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1 DIAMOND NUCLEATION FROM AN ACTIVATED VAPOR PHASE Boris V. Spitsyn Institute of Physical Chemistry RAS, 31 Leninsky Pr., 119991 Moscow, RUSSIA.

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Presentation on theme: "1 DIAMOND NUCLEATION FROM AN ACTIVATED VAPOR PHASE Boris V. Spitsyn Institute of Physical Chemistry RAS, 31 Leninsky Pr., 119991 Moscow, RUSSIA."— Presentation transcript:

1 1 DIAMOND NUCLEATION FROM AN ACTIVATED VAPOR PHASE Boris V. Spitsyn Institute of Physical Chemistry RAS, 31 Leninsky Pr., Moscow, RUSSIA

2 2  Introduction  Basic parameters  The classical theory of nucleation  Homogeneous nucleation  Discovery the CVD heteronucleation. Synthesis of nanodiamond particles  Modern research of diamond nucleation on carbide forming substrates  Concentration carbon precursors and total pressure in gas phase  Substrate temperature  Topography of a surface  Electrical bias  Conclusion CONTENTS

3 3 INTRODUCTION Nucleation is one of the most important initial stages of synthesis of diamond from a gas phase. To no one problem in CVD of diamond does not devoted so significant number of the publications. At the same time many regularities of this major process not completely are found out. It and it is no wonder, as the process diamond nucleation depends on many conditions of experiment, which in a number of cases can vary in time. Now from knowledge and skill in nucleation area depends critically perfect thin film growth, adhesion, and progress in heteroepitaxy of diamond. Due to growing interest to nanomaterials CVD diamond at early stage of its emergence offer direct way to nanodiamond formation. Consideration of influence some, in our opinion, most important peculiarities of the diamond nucleation from activated gas phase this brief review is devoted.

4 4 Initial discovery of heterogeneous nucleation of diamond on foreign substrates In initial process of chemical transport reaction on copper and gold surface, and then and on carbideforming substrates, such as the silicon, tungsten, molybdenum was revealed in the first time nucleation and growth of microcrystals of diamond with characteristic cubo-octahedral habit. It is remarkable, that already in these first experiments and followed publications some of the most essential regularities of heterogeneous nucleation of diamond were established.

5 5 Original chemical transport reaction

6 6 THE BASIC PARAMETERS Probability of homogeneous nucleation at CVD of diamond to be determined by following parameters of a gas phase: Chemical content, presence in it of ions, temperature, level of activation, gas flow through activation zone, total pressure, At heterogeneous nucleation it is necessary to add: chemical, phase structure and topography of substrate, temperature of surface, electrical properties and charge of a substrate in relation to a gas phase, effective distance between activation zone and substrate surface.

7 7 Nanometric diamond Selfnucleation B.V.Spitsyn, L.L.Bouilov, and B.V.Derjaguin, Growth of diamond on diamond and another surfaces, J.Cryst. Growth 52, (1981)

8 8 Selectivity Y.Tzeng et al., ICNDST- 4,Program and Abstrcts, Kobe, Japan, July 18-22, 1994, p. 63. Diamond microcrystal growth at ~ C. J.E.Butler, in Industrial Diamonds and Diamond Films, ed. by M.A.Prelas et al., NY, Reversibility of C=C bond formation in presence of atomic hydrogen

9 9 CVD diamond doping B.V.Spitsyn, Dr.Sciences Thesis, Institute of Physical Chemistry, Moscow 1973.

10 10 The CLASSICAL THEORY of NUCLEATION the probability of homogeneous nucleation in monoatomic vapor phase is: J = A exp (-  G a /kT) exp (-16  2  3 /3kT  2 ) (1), where J - number of germs arising in unit of time in unit of volume;  - specific volume come on one particle in a crystal; A - preexponential term, A is proportional to density of these particles in parent phase; k – Boltzmann constant Больцмана;  - specific free energy of crystal – environment boundary;  G a - free energy of activation of a new elementary particle addition to a germ;  - difference of chemical potentials between initial and final phases. A.A.Chernov, Crystallization, in: Annual Reviews of Materials Science, in: R.A.Huggins, et al., eds., 1973, vol.3, 397

11 11 Ways of the surface energy reduction The formula (1) testifies, that it, apparently, one of strongest dependence known in physics and physical chemistry, as the superficial energy,  - enters in a degree 3 under exponent in numerator, and the natural logarithm of supersaturation, kT ln p/p o, in a degree 2 is included into a denominator. Superficial energy of diamond - one of highest of known for solids. However it is essentially reduced, in ~ 10 times, at chemisorption of noncarbon atoms. P.Demo et al., Diamond and Relat. Mater. 6 (1997). The superficial energy of nonequilibrium surface at course of heterogeneous chemical reactions, can undergo additional reduction.] A.A.Zhukhovitsky, V.A.Grigoryan, and E.Mikhalik, Dokl. Akad. Nauk SSSR 155, 392 (1964). By all by it can be caused the observable homogeneous nucleation of diamond.

12 12 Experimental on homogeneous nucleation of diamond By M.Frenklach,, J.Appl. Phys. 66 (1989) 1247 it was revealed, that on exit from the activation zone from CH 4 - H 2 - O 2 initial gas mixture< converted in mW plasma can be found out as nanoparticles of cubic diamond, and diamond polytipes, as well. As demonstrate high-voltage TEM nanodiffraction most pronounced ids formation of polytypes, crystallochemically situated between sphaleritic (3C-) and wurtzitic,or lansdelite (2H-) structures. Particularely 6H- and 8H- polymorphs have been observed. It suggest that nucleation at extremely high nonequilibrium, at least in relation to diamond, took place. The nucleation frequency in conditions of the above mentioned work was about 10 3 cm -3 s -1

13 13 Basic finding on heterogeneous nucleation The nucleation rate of diamond on nondiamond substrates changed from 10 3 up to 10 8 cm -2 depending on conditions of synthesis, material of a substrate and its preparation procedure: polishing, etching, annealing. The occurrence of diamond nuclea was observed mostly on defects, such as scratches and grain boundaries. The nucleation rate of diamond in was several times lower on single crystalline substrates in comparison with polycrystalline substrates of the same material and after similar preliminary superficial processing. The nucleation of diamond on carbide forming substrates (silicon, tungsten, molybdenum ) was on two and more orders of magnitude higher than on noncarbide-forming substrates (copper, gold). At late stages of nucleation the increase of the sizes of the originally formed germs and the frequency of occurrence of new germs on sites of the surfaces which have been not covered with diamond, was reduced.

14 14 Substrate nature time [s] a) b) Fig.1. Approximate temporary dependence for nucleation density at initial stages of the diamond CVD on: a) non-carbide forming substrates (like Cu, Au) and b) carbide forming substrates (Si, Mo, W)

15 15 Modern research of diamond nucleation on carbideforming substrates Research, carried out in 80-ties by Prof. B. Lux and co-authors have confirmed the regularities, originally found by the Russian researchers. Alongside with it, was shown, that nucleation of diamond on a number of metals, such as Mo, W, Nb, Ta, Fe, etc. demonstrate certain delay in the beginning of nucleation of diamond particles. It connected with various carbide forming ability of these materials, and also to various diffusion coefficient value. Really at use of substrates with high carbon in metal diffusion, the nucleation came with a delay in time. It was explained by the large time necessary for saturation by carbon of a material of a substrate and the greater thickness subsurface layers, subjected by carbonisation. Only after finishing of the process the nucleation centers can to emerge and to grow.

16 16 Enthalpy of carbide formation S.D. Wolter et al., J. Appl. Phys. 77, 5119 (1995).

17 17 Carbon precursor concentration and total pressure The increase of concentration carbon precursorsat preservation about the same level of activation of a gas phase will result in increase carbon precursors, C n H m, concentration At the same time stationary concentration of atomic hydrogen falls at the presence of other radicals such, as methyl. Therefore working supersaturation, as was shown earlier, should grow considerably and to provide more intensive nucleation. The experimental data are in the good consent with such assumption, but only in the limited range of total pressure values. Recently was established, that density of nucleation in mW plasma can be very low near pressure ~ 1 Тorr and then, passing through a maximum, again is reduced. The experiments were carried out with application of electrical bias on a substrate. That’s why at low pressure action of ions with higher energy more pronounced. It could result in partial destruction of diamond nuclea. New nucleation mechanism with basic precursor C 2 molecule was discovered by Gruen by using fullerene–argon or methane–argon mixtures with very low content of hydrogen. It was revealed original path for new carbon atom addition through insertion of the C 2 molecules in C-C and C-H bonds. Because much lower kinetic barriers of the reactions, nucleation density grow up 6 decimal orders of magnitude, what results to nano-DF formation with crystallite size 3 to 15 nm.

18 18 Substrate temperature The significant role of substrate temperature in a stage of critical and even subcritical nucleation is played mostly by rate new atoms addition by diamond crystallization. Growth rate o macroscopic DF, after some maximum at temperature about 900 oC, is reduced. The similar character in nucleation frequency was observed in some circumstances. It finds an explanation in preferable destruction of sub critical diamond clusters under action of atomic hydrogen. So most probable nanodiamond heterogeneous formation at nearly 700 o C takes place. It must be stressed that the super-saturation, or chemical potential difference between activated vapor phase and diamond phase generally should be  = kT ln p/p o, where p and p o are acting and equilibrium partial pressures, need special comments. The thermodynamic driving force, or super-saturation of condensed carbon formation by ACVD consists of two members. In the case, e.g., hot filament diamond CVD with stationary activated vapor phase CH 3 -H-H 2 composition, we shall write down  = kT ln P(CH 3 )/P o (CH 3 ) - kT ln P(H)/P o (H), where P(CH 3 ) and P(H) - working partial pressures of methyl radical and atomic hydrogen, and P(CH 3 ) and P o (H) - their equilibrium values.

19 19 Surface geometry Surface geometry role in the diamond nucleation probability include several factors. First of all the sharp tips at the carbide – forming substrate surface should pass the carburizing/carbidization stage more early, and than be preferentially ready for the diamond nuclei formation (see Sect.3, Fig.2). Secondly, ‘wetting’ by diamond nucleus, due to very high surface energy of diamond, of convex parts of the surfaces much more pronounced, according to the Wentzel- Derjaguin formula Cos  r = r Cos  a (2), where  r and  a are wetting angles for the rough and flat surfaces, respectively; r = S r/ S r is ratio of the real and appearing (projection to the real) surfaces. Such opposite influence on wetting contact angle demonstrate next slide.

20 20 Wetting of rough surface Θ smooth Θ rought a) Wetting surface Θ>90 o, ΔΘ<0 b) Non-wetting surface Θ>90 o, ΔΘ<0 Θ rought Θ smooth solid liquid

21 21

22 22 E.I.Givargizov et al., Inst. Of Crystallography RAS, Moscow

23 23 Electrical bias It phenomenon was discovered by S.Yugo et al. The nucleation enhancement started only at methane concentration in hydrogen more 5 %, and relative to smooth Si substrate bias, Ub –70 V. Most pronounced effect was achieved by 5 min action of seeding conditions at 40 % of methane in the incoming vapor phase and U b = V. The procedure provide great nucleation promotion up to cm –2. Then usual growing conditions (methane concentration in hydrogen ~1%, no bias) provide submicrometer continuous DF regrowth on Si substrate. Authors explain influence of negative biasing of substrate by extra activation of precursors of diamond (or mixed sp 3 / sp 2 clusters) by impingement of arriving to the surface positive ions with some optimal energy. Also the effect just partially may originate from the enhancement of surface diffusion as well.

24 24 Modern Diamond CVD Isothermal CVD Stationary content of a gas phase Variable content of a gas phase Activated chemical crystallization of diamond Thermal activation Electrical activation Chemical activation Photochemical activation Chemical transport reaction Heat transporting gas apparatus Hot filament reactor DC discharge DC arc-jet AC discharge RFmWECR Acetylene-oxygen torch Nonequilibrium oxidation chemical reaction Hybrid techniques

25 25 Hybrid CVD Charging of surface irrespective of a sighn of this extra charge can lower energy of formation of the transitive activated complex up to 20 kcal/mole, if this complex contains polar chemical bonds. V.B.Kazansky and N.D.Ttshuvylkin, Dokl. Akad. Nauk SSSR 223, (1975) 910. It provide remarkable gain in DF and diamond nuclea transfer through critical size by hybrid diamond CVD’es.

26 26 Hybrid CVD SEM image of the surface morphology of DF’s grown by HF technique, at biases: a) # 14-80, 0 V, b) # 14-82, +70 V, c) # 14-81, +85 V. Raman spectra of the DF

27 27 Basic features of diamond CVD

28 28 Basic features of diamond CVD

29 29 Basic features of diamond CVD

30 30 Conclusion The nucleation of diamond from activated gas phase allows to receive both isolated free diamond nanopowders, and regrowing on surface of nondiamond materials. There exist basic opportunity of nanodiamond synthesis with controllable composition, structure and arrangement on a surface of substrates. Significant potential of the CVD nanodiamond in the favour of emergent nanoscience and nanotechnology will be most comprehensive realized in frameworks of interdisciplinary and international research and development.

31 31 Acknowledgements I would like to express my gratitude to A.E.Alexenko, A.A.Botev. L.L.Bouilov and G.A.Sokolina for many years cooperation. Slide preparation by A. Spitsyn, A.Velez, D. Rangaraj, highly appreciated.

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