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The Effect of Various Dopants on Diamond Growth: A Combined Experimental & Theoretical Approach
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Diamond is a unique material with many exceptional properties. It has therefore been proven to be an important material for many applications. Moreover, the introduction of dopant species into the gas phase during the CVD growth process has been shown to strongly influence not only the properties and morphology of diamond, but also the growth rate. The purpose with the theoretical part of the present study has been to support and explain the experimental observations regarding the effect of various dopants (nitrogen, phosphorous, sulphur, and boron) on the diamond growth rate. Commonly observed H-terminated diamond surfaces [(111), (110) and (100)-2×1], were thereby carefully investigated using density functional theory under periodic boundary conditions. Based on the assumption that the hydrogen abstraction reaction is the growth rate-limiting step, both the thermodynamic and kinetic aspects of the diamond growth process were found to be severely affected by various dopants. More specifically, the results showed that nitrogen and phosphorous dopants (positioned within the 2nd, 3rd or 4th carbon layer) will cause an enhancement in the growth rate (as compared with non-doped situations). On the other hand, any growth rate improvement does only occur when positioning boron in the 2nd, and sulphur in the 4th, atomic carbon layer. With boron, and sulphur, positioned within the other atomic carbon layers, the growth rates were observed to decrease. In addition, the main purpose with the experimental part of the present study has been to investigate the effect of one specific dopant precursor (TMB) on the boron-doped diamond growth process. The result has shown that the increasing mass flow of TMB will not affect the mechanism of the HFCVD growth process of boron doped diamond. However, a linear boron carrier concentration in the diamond film vs. mass flow rate of TMB was observed. 

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2016. , 71 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1333
Keyword [en]
Diamond, Growth rate, HFCVD, Doping, Activation energy, Reaction order
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-271491ISBN: 978-91-554-9447-6 (print)OAI: oai:DiVA.org:uu-271491DiVA: diva2:892058
Public defence
2016-02-29, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Funder
Swedish Research Council
Available from: 2016-02-04 Created: 2016-01-08 Last updated: 2016-02-12
List of papers
1. Effect of CVD diamond growth by doping with nitrogen
Open this publication in new window or tab >>Effect of CVD diamond growth by doping with nitrogen
2013 (English)In: Theoretical Chemistry accounts, ISSN 1432-881X, E-ISSN 1432-2234, Vol. 133, no 2, 1432- p.Article in journal (Refereed) Published
Abstract [en]

The purpose with the present investigation has been to support and explain the experimental observation made regarding the enhancing effect by N doping on especially the diamond (100)-2 x 1 growth rate. Within the present study, also the commonly observed diamond (111) and (110) surfaces were included, all assumed to be H-terminated. Density functional theory calculations were used, based on a plane wave approach under periodic boundary conditions. It was shown that the surface H abstraction reaction is most probably the rate-limiting step during diamond growth. In addition, the results showed that it is N, substitutionally positioned within the upper diamond surface, that will cause the growth rate improvement, and not nitrogen chemisorbed onto the growing surface in the form of either NH (or NH2). The here presented numerical value for the growth rate enhancement for the diamond (100)-2 x 1 surface is almost identical with the experimentally obtained one (3.7 vs. 3.6). In addition, the (111) and (110) surfaces were shown to undergo a different growth rate enhancement, with about half as much for the (111) and (110) surfaces as compared to the diamond (100)-2 x 1 surface (1.9, 1.7 vs. 3.7). Despite the rate improvement for all surface planes, this difference will bring about a preferred diamond (100) surface texture.

Keyword
Diamond, Growth rate enhancement, CVD, Ab initio theory, N doping
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-214015 (URN)10.1007/s00214-013-1432-y (DOI)000328347100001 ()
Available from: 2014-01-08 Created: 2014-01-07 Last updated: 2017-12-06Bibliographically approved
2. Effect of Sulphur and Phosphorous Doping on the Growth Rate of CVD Diamond (111)
Open this publication in new window or tab >>Effect of Sulphur and Phosphorous Doping on the Growth Rate of CVD Diamond (111)
(English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731Article in journal (Refereed) Submitted
Abstract [en]

The purpose with the present study has been to theoretically investigate the effect of P (or S) doping on the diamond growth rate. The highly symmetric diamond (111) surface, terminated by H atoms, was thereby carefully investigated using density functional theory calculations under periodic boundary conditions. It was shown that both the thermodynamic and kinetic aspects of P (or S) doping during diamond growth will be severely affected by the dopants (as compared with the non-doped situations). More specifically, the results showed that P (positioned within the 2nd, 3rd or 4th layer), will cause an enhancement in the growth rate. On the other hand, any growth rate improvement do only occur when positioning S in the 4th atomic C layer. With S in atomic layers 1, 2 and 3, the growth rates were observed to decrease. These observations did correlate with experimental results.

Keyword
Growth rate, CVD, Ab initio theory, P doping, S doping
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-271511 (URN)
Available from: 2016-01-08 Created: 2016-01-08 Last updated: 2017-12-01
3. Effect of Boron Doping on the CVD Growth Rate of Diamond
Open this publication in new window or tab >>Effect of Boron Doping on the CVD Growth Rate of Diamond
2016 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 19, 10658-10666 p.Article in journal (Refereed) Published
Abstract [en]

The purpose with the present study has been to theoretically investigate the effect of boron doping on the diamond growth rate. The most frequently observed diamond surface planes (100), (111) and (110) were thereby carefully investigated using density functional theory calculations under periodic boundary conditions. It was shown that both the thermodynamic and kinetic aspects of the diamond growth process will be severely affected by the B dopant (as compared with the non-doped situations). More specifically, the results showed that B (positioned within the 2nd atomic C layer) will cause an enhancement in the growth rate. On the other hand, the effect of B positioned in the other atomic C layers showed a decreased growth rate. These observations did not only correlate with experimental results but did also explain the anomalous variations in the diamond growth rate (i.e., either increase or decrease) with B doping.

Keyword
Diamond, Growth rate, CVD, Ab initio theory, B doping
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-271512 (URN)10.1021/acs.jpcc.6b02227 (DOI)000376417500059 ()
External cooperation:
Funder
Swedish Research Council
Available from: 2016-01-08 Created: 2016-01-08 Last updated: 2017-12-01Bibliographically approved
4. Kinetic Study on the Growth of HFCVD B-doped Diamond
Open this publication in new window or tab >>Kinetic Study on the Growth of HFCVD B-doped Diamond
(English)Manuscript (preprint) (Other academic)
Abstract [en]

The purpose with the present study has been to investigate the effect of trimethylborate on the diamond growth kinetics as a function of the boron carrier concentration in that diamond film. The kinetics of diamond hot filament CVD as a function of different gas compositions and various substrate temperatures were carefully studied. It was shown that the boron carrier concentration depended mainly on the boron concentration in the gas phase, but it is also various relative to the growth mechanism changes from surface kinetic to mass transport. However, trimethylborate did not alter the kinetics or HFCVD diamond growth mechanism at a measurable level. Moreover, Raman spectroscopy revealed that trimethylborate affected the quality of B-doped diamond films. 

Keyword
Boron doped diamond, HFCVD, Trimethylborate, Chemical kinetic, Boron carrier concentration
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-271513 (URN)
Available from: 2016-01-08 Created: 2016-01-08 Last updated: 2016-02-12

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