updated: 2017-12-06Bibliographically approved

Open Access in DiVA

fulltext(2791 kB)416 downloads
File information
File name FULLTEXT01.pdfFile size 2791 kBChecksum SHA-512
ca965beea0b4b16e80872c8052dfa51ee4e9c546a3366f1aff9cf7fc48822f08cc367af9ce7c8de3bb4fa1bc632812ac7053b7f67f737c78a2950ef9963b5a7c
Type fulltextMimetype application/pdf
Buy this publication >>

Search in DiVA

By author/editor
Karlsson, Johan
By organisation
Inorganic Chemistry
Inorganic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 416 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 943 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf