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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: plotnikov@phys.asu.ru

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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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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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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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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Fig. 3. Light-field electron-microscopic image of a film,and an electron diffraction pattern of a part of the film inthe inset.

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10. M. A. Zaporozhets, S. V. Savilov, O. M. Zhigalina,S. N. Sul’yanov, V. V. Volkov, V. I. Nikolaichik,S. P. Gubin, and A. S. Avilov, Crystallogr. Rep. 57,426 (2012).

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15. S. A. Petrov, Vestn. BGU, Ser. 1, No. 1, 43 (2012).16. V. A. Plotnikov, B. F. Dem’yanov, K. V. Solomatin,

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17. R. K. Yafarov and N. M. Kotina, Fundam. Probl.Sovrem. Materialoved. 16, 534 (2016).

Translated by M. Tagirdzhanov

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