Diamond & Related Materials 20 (2011) 12871301

Contents lists available at SciVerse ScienceDirect

Diamond & Related Materials

journal homepage: www.elsevier.com/locate/diamond

A review of diamond synthesis by CVD processes

Michael Schwander , Knut Partes
BIAS Bremer Institut fr angewandte Strahltechnik GmbH, Klagenfurter Str. 2, D-28359 Bremen, Germany

a r t i c l e

i n f o

Article history:
Received 17 September 2010
Received in revised form 2 August 2011
Accepted 13 August 2011
Available online 27 August 2011
Keywords:
CVD
Hot lament
Plasma CVD
Cathodic arc discharge
Combustion synthesis

a b s t r a c t
Diamond has some of the most extreme mechanical, physical and chemical properties of all materials. Within
the last 50 years, a wide variety of manufacturing methods have been developed to deposit diamond layers
under various conditions. The most common process for diamond growth is the chemical vapor deposition
(CVD). Starting from the rst publications until the latest results today, a range of different developments
can be seen. Comparing the basic conditions and the process parameters of the CVD techniques, the technical
limitations are shown. Processes with increased pressure, ow rate and applied power are the general
tendency.
2011 Elsevier B.V. All rights reserved.

Contents
1.
2.
3.

Introduction . . . . . . . . . . . . . . . . . . . .
Applications of diamond coatings . . . . . . . . . .
The chemical vapor deposition process . . . . . . .
3.1.
Thermal induced . . . . . . . . . . . . . .
3.1.1.
Transport processes from hot lament
3.1.2.
Techniques for synthesis of diamonds
3.1.3.
Diamond coatings . . . . . . . . .
3.2.
Chemical induced . . . . . . . . . . . . . .
3.2.1.
Exothermic combustion . . . . . . .
3.2.2.
Techniques for synthesis of diamonds
3.2.3.
Diamond coatings . . . . . . . . .
3.3.
Electromagnetic excitation . . . . . . . . . .
3.3.1.
Absorption of electromagnetic waves
3.3.2.
Techniques for synthesis of diamonds
3.3.3.
Diamond coatings . . . . . . . . .
3.4.
Electrical induced . . . . . . . . . . . . . .
3.4.1.
Heating from apply voltage . . . . .
3.4.2.
Techniques for synthesis of diamonds
3.4.3.
Diamond coatings . . . . . . . . .
4.
Discussion . . . . . . . . . . . . . . . . . . . . .
5.
Conclusion. . . . . . . . . . . . . . . . . . . . .
Acknowledgments. . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . .

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1. Introduction
Corresponding author. Tel./fax: +49 421 2185036.
E-mail address: michael.schwander@gmx.de (M. Schwander).
0925-9635/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2011.08.005

The range of industrial used tools reaches from single bulk material,
coated and treated systems to multilayer devices. Depending on the

1288

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

requirement of the system, different material compositions can be chosen. Because of its extreme properties, diamond is one of the most versatile usable materials for coated systems. Almost all diamond
properties are in a higher or lower limit of possible desirable behavior.
Diamond is for example the hardest known material and at the same
time it has the lowest coefcient of thermal expansion. Other advantages are attributes like being chemically inert, highly wear-resistant,
highly thermally conductive, electrically insulate and broadly opticallytransparent from the ultraviolet (UV) to the far infrared (IR) [107].
Diamond consists of carbon atoms, which are bounded over tetrahedral sp 3 hybrid orbitals in a face centered cubic (fcc) crystal system.
Furthermore, each primitive (Bravais) cell consists of two carbon
atoms. The structure can be seen, as two face-centered cubic lattices
interpenetrating along the body diagonal (1/4 1/4 1/4) of the cubic
unit cell [84].
The industrial use of diamond began with the rst synthesis by
General Electrics in 1955 [14]. High pressure and high temperature
(HPHT) surrounding conditions were generated, which were similar
to the conditions for natural diamond growth. The conversion of carbon depended on the fact, that diamond is the densest allotrope form
of carbon. With this technique, monocrystalline diamonds with high
purity can grow up to several millimeters. Most of these diamonds
are used for grinding and cutting tools. Nevertheless, there are also
strong disadvantages like the highly expensive equipment and the
limited size of the diamonds.
Since the middle of the 1950s, the interest in diamond increased
with the possibility of growing carbon by using a wide variety of
chemical vapor deposition (CVD) techniques. These techniques
allow the deposition of four different types of carbon: amorphous carbon with sp 2-bonded atoms (a-C), tetrahedral bonded amorphous
carbon (ta-C), polycrystalline and monocrystalline diamonds [3].
This review focuses on the various deposition techniques by using
CVD for poly- and monocrystalline diamond growth and on the basic
energy transfer concepts. Special attention is given to the different
energy supply, associated temperature and density distribution. The
review concludes with a comparison of process parameters, which
are measured for all types of CVD apparatuses.
2. Applications of diamond coatings
Due to the notable properties, diamond coatings nd use on a variety of applications including, as semiconductor, as an optical component, as heat sink and as wear-resistant coating.
The advantages of semiconductor are the wide band gap, the very
high electric breakdown and the thermal conductivity. For the applications diamond can be doped by boron, which results in a p-type
semiconductor with a bandgap about 0.37 eV from the valence band
maximum [76]. The phosphorus doping can result in an n-type semiconductor and a donor level of 0.6 eV from the conduction band minimum [32]. Without doping the wide bandgap at 300 K of 5.5 eV from
diamond is used for photodetectors. These photodetectors are interesting for investigation of inammation and explosion dynamic because of the sensitivity in the range of 185 to 250 nm [36]. One
advantage is the transmission of near-UV (300400 nm), visible and
IR radiation, so that diamond can be used as solar-blind UV photodetectors, even on a daylight background.
The features of hardness, highest bulk modulus, lowest compressibility, high wear resistance and a low friction coefcient against a
wide range of materials are used for diamond coatings onto cuttings
tools. MMCs, aluminumsilicion alloys and Co-cemented tungsten
carbide tools are used [2] as substrates. But Co-cemented tungsten
carbide (WCCo) is commonly considered the most suitable substrate
to receive a diamond layer for tooling applications [81]. However, the
major drawback is a very good solvent (0.20.3 wt.%) of carbon into
cobalt (Co) and the resulting poor adhesion which is the main technical limit for diamond-coated tools [19]. Besides, the presence of

metallic cobalt suppresses the diamond nucleation through catalyzing the formation of graphite. Because of these facts, the Co binder
is removing from the substrate surface by using Murakami reagent
and acid etching. This can result in an optimally conditioned substrate
surface for diamond coating [23].
The thermal, mechanical and optical properties of diamond are
used in optical windows, especially for high-power IR lasers and airborne IR sensor systems. The diamond windows combine withstand
again high power irradiation, high temperatures and aerodynamic
load [112].
The physical properties of CVD diamond can differ signicantly
from their single-crystalline counterparts due to intentionally or
unintentionally added impurities, grain boundaries and other extended
defects. For any industrial application precise knowledge of the relevant
material is necessary [112]. Therefore, this paper makes no statement
about the quality of diamond lms, it only gives a brief summary of
the produced layers in each chapter.
3. The chemical vapor deposition process
As its name implies, chemical vapour deposition (CVD) involves
chemical reaction inside a gas-phase as well as deposition onto a substrate surface. An early work which deals with chemical processes
that is important for the diamond generation had been published in
1993 by J. E. Butler et al. [15]. However, the processes have been developed since this time. The process procedure with the whole
range of selectable process parameters is shown in Fig. 1. The sketch
illustrates the various direct and indirect adjustable parameters. The
rst group shows the different selectable process gases which can
be used for CVD. The second group reects a selection of energy
sources for the activation of the chemical process, followed by ensuring parameters. Below that, there is the substrate with the growing
diamond layer.
However, in most cases a mixture of hydrogen and methane is
used for diamond growth. It is generally accepted that atomic hydrogen (or oxygen) is the most critical component in the gas phase mixture and methane or other hydrocarbon molecules are only needed
for the supply of carbon atoms. The primary function of hydrogen
(or oxygen) is to terminate the dangling carbon bonds on the surface
of the diamond layer or diamond nucleus. Beyond this, the hydrogen
atoms can cleave the neutral hydrocarbons and create reactive radicals such as CH2. This excited hydrocarbon can bond on this exposed
carbon and form trigonal sp 2 (a-C) graphite or tetrahedral sp 3 (ta-C)
bonded carbon [5]. Another purpose of hydrogen is to prevent the
growth of graphite. This is possible due to the fact, that atomic

Fig. 1. Schematic diagram of the mechanism from CVD processes for diamond growth.

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

hydrogen etches sp 2 bonded graphite much faster than diamond like

sp 3 carbon. Therefore, diamond growth can be described as ve steps
forward, but four steps back [63]. In the same way as hydrogen
cleaves hydrocarbons it also suppresses the build-up of polymers or
large ring structures which might deposit onto the growing surface.
In addition to the functional principle of the diamond growth, the
CVD processes have several consistent settings and practices. This includes the substrate selection, the pretreatment of the samples and
the temperature range. Mostly used substrates in current publications
are molybdenum, silicon nitride and tungsten carbide. As pretreatment abrasion by mechanical polishing at diamond powder of 0.1
10 m particle size or through an ultrasonically bath slurry with a
mixture of abrasive grit in a hydrocarbon medium is made.
The temperature of the substrate is restricted to the range from
1000 to 1400 K, since the deposition rates reduce at lower temperatures and the growth of graphite dominates at higher temperature.
Depending on the energy supply, the pressure range and the gas temperature, the substrate has to be either cooled down or heated up.
Bachmann et al. were the rst who demonstrated, that diamond
synthesis is only possible in a small area of the C/H/O-gas-phase compositional diagram, shown in Fig. 2 [6]. Most of the present processes
straddle the line, represented by identical concentration of C and O
atoms. As a consequence it is possible to grow diamond lms by
using oxygen or hydrogen free gas mixture with different methane
concentrations. Prijaya et al. [82] calculated the solubility of carbon
in the gas phase composition by a thermal equilibrium system,
which consists of a solid graphite disk and hydrogen/oxygen gases
at constant pressure, shown in Fig. 3. According to Bachmann's results, he found a similar composition in a temperature range from
1400 to 3000 K, which corresponds to the temperature range of the
most CVD processes. This shows that at the presence of temperature
equilibrium and a uniform distribution of the gas molecules, the deposition process is exclusively dependent on the carbon-tohydrogen-to-oxygen ratio.
However, in real CVD processes the temperature distribution, solubility and internal energy clearly depend on the type of excitation.
Therefore, the signicant difference of CVD processes for diamond
synthesis is based on the sort of energy supply. The activation can
be generated by microwave (MW), radiofrequency (RF), laser induced (LI), direct current (DC), hot lament (HF) and chemical activation (CA). In the same surrounding condition like pressure, ow

Fig. 2. CHO phase diagram for diamond growth [6].

1289

Fig. 3. Calculated solubility of carbon at constant pressure and different temperatures

[82].

rate, size of the heated area and applied power, different energy supplies generates different mole fractions and temperature distributions. On that account, this review mainly deals with the function
and construction of different types of energy supply. Nevertheless,
according to Spitsyn et al. the CVD processes can be separated into
four different types shown in Fig. 4 [98]. Firstly, it is subdivided into
heated gas and ionization plasma. A further breakdown is made on
the nature of excitation through thermal, chemical, electrical or electromagnetically activation. That processes are united in hybrid systems which use more than one energy supply.
Through thermal and chemical activation, the gas phase can be
heated up to 3500 K. At this temperature, the distribution and density
can sometimes be estimated by equilibrium systems. However, due to
electrical and electromagnetically activation the gas-phase ionizes
and produces a plasma ball or a jet formation. After the plasma activation, the stable molecules convert into neutral and charged particles:
C2H2, C2H4, CH3, C2H, CH2, C2, CH +, CH2+, etc. proceeds. The fraction of
hydrogen molecules dissociates to H atoms and also to ions H +, H3+,
and H . Inside the plasmas, there are different temperatures for electrons (Te) and molecules (Th). Depending on the interaction, the temperatures can be similar or vary in orders of magnitude.
Thermodynamic equilibrium (LTE) means, that the temperatures are
similar and non-local thermodynamic equilibrium (non-LTE) means
that the temperatures are different [101]. In LTE plasma each kind
of collision must be balanced by its inverse: excitation/deexcitation
and ionization/recombination. Inelastic collisions between electrons
and atoms create the plasma reactive species whereas elastic collisions heat the gas. The molecules' temperature is close to the electron
temperature. Tendero [101] for example, species the temperatures
Te and Th in the arc plasma core at round about 10,000 K. However,
most plasmas, used for diamond deposition, deviate from LTE. In
non-LTE plasma, inelastic collision between electrons and heavy particle induce the plasma chemistry, too. But due to the fact, that the
heavy particles are slightly heated by only a few collisions, the temperature of electrons can increase from 10,000 to 100,000 K. During
this process the molecule's temperature itself can only rise from 300
to 10,000 K. The temperature of non-LTE plasma can be estimated
by spectrometric-, Langmuir probe- and thermocouple measurements. In the majority of cases the temperature is unknown because
of the high technique requirements.

1290

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

Fig. 4. Diamond CVD techniques [98].

3.1. Thermal induced

In thermal induced CVD processes for diamond deposition the gas
phase is activated by hot laments or hot surfaces. In contrast to excitation with electromagnetic waves or by direct current, the gas
reaches only temperatures of about 2300 to 2900 K [31]. Using this
temperature and the classic thermodynamic ideal gas equation it
can be shown, that the internal energy is factor 100 lower than the
ionization energy. For this reason it is only spoken about thermal
heated gas.
3.1.1. Transport processes from hot lament
The energy- and mass-transport in thermal heated gases can be
described by uid mechanics and thermodynamic processes. These
fundamentals are given by an example of a hot lament process illustrated in Fig. 5. As shown, the process gas ows into the chamber and
is heated up by a hot lament. Since the chemical and thermal reaction close to the wire is not well understood, the heated zone near
the lament is described by an approximation, which assumes a constant temperature and chemical composition. As a clue for the approximation, the temperature of the gas near the lament can be
determined by thermocouples [38] or laser scattering [86] and is
about 2000 K. However, the lament temperature itself can only be
measured through a pyrometer and amounts to about 2600 K. The
distance between the lament and the substrate is normally 5 mm
[64], 5 to 6 mm [16], or 7 mm [83]. In individual cases, this amount
can vary up to 20 mm [75]. Through this distance and a substrate
temperature around 1000 and 1200 K, the temperature gradient and

chemical conversion, which depends on convection and thermal conductivity of the gas, can be set.
To determine the chemical composition in the areas around the
hot lament and between lament and substrate it is necessary to
know the temperature distribution and chemical ratio around the lament. Therefore, Harris and Weiner determine the chemical ratio
of CH4/C2H2 with on-line mass spectrometry as 1:1. Additionally
Goodwin et al. calculated the chemical compounds of H2, C2H2, H,
CH4 and C2H4 around the lament by the assumption of an interaction
time around 0.1 to 0.2 s. This is necessary for an inlet gas to generate a
ratio from CH4/C2H2 with 1:1 at a temperature of 2000 K.
Under the conditions of low pressure (typical 2600 Pa), a distance
of 5 mm, a gas velocity on the order of 0.5 cm/s and the above given
conditions of temperature and chemical compounds, the following
assumptions can be made [31,38,35]:
The gas ow can be described as a continuum laminar ow without
roll cells in the area of chemical conversion.
The temperature prole can be assumed to be independent from
the chemical gradient and only dominated by the conduction of
the gas.
The temperature prole can be assumed to be linear, as shown in
Fig. 5.
The energy transport from the lament to the substrate is dominated
by conduction and transport of atomic hydrogen recombination.
The mass ux is mainly generated by molecular diffusion.
Gas phase recombination of atomic hydrogen is signicantly inuenced by the reaction H + CH4 _ H2 + CH3

Fig. 5. Schematic representation of a hot lament CVD process.

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

3.1.2. Techniques for synthesis of diamonds

Matsumoto et al. were the rst who achieved the diamond deposition on substrates other than diamond [61]. The standard experiment set-up and the process variable are shown in Fig. 5 and have
been described in the previous chapter. The reasons for the wide
use of that technique are the simple process and the cheap
equipment.
A recent hybrid system, which is mainly based on a hot lament
process, for silicon [60] and for WC/Co [45] is shown in Fig. 6. The
set-up is used for bias enhanced nucleation of diamond lms with
methane as carbon source. Therefore, negative voltage is applied to
the substrate and positive voltage is applied to a grid placed on top
of three tungsten laments. A feature of this process is the stable plasma between grid and laments. Due to a negative voltage on the substrate, ions from this plasma can diffuse to it.
Instead of using a carbon-containing gas source, it is also possible
to use a solid disk or rod, consisting of graphite as carbon source [85].
In this case, the hot zone is created either by a hot lament, [95] or by
a heated graphite disk [7]. During the deposition hydrogen is supplied
to the process. This process is called chemical transport reaction
(CTR) and is shown in Fig. 7.
In the lower sketch of Fig. 7 an experiment set-up, which has already been used in 1966 by Spitsyn et al. for epitaxial regrowth of
natural diamond, is portrayed [98]. In this early study, diamond
growth occurs by diffusion of carbon from the 2300 K hot graphite
layer to the overlying diamond seed. A major drawback of this process is the concentration of carbon in the gas phase, which cannot
be controlled independently by the excitation temperature.
The advantage of using a hot lament in contrast to a hot disk
without methane or another gas carbon source, is the absence of carbon around the lament and the high concentration on the substrate
surface. In this way a higher gas ow up to 1 slpm can be realized
[95]. The use of methane as carbon source would lead to a graphite
growing on the lament, the vanishing of the catalytic effect of the
tungsten lament and a degradation of the diamond quality. Typical
conditions and results for thermal induced diamond deposition are
summarized in Table 1.
3.1.3. Diamond coatings
Thermal induced CVD-processes are used under gas mixtures of
H2, CH4 and trimethyl borate or similar boron-containing precursors
to deposited boron doped diamond layers. In this way carrier concentration up to 10 22 cm 3 has been obtained [109]. Among other, these
layers are used as electrode layers with diamond resistivity of 0.01

1291

Fig. 7. Homoepitaxial growth of diamond from an etched carbon source with a hot lament and a heated graphite disk [98].

cm for nitrate elimination [20] and as electrode for a green process of

aluminum electrolysis [110].
Due to the good reproducibility and surface structure of thermal
induced CVD-processes as HFCVD, coatings have been deposited
early on cutting, milling and grinding tools. The research deals currently with the increase of attachment to turning tools [16] and the
inuence of micro-, submicro and nanometric diamond crystallite
size on machining [2,29].
Other applications are thin transparent electrodes. These are used
in optical micro-electro-mechanical systems (MEMS) [13] and in
Micro Electrode Arrays (MEAs) for biochemical application [30]. Suitable substrates are transparent materials like sapphire, quartz and
bio-glass.
3.2. Chemical induced
In 1988 Hirose et al. rst described the chemical vapor deposition
of diamond on using a combustion ame [42]. The temperature of this
type of combusting ame reached only values in the range of 2000 to
3550 K [62]. As in the case of hot thermal induced CVD processes, the
generated internal energy is about factor 100 lower than the ionization energy. Therefore, the major interest is the exothermic chemical
conversion of the process gases.

Table 1
Parameter and operation range of thermal activated CVD processes for diamond
synthesis.
Thermal activated
Total gas ow [slpm]
Typical process gas
Typical mixture range H2/CH4
Pressure [Pa]
Deposition area [mm2]
Common linear growth rate [m/h]
Advantages

Drawbacks
Fig. 6. Schematic diagram of a double bias-assisted hot lament CVD method [60].

0.1 to 0.5
H2/CH4
Typical 99/1
600 to 14,000
Up to 100,000
110
Large area at low pressure
Comprehensible process parameter
Simple set-up
Low-priced equipment
High quality of diamond layers
Low growth rate
Chamber is required
Degradation of the lament

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M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

Table 2
Abstract of chemical reactions in a combusting ame [41].
Reaction

A
(mol, cm, s)

C2H3 + H C2H2 + H2
C2H3 + OH C2H2 + H2O
C2H3 + O2 C2H2 + HO2
C2H3 + O2 C2H3O + O
C2H3 + O2 CHO + CH2O
C2H2 + CH2 C3H3 + H

4.0 1013
2.0 1013
1.12 108
3.64 1011
4.6 1016
2.4 1013

E
(kJ/mol)

0.913
0.27
1.39

0.83
0.423
4.25
27.71

3.2.1. Exothermic combustion

In contrast to other CVD processes for diamond deposition, the
heating occurs not by an additional external energy source, but by
an exothermic conversion of the process gas. Most studies have applied acetylene and oxygen as fuel for the combustion [26,3], at a substrate temperature between 770 and 1470 K [71]. According to
Murakava and Takeuci [73] the primary and secondary procedures
of chemical reaction are given through Eqs. (1) and (2).
O2 C2 H4 2CO H2 448

kJ
mol

3
kJ
2CO H2 O2 2CO2 H2 O 850
:
2
mol

1
2

On the supposition that the process occurs without any work, volume change, heat transfer, changes in kinetic or potential energy and
a given pressure, the adiabatic ame temperature arises. Thereby the
upper limit of the gas temperature can be estimated to 3550 K [62].
The complete gas-phase chemistry of a hydrocarbon ame typically
consists of 40 species and 200 reversible elementary chemical reactions [49]. It can be assumed, that each reaction proceeds according
to the Arrhenius equation:
n

kf AT e

EA
RT

:

In theses equation kf denotes the rate constant of chemical reaction; A the pre-exponential factor; T the absolute temperature; R
the gas constant; EA, the activation energy; and n the temperature
dependent on the pre-exponential factor. By measurement or simulation of the temperature a declaration about the chemical composition
of the ame can be made [34]. An abstract of chemical reactions in a
combusting ame for diamond deposition with the corresponding parameter is shown in Table 2.
The structure of an acetyleneoxygen ame is illustrated on
the left side of Fig. 8. The ame can be split into three subdivision

Fig. 9. The simplest form of process set-up for premixed torch apparatus.

regions: () the dark ame core, with a temperature less than

700 K consisting of acetylene and oxygen; () the hot and bright
area, called acetylene feather, with a high decay of acetylene in hydrogen and carbon-monoxide by Eq. (1) at a temperature up to
3550 K; and () the outside ame with the secondary chemical reaction of Eq. (2), which produces carbon-dioxide and vaporizes water at
a temperature of 1500 to 2700 K [26,41].
The second sketch in Fig. 8 shows the ame with three different
ratios of O2/C2H2: the acetylene-rich ame (a) has an O2/C2H2 ratio
of 0.7 to 0.98; the neutral ame (b), which was already described previously, with a ratio of 1; and the oxygen-rich ame (c), with a ratio
higher than 1. Diamond is synthesized with a ratio from 0.7 to 0.98
only in the area of acetylene feather [43].
3.2.2. Techniques for synthesis of diamonds
The simplest form of a process set-up for the premixed torch apparatus is shown in Fig. 9. The ame is generated through a commercial oxyacetylene torch and is perpendicular to the substrate, which is
mounting on a water cooled block.
Usually, the process is controlled by measuring the substrate temperature (pyrometer or thermocouples) and by adjusting the ratio of
O2/C2H2 through a regulated mass ow. To increase the deposition
area, the ame is scanned across the substrate with the use of a rail.
A problem of this procedure can be the oxidation of the lm during
the scanning process.
A further technique to increase the deposition area is the usage of
multiple torches. Tzent et al. have operated with a linear array of nine
torches aimed at a rotating substrate [104]. The process set-up of
Murakawa and Takeuchi is shown in Fig. 10. Based on the application
of this multi ame deposition in a chamber, they determined three
advantages:
Lower heat transfer to the substrate by transferring the second
chemical reaction out of the chamber.

Fig. 8. Structure of an acetyleneoxygen neutral ame and the three different ratios of O2/C2H2 0.7 to 0.98/1/N1 [25,33].

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

1293

Table 3
Data for chemical induced diamond deposition.
Chemical activated
Total gas ow [slpm]
Typical process gas
Typical mixture range C2H2/O2
Pressure [Pa]
Deposition area [mm2]
Common linear growth rate [m/h]
Advantages

Drawbacks
Fig. 10. Process set-up developed from Murakawa and Takeuchi [73].

Prevention of oxidation via the exclusion of air.

Larger deposition area by the use of multiple torches.
An alternative to multiple torches for an enlargement of the deposition area is a at ame burner. Flat ame burners have achieved
large uniform areas at atmospheric [72] and reduced pressure [52].
An example of a at ame at reduced pressure and enlarged deposition area is portrayed in Fig. 11. Due to the low-pressure, the oxygen
and methane ame expands after passing the nozzle and the temperature of the acetylene feather drops from 3500 K to 2290 K [33]. A
disadvantage of this low-temperature, low-pressure ame, is the
uncompleted oxidation of the fuel in the primary ame front and
the associated substantial hydrocarbon concentration in the postame region. Typical data for chemical induced diamond deposition
are summarized in Table 3.
3.2.3. Diamond coatings
In addition to other CVD-processes the deposition of diamond
layers by use of combustion ame is not signicant in application. Despite the industrial advantages of open atmosphere deposition, most
publications only deal with results of the success or failure of synthesis
under certain experimental conditions. The few application-oriented
publications deal with deposition on substrates of molybdenum [4]
and tungsten carbide [25] to use as wear resistance by sliding against
Al alloys [90] or for use in electronic device as resistor with 1010
1013 m [77].
Most of the recent publications, by the small community of researchers, deal with the combination of a combusting ame and
CO2 laser radiation [54]. The aim of those studies is to determine
the effect of laser power, density and wavelength on growth rate,
grain size, surface morphology and crystal orientation [113]. Some
scientists assume that the improvement of the diamond growth
during the combination with CO2 laser radiation is given because
of resonant excitation of C2H4 molecules and not only as a result
of localized heating [114].
3.3. Electromagnetic excitation
Excitations of gases with electromagnetic waves for CVD processes
are used with a large bandwidth of wavelengths. The publications are
dominated by three different main focuses: radiofrequency (RF) [12],

210
C2H2/O2
0.9/1 to 1.3/1
5000100,000
up to 5000
10200
High linear growth rates
No chamber is required
Simple set-up
Low-priced equipment
High heating of the samples
Small deposition area without rail
Flash-back and/or blow-off occurs easily

microwave (MW) [10,96] and laser induced plasma (LIP) [50,108]. RF

range is from 3 kHz (very low frequency) to 3 GHz (ultra high frequency), whereby it mostly means an inductive coupled wave with
a frequency in the range up to several MHz. MW is in the range
from 300 MHz to 300 GHz. However, frequency of 2.45 GHz [24] is
usually applied, because of its wavelength is often used in industry
microwave heaters and therefore available with high power [102].
The power distribution in a novel reactor has been presented by
Silva in 2010 [97]. For LIP, different types of laser are used. Some examples are Excimer (3000 THz), Nd:YAG (281 THz) [67] and CO2 laser
(28.3 THz) [108].
3.3.1. Absorption of electromagnetic waves
The two aggregate phases, gaseous and plasma, which are present
in CVD processes, can absorb electromagnetic waves in different
ways. An abstract of the important absorption mechanisms is shown
in Fig. 12.
The absorption of electromagnetic radiation is described by the interaction of electrons, photons, ions, atoms and molecules. This includes a wide range of excitation and collision processes [65].
However, in the beginning of most of the processes only the gas
phase exists. Since the gas has no free carriers, the absorption of electromagnetic waves can only emerge through electrically neutral
atoms and molecules. The energy of the individual photons, in the
used frequency range, is generally not high enough for absorption
by the photoelectric effect or pair production. Instead, the gas is
heated by dielectric heating and multiphoton absorption.
3.3.1.1. Dielectric heating. Dielectric heating is the process in which
electromagnetic waves heat the material through dipole rotation.
The absorption is based on the ability of the electric eld to polarize
the charge carrier in neutral material and the inability of this polarization to follow extremely rapid reversals of the electric eld [79]. In
addition to the rotation, the dipoles of molecules are able to absorb
electromagnetic waves through vibration. The vibrational and rotational modes are associated with different amounts of energy. Therefore, different molecules absorb different frequencies of the
electromagnetic wave. A popular example is the absorption of solar
radiation by the molecules of the atmosphere [56].

Fig. 11. Flat ame burner for CVD [34].

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M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

Fig. 12. Abstract of absorption mechanisms for electromagnetic waves.

The maximum absorption appears if the wavelength and resonance frequency of the molecules vibration or rotation states are
equal. To prevent the absorption at the surface and to increase the
penetration depth of the electromagnetic wave, a frequency which
is a factor ten smaller than the resonance frequency is usually used.
This setting is, for example, used in microwave heaters.
At a sufciently high power density, the absorption can lead to an increase of internal energy and through scattering to an ionization of the
molecules in the gas [87]. After the ionization of the gas, the absorption
of electromagnetic radiation is based largely on the charged particles.
3.3.1.2. Multiphoton absorption. The second absorption process for a
gas, shown in Fig. 12, is called multiphoton absorption [70]. It describes the direct absorption of a large number of photons by atoms
to cause photoionization without the necessity for interaction with
free electrons. Normally a single-photon can only be absorbed by an
atom if the photon energy is higher or equal to the energy gap between two different states. In the case of multiphoton absorption an
electron is excited into a virtual state, having the same energy of
the incoming photon [70]. This has to be done in a certain time slot,
given by the uncertainty principle. If a second photon is absorbed
within this time slot, a higher virtual state can be achieved which corresponds to the energy of two photons. By successively absorbing
photons, an atom can be ionized.
By the supply of charged particles in a gas, the absorption can increase and the required power density for a gas breakthrough can be
reduced. As example, Schubnov et al. reduced the required energy
density of a CO2 laser-assisted plasma process, by the ejection of electrons from a briey inserted titanium rod [92]. After ignition, the plasma generates more electrons through impact ionization. An
additional supply of electrons is no longer necessary.
With the conversion of gas into plasma, the number of absorption
and interaction mechanisms increase [65]. Three important additional absorption mechanisms shown in Fig. 12 are: freefree absorption,
stochastic plasma heating and ohmic plasma heating.
3.3.1.3. Freefree absorption. The freefree absorption, which is also
known as Inverse Bremsstrahlung describes the absorption of a
photon by an electron in the vicinity of a charged particle. From a
classical point of view, an electron in an alternating electric eld can
be excited to oscillation [94]. If the electron does not interact with
other particles in plasma, it returns the energy back to the electromagnetic wave. However, for an energy transfer to the plasma, it is
necessary that the oscillating electron interacts with another particle.
Hence, one important parameter in the plasma is the collision rate
eff, which is proportional to the freefree absorption. The collision
rate itself is a function of electron density, temperature and the intensity of the incoming electromagnetic eld [47].
3.3.1.4. Ohmic heating. Since plasma is an electrical conductor, it can
be heated up by a current that passes through it. If the induced current density can be described by a local relationship between the
electromagnetic eld and the conductivity of the plasma, the process

is called ohmic heating [50]. The absorption of the energy happens

again, as in the freefree absorption, through collisions of the accelerated electrons with other particles inside the plasma. By means of an
increasing temperature, the resistance of the plasma decreases and
the ohmic heating becomes less effective.
The direction of the electrical current for ohmic heating depends on
the type of excitation. It can be separated into capacitive-coupled plasma (CCP) and inductive-coupled plasma (ICP) [22]. CCP reactors usually
consist of two electrodes built like a capacitor with a power supply of
usually 13.56 MHz [12]. The induced electrical current oscillates perpendicular to the electrodes in the direction of the displacement current. In the case of ICP, the reactor consists of an arrangement that
corresponds to a transformer, where the second coil has been replaced
by the conductive plasma. If a time-varying electric current is passed
through the rst coil, it creates a time varying magnetic eld, which induces a circular electric current in the plasma [11].
3.3.1.5. Stochastic heating. The plasma can be separated into the quasineutral region, in which electrons are present and conduction current
is dominated and regions without electrons, where displacement current is dominated. The electron-less positive space charge region is
denoted as the sheaths, which cyclically expand and collapse. The
expanding and collapsing depends on the electromagnetic eld and
the polarity of the current changes. The narrow interface region between the sheaths and the quasi-neutral plasma, which reects incident electrons, is called the sheath edge. The oscillation of the
sheath edge can increase the electron energy during the reection
and thereby heating the plasma. This process is called stochastic
heating or collisionless heating. If the electron collision frequency
is less than the angular frequency of the induced current and the electron mean free path is comparable to the maximum sheath width,
stochastic heating is the dominated heating processes.
3.3.2. Techniques for synthesis of diamonds
It is evident, that pressure and wavelength have to be known, to
use electromagnetic waves (EM-CVD) for diamond deposition. Therefore, in most of the cases the process is characterized by these parameters. For the deposition processes it is moreover necessary to know
the chemical composition, ionization, molecule fraction and temperature above the substrate. However, these parameters are unknown in
many cases, due to the highly technical requirements and the dependency on the layout. The simplest classication of plasma is the division into plasma-jet and plasma-ball formation.
3.3.2.1. Plasma-jet. The plasma-jet results from a point excitation, with
a gas ow through it. The shape of the plasma-jet depends on several
factors, such as the domination absorption mechanisms, the design of
the nozzle and the waveguide. The used process arrangements are
similar to one of the three examples shown in Figs. 1315.
Fig. 13(a) depicts a type of torche Injection Axial (TIA) [46]. The
reactor consists of two waveguides which are arranged perpendicular
to each other. The eld enhancement is generated through the Beenakker cavity which produces a standing wave pattern inside the cavity
[68]. Depending on the nozzle structure, a thin converging cone with
a tail ame on top of it can be created. Combined with the microwave
plasma torches (MPT), which exhibit a similar composition, it represents the most frequently used process for diamond deposition by electromagnetic induced plasma-jet formation. In most of the cases, a
2.45 GHz generator is utilized to excite the process gas. The dominating
absorption mechanisms are the multiphoton absorption and the inverse
Bremsstrahlung [47]. The following inuence parameters have a significant impact on the process parameters:

Nozzle geometry
Waveguide and conductor structure.

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

1295

Fig. 15. Laser induced plasma (LIP) process [66].

absorption, inverse Bremsstrahlung and electron oscillation of the

plasma. The inuence parameters are:

Fig. 13. Torche Injection Axial (TIA) plasma-jet [46].

Fig. 14 shows a typical construction of inductive coupled plasma

(ICP) [11]. The major driving force for ICP, is the availability of fully
developed equipment with an output of 4080 KW. Due to this high
available power, the gas ow can reach up to 100 slpm [8]. In contrast
to TIA and MPT, the plasma excitation is not generated in a single
point, but an annular ohmic heating area is produced because of a circular acceleration electron ow. The inuence parameters with signicant impact are:
Convolution density, diameter and length
Electrical supply of the coil.
Fig. 15 illustrates a laser induced plasma (LIP) process [66]. The
laser beam, which is typically located between 200 nm and 10 m,
is guided through mirrors into the operation range. A focusing mirror
is used to produce a breakdown in the gas ow and to generate a local
plasma [55]. The heating and ionization depends on multiphoton

Fig. 14. Inductive coupled plasma (ICP) process [11].

Laser spot, wavelength

Power density, pulse length.
3.3.2.2. Plasma-ball. To generate a plasma-ball formation, the incoming wave has to be absorbed in a larger area then at LIP or MPT.
This can be achieved by the modulation of a resonator chamber and
the adjustment of the absorption conditions resulting into a standing
wave inside the chamber. Here, care has to be taken, that the penetration depth of the incoming electromagnetic wave into the plasma is in
the order of the chamber. If the absorption coefcient of the plasma is
too high, the plasma formation might be too close to the quartz window, where the radiation is coupled into the chamber. If the absorption coefcient is too low, the energy transfer might be not high
enough to keep the plasma ball excited and the etching of the reactor
wall can cause severe contamination of the growing lm. The absorption coefcient depends on the pressure. Hence, the pressure has to
stay in a certain range to keep the process running. However, the
plasma-ball allows a larger and homogeneous diamond deposition.
Three different types of resonators, which generate a plasma-ball formation, are shown in Figs. 1618.
One of the rst used plasma-ball reactors is the tubular reactor
(TR) [8]. An early version of this reactor from 1982, which was actually developed by Kamo et al. [48], is shown in Fig. 16. The position of
the plasma-ball is adjusted in the center of the deposition chamber.
The electromagnetic wave is radiated perpendicular to the reactor
tube, where the substrate is placed.
In Fig. 17 the circumferential antenna plasma (CAP) reactor is
depicted in cross section and 3-D view. The reactor, which was developed by Pleuler et al. [80] in 2002, has been optimized for a homogeneous at plasma distribution. The microwave is guided via a coaxial
waveguide and coupled into the chamber via a circumferential ringshaped quartz window, embedded in the metallic wall of the chamber [21]. Through the uniform amplitude and phase distribution, a rotational symmetry plasma-ball is formed directly on the substrate.
An improved bell-jar reactor, developed in 2009 at the Michigan
State University [96] is illustrated in Fig. 18. The reactor has an elliptical shape and owns a quartz bell in the range of plasma excitation.
The reactor is optimized for high density plasmas and a homogeneous
diamond deposition on up to 80,000 mm 2.
In contrast to plasma-jet constrictions, the inuence parameters
are the chosen resonance mode, the coupling technique and the
shape and location of the quartz window [100]. The skills are the locally enhance eld in front of the substrate with the possibility of
large and uniform deposition areas. Typical conditions and results

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M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

Fig. 18. Bell-jar reactor for plasma-ball formation [96].

Fig. 16. Tubular reactor (TR) for plasma-ball formation [48].

for electromagnetic wave induced diamond deposition are listed in

Table 4.
3.3.3. Diamond coatings
In addition to the thermal excitation, excitation by electromagnetic
radiation has the largest applications area. By supplying solid or
gaseous precursor, boron [37,1], beryllium and phosphorus doped
semiconductors are produced. The resulting band gaps are 0.37 eV
for boron [76], 0.6 eV for phosphorus [32] and 4.760 eV for beryllium
[105].
In the domain of tool coating, deposition by electromagnetic radiation excitation is also used for industrial research. In the majority of
cases, the researchers do no longer deal with the process, but with the
application of layers for drilling [51], machining [58] and cutting
[106]. The studies are focused on the wear of the lms at different
mechanical loads in tribological systems.
Depending on the high homogeneity, the fast growth rates and deposition areas with diameter up to 160 mm [96], a recipient of application is the production of freestanding large undoped and doped

single crystal diamond lms. To remove the layers from the coated
substrates, mostly a lift-off process is used. The optical transparency
of undoped lms in the wavelength range of 220 to 2500 nm is as
high as the transparency of HPHT type-IIa diamond [103,69]. By
using partially stabilized zirconia substrates, it was also shown that
the growth of free-standing boron doped CVD diamond lms [27] is
possible.
3.4. Electrical induced
Within this chapter all processes, which are based on a direct current (DC) plasma discharge between two electrodes for diamond deposition, are combined. The two used applications of glow discharge

Table 4
Data electromagnetic activated diamond deposition.
Electromagnetic activated
Total gas ow [slpm]
Typical process gas
Typical mixture range H2/CH4
Pressure [Pa]
Deposition area [mm2]
Common linear growth rate [m/h]
Advantages

Drawbacks

Total gas ow [slpm]

Typical process gas
Typical mixture range H2/CH4
Pressure chamber [Pa]
Deposition area [mm2]
Common linear growth rate [m/h]
Advantages

Drawbacks

Fig. 17. Circumferential antenna plasma (CAP) for plasma-ball formation [80].

Plasma-jet
0007150
Ar/H2/CH4
100/1 to 3/1
500100,000
202000
170
High growth rate at large deposition area
No chamber is required
High power available
High power and gas consumption
Process control difcult
Expensive equipment
Plasma-ball
0.11.5
Ar/H2/CH4
50/1 to 2/1
4030,000
Up to 80,000
0.134
Excellent quality of diamond layers
Stable deposition parameter
Very large deposition area
Chamber is required
Simulation of chamber is required
3D-deposition difcult
Low growth rates

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

1297

and arc discharge are mainly inuenced by the applied voltage, the
current ow, the electrode arrangement and the prevailing pressure.
3.4.1. Heating from apply voltage
Through the appliance of voltage over a gas ooded chamber,
charge carrier can be accelerated and by impact ionization the gas
can be ionized. If the voltage is high enough, the ionization may be
enhanced through an electron avalanche. The steady increase of the
electrical power results in a currentvoltage curve, shown in Fig. 19.
The curve can be divided into four areas [50]:
By applying voltage, a very small amount of free electrons accelerate. After exceeding the breakdown voltage, the electrons can ionize
the gas. This leads to an electron avalanche which is described by
the Townsend coefcient. This range is normally not used for diamond deposition.
After increasing the voltage over the requirement of glow discharge, an increase of power leads to an expansion of the plasma region. This happens until the whole electrode is capped. Through
CVD processes, a sample can be deposited on one of the electrodes.
Therefore, by the expansion of the electrodes, this range is mostly
used for depositing large and uniform diamond layers at low
pressure.
When the whole electrode is covered, the current can only increase
by an increase of the voltage. In the case of plate capacitor, this
curve can be described by the ChildLangmuir Law.
With a further increase of the current, the surface of the electrode
heats up. Thereby, electrons can pass out by thermal emission and
the transition until an arc discharge occurs. The arc discharge is
characterized by high current and low voltage. In the range of 10
to 100 kW applied power, a plasma core, which can be described
on the basis of a local thermal equilibrium (LTE), is generated.
This discharge is used to generate a plasma-jet for diamond
deposition.

3.4.2. Techniques for synthesis of diamonds

The simplest way of direct current (DC) plasma discharge at low
pressure is shown in Figs. 20 and 21. The two examples have been developed in 1986 and 1987 by Sawabe and Suzuki [99,88]. The reactors
consist of two electrodes which are arranged parallel to each other. In
Fig. 20 the cathode depends on a grid over which the process gas is
supplied. In contrast, the process gas in Fig. 21 is fed via a separate entrance. Depending on the plasma density and the temperature, the
desired substrate temperature of 1100 K can be achieved by using a
cooled or heated water-ooded anode. Through a given pressure,
the maximal power input into a hydrogen discharge can always be
dened sharply. Due to the characteristics that the voltage for stable
plasma discharge is higher for lower pressures and the deposition
area gets smaller at higher pressure and lower power, it has to be

Fig. 19. Characteristic curve of a direct current (DC) plasma discharge [50].

Fig. 20. Direct current (DC) plasma process at low pressure used 1986 by Sawabe and
K. Suzuki [99].

decided between a high deposition rate and the possibility of large

areas up to 70 cm [48].
For diamond deposition the plasma size is generally similar to the
cathode size. Since the deposition area is determined by the plasma
size, it can be increased by using larger sized cathodes. The main
problem is the generation of arcs between the electrodes and the stability of the plasma. A frequently used method to avoid the formation
of arc discharge [93] and to enlarge the deposition area [9], is the use
of pulsed DC [39,40]. Another possibility is to stabilize the process by
a magnetic eld [74].
A further increase of pressure and power leads to an arc discharge.
The setup of conventional high power industrial arc is shown in
Fig. 22. The cathode, which is not illustrated in this Figure, is normally
made of WCe and the anode is usually made of oxygen-free copper.
In early works of diamond deposition, the setup was simply copied
from a plasma thermal spray, which is basically very similar. Within
the depicted schematic diagram, the arc rotates with a proper speed
around the anode. The carbon source is above the nozzle and forms
a stream around the hot plasma arc. After the ow through the arc,
a uniform plasma jet is passing through the orice. Due to the limited
expansion shape of the plasma jet, only a small deposition area with
varying quality and thickness can be deposited. Furthermore, the
plasma jet is not as uniform as desired, because of the use of conventional plasma torches, which consist of a cathode rod and a cylindrical
anode.
For a further increase of power, the arc plasma has to be stabilized
by some changes in the setup. One possibility is shown in Fig. 23. The
DC arc plasma torch, developed by Zhang et al., owns a comparative

Fig. 21. Direct current (DC) plasma process at low pressure used 1987 by Sawabe and
K. Suzuki [88].

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M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

Fig. 24. Arc-jet stabilized by four DC plasma torches [44].

Fig. 22. Schematic diagram of an arc discharge [59].

long arc discharge and an external magnetic eld [59]. Within

this eld the electrons follow the magnetic eld lines which enable
a better heat transfer. The process reaches a power of about 100 kW
and allows a growth rate of 40 m/h.
Another possibility to stabilize the plasma jet at high power has
been developed by Hirata et al. and is portrayed in Fig. 24 [44].
The electrode conguration is made of four DC plasma torches. One
plasma torch is mounted perpendicular to the three shown plasma
torches in the schematic diagram. The three changeable torches are
attached in the plane along their axes. Arcs are struck between
the cathode and the three anodes, so that the discharge area can be
widened in radial direction of the plasma jet. Another unique feature
is the high process pressure of up to 26.7 kPa. Furthermore, the carbon source gas is induced into the plasma jet and not induced into
the generator.
Up to the present day, the highest deposition rate of 930 m/h
with a DC plasma jet, is achieved by Ohtake et al. [78]. The used
setup is shown in the schematic diagram of Fig. 25. In this apparatus
the plasma jet consists only of Ar and H2. The carbon carrier gas is not
injected directly into the generator but instead mixed into the plasma
jet. The cathode is made of pure tungsten and the anode is made of
pure copper. Particularly, there are also three independent gas inlets
of the cathode system. The process parameters for diamond

Fig. 23. Magnetic stabilized arc for high power deposition [59].

deposition are 25 kPa with 9.45 kW applied power. The achieved

layer thickness is 3 mm with a 10 10 mm 2 large molybdenum
substrate.
Another electrical induced deposition is the pulsed arc discharge,
which is characterized by the repetition of short current pulses up
to several 1000 A. Since the deposited layers only consist of amorphous carbon, they are not interesting at this point. Typical data for
glow discharge and arc discharge deposition of diamonds is given in
Table 5.

3.4.3. Diamond coatings

As for electromagnetic excitation, DC processes are used as a source
for plasma-jet and for homogeneous plasma distribution. Therefore, it is
not surprising that also by the addition of boron-containing gases,
boron doped semiconductors are produced by direct current plasma
chemical vapor deposition (DC-PCVD)[28]. Although it was shown
that at comparable ratios of PH3/CH4 the P content is approximately
ten times greater by using DC rather than microwave excitation [89],
there are only a few publications which use DC as a source for doping
with phosphorus.
The major advantage of DC processes is the production of large
free-standing diamond layers with a pronounced diamond structure.
By using DC arc plasma-jet and destroyable Ti interlayer on graphite,
crack-free free-standing diamond lms with thickness of 300 m and

Fig. 25. DC arc-jet setup with the highest published diamond growth rate [78].

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

1299

Table 5
Data electrical activated diamond deposition.
Electrical activated
Total gas ow [slpm]
Typical process gas
Typical mixture range H2/CH4
Pressure [Pa]
Deposition area [mm2]
Common linear growth rate [m/h]
Advantages

Drawbacks

Glow discharge
0.1 to 0.5
H2/CH4
100/1 to 10/1
6000 to
70,000
1080
Large area at low pressure
Simple set-up
Low-priced equipment
High quality diamond layers
Small deposition area at high pressure
Low growth rates at low pressure
Chamber is required

Arc discharge
Total gas ow [slpm]
7.8 to 500
Typical process gas
Ar/H2/CH4
Typical mixture range H2/CH4
100/1 to 20/1
Pressure [Pa]
7 to 101,330
Deposition area [mm2]
11,000
Common linear growth rate [m/h] 10 to 930
Advantages
Highest linear growth rate
High diamond quality
Drawbacks
Small deposition areas
Process control difcult
Expensive equipment
High power and gas consumption
Contamination through electrode
degradation
Chamber is required

diameter of 60 mm are published [57]. Under the condition of

10 m/h they achieved grain size of about 1 1 1 mm 3 [18].
Even larger free-standing diamond layers, with diameters up to
203.2 mm (8-inch), are produced with the diode-type electrode conguration [17]. The advantages of these layers which grow at 7 to
9 m/h are the excellent uniformity in thickness, crystallinity and
thermal conductivity. Up to now, coatings with larger surfaces
(500 1000 mm) were only made by HFCVD method. However, the
growth rates and purities are inferior to the DC and microwave excitation processes [91]. Therefore HFCVD is not used for free-standing
diamond layers.
As for other plasma-based processes, electrical induced synthesis
is also used for coatings on WCCo hard metal [23], SiC [111] or further materials, which are usable for tools. However, since tools mostly
need a small coating area, only the plasma jet process is used for deposition [23].
4. Discussion
Today, different equipment for diamond synthesis by CVD is
available. Although these techniques differ in energy supply, temperature range, pressure range and chemical composition, they have to
possess the same requirements of desired diamond quality, growth
rate and layer size. For industrial applications, gas consumption, economic efciency and velocity of the process are also important.
Therefore, each technique has a eld of application with different
process parameters. By the analysis of more than 100 related publications, a comparison of pressure and absolute ow is given in Fig. 26.
The total gas ow consists of process gases like methane and hydrogen and the additives gases such as argon and nitrogen. The exception
is the chemical combustion, in which acetylene and oxygen are used
as process gases. Due to the fact, that not every publication shows
the details of pressure, gas ow and growth, the displayed values
are decoupled from each other. Therefore, the number of measurement points varies slightly for the two axes.

Fig. 26. Pressure [Pa] and absolute ow [slpm] out of more than 100 highly regarded
publications for different CVD processes.

However, unlike the gas ow, the pressure owns a maximum

around atmosphere pressure at 10 5 Pa. This particular limit is not
given because it would not be feasible, but the use of hydrogen or oxygen in a pressure reactor is associated with a risk of explosion and
therefore with a high technical effort. Furthermore, it can be seen,
that the process windows for electric and electromagnetic excitation
are much larger than for thermal and chemical excitation. The restriction of chemical processes in the range of 10 4 to 10 5 Pa, is conditioned
by thermal quenching of the ame at low pressure [53]. In contrast,
thermal heating is mostly used in the range from 10 3 to 10 4 Pa. The
restriction of thermal heating is generally the maximum temperature
of the heated lament or layer, which results in a maximum ow and
pressure.
In contrast to this, plasma generated processes can be used over
the range of ve magnitudes from 10 1 to 10 5 Pa for diamond deposition. In Figs. 27 and 31 the values of pressure and gas ow are combined in a statistic view with the following characteristics:
maximum and minimum values are given by the star; whiskers
gone from 5 to 95% probability; diamond formed boxes shown 25,
50 and 75% probability; the square represent the arithmetic mean.
The growth rate in comparison with the absolute ow rate can be
seen in Fig. 28. As expected, the growth rate's tendency increases to
higher values with higher absolute ow at different processes. This
can particularly be seen on the comparison of the statistic diagrams
in Figs. 30 and 31.
For free standing diamond layers thermal induced CVD diamond
coating techniques are not suitable. This can also be concluded from
the growth rate comparison. Thermal induced CVD techniques show
the lowest possible gas ows and hence the lowest growth rates.
However, the growth rate is not sufcient information in order to
conclude what application is possible. For example, chemical CVD

Fig. 27. Statistic view from the pressure eld of applications.

1300

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

Fig. 28. Growth rate [m/h] and absolute ow rate [slpm] out of more than 100 highly
regarded publications for different CVD processes.

Fig. 31. Statistic view of absolute ow [slpm] for different CVD processes.

as described in the rst chapter. Despite these simplications, the interrelationship between the gas ow and the growth rate for the different processes shown in Figs. 30 and 31 behaves very similarly.
Additional to the decoupled measurement points, Fig. 29 shows
the direct correlation of growth rate and gas ow. Due to the requirement of both specications in a publication, the number of measurement points is reduced. Furthermore, the gas ow only consists of the
process gases methane, hydrogen, acetylene and oxygen without additives gases such as argon and nitrogen. As also shown in Figs. 26 and
28, the process window for electrical and electromagnetic excitation
differs from thermal and chemical excitation. Moreover, it can be
seen that the growth rate is rather dependent on the gas ow than
on the process itself. Hence it can be concluded that the upper limit
of the growth rate is mainly depending on the upper limit of the gas
ow rate. However this is only valid if arbitrary amounts of power
are available.
Fig. 29. Growth rate [m/h] and ow rate [slpm] from methane, hydrogen, acetylene
and oxygen for different processes.

techniques are also not used for the generation of large free standing
layers which is caused by the process geometry condition. However,
it must be taken into account that the diagrams do not distinguish between processes where only methane and hydrogen are used and
processes with a major share of argon and nitrogen, which is often
the case in plasma-based processes. Additionally, it is considered
that the deposition rate was specied for different substrate sizes
and the specication in volume growth would be more accurate. Furthermore, the power of the used energy supply is neglected, as it is
assumed that the efciency of the processes do not deviate strongly
from each other and the experiments are running at best settings,

5. Conclusion
As shown in this review, the technical environment for diamond
deposition goes from a simple single excitation at low pressure to
large deposition areas with multi-ame and enlarged plasmas at atmosphere pressure with increased power. Until today, the deposition
rate has risen further as a result of the increasing power and gas ow,
without a physical limitation. The only known limitation is the increase to the atmosphere pressure. Hence the growth rate is technically limited by the energy supply, which also limits the
temperature and the maximum gas ow. Finally, there have to be
more investigation on the technical and physical growth rate in the
future.
Acknowledgments
This work was supported by the Deutsche Forschungsgemeinschaft
(DFG) under contract no. VO 530/18-2 which the authors gratefully
acknowledge.
References

Fig. 30. Statistic view of growth rate for different CVD processes.

[1] A. Aleksov, A. Vescan, M. Kunze, P. Gluche, W. Ebert, E. Kohn, A. Bergmaier, G.

Dollinger, Diam. Relat. Mater. 8 (1999) 941.
[2] F.A. Almeida, M. Amaral, F.J. Oliveira, R.F. Silva, Diam. Relat. Mater. 15 (2006)
2029.
[3] Y. Ando, S. Tobe, T. Saito, J.-i. Sakurai, H. Tahara, T. Yoshikawa, Thin Solid Films
457 (2004) 217.
[4] Y. Ando, S. Tobe, H. Tahara, Vacuum 83 (2009) 102.
[5] M.N.R. Ashfold, P.W. May, C.A. Rego, Chem. Soc. Rev. 23 (1994) 21.
[6] P.K. Bachmann, D. Leers, H. Lydtin, Diam. Relat. Mater. 1 (1991) 1.
[7] P.K. Bachmann, in: Gordon Davies (Ed.), Properties and Growth of Diamond,
Institution of Electrical Engineers, London, 1994, p. 349.
[8] P.K. Bachmann, in: Davies Gordon (Ed.), Properties and Growth of Diamond,
Institution of Electrical Engineers, London, 1994, p. 354.

M. Schwander, K. Partes / Diamond & Related Materials 20 (2011) 12871301

[9] Y.J. Baik, J.K. Lee, W.S. Lee, K.Y. Eun, Thin Solid Films 341 (1999) 202.
[10] L. Brdos, H. Barnkov, Yu.A. Lebedev, T. Nyberg, S. Berg, Diam. Relat. Mater. 6
(1997) 224.
[11] J.O. Berghaus, J.L. Meunier, F. Gitzhofer, Int. J. Refract. Met. Hard Mater. 16
(1998) 201.
[12] H. Berthou, C. Faure, W. Hnni, A. Perret, Diam. Relat. Mater. 8 (1999) 636.
[13] H. Bjrkman, P. Rangsten, K. Hjort, Sens. Actuators 78 (1999) 41.
[14] F.P. Bundy, H.T. Hall, H.M. Strong, R.H. Wentorf, Nature 176 (1955) 51.
[15] J.E. Butler, R.L. Woodin, L.M. Brown, P. Fallon, Philos. Trans. Phys. Sci. Eng. 342
(1993) 1664.
[16] A. Chattopadhyay, S.K. Sarangi, A.K. Chattopadhyay, Appl. Surf. Sci. 255 (2008)
1661.
[17] K.W. Chae, Y.J. Baik, J.K. Park, W.S. Lee, Diam. Relat. Mater. 19 (2010) 1168.
[18] G.C. Chen, B. Li, H. Li, H. Lan, F.W. Dai, Q.J. Xue, X.Q. Han, L.F. Hei, J.H. Song, C.M.
Li, W.Z. Tang, F.X. Lu, Diam. Relat. Mater. 19 (2010) 1078.
[19] M.S. Raghuveer, S.N. Yoganand, K. Jagannadham, R.L. Lemaster, J. Bailey, Wear
253 (2002) 1194.
[20] C. Lvy-Clment, N.A. Ndao, A. Katty, M. Bernard, A. Deneuville, C. Comninellis,
A. Fujishima, Diam. Relat. Mater. 12 (2003) 606.
[21] M.L. McConnell, D.P. Dowling, C. Pope, K. Donnelly, A.G. Ryder, G.M. O'Connor,
Diam. Relat. Mater. 11 (2002) 1036.
[22] I.B. Denysenko, S. Xu, J.D. Long, P.P. Rutkevych, N.A. Azarenkov, K. Ostrikov,
J. Appl. Phys. 95 (2004) 2713.
[23] F. Deuerlera, H. Grunerb, M. Pohlc, L. Tikanac, Surf. Coat. Technol. 142144
(2001) 674.
[24] K. Donnelly, D.P. Dowling, M.L. McConnell, R.V. Flood, O. Berkefelt, J. Svennebrink,
Diam. Relat. Mater. 9 (2000) 693.
[25] J.B. Donnet, H. Oulanti, T. Le Huu, M. Schmitt, Carbon 44 (2006) 374.
[26] R.J.H. Klein-Douwel, J.J. ter Meulen, J. Appl. Phys. 83 (1998) 4734.
[27] L.E.V.S. Brandaoa, R.F. Pires, N.M. Balzaretti, Vib. Spectrosc. 54 (2010) 84.
[28] Y. Feng, J. Lv, J. Liu, N. Gao, H. Peng, Y. Chen, Appl. Surf. Sci. 257 (2011) 3433.
[29] J. Gbler, S. Pleger, Int. J. Mach. Tools Manuf. 50 (2010) 420.
[30] Z. Gao, V. Carabelli, E. Carbone, E. Colombo, F. Demaria, M. Dipalo, S. Gosso, C.
Manfredotti, A. Pasquarelli, S. Rossi, Y. Xu, E. Vittone, E. Kohn, Diam. Relat.
Mater. 19 (2010) 1021.
[31] R. Gat, J.C. Angus, in: Gordon Davies (Ed.), Properties and Growth of Diamond,
Institution of Electrical Engineers, London, 1994, p. 325.
[32] E. Gheeraert, S. Koizumi, T. Teraji, H. Kanda, M. Nesladek, Diam. Relat. Mater. 9
(2000) 948.
[33] N.G. Glumac, D.G. Goodwin, Thin Solid Films 212 (1992) 122.
[34] N.G. Glumac, D.G. Goodwin, Combust. Flame 105 (1996) 321.
[35] D.G. Goodwin, G.G. Gavillet, J. Appl. Phys. 68 (1990) 6393.
[36] E.V. Gorokhov, A.N. Magunov, V.S. Feshchenko, A.A. Altukhov, Instrum. Exp.
Tech. 51 (2) (2008) 280.
[37] M.C. Granger, M. Witek, J. Xu, J. Wang, M. Hupert, A. Hanks, M.D. Koppang, J.E.
Butler, G. Lucazeau, M. Mermoux, J.W. Strojek, G.M. Swain, Anal. Chem. 72
(2000) 3793.
[38] S.J. Harris, A.M. Weiner, T.A. Perry, Appl. Phys. Lett. 53 (1988) 1605.
[39] P. Hartmann, R. Haubner, B. Lux, Diam. Relat. Mater. 5 (1996) 850.
[40] P. Hartmann, R. Haubner, B. Lux, Int. J. Refract. Met. Hard Mater. 16 (1998) 207.
[41] L.M. Hanssen, W.A. Carrington, J.E. Butler, K.A. Snail, Mater. Lett. 7 (1988) 289.
[42] Y. Hirose, N. Kondo, Extended Abstracts of 35th Spring Meeting of the Japanese
Society, Applied Physics and Society, Tokyo, 1988, p. 343.
[43] Y. Hirose, S. Amanuma, K. Komaki, J. Appl. Phys. 68 (1990) 6401.
[44] A. Hirata, M. Yoshikawa, Diam. Relat. Mater. 4 (1995) 1363.
[45] T. Izk, M. Marton, M. Varga, M. Vojs, M. Vesel, R. Redhammer, M. Michalka,
Vacuum 84 (2009) 49.
[46] J. Jonkers, J.M. de Regt, J.A.M. van der Mullen, H.P.C. Vos, F.P.J. de Groote, E.A.H.
Timmermans, Spectrochim. Acta, Part B 51 (1996) 1385.
[47] C.M. Jost, Untersuchung optischer-feldionisierter Wasserstoff- und DeuteriumPlasmen mittels Thomson-gestreuten Laserlichtes, Ludwig-Maximilians-Universitt,
Mnchen, 2001.
[48] M. Kamo, Y. Sato, S. Matsumoto, N. Setaka, J. Cryst. Growth 62 (1983) 642.
[49] R.J. Kee, J.A. Miller, Physica D 12 (1984) 198.
[50] A. von Keudell, Plasma-Oberchen-Wechselwirkung, Ruhr-Universitt Bochum,
Unpublished Results (2008).
[51] Y.K. Chou, R.G. Thompson, A. Kumar, Thin Solid Films 518 (2010) 7487.
[52] J.S. Kim, M.A. Cappelli, Surf. Coat. Technol. 7677 (1995) 791.
[53] N.I. Kim, T. Kataoka, S. Maruyama, K. Maruta, Combust. Flame 141 (2005) 78.
[54] T. McKindra, M.J. O'Keefe, Z. Xie, Y. Lu, Mater. Charact. 61 (2010) 661.
[55] V.I. Konov, A.M. Prokhorov, S.A. Uglov, A.P. Bolshakov, I.A. Leontiev, F. Dausinger,
H. Huegel, B. Angstenberger, G. Sepold, S. Metev, Appl. Phys. A Mater. Sci. Process. 66 (1998) 575.
[56] S. Kshudiram, The Earth's Atmosphere, Book, Spirnger-Verlag, Berlin Heidelberg
978-3-540-78426-5, 2008.
[57] C. Li, L. Wang, L. Chen, Z. Liu, L. Hei, F. Lu, Diam. Relat. Mater. 18 (2009) 1348.
[58] Q. Liang, Y.K. Vohra, R. Thompson, Diam. Relat. Mater. 17 (2008) 2041.
[59] F.X. Lu, G.F. Zhong, J.G. Sun, Y.L. Fu, W.Z. Tang, J.J. Wang, G.H. Li, J.M. Zang, C.H.
Pan, C.X. Tang, T.L. Lo, Y.G. Zhang, Diam. Relat. Mater. 7 (1998) 737.

1301

[60] V. Malcher, A. Mrska, A. Kromka, A. Satka, J. Jank, Curr. Appl. Phys. 2 (2002) 201.
[61] S. Matsumoto, J. Mater. Sci. 17 (1982) 3106.
[62] K.J. Matthes, E. Richter, Schweitechnik. Schweien von metallischen
Konstruktionswerkstoffen, Carl Hanser Verlag, Mnchen, 2008.
[63] P.W. May, Philos. Trans. Math., Phys. Eng. Sci. 358 (2000) 473.
[64] P.W. May, J.A. Smith, Yu.A. Mankelevich, Diam. Relat. Mater. 15 (2006) 345.
[65] D. Meschede, Gerthsen Physik, Book, Spirnger-Verlag, Berlin Heidelberg, 2005,
p. 23, ISBN-10 3-540-254221-8.Auage.
[66] S. Metev, A. Stephen, J. Schwarz, C. Wochnowski, Focused on Laser Precision
Microfabrication (LPM 2002), 2003.
[67] P. Mistry, M.C. Turchan, G.O. Granse, T. Baurmann, Mater. Res. Innov. 1 (1997)
149.
[68] M. Moisan, G. Sauve, Z. Zakrzewski, J. Hubert, Plasma Sources Sci. Technol. 3
(1994) 584.
[69] Y. Mokuno, A. Chayahara, H. Yamada, N. Tsubouchi, Diam. Relat. Mater. 18
(2009) 1258.
[70] C.G. Morgan, Rep. Prog. Phys. 28 (1975) 621.
[71] P.W. Morrison Jr., J.T. Glass, in: Gordon Davies (Ed.), Properties and Growth of
Diamond, Institution of Electrical Engineers, London, 1994, p. 368.
[72] M.K. Murayama, S. Kojima, K. Uchida, J. Appl. Phys. 69 (1991) 7924.
[73] M. Murakawa, S. Takeuchi, Surf. Coat. Technol. 5455 (1992) 403.
[74] M. Nesldek, Diam. Relat. Mater. 2 (1993) 357.
[75] C. Nrgrd, A. Matthews, Diam. Relat. Mater. 5 (1996) 332.
[76] H. Okazaki, R. Yoshida, T. Muro, T. Nakamura, T. Wakita, Y. Muraoka, M. Hirai, H.
Kato, S. Yamasaki, Y. Takano, S. Ishii, T. Oguchi, T. Yokoya, Appl. Phys. Lett. 98
(2011) 082107.
[77] Y. Okumura, K. Kanayama, K. Shogaki, Combust. Flame 157 (2010) 1052.
[78] N. Ohtake, M. Yoshikawa, J. Electrochem. Soc. 137 (1990) 717.
[79] P. Peregrinus, A.C. Metaxas, R.J. Meredith, Industrial Microwave Heating, Book,
Institution of electrical engineers0-906048-89-3, 1993.
[80] E. Pleuler, C. Wild, M. Fner, P. Koidl, Diam. Relat. Mater. 11 (2002) 467.
[81] R. Polini, M. Barletta, G. Cristofanilli, Thin Solid Films 519 (2010) 1629.
[82] N.A. Prijaya, J.C. Angus, P.K. Bachmann, Diam. Relat. Mater. 3 (1994) 129.
[83] S.A. Rakha, Z. Xintai, D. Zhu, Y. Guojun, Curr. Appl. Phys. 10 (2010) 171.
[84] A.K. Ramdas, in: Gordon Davies (Ed.), Properties and Growth of Diamond,
Institution of Electrical Engineers, London, 1994, p. 13.
[85] L.L. Regel, W.R. Wilcox, Acta Astronaut. 48 (2001) 129.
[86] J. Reiche, Nichtresonante Laserstreudiagnostik an Hochdruckgasentladungen,
Universitt Hannover, Unpublished results (2003)
[87] B. Rosenkranz, J. Bettmer, TrAC, Trends Anal. Chem. 19 (2000) 138.
[88] A. Sawabe, H. Yasuda, T. Inuzuka, K. Suzuki, Appl. Surf. Sci. 3334 (1988) 539.
[89] S.N. Schauer, J.R. Flemish, R. Wittstruck, M.I. Landstrass, M.A. Plano, Appl. Phys.
Lett. 64 (9) (1994) 28.
[90] M. Schmitt, D. Paulmier, Tribol. Int. 37 (2004) 317.
[91] L. Schfer, M. Hfer, R. Krger, Thin Solid Films 515 (2006) 1017.
[92] A. Schubnov, F. Vollertsen, Vak. Forsch. Prax. 21 (2) (2009) 24.
[93] S. Sciortino, S. Lagomarsino, F. Pieralli, E. Borchi, E. Galvanetto, Diam. Relat.
Mater. 11 (2002) 573.
[94] J.F. Seely, E.G. Harris, Phys. Rev. A 7 (1973) 1064.
[95] S.D. Shin, N.M. Hwang, D.Y. Kim, Diam. Relat. Mater. 11 (2002) 1337.
[96] F. Silva, K. Hassouni, X. Bonnin, A. Gicquel, J. Phys. Condens. Matter 21 (2009)
364202.1.
[97] F. Silva, X. Bonnin, J. Scharpf, A. Pasquarelli, Diam. Relat. Mater. 19 (2010) 397.
[98] B.V. Spitsyn, L.L. Bouilov, A.E. Alexenko, Braz. J. Phys. 30 (2000) 471.
[99] K. Suzuki, A. Sawabe, T. Inuzuka, Jpn. J. Appl. Phys. 29 (1990) 153.
[100] W. Tan, T.A. Grotjohn, Diam. Relat. Mater. 4 (1995) 1145.
[101] C. Tendero, C. Tixier, P. Tristant, J. Desmaison, P. Leprince, Spectrochim. Acta,
Part B 61 (2006) 2.
[102] E.A.H. Timmermans, Atomic and Molecular Excitation Processes in Microwave
Induced Plasmas, Eindhoven University of Technology, Unpublished Results
(1999)
[103] N. Tsubouchi, Y. Mokuno, A. Chayahara, S. Shikata, Diam. Relat. Mater. 19 (2010)
1259.
[104] Y. Tzeng, R. Phillips, C. Cutshaw, T. Srivinyunon, B.H. Loo, P. Wang, Appl. Phys.
Lett. 58 (1991) 2645.
[105] K. Ueda, M. Kasu, Diam. Relat. Mater. 18 (2009) 121.
[106] V.V.S.S. Srikanth, X. Jiang, A. Kpf, Surf. Coat. Technol. 204 (2010) 2362.
[107] Verein Deutsche Ingenieure, Kohlenstoffschichten Grundlagen, Schichttypen
und Eigenschaften, Beuth Verlag GmbH, Berlin, 2005.
[108] F. Vollertsen, K. Partes, A. Schubnov, Prod. Eng. 4 (2010) 9.
[109] Z.L. Wang, C. Lu, J.J. Li, C.Z. Gu, Appl. Surf. Sci. 255 (2009) 9522.
[110] S. Wang, G. Chen, F. Yang, Thin Solid Films 517 (2009) 3559.
[111] T. Wang, L. Xiang, W. Shi, X. Jiang, Surf. Coat. Technol. 205 (2011) 3027.
[112] M. Werner, R. Locher, Rep. Prog. Phys. 61 (1998) 1665.
[113] Z. Xie, Y. Zhou, X. He, Y. Gao, J. Park, H. Ling, L. Jiang, Y. Lu, Cryst. Growth Des. 10
(2010) 1762.
[114] Z.Q. Xie, X.N. He, W. Hu, T. Guillemet, J.B. Park, Y.S. Zhou, J. Bai, Y. Gao, X.C. Zeng,
L. Jiang, Y.F. Lu, Cryst. Growth Des. 10 (2010) 4928.