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Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II: CH4/N2/H2 plasmas

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Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II : CH4/N2/H2 plasmas. / Truscott, Benjamin S; Kelly, Mark W; Potter, Katie J ; Ashfold, Michael N R ; Mankelevich, Yuri A.

In: Journal of Physical Chemistry A, Vol. 120, No. 43, 03.11.2016, p. 8537-8549.

Research output: Contribution to journalArticle

Harvard

Truscott, BS, Kelly, MW, Potter, KJ, Ashfold, MNR & Mankelevich, YA 2016, 'Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II: CH4/N2/H2 plasmas' Journal of Physical Chemistry A, vol. 120, no. 43, pp. 8537-8549. DOI: 10.1021/acs.jpca.6b09009

APA

Truscott, B. S., Kelly, M. W., Potter, K. J., Ashfold, M. N. R., & Mankelevich, Y. A. (2016). Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II: CH4/N2/H2 plasmas. Journal of Physical Chemistry A, 120(43), 8537-8549. DOI: 10.1021/acs.jpca.6b09009

Vancouver

Truscott BS, Kelly MW, Potter KJ, Ashfold MNR, Mankelevich YA. Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II: CH4/N2/H2 plasmas. Journal of Physical Chemistry A. 2016 Nov 3;120(43):8537-8549. Available from, DOI: 10.1021/acs.jpca.6b09009

Author

Truscott, Benjamin S ; Kelly, Mark W ; Potter, Katie J ; Ashfold, Michael N R ; Mankelevich, Yuri A. / Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II : CH4/N2/H2 plasmas. In: Journal of Physical Chemistry A. 2016 ; Vol. 120, No. 43. pp. 8537-8549

Bibtex

@article{731900d0661547e88b844fa2d5de0507,
title = "Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II: CH4/N2/H2 plasmas",
abstract = "We report a combined experimental and modelling study of microwave-activated dilute CH4/N2/H2 plasmas, as used for chemical vapour deposition (CVD) of diamond, under very similar conditions to previous studies of CH4/H2, CH4/H2/Ar and N2/H2 gas mixtures. Using cavity ring-down spectroscopy, absolute column densities of CH(X, v=0), CN(X, v=0) and NH(X, v=0) radicals in the hot plasma have been determined as functions of height, z, source gas mixing ratio, total gas pressure, p, and input power, P. Optical emission spectroscopy has been used to investigate, with respect to the same variables, the relative number densities of electronically excited species, namely H atoms, CH, C2, CN and NH radicals, and triplet N2 molecules. The measurements have been reproduced and rationalised from first principles by 2-D (r, z) coupled kinetic and transport modelling, and comparison between experiment and simulation has afforded a detailed understanding of C/N/H plasma-chemical reactivity and variations with process conditions and with location within the reactor. The experimentally-validated simulations have been extended to much lower N2 input fractions and higher microwave powers than were probed experimentally, providing predictions for the gas-phase chemistry adjacent to the diamond surface and its variation across a wide range of conditions employed in practical diamond-growing CVD processes. The strongly bound N2 molecule is very resistant to dissociation at the input MW powers and pressures prevailing in typical diamond CVD reactors, but its chemical reactivity is boosted through energy pooling in its lowest-lying (metastable) triplet state and subsequent reactions with H atoms. For a CH4 input mole fraction of 4{\%}, with N2 present at 1–6000 ppm, at pressure p = 150 Torr and with applied microwave power P = 1.5 kW, the near-substrate gas-phase N atom concentration, [N]ns, scales linearly with the N2 input mole fraction and exceeds the concentrations [NH]ns, [NH2]ns, and [CN]ns of other reactive nitrogen-containing species by up to an order of magnitude. The ratio [N]ns/[CH3]ns scales proportionally with (but is 102–103 times smaller than) the ratio of the N2 to CH4 input mole fractions for the given values of p and P, but [N]ns/[CN]ns decreases (and thus the potential importance of CN in contributing to N-doped diamond growth increases) as p and P increase. Possible insights regarding the well-documented effects of trace N2 additions on the growth rates and morphologies of diamond films formed by CVD using MW-activated CH4/H2 gas mixtures are briefly considered.",
author = "Truscott, {Benjamin S} and Kelly, {Mark W} and Potter, {Katie J} and Ashfold, {Michael N R} and Mankelevich, {Yuri A}",
year = "2016",
month = "11",
day = "3",
doi = "10.1021/acs.jpca.6b09009",
language = "English",
volume = "120",
pages = "8537--8549",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "43",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Microwave plasma-activated chemical vapour deposition of nitrogen-doped diamond, II

T2 - Journal of Physical Chemistry A

AU - Truscott,Benjamin S

AU - Kelly,Mark W

AU - Potter,Katie J

AU - Ashfold,Michael N R

AU - Mankelevich,Yuri A

PY - 2016/11/3

Y1 - 2016/11/3

N2 - We report a combined experimental and modelling study of microwave-activated dilute CH4/N2/H2 plasmas, as used for chemical vapour deposition (CVD) of diamond, under very similar conditions to previous studies of CH4/H2, CH4/H2/Ar and N2/H2 gas mixtures. Using cavity ring-down spectroscopy, absolute column densities of CH(X, v=0), CN(X, v=0) and NH(X, v=0) radicals in the hot plasma have been determined as functions of height, z, source gas mixing ratio, total gas pressure, p, and input power, P. Optical emission spectroscopy has been used to investigate, with respect to the same variables, the relative number densities of electronically excited species, namely H atoms, CH, C2, CN and NH radicals, and triplet N2 molecules. The measurements have been reproduced and rationalised from first principles by 2-D (r, z) coupled kinetic and transport modelling, and comparison between experiment and simulation has afforded a detailed understanding of C/N/H plasma-chemical reactivity and variations with process conditions and with location within the reactor. The experimentally-validated simulations have been extended to much lower N2 input fractions and higher microwave powers than were probed experimentally, providing predictions for the gas-phase chemistry adjacent to the diamond surface and its variation across a wide range of conditions employed in practical diamond-growing CVD processes. The strongly bound N2 molecule is very resistant to dissociation at the input MW powers and pressures prevailing in typical diamond CVD reactors, but its chemical reactivity is boosted through energy pooling in its lowest-lying (metastable) triplet state and subsequent reactions with H atoms. For a CH4 input mole fraction of 4%, with N2 present at 1–6000 ppm, at pressure p = 150 Torr and with applied microwave power P = 1.5 kW, the near-substrate gas-phase N atom concentration, [N]ns, scales linearly with the N2 input mole fraction and exceeds the concentrations [NH]ns, [NH2]ns, and [CN]ns of other reactive nitrogen-containing species by up to an order of magnitude. The ratio [N]ns/[CH3]ns scales proportionally with (but is 102–103 times smaller than) the ratio of the N2 to CH4 input mole fractions for the given values of p and P, but [N]ns/[CN]ns decreases (and thus the potential importance of CN in contributing to N-doped diamond growth increases) as p and P increase. Possible insights regarding the well-documented effects of trace N2 additions on the growth rates and morphologies of diamond films formed by CVD using MW-activated CH4/H2 gas mixtures are briefly considered.

AB - We report a combined experimental and modelling study of microwave-activated dilute CH4/N2/H2 plasmas, as used for chemical vapour deposition (CVD) of diamond, under very similar conditions to previous studies of CH4/H2, CH4/H2/Ar and N2/H2 gas mixtures. Using cavity ring-down spectroscopy, absolute column densities of CH(X, v=0), CN(X, v=0) and NH(X, v=0) radicals in the hot plasma have been determined as functions of height, z, source gas mixing ratio, total gas pressure, p, and input power, P. Optical emission spectroscopy has been used to investigate, with respect to the same variables, the relative number densities of electronically excited species, namely H atoms, CH, C2, CN and NH radicals, and triplet N2 molecules. The measurements have been reproduced and rationalised from first principles by 2-D (r, z) coupled kinetic and transport modelling, and comparison between experiment and simulation has afforded a detailed understanding of C/N/H plasma-chemical reactivity and variations with process conditions and with location within the reactor. The experimentally-validated simulations have been extended to much lower N2 input fractions and higher microwave powers than were probed experimentally, providing predictions for the gas-phase chemistry adjacent to the diamond surface and its variation across a wide range of conditions employed in practical diamond-growing CVD processes. The strongly bound N2 molecule is very resistant to dissociation at the input MW powers and pressures prevailing in typical diamond CVD reactors, but its chemical reactivity is boosted through energy pooling in its lowest-lying (metastable) triplet state and subsequent reactions with H atoms. For a CH4 input mole fraction of 4%, with N2 present at 1–6000 ppm, at pressure p = 150 Torr and with applied microwave power P = 1.5 kW, the near-substrate gas-phase N atom concentration, [N]ns, scales linearly with the N2 input mole fraction and exceeds the concentrations [NH]ns, [NH2]ns, and [CN]ns of other reactive nitrogen-containing species by up to an order of magnitude. The ratio [N]ns/[CH3]ns scales proportionally with (but is 102–103 times smaller than) the ratio of the N2 to CH4 input mole fractions for the given values of p and P, but [N]ns/[CN]ns decreases (and thus the potential importance of CN in contributing to N-doped diamond growth increases) as p and P increase. Possible insights regarding the well-documented effects of trace N2 additions on the growth rates and morphologies of diamond films formed by CVD using MW-activated CH4/H2 gas mixtures are briefly considered.

U2 - 10.1021/acs.jpca.6b09009

DO - 10.1021/acs.jpca.6b09009

M3 - Article

VL - 120

SP - 8537

EP - 8549

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 43

ER -