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Diamond
OTTO VOHLER, former Sigri GmbH, Meitingen, Germany
GABRIELE NUTSCH, former Technische Universitat Ilmenau, Ilmenau, Germany
FERDINAND VON STURM, former Sigri GmbH, Meitingen, Germany
ERHARD WEGE, former Sigri GmbH, Meitingen, Germany
1.
2.
2.1.
2.2.
2
4
5
2.3.
2.3.1.
2.3.2.
2.3.3.
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9
10
12
13
Carbon, 2. Diamond
Gem
Industrial
Total
Australia
Russia
Congo
Botswana
Rep. of South Africa
Angola
Namibia
Brazil
China
Ghana
Other
World
18.897
9.250
3.000
11.000
5.360
3.600
1.300
0.700
0.230
0.125
1.955
55.400
23.096
9.250
15.000
5.000
6.000
0.400
41.993
18.500
18.000
16.000
11.300
4.000
1.300
1.300
1.130
0.630
2.807
117.000
0.600
0.900
0.505
0.852
61.600
1995
1997
1999
Belarus
China
Czech Republic
France
Greece
Ireland
Japan
Poland
Romania
Russia
Slovakia
South Africa
Sweden
Ukraine
United States
Total
25.0
15.5
5.0
3.0
1.0
60.0
32.0
0.256
5.0
80.0
5.0
60.0
25.0
8.0
115.0
440.0
25.0
16.0
5.0
3.0
0.75
60.0
32.0
0.26
5.0
80.0
5.0
60.0
25.0
8.0
125.0
451.0
25.0
16.5
3.0
3.0
0.75
60.0
32.0
0.2
3.0
80.0
3.0
60.0
25.0
8.0
208.0
467.0
Carbon, 2. Diamond
Figure 2. Bonding hybridization and corresponding crystal structure of the carbon allotropes [1]
Carbon, 2. Diamond
2. Diamond Synthesis
According to the phase diagram (Fig. 1)
there are only a few ways to synthesize diamond: by shockwaves (mostly used in Japan),
by high pressure and high temperature (HPHT
synthesis), and by chemical vapor deposition
(CVD) at relatively low pressures and moderate
temperatures.
Carbon, 2. Diamond
Carbon, 2. Diamond
net reaction:
CH4 gactivation energy ! Cdiamond2 H2 g
Carbon, 2. Diamond
Carbon, 2. Diamond
Carbon, 2. Diamond
10
Carbon, 2. Diamond
Carbon, 2. Diamond
11
Figure 11. Linear growth rate of various plasma jet techniques in comparison to other techniques, such as HF (Hot
Filament), MW (microwave), RF and DC (radio-frequency
and d.c. nonthermal plasma processes)
Figure 12. Ellipsoidal microwave reactor AIX P6 [68]
12
Carbon, 2. Diamond
equilibrium. Typically, the arc is generated inside a torch, similar to a DC plasma torch. The
jet leaves the converging/diverging nozzle
(Fig. 14) with a minimum diameter of about
1 mm in the reactor chamber, maintained at a
pressure of 23 kPa [70], which is much lower
than that in the torch (ca. 0.6 MPa). The high
pressure difference is responsible for the gas
dynamic conversion of thermal arc energy into
high kinetic energy of the jet, which expands
into the reactor with supersonic velocities
(110 km/s) [71]. The temperatures in the jet
are not higher than 2 kK, and reach the highest
values of up to 5 kK in the bow shock near the
substrate [72]. This kind of jet shows a large
deviation from the local kinetic and chemical
equilibria. The high flow velocities lead to small
transport timescales relative to the chemical
kinetic timescales [73]. Therefore, the recombination of atomic hydrogen is reduced and the
carbon-utilization rate is high. The growth rate
ranges between 6 [74] and 10 mm/h [75], which
is much higher compared to the other nonthermal plasma techniques operating in the same
pressure region (see Fig. 11). This results from
the thinning of the boundary layer thickness due
to the high flow velocities.
2.3.2. Thermal Plasma Diamond CVD
A promising alternative to the conventional
low-pressure gas discharges is the use of
high-pressure thermal plasma jets. Plasma jets
are generated by electric discharges at
Carbon, 2. Diamond
13
14
Carbon, 2. Diamond
temperature (ca. 2200 C) of the filament restricts the quantity of atomic hydrogen produced. To overcome this, low pressures (e.g.,
< 10 kPa) are used to enhance its production
and transport to the substrate. The substrate
distance is relatively small (ca.120 mm). However, the low gas-phase concentration permits
only relatively low growth rates compared to the
plasma jet techniques (Fig. 11). Because of its
low cost and its very simple construction, the hot
filament process has been the most frequently
used method since it was first reported [87]. The
methane content based on the flow rate of
molecular hydrogen is always less than
5% [88]. A higher methane content lowers
substantially the rate of recombination of atomic hydrogen at the substrate surface. Besides the
relatively low growth rate, another drawback is
filament recrystallization due to exposure to the
carbon-containing atmosphere. The wire materials, such as tungsten and tantalum, change
their structure as a result of carburization and
hydrogen embrittlement. Cracks are formed,
and the lifetime is limited to about 20 h,
depending on the operating temperature [89].
Rhenium filaments allow carbon to diffuse
Carbon, 2. Diamond
15
References
Specific References
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Materials, University of Alicante, Alicante 2000.
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3 General Electric Comp., US 2 992 900, 1961 (H.P. Bovenkerk).
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6 B.V. Spitsyn, B.V. Derjaguin, patent application 10.7.56.
7 US 3 0301 87 and 3 030 188, 1962 (W. Eversole)
8 J. E. Field (ed.): The Properties of Diamond, Academic Press,
London 1979.
9 R. Berman, Physical Properties of Diamond, Clarendon Press,
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10 V.R. Howe, Proc. Phys. Soc. London 80 (1962) 648.
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16
Carbon, 2. Diamond
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17
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