Nanocrystalline diamond

Recently Butler et al. [4] reported the deposition of nanocrystalline diamond films with the conventional deposition conditions for micrometer-size polycrystalline diamond films. The substrate pretreatment by the deposition of a thin H-terminated a-C film, followed by the seeding of nanodiamond powder, increased the nucleation densities to more than 10 /cm on a Si substrate. The resultant films were grown to thicknesses ranging from 100 nm to 5 fim, and the thermal conductivity ranged from 2.5 to 12 W/cm K. 

In addition to microwave plasma, direct current (dc) plasma [19], hot-filament [20], magnetron sputtering [21], and radiofrequency (rf) [22-24] plasmas were utilized for nanocrystalline diamond deposition. Amaratunga et al. [23, 24], using CH4/Ar rf plasma, reported that single-crystal diffraction patterns obtained from nanocrystalline diamond grains all show 111 twinning. 

From a theoretical point of view, the stability of nanocrystalline diamond was discussed by several authors. Badziag et al. [25] pointed out that, according to semi-empirical quantum chemistry calculations, sufficiently small nanocrystalline diamond (3-5 nm in diameter) may be more stable than graphite by forming C-H bonds at the growing surface. Barnard et al. [26] performed the ab initio calculations on nanocrystalline diamond up to approximately 1 nm in diameter. The results revealed that the surfaces of cubic crystals exhibit reconstruction and relaxations comparable to those of bulk diamond, and the surfaces of the octahedral and cubooctahedral crystals show the transition from sp to sp bonding. 

Whereas a microwave plasma is most commonly used for the PE-CVD of diamond films, an ECR is the only plasma that is used for diamond deposition below 1 Torr [27-29]. Although Bozeman et al. [30] reported diamond deposition at 4 Torr with the use of a planar ICP, there have been a few reports that describe the synthesis of diamond by low-pressure ICP. Okada et al. [31-33] first reported the synthesis of nanocrystalline diamond particles in a low-pressure CH4/CO/H2 ICP, followed by Teii and Yoshida [34], with the same gas-phase chemistry. 

The TED and XRD patterns revealed that the deposit is not amorphous carbon but nanocrystalline diamond. Nonetheless, the 514-nm excited Raman spectra do not exhibit a clear diamond peak at 1332 cm though the peak due to the sp -bonded carbon network appears at 1150 cm The Raman cross section of the sp -bonded carbon network with visible excitation is resonantly enhanced [43, 48-50]. It consequently makes the 1332 cm diamond peak overlap with the peaks due to sp -bonded carbon. 

The 244-nm excited Raman spectra of t-aC films exhibit the appearance of the peak at 1150 cm and the increase in the intensity proportional to the amount of sp bonding in the films [50, 51]. However, the diamond peak at 1332 cm is enhanced in this study because the deposit obtained is not amorphous carbon but nanocrystalline diamond. The peak at --1150 cm is probably disappearing because of the striking enhancement of the diamond peak at 1332 cm T... 

Figure 8. HREELS spectra of the nanocrystalline diamond and diamond-like carbon films with various [CH4]/[CO]. (a) [CH4]/[CO] = 4.5.0/0. (b) [CH4MCO] = 4.5/1.0. (c) [CH4]/[CO] = 4.5/10 seem. The elastic peak for (c), reduced by a factor of 25, is shown for comparison. Reprinted with permission from [66], K. Okada et al.. Diamond Relat. Mater. 10, 1991 (2001). 2001, Elsevier Science.

According to the characterizations by TEM and XRD, the sample prepared from a CH4/H2 plasma was composed of nanocrystalline diamond and disordered microcrystalline graphite. Then nondiamond carbon was effectively removed with an increase in [CO]. It is therefore concluded that the VDOS of the nanocrystalline diamond and DEC films extracted from the HREELS data is in qualitative agreement with the characterizations of TEM and XRD. Although the HREELS probes only the region near the surface, the agreement suggests that the surface dynamics do not differ dramatically from those of the bulk. 

Figure 9. (a) High-resolution transmission electron microscope image of an outer part of a nanocrystalline diamond particle and (b) enlargement of the left-hand side of (a). 

The same skepticism applies to nanocrystalline diamond that is reported to be harder than diamond single crystals (Sumiya and Irifune, 2007). Other cases in which rough surfaces may have skewed the measurements are TiN/SiN coatings (Kauffmann et al., 2005) and (AlMgB14 + TiB2) mixtures (Cook et al., 2000). 

A pure form of sp3 hybridized carbon is known as diamond and this may also be synthesized at the nanoscale via detonation processing. Depending on their sizes, these are classified as nanocrystalline diamond (10 nm 100 nm), ultrananocrystalline diamond (< 10 nm) and diamondoids (hydrogenated molecules, 1 nm-2 nm). Nanodiamond exhibits low electron mobility, high thermal conductivity and its transparency allows spectro-electrochemistry [20,21]. However, ultrananocrystalline diamond exhibits poor electron mobility, poor thermal conductivity and redox activity [21,22]. 

B. Fausett, M. C. Granger, M.L. Hupert, J. Wang, G. M. Swain, D. M. Gruen, The electrochemical properties of nanocrystalline diamond thin-films deposited from C60/Argon and Methane/Nitrogen gas mixtures, Electroanal., vol. 12, pp. 7-15, 2000. 

Nanocarbon emitters behave like variants of carbon nanotube emitters. The nanocarbons can be made by a range of techniques. Often this is a form of plasma deposition which is forming nanocrystalline diamond with very small grain sizes. Or it can be deposition on pyrolytic carbon or DLC run on the borderline of forming diamond grains. A third way is to run a vacuum arc system with ballast gas so that it deposits a porous sp2 rich material. In each case, the material has a moderate to high fraction of sp2 carbon, but is structurally very inhomogeneous [29]. The material is moderately conductive. The result is that the field emission is determined by the field enhancement distribution, and not by the sp2/sp3 ratio. The enhancement distribution is broad due to the disorder, so that it follows the Nilsson model [26] of emission site distributions. The disorder on nanocarbons makes the distribution broader. Effectively, this means that emission site density tends to be lower than for a CNT array, and is less controllable. Thus, while it is lower cost to produce nanocarbon films, they tend to have lower performance. 

Figure 29. Fiuman osteoblast-like MG 63 cells in cultures on material surfaces modified with carbon nanoparticles. A fullerene Cgo layers deposited on carbon fibre-reinforced carbon composites (CFRC), B fullerene C o layers deposited on microscopic glass coverslips, C terpolymer of polytetrafluoroethylene, polyvinyldifluoride and polypropylene, mixed with 4% of single-wall carbon nanohorns, D the same terpolymer with high crystalline electric arc multi-wall nanotubes, E diamond layer with hierarchically organized micro- and nanostmcture deposited on a Si substrate, F nanocrystalline diamond layer on a Si substrate. Standard control cell culture substrates were represented by a PS culture dish (G) and microscopic glass coverslip (FI). Immunofluorescence staining on day 2 (A) or 3 (B-Fl) after seeding, Olympus epifluorescence microscope IX 50, digital camera DP 70, obj. 20x, bar 100 pm (A, C, D, G,H)or 200 pm (B, E, F) [16].

In addition to C onions, C atoms condense into various kinds of chemically bonded forms, and they are known to have excellent physical properties depending on the bonding nature. This means that research and applications not only in the materials science but also in other scientific fields are expected. At JAERI, the optimum growth conditions have been successfully obtained for the preparation of high-quality Cgo, diamondlike carbon, and nanocrystalline diamond by means of ion-beam-assisted deposition [80-82]. The susceptibility of Ni/Cgo thin films to thermal treatment, the formation of nanocrystalline diamond and nanotubes due to codeposition of Co and Ceo, and the surface modification of glassy... 

Ku, C. H. and Wu, J. J. (2004), Effects of CCI4 concentration on nanocrystalline diamond film deposition in a hot-filament chemical vapor deposition reactor. Carbon, 42(11) 2201-2205. 

Soga, T., Sharda, T. and Jimbo, T. (2004), Precursors for CVD growth of nanocrystalline diamond. Phys. Solid State, 46(4) 720-725. 

Yoshikawa, H., Morel, C. and Koga, Y. (2001), Synthesis of nanocrystalline diamond films using microwave plasma CVD. Diam. Relat. Mater., 10(9-10) 1588-1591. 

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