Etching effects during the chemical vapor deposition of (100) diamond

Battaile, Corbett Chandler.; Srolovitz, David J.; Oleinik, I. I.; Pettifor, D. G.; Sutton, A. P.; Harris, Stephen J.; Butler, James E.

doi:10.1063/1.479727

Cited by 73 publications

(59 citation statements)

References 55 publications

(84 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The preferentially occurring desorption of CH 3 radicals at flat sites away from step edges as postulated in Ref. [19] may additionally take place. However, surface diffusion of growth species has to be taken into account when trying to explain such extremely flat faces featuring some degree of long distance order of step edges after long growth times at high substrate temperatures.…”

Section: Morphologymentioning

confidence: 84%

CVD-diamond single-crystal growth

Schwarz

Rottmair

Hirmke

et al. 2004

Journal of Crystal Growth

View full text Add to dashboard Cite

Section: Morphologymentioning

confidence: 84%

CVD-diamond single-crystal growth

Schwarz

Rottmair

Hirmke

et al. 2004

Journal of Crystal Growth

View full text Add to dashboard Cite

“…Previous researchers have used quantum chemical methods to model the energy barrier for etching in a variety of microscopic models of the growing diamond surface. 16,29,30 The energy barriers were also used, together with transition-state theory, to obtain microscopic rate constants for etching. The barrier heights are, however, somewhat dependent on the level of quantum-mechanical theory used.…”

Section: Processmentioning

confidence: 99%

Three-dimensional kinetic Monte Carlo simulations of diamond chemical vapor deposition

Rodgers

May

Allan

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

A three-dimensional kinetic Monte Carlo model has been developed to simulate the chemical vapor deposition of a diamond (100) surface under conditions used to grow single-crystal diamond (SCD), microcrystalline diamond (MCD), nanocrystalline diamond (NCD), and ultrananocrystalline diamond (UNCD) films. The model includes adsorption of CH x (x = 0, 3) species, insertion of CH y ( y = 0-2) into surface dimer bonds, etching/desorption of both transient adsorbed species and lattice sidewalls, lattice incorporation, and surface migration but not defect formation or renucleation processes. A value of ∼200 kJ mol −1 for the activation Gibbs energy, ∆G ‡ etch , for etching an adsorbed CH x species reproduces the experimental growth rate accurately. SCD and MCD growths are dominated by migration and step-edge growth, whereas in NCD and UNCD growths, migration is less and species nucleate where they land. Etching of species from the lattice sidewalls has been modelled as a function of geometry and the number of bonded neighbors of each species. Choice of appropriate parameters for the relative decrease in etch rate as a function of number of neighbors allows flat-bottomed etch pits and/or sharp-pointed etch pits to be simulated, which resemble those seen when etching diamond in H 2 or O 2 atmospheres. Simulation of surface defects using unetchable, immobile species reproduces other observed growth phenomena, such as needles and hillocks. The critical nucleus for new layer growth is 2 adjacent surface carbons, irrespective of the growth regime. We conclude that twinning and formation of multiple grains rather than pristine single-crystals may be a result of misoriented growth islands merging, with each island forming a grain, rather than renucleation caused by an adsorbing defect species. C 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License. [http://dx

show abstract

“…However, recent theoretical models have shown that the addition of surface diffusion to models would lead to higher growth rates than are experimentally observed [11]. Other mechanisms that have been proposed to explain the growth of smooth diamond (100) films are anisotropic etching [12] and preferential etching of under-coordinated atoms [11]; however, there has not yet been any direct evidence for these processes. In this paper, we report, for the first time, atomic resolution UHV STM studies of the temperature dependence of the etching of epitaxial diamond (100) films by atomic hydrogen, and these results support the anisotropic etching model.…”

mentioning

confidence: 99%

“…Diffusion on the diamond (100) surface during growth has been modeled as occurring along surface sites where hydrogen has been removed by abstraction [10]. However, recent theoretical models have shown that the addition of surface diffusion to models would lead to higher growth rates than are experimentally observed [11]. Other mechanisms that have been proposed to explain the growth of smooth diamond (100) films are anisotropic etching [12] and preferential etching of under-coordinated atoms [11]; however, there has not yet been any direct evidence for these processes.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Scanning Tunneling Microscopy Studies of Temperature-Dependent Etching of Diamond (100) by Atomic Hydrogen

Stallcup

Pérez

2001

Phys. Rev. Lett.

View full text Add to dashboard Cite

We present a technique for obtaining atomic resolution ultrahigh vacuum scanning tunneling microscopy images of diamond (100) films, and use this technique to study the temperature dependence of the etching of epitaxial diamond (100) films by atomic hydrogen. We find that etching by atomic hydrogen is highly temperature dependent, resulting in a rough and pitted surface at T ഠ 200 and 500 ± C, respectively. At T ഠ 1000 ± C etching results in a smooth surface and is highly anisotropic, occurring predominantly in the direction of dimer rows. This observation supports recent theoretical models that propose anisotropic etching as the mechanism for the growth of smooth diamond (100) films. DOI: 10.1103/PhysRevLett.86.3368 PACS numbers: 81.65.Cf, 68.37.Ef Diamond films grown using chemical vapor deposition (CVD) [1] have recently attracted considerable interest due to the unique mechanical and electronic properties of this material [2]. CVD growth of diamond films is not as well understood as CVD growth of Si and other semiconductors. Growth of diamond films requires a large ratio of molecular hydrogen ͑H 2 ͒ to hydrocarbon gas. During growth, H 2 is dissociated into atomic hydrogen by a hot-tungsten filament or microwaves. It is known that atomic hydrogen etches away graphite, and promotes diamond growth by terminating the diamond surface in an sp 3 configuration [1][2][3]. It is also known that atomic hydrogen etches diamond [1][2][3]. However, the effects of atomic hydrogen etching of diamond during growth are not well understood. Scanning tunneling microscopy (STM) in ultrahigh vacuum (UHV) has been extensively used to study the etching and growth of Si [4,5] and other semiconductors [5] at the atomic scale. To our knowledge, UHV STM has not been extensively used to study diamond. Most STM studies of diamond have been performed in air where sample preparation is limited to room temperature techniques and usually a hydrogen-terminated surface [6][7][8]. A recent study reported that STM was not possible in UHV because the diamond surface was not conductive enough until it was exposed to air [7]. One would like to see results of UHV STM of diamond comparable in quality to those that have been reported for Si.Epitaxial diamond (100) films are of particular interest because such films grow smooth at substrate temperatures T ഠ 1000 ± C [9], unlike epitaxial diamond (110) and (111) films that grow rough. The growth of smooth diamond (100) films is not well understood. Surface diffusion of adsorbates, which is responsible for the growth of most smooth films, is not widely accepted as responsible for the growth of smooth diamond (100) films because the hydrogen-terminated surface prevents diffusion [3]. Diffusion on the diamond (100) surface during growth has been modeled as occurring along surface sites where hydrogen has been removed by abstraction [10]. However, recent theoretical models have shown that the addition of surface diffusion to models would lead to higher growth rates than are experimentally observed [11...

show abstract

Etching effects during the chemical vapor deposition of (100) diamond

Cited by 73 publications

References 55 publications

CVD-diamond single-crystal growth

CVD-diamond single-crystal growth

Three-dimensional kinetic Monte Carlo simulations of diamond chemical vapor deposition

Scanning Tunneling Microscopy Studies of Temperature-Dependent Etching of Diamond (100) by Atomic Hydrogen

Contact Info

Product

Resources

About