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359
ISSN 1063-7850, Technical Physics Letters, 2019, Vol. 45, No. 4,
pp. 359–363. © Pleiades Publishing, Ltd., 2019.Russian Text © V.A.
Plotnikov, B.F. Dem’yanov, S.V. Makarov, A.I. Zyryanova, 2019,
published in Pis’ma v Zhurnal Tekhnicheskoi Fiziki, 2019, Vol. 45,
No. 7, pp. 52–56.
Self-Organization of Detonation-Diamond Particles on a Substrate
in Carbon Condensation
from the Vapor–Gas PhaseV. A. Plotnikova*, B. F. Dem’yanova, S.
V. Makarova, and A. I. Zyryanovaa
a Altai State University, Barnaul, Russia*e-mail:
[email protected]
Received July 26, 2018; revised January 10, 2019; accepted
January 17, 2019
Abstract—Processes in which the island structure is ordered
occur in composite carbon films produced bypreliminary population
of an amorphous substrate with a detonation-diamond system and
subsequent con-densation of carbon from the vapor–gas phase. These
processes, observed already upon filling of the substratewith
diamond-growth centers, are manifested in that there appears a
structural periodicity of the islands. Itwas found that the
condensation of carbon on the populated substrate is accompanied by
the evolution of theisland structure of primary growth centers.
This consists in that a hexagonal packing of the islands is
formed,with the size of these islands increasing by two orders of
magnitude. All these structural features of how acomposite
diamond-carbon film is formed indicate that self-organization
processes occur in the system ofdiamond islands when carbon atoms
are condensed and interact with primary diamond crystals.
DOI: 10.1134/S1063785019040126
The discovery of a large number of new allotropicmodifications
of carbon has resulted in the creation ofmaterials with a wide
variety of physical and mechan-ical properties [1]. Such materials
as diamond, nano-tubes, fullerenes, and amorphous carbon films
possessa unique combination of properties: high chemical,thermal,
radiation, hardness, and wear resistance; asmall thermal expansion
coefficient; low specific heat;high heat conductivity; a wide
energy gap; and trans-parency in a wide spectral range. The
classification ofthese carbon allotropes is based on the property
ofhybridization of valence orbitals [2].
Another classification of carbon materials is basedon the number
of nearest atoms (2, 3, 4) with whicheach atom forms covalent bonds
[3]. The already-developed classifications can be used to engineer
car-bon nanostructures that are promising for creatingmaterials
with prescribed physicomechanical proper-ties. For example,
detonation nanodiamond can beused to form carbon composite
structures with quan-tum dots [4]. If a composite carbon structure
is pro-duced in the thin-film form, a high elasticity and
goodtribological characteristics are noted, which is a con-sequence
of the self-organization of its structure [5]. Itis important to
note that carbon in composites withdiamond enables control over
many of their proper-ties, such as heat conductivity, electrical
conductivity,and magnetism [6].
As they possess the property of self-organization,composite and
hybrid carbon materials can form
superlattices of nanosize particles incorporated into
ahomogeneous matrix. Therefore, detonation diamondcan be the main
element in carbon composite struc-tures because of making it
possible to control theproperties of a system via both the size of
a superlatticeand the properties of a nanoparticle [7].
However,problems are observed in this case, one of which con-sists
in providing a high periodicity of self-organiza-tion
superstructures and the resulting stability of theproperties of
carbon composites.
Self-organization processes can yield orderedstructures that
possess elements of symmetry [8]. Forexample, coarse (up to 80 nm)
diamond particles withdecahedral and icosahedral faceting are
formed in thesystem of chaotically oriented particles of
detonationdiamond under the action of high temperatures
andpressures [8]. Diamond particles of this kind havebeen formed
under thermobaric conditions viaordered self-assembly of the
starting particles; i.e., thestarting nanoparticles are
self-organization elements.It has been found that the growth of
diamond crystalsunder high-pressure and -temperature conditions in
amixture of detonation-diamond nanocrystals with asaturated acyclic
hydrocarbon occurs by the mecha-nism of oriented addition of both
separate carbonatoms and their small clusters [9].
The phenomenon of self-organization of nanopar-ticles to give
ordered superstructures is presumably ofmore general nature. It is
also observed in depositiononto a substrate of not only carbon, but
metallic and
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TECHNICAL PHYSICS LETTERS Vol. 45 No. 4 2019
PLOTNIKOV et al.
semiconductor particles as well. For example, deposi-tion of Au
and CdSe nanoparticles onto a carbon filmyields a close-packed 2D
structure, which is a “super-lattice” with a sixth-order symmetry
axis. In addition,CdSe crystals have been seen to have a
pronouncedtexture in which the [001] crystallographic direction
ofall the nanoparticles was oriented perpendicularly tothe plane of
the carbon substrate [10].
It is known that detonation nanodiamond tends toform chain
aggregates: strong primary with sizes of upto 100 nm and weaker
secondary with sizes of about1 m [11]. For films to be formed from
detonationnanodiamond crystals, it is necessary to disperse
start-ing conglomerates of diamond particles to sizes of sep-arate
crystals. We present data on the structures of dia-mond films
produced by laser dispersion of detona-tion-nanodiamond targets in
a vacuum and depositionof particles onto silicate glass
substrates.
Compacted detonation-nanodiamond targets weredispersed in an
evacuated volume (residual pressure10–5 mmHg) under the action of
focused light with awavelength of 1064 nm, pulse energy of 1–3 J,
andpulse width of about 1 ms. Detonation-diamond par-ticles and
coarser conglomerates were deposited fromthe f lare formed by the
ablation of the target onto sili-cate glass substrates.
The island structure of a diamond film formed bythe transfer of
the target substance to the substrate bythe ablation is shown in
Fig. 1. The island structurewas examined with a SOLVER NEXT
scanning probeelectron microscope. This was done by a Fourier
anal-ysis of the island structure of the film with the use ofan
Image Analysis P9 image-processing unit, shippedwith the probe
microscope. The Fourier image of theisland structure (Fig. 1b)
contains, in addition to thecentral spot, two reflections that are
symmetrical withrespect to this spot. This indicates that coarse
con-
Fig. 1. (a) Island structure of a film of detonation diamond,
(b) Fourier image of the island structure of the diamond film,
and(c) radial distribution function. The arrows show the
reflections from a periodic structure with small periodicity
parameter.
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TECHNICAL PHYSICS LETTERS Vol. 45 No. 4 2019
SELF-ORGANIZATION OF DETONATION-DIAMOND PARTICLES 361
glomerates coexist with fine particles the periodic-ity
parameter of which on the substrate is 5.7 nm(found from an
analysis of the cross-section profilein Fig. 1c). Thus, the laser
dispersion (laser ablation)of a nanodiamond target makes it
possible to populatethe substrate with growth centers with sizes of
severalnanometers to several micrometers. It is importantthat
separate detonation-diamond crystals (averagenanocrystal size 4.5
nm) densely occupy the substratesurface (periodicity parameter 5.7
nm).
To diminish the free space between detonation-diamond particles,
carbon was condensed onto a sub-strate preliminarily populated with
detonation-dia-mond nanocrystals from a vapor–gas phase producedby
evaporation of a graphite substrate with a defocusedlaser beam at a
light density no lower than 1.6 ×104 W/cm2. Figure 2 shows the
island structure of thediamond film after the condensation of
carbon. Thesedata are indicative of a significant change of the
islandstructure of the composite film. The size of the
islandssubstantially increased as compared with the initialvalue.
Fourier analysis of the island structure (Fig. 2b)
demonstrates a clearly pronounced periodicity in thearrangement
of diamond particles (according to thedata in Fig. 2c, the
periodicity parameter found fromthe position of the maximum in the
radial-distributionfunction was 285.2 ± 0.6 nm) and ordered
close-packed diamond islands on the surface of a substratewith
hexagonal symmetry.
Thus, an expansion of nanosize particles from 4.5to about 285.2
nm is observed in the course of carboncondensation on a substrate
preliminarily populatedwith nucleation centers with periodicity of
5.7 nm. Anensemble of these particles (islands) forms a
close-packed hexagonal island structure of the diamondfilm. This
structure has the form of a polycrystallineaggregation of islands
with average size of 285.2 nm,which are similarly oriented with
respect to the filmsurface.
It can be supposed that amorphous carbon con-densed on the
substrate is transformed at interfacesinto diamond. This conclusion
is not unexpected. Itwas noted in a number of publications that a
nanodia-mond about 4 nm in size is thermodynamically more
Fig. 2. (a) Island structure of a detonation diamond–carbon
condensate composite film, (b) Fourier image of the island
structureof the diamond film, and (c) radial distribution
function.
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TECHNICAL PHYSICS LETTERS Vol. 45 No. 4 2019
PLOTNIKOV et al.
stable than graphite. Therefore, it seems possible thatpart of a
graphite-like layer of carbon acquires a dia-mond structure.
The action of a laser on a detonation-diamond tar-get not only
leads to its dispersion into fragments, butis also accompanied by
their purification, removingimpurities, primarily volatile
compounds [13], whichactivates the unfilled carbon bonds at the
interfaces. Italso seems apparent that the evaporation of the
graph-ite target by a laser leads to ionization and excitation
ofcarbon in the vapor–gas phase. Thus, carbon activelyinteracts in
the course of condensation with the start-ing nanodiamond crystals,
which leads to their signif-icant growth. It is not inconceivable
that the startingcrystals are combined into a single-crystal block
whena large number of activated carbon atoms appear at
theinterfaces. All these processes result in the formationof an
ordered structure of diamond islands.
The presence of a diamond, or more precisely, dia-mond-like
structure of the carbon film is confirmedby analysis on a Philips
CM 30 transmission electronmicroscope. Figure 3 shows the structure
and an elec-tron diffraction pattern of the part of a film
understudy. An interpretation of the diffraction
patterndemonstrated that the rings (diffraction peaks) corre-spond
to the diffraction from the (111) and (220)planes of the diamond
lattice. The interplanar spac-ings have the values d111 = 0.207 and
d220 = 0.119 nm.Comparison with the interplanar spacings for
coarse-crystalline diamond, d111 = 0.205 and d220 = 0.125 nm,shows
that the values obtained differ from those tabu-lated. In the film,
interplanar spacing d111 is larger,while d220 is smaller than those
for the equilibrium lat-tice. This lattice distortion is
characteristic of dia-mond-like thin films. For example, thin
carbon films
produced by laser evaporation and carbon condensa-tion were
examined in [14]. For these films, the inter-planar spacings were
d111 = 0.208 and d220 = 0.117 nm.In other studies, the values d111
= 0.207 nm wereobtained [15]. These data give reason to believe
that, inall probability, the interatomic distances areunchanged,
the length of the C–C bond remains con-stant, but the angles
between the bonds change, asoccurs in carbon nanotubes and
fullerenes [16].
As can be seen from the configuration of the islandsin Fig. 2a,
it can be considered that about six diamondparticles are situated
on an area of 0.25 m2, i.e., thenumber of particles in 1 cm2 is
about 24 × 108. Accord-ing to modern understandings, such a density
of parti-cles is optimal for, e.g., fabrication of cathode
materi-als [17]. Thus, the laser method can form a
compositeconstituted by the detonation nanodiamond and a car-bon
diamond-like film, with the required concentra-tion of structural
elements determining its emissionproperties.
Experiments in which a composite film made
ofdetonation-diamond–carbon condensate is formedare indicative of
an ordered structure of islands hexag-onally close-packed on the
surface of the amorphoussubstrate. It is worth noting the strong
(by two ordersof magnitude) growth of the starting
detonation-dia-mond crystals in the condensation of carbon from
thevapor–gas phase onto the amorphous substrate pre-liminarily
populated with growth centers. The effectsof ordering in the system
of islands are indicative of theactivation of self-organization
processes in carboncondensation onto a substrate populated with
dia-mond growth centers.
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111 220
100 nm
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SELF-ORGANIZATION OF DETONATION-DIAMOND PARTICLES 363
10. M. A. Zaporozhets, S. V. Savilov, O. M. Zhigalina,S. N.
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Translated by M. Tagirdzhanov
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