Hard graphite-like material bonded by diamond-like framework

The present invention provides a novel class of hard nano-structured materials comprising sp.sup.2 bonded graphite-like layers bonded together by sp.sup.3 three-dimensional diamond-like frameworks, wherein the whole carbon structure is stabilized with at least two alloying elements: the first alloying element selected from the group consisting of O, H, N, and a combination thereof; and the second alloying element selected from the group consisting of Si, B, Zr, Ti, V, Cr, Be, Hf, Al, Nb, Ta, Mo, W, Mn, Re, Fe, Co, Ni, Mn, Re, Fe, Co, Ni and a combination thereof. Also disclosed, are methods of manufacture of the novel class of materials.

BACKGROUND OF INVENTION 
1. Field of the Invention 
The present invention relates generally to a new class of hard 
nano-structured materials, including coatings and bulk solid thereof, and 
methods of their manufacture. More particularly, the present invention 
provides hard carbon materials comprising sp.sup.2 bonded graphite-like 
layers bonded together by sp.sup.3 three-dimensional diamond-like 
frameworks, wherein the whole carbon structure is stabilized with at least 
two alloying elements: the first alloying element selected from the group 
consisting of O, H, N, and a combination thereof; and the second alloying 
element selected from the group consisting of Si, B, Zr, Ti, V, Cr, Be, 
Hf, Al, Nb, Ta, Mo, W, Mn, Re, Fe, Co, Ni and a combination thereof. The 
graphite-like layers are mutually parallel with no azimuth order in-plane, 
and the diamond-like framework is fully amorphous. The ratio between 
graphite-like sp.sup.2 bonds and diamond-like sp.sup.3 bonds, and/or bonds 
between carbon and stabilizing elements may be gradually modulated forming 
a hierarchical structured material. 
2. Description of the Prior Art 
Structuring composite materials in micro, sub-micro, and nano scales 
constitutes one of the major areas of research in material engineering 
technology today. Such research combines different forms of carbon, 
including organic materials, nonorganic carbon-based materials, and 
diamond and/or diamond-like carbon to form composite materials exhibiting 
different physical properties. 
Another area of research in the field of composite materials includes the 
hierarchical composites possessing a one-, two-, or three-dimensional 
artificially ordered structure. A traditional approach for hierarchical 
composite manufacturing is based on the combination of several known 
technologies to form composite components using the process of sintering 
to form artificial, bulk materials. However, approaches are limited by the 
structural resolution. At, or close to the structural resolution limits, 
the productivity of the composite declines, and the cost correspondingly 
grows. Consequently, many new technologies have recently emerged in an 
effort to create new and improved composite materials. 
One such process which has been shown to be effective to the control 
nanoscale structure of the composite material is intercalation. This 
process comprises polymerization of the interlayer spaces of layered clay 
mineral, montmorillonite, followed by calcination of the folded silica 
sheets and organic cations, resulting in a highly ordered, mesoporous 
nanostructured material Fulushima, Yoshiaki, Toyota Central Res. & 
Development Lab Inc., Journal of Japan Society of Powder and Powder 
Metallurgy v. 41, No 10, 1984, p. 1189-1192, which disclosure is hereby 
incorporated by reference). 
Intercalation, however, allows synthesis of specific structures only 
because this method is based on pre-manufactured crystalline materials 
which limits the design and manufacturing of artificial composite 
materials in both micro- and nano-scales. Because of this restriction, 
much effort recently has been employed toward the synthesis of 
amorphous-based composite materials by organic and/or nonorganic 
synthesis. 
For example, polymer-derived micro-nano-structured Si.sub.3 N.sub.4 
/SiC-composites were prepared by liquid-phase sintering or either 
amorphous, polymer derived Si-C-N powder or SiC coated Si.sub.3 N.sub.4 
powder. However, following gas pressure sintering, the composites 
comprised nanosized SiC inclusions embedded in microcrystalline Si.sub.3 
N.sub.4 grains (Greiner, Axel, Bill, Joachim, Riedel, Ralf, 
Max-Planck-Inst.; Proceeding of Materials Research Society, v 346, 1994, 
p. 611-616, Pittsburg, Pa., USA, which disclosure is hereby incorporated 
by reference). 
U.S. Pat. No. 5,206,083 (1993) to Raj et al., hereby incorporated by 
reference, discloses diamond films deposited on a metal or ceramic 
composite comprising a matrix having dispersed therein finely divided 
diamond or diamond-like particles. These composites are useful in 
improving the erosion resistance of materials used for long wave infrared 
transmitting applications such as domes and infrared windows. 
U.S. Pat. No. 4,948,388 (1990) to Ringwood, hereby incorporated by 
reference, discloses a diamond compact comprised of 60-95 volume percent 
of diamond crystals which have plastically deformed so that they form a 
rigid framework structure. The contacts between the diamond crystals occur 
over surfaces arising from plastic deformation of the diamond crystals 
during formation of the compact under pressure and temperature conditions 
within the graphite stability field. The diamond framework structure is 
bonded together by interstitial refractory carbide phases or metallic 
phases comprised of metal not forming carbides in the presence of carbon. 
The compact comprises less than about 2 percent volume of graphite and a 
compressive strength greater than 10 kbars. 
U.S. Pat. No. 5,198,285 (1993) to Arai et al., hereby incorporated by 
reference, discloses a thin film of amorphous carbon-hydrogen-silicon 
comprising carbon and hydrogen as major components. The remaining 
composition comprises a silicon based material containing diamond-like 
carbon. The content of hydrogen is from about 30 to 50 atomic % weight. 
The content of carbon is about 70 atomic % weight or greater with respect 
to the total composition, except hydrogen and iron based metallic 
material. The film of amorphous carbon-hydrogen-silicon is very hard and 
has a small coefficient of friction. 
U.S. Pat. No. 5,183,602 (1993) Raj et al., hereby incorporated by 
reference, discloses an improved carbon-metal composite comprising a 
carbon matrix and metal fibers distributed in the carbon matrix. The 
surfaces of at least a portion of the fibers are coated or alloyed with 
another material which has a tendency to form carbides which is equal or 
lower than that of metal constituting the metal fibers. The metal fibers 
are distributed in the carbon matrix in such a manner that their content 
varies along the thickness of composite, thereby imparting to the 
composite improved properties with respect to at least one of the 
following properties: mechanical strength, impact resistance, wear 
resistance, and electrical conductivity of a dispersion of small particles 
of diamonds in a matrix having infrared transmission properties and 
refractive index substantially similar to that of diamonds. The composites 
exhibit mechanical toughness and durability 2-4 times that of the 
similarly treated matrix alone without adverse effect on optical 
properties. 
U.S. Pat. Nos. 5,352,493 (1994) to Dorfman et al., and 5,466,431 (1995) to 
Dorfman et al., which disclosures are hereby incorporated by reference, 
disclose a class of diamond-like materials formed from interpenetrating 
networks of carbon and alloying elements, as well as methods of 
fabricating such nanocomposite films. The films possess a unique 
combination of chemical and mechanical resistance, temperature stability, 
and wide range of electronic properties including low-temperature 
superconductivity. They may be used as protective coatings, electronic 
material, sensors, biocompatible materials. The method of these materials 
fabricating is based on co-deposition of the clusterless beams, wherein at 
least 50% of carbon particles comprise an energy above 100 eV, and the 
temperature of the substrate during the growth is less than about 
500.degree. C. Common range of the carbon particles energy is 0.3 to 5 
keV, and usually is about 1 to 1.5 keV, and the substrate temperature 
during the growth is less than about 200.degree. C. However, the growth 
rate is very limited, usually is in the range of 0.3 to 3.0 mm/h. Further, 
the material can be produced as a film, but its manufacturing requires a 
high-voltage power supply. Also, the hardness of these composite films is 
limited with about 20-22 GPa maximum, and usually does not exceeds about 
12-15 Gpa. 
Although this material is very stable against graphitization, during growth 
its structure is very sensitive to the particles energy and substrate 
temperature due to the possible graphite-like carbon forming. While 
Graphite is a layered substance whose structure and properties can be 
altered in a wide range, graphite is very fragile upon the application of 
mechanical stress, which is inherent to the week van der Vaals interaction 
between layers (Yudasaka et al., Yoshimura p-Electron Project, Japan; 
Appl. Phys. Lett. 64(7), 1994, which disclosure is hereby incorporated by 
reference). It has been recently demonstrated that interface between 
amorphous carbon and graphite usually creates unbonded radicals which 
weaken the structural rigidity of the materials, thereby providing a 
fracture path under stress (Yoon et al., Cambridge, Mass.; Interface 
Science, v. 3, 1995, p. 85-100, which disclosure is hereby incorporated by 
reference). 
The present invention provides novel hard carbon materials which are 
believed to overcome the problems associated with the above described 
processes. The materials of the present invention comprise both, 
graphite-like and diamond-like carbon in a hierarchical structure, wherein 
the graphite-like layers are bonded together by the diamond-like framework 
such that the whole carbon structure is stabilized with at least two 
alloying elements. The materials of the present invention can be produced 
as coatings, as well as, bulk solid matter in a wide substrate temperature 
range using low voltage equipment. The growth rate of the materials of the 
invention can exceed 20 .mu.m/h, and hardness is usually in the range of 
about 20 to 35 GPa, but can exceed 50 Gpa. Elastic modules is usually in 
the range of about 150 to 250 Gpa, but can exceed 500 GPa. 
SUMMARY OF THE INVENTION 
A primary object of the present invention is to provide a new class of 
solid-state, carbon materials comprising sp.sup.2 bonded graphite-like 
layers bonded together by sp.sup.3 bonded, three-dimensional diamond-like 
frameworks, wherein the whole carbon structure is stabilized with at least 
two alloying elements. 
Another object of the present invention is to provide such carbon 
materials, wherein the components of the sp.sup.3 and sp.sup.2 
carbon-carbon bonds, and/or carbide, silicide, and oxide bonds, can be 
modulated between the carbon and the stabilizing elements in nanometer 
scale and/or micrometer scale. 
Another object of the present invention is to provide such carbon 
materials, wherein the nanocrystals or clusters of diamond, and/or 
carbides, silicides, oxides, and/or metals are embodied in the amorphous 
structure of said materials. 
Another object of the present invention is to provide such carbon 
materials, wherein the layers of stabilizing elements and/or their 
compounds are embodied in the amorphous structure, and the thickness of 
said stabilizing layers is in the range of about 1 nm to 1,000 nm. 
Accordingly, the present invention provides a novel class of hard carbon 
materials comprising sp.sup.2 bonded graphite-like layers bonded together 
by sp.sup.3 bonded three-dimensional diamond-like frameworks. The 
graphite-like layered structure is bonded together by the diamond-like 
framework such that the graphite-like layers are mutually parallel with no 
azimuth order in-plane, and the diamond-like framework is amorphous. The 
carbon structure is stabilized with at least two alloying elements. More 
preferably, the carbon structure is stabilized with two alloying elements 
designated a first alloying element and a second alloying element. The 
first alloying element comprises an element selected from the group 
consisting of O, H, N and a combination thereof The second alloying 
element comprises an element selected from the group consisting of Si, B, 
Zr, Ti, V, Cr, Be, Hf, Al, Nb, Ta, Mo, W, Mn, Re, Fe, Co, Ni and a 
combination thereof. 
The carbon content in the material of the invention comprises from about 40 
to about 90 atomic % of the sum of carbon plus the total alloying 
elements. The sp.sup.2 carbon-carbon bond content in the material of the 
invention comprises from about 15 to about 90 atomic % of the sum of 
carbon-carbon bonds in said material The diamond-like sp.sup.3 
carbon-carbon bond content in the material of the invention comprises from 
about 15 to about 90 atomic % of the sum of carbon-carbon bonds. The sum 
of concentration of the total alloying elements in the material of the 
invention comprises from about 10 to about 60 atomic weight % of the sum 
of carbon plus the total alloying elements. 
The novel class of carbon materials of the present invention exhibit high 
mechanical properties (hardness, fatigue, specific modulus, tribological 
characteristics, etc.), low specific weight, variable electrical 
properties, thermal stability, corrosion resistance, wear resistance, high 
adhesion to virtually any substrate. The materials of the invention can be 
deposited upon metals, ceramics, composites, glasses, and plastics, 
including Teflon.RTM.. The materials of the invention can be used as 
protective coatings for various applications, for aerospace and automotive 
industries, for electronics and as an orthopedic material. 
Also disclosed are methods of fabricating the novel carbon materials of the 
present invention. The methods of the invention comprise vacuum plasma 
technology combined with electrical-magnetic energizing of the incident 
particles, and thermal activation of the surface growth. The methods of 
fabrication can also comprise a high speed rotating substrate holder and 
multiple plasmatrons.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention provides a novel class of hard carbon materials 
comprising sp.sup.2 bonded graphite-like layers bonded together by 
sp.sup.3 bonded three-dimensional diamond-like frameworks. The 
graphite-like layered structure is bonded together by the diamond-like 
framework such that the graphite-like layers are mutually parallel with no 
azimuth order in-plane, and the diamond-like framework is amorphous. The 
carbon structure is stabilized with at least two alloying elements. More 
preferably, the carbon structure is stabilized with two alloying elements 
designated a first alloying element and a second alloying element. The 
first alloying element comprises an element selected from the group 
consisting of O, H, N and a combination thereof The second alloying 
element comprises an element selected from the group consisting of Si, B, 
Zr, Ti, V, Cr, Be, Hf, Al, Nb, Ta, Mo, W, Mn, Re, Fe, Co, Ni and a 
combination thereof The graphite-like layered structure is bonded together 
by the diamond-like framework such that the graphite-like layers are 
mutually parallel with no azimuth order in-plane, and the diamond-like 
framework is amorphous. 
As used herein, the term "graphite-like bonding" refers to the sp.sup.2 
carbon-carbon bondings. The term "graphite-like layered or layers" refers 
to the carbon-based layers wherein the graphite-like bondings are oriented 
predominantly in a plane. The term "graphite-like material" refers to a 
material comprising graphite-like layers. The term "diamond-like bondings" 
refers to the sp.sup.3 carbon-carbon bondings. The term "diamond-like 
framework" refers to a three-dimensional, predominantly sp.sup.3 carbon 
network chemically bonded with graphite-like layers which penetrate 
through the whole structure of the carbon material. The term "Quasam" is a 
"coined" term referring to the hard carbon material(s) of the invention 
and is interchangeable with "carbon material(s) and/or material(s)". The 
term "alloying elements" refers to any element of the Periodic Table, 
excluding carbon and hydrogen. The term effective bias potential refers to 
the accelerating potential of the substrate relative to the plasma 
discharge. 
In one embodiment of the invention, as shown in FIG. 1, the carbon 
materials comprise a layered arrangement whereby there is no order 
in-plane in the graphite-like layers or in the diamond-like framework of 
the materials. The carbon material of the invention combines the features 
of both ordered and amorphous solid matters and thus can be designated as 
"Quasi-amorphous." The carbon concentration in the material of the 
invention comprises from about 40 to about 90 atomic % of the sum of the 
concentration of carbon plus the total alloying elements. The 
concentration of sp.sup.2 carbon-carbon bondings in the material comprises 
from about 15 to about 90 atomic % of the sum of the carbon-carbon bonds 
in the material. The concentration of sp.sup.3 carbon-carbon bondings in 
the material comprises from about 15 to about 90 atomic % of the sum of 
carbon-carbon bonds in the material. The sum of concentration of the 
alloying elements in the material is form about 10 to about 60 atomic % of 
the sum of carbon plus the alloying elements. 
In a more preferred embodiment of the invention, the concentration of 
sp.sup.2 carbon-carbon bondings in the material comprises from about 20 to 
about 80 atomic % of the sum of the carbon-carbon bonds in the material, 
the concentration of sp.sup.3 carbon-carbon bondings in the material 
comprises from about 20 to about 80 atomic % of the sum of carbon-carbon 
bonds in the material, the carbon concentration in the material of the 
invention comprises from about 40 to about 90 atomic % of the sum of the 
concentration of carbon plus the total alloying elements, and the sum of 
concentration of the alloying elements in the material is from about 10 to 
about 60 atomic % of the sum of carbon plus the alloying elements. 
In still a more preferred embodiment of the invention, the concentration of 
sp.sup.2 carbon-carbon bondings in the material comprises from about 30 to 
about 55 atomic % of the sum of the carbon-carbon bonds in the material, 
the concentration of sp.sup.3 carbon-carbon bondings in the material 
comprises from about 45 to about 70 atomic % of the sum of carbon-carbon 
bonds in the material, the carbon concentration in the material of the 
invention comprises from about 55 to about 80 atomic % of the sum of the 
concentration of carbon plus the total alloying elements, and the sum of 
concentration of the alloying elements in the material is from about 20 to 
about 45 atomic % of the sum of carbon plus the alloying elements. 
Preferably, the carbon concentration in the material of the invention 
comprises at least 40 atomic % of the sum of the concentration of carbon 
plus the total alloying elements, and the sp.sup.2 carbon-carbon bondings 
in the material comprises at least 15 atomic % for optimal structure 
formation. 
In accordance with the present invention, it is possible to synthesize a 
hierarchical structured material by gradually varying and/or modulating 
the ratio between the graphite-like sp.sup.2 carbon-carbon bonds and the 
diamond-like sp.sup.3 carbon-carbon bonds in a nanometer and/or micrometer 
scale, as shown in FIG. 2. The resultant structure possesses properties of 
increased flexibility and fracture strength, while exhibiting a decrease 
in intrinsic stress. Preferably, the ratio between the graphite-like 
sp.sup.2 carbon-carbon bonds and the diamond-like sp.sup.3 carbon-carbon 
bonds are periodically varied and/or modulated in the range of from about 
10 nm to about 100 mm. It is also possible in accordance with the 
invention to synthesize the hierarchical material structure wherein the 
contents of the sp.sup.3 and sp.sup.2 carbon-carbon bonds, and/or carbide, 
silicide, and oxide bonds, between the carbon and alloying elements are 
gradually varied and/or modulated in nanometer and/or micrometer scale. 
In another embodiment of the invention, the concentration of graphite-like 
sp.sup.2 carbon-carbon bonds preferably is greater than about 15 atomic % 
of the sum of carbon-carbon bonds in the material, the concentration of 
diamond-like sp.sup.3 carbon-carbon bonds is greater than about 15 atomic 
% of the sum of carbon-carbon bonds in the material, and the sum of 
concentration of alloying elements in the material is greater than about 
10 atomic % of the sum of carbon plus the total alloying elements. 
The alloying elements in the material of the invention provide 
stabilization to the material. That is, given the basic thermodynamic 
properties of the solid carbon phases, any combination of graphite-like 
and diamond-like carbon in one solid matter is usually unstable and 
typically results in transition of the matter to a common, graphite 
structure. The alloying elements in the material, however, prevent the 
diamond-graphite transition and allow use of the material of the invention 
under a wide range of temperature, mechanical stress and environmental 
conditions. 
The stabilizing alloying element can comprise Si, B, Cr, Be, Al or any 
element selected from the hard-melting transition metals. More preferably, 
the alloying element is a complex alloying element comprising at least two 
alloying elements. The first alloying element comprises an element 
selected from the group O, H, N, and a combination thereof. The second 
alloying element comprises an element selected from the group comprising 
Si, B, Zr, Ti, V, Cr, Be, Mg, Ca, Hf, Nb, Ta, Mo, W and a combination 
thereof Alternatively, the alloying element can comprise a combination of 
elements selected from the first alloying element group used together with 
a combination of elements selected from the second alloying element group. 
The sum of concentration of the alloying elements in the material comprises 
from about 10 to about 60 atomic % of the sum of carbon plus the total 
alloying elements. Preferably, the sum of concentration of the alloying 
elements comprises from about 20 to 45 atomic % of the sum of carbon plus 
alloying elements. Typically, if the sum of concentration of the alloying 
element falls below 10 atomic % the stabilizing effect is too weak, while 
above 60 atomic %, formation of the carbon material structure of the 
invention is poor. 
The most preferred combination of alloying elements comprises silicon and 
oxygen. This combination has been found to provide a very stable 
non-stoichiometric amorphous silica network SiO.sub.x. The stable 
amorphous silica SiO.sub.x network prevents growth of the graphite 
microcrystals, and therefore optimizes stabilization of the carbon 
material structure. An advantage of using silicon (Si) and oxygen 
(O.sub.x) as the alloying elements, is that both of these elements are 
equally effective to bond the free valence electrons of both graphite-like 
and diamond-like carbon. Thus, the thermal stability of the carbon 
material structure is increased. This, in turn, improves the mechanical 
properties of the material while decreasing it intrinsic stress. 
While the Si-C bondings provide stronger cohesion between the graphite-like 
layers and the diamond-like carbon framework, and the amorphous silica 
network, result in a material exhibiting superior hardness and a wide 
electronic and optical gap, it has been determined that using Si-O-C bonds 
between the carbon structures and silica networks provides the material 
structure with a higher flexibility. Based upon the precursors type, 
concentration selection, and growth conditions, a wide range of Si-C to 
Si-O-C bonding ratios can be used in the materials of the invention. For 
example, the bonding ratio can vary from equal concentrations of Si-C and 
Si-O-C bondings to predominantly Si-O-C bondings. Also, the ratio between 
Si-O and C-O bondings can be varied and, preferably is in the range of 
(Si-O):(C-O)&gt;10:1. By varying the bonding ratios, it is possible to vary 
the mechanical properties of the material. 
Another important feature of the material of the invention is that the 
SiO.sub.x network can easily form chemical bonds with virtually any 
substrate, and hence exhibits high adhesion to virtually any substrate 
without requiring a special inter-layer. In addition, the elements, 
carbon, silicon, and oxygen possess low specific weight, are inexpensive, 
and do not produce any harmful emission during synthesis or use. 
The sum of silicon and oxygen content in non-stoichiometric amorphous 
silica network SiO.sub.x is preferably in the range of from about 10 to 
about 60 atomic % of the sum of concentration of carbon plus the alloying 
elements, and more preferably in the range of from about 15 to about 45 
atomic % of the sum of concentration of carbon plus alloying elements. 
Most preferably, the sum of silicon and oxygen content is in the range of 
from about 15 to about atomic % of the sum of concentration of carbon plus 
alloying elements. The oxygen concentration "x" in the non-stoichiometric 
amorphous silica network, SiO.sub.x, preferably is in the range of from 
about 0.5 to about 2.0, and more preferably in the range of from about 0.5 
to about 1.5, and most preferably, in the range of from about 0.5 to about 
0.9. Such a non-stoichiometric ranges provide the most favorable 
conditions for the amorphous stabilizing network formation during Quasam 
synthesis. In addition, such ranges provide the best condition for the 
mutual saturation of free carbon and stabilizing element bonding. 
In a preferred embodiment, the concentration of silicon in the material is 
in the range of from about 10 to about 20 atomic % of the sum of 
concentration of carbon plus alloying elements, the concentration of 
oxygen is in the range of 5 to 15 atomic % of the sum of concentration of 
carbon plus alloying elements; while the total sum of silicon and oxygen 
is in the range of about 15 to about 30 atomic % of the sum of 
concentration of carbon plus alloying elements. Alternative alloying 
element combinations comprise TiO.sub.x, ZrO.sub.x, HfO.sub.x. Bn.sub.x, 
TiN.sub.x ZrN.sub.x, HiN.sub.x. The nitrogen content "x" preferably is in 
the range of from about 0.5 to about 1.0. 
The carbon material optionally can comprise hydrogen in the structure. 
Hydrogen also saturates the free carbon bondings and facilitates 
stabilization of the structure thereby providing the material with 
additional flexibility. However, hydrogen can decrease the thermal 
stability and hardness of Quasam. Hydrogen can also cause gas emission 
which is not particularly favorable in high vacuum applications of the 
material. The maximum concentration of hydrogen is preferably about 100 
atomic % of the carbon concentration and, more preferably, the hydrogen 
concentration is less than about 50 atomic % of the carbon concentration. 
Most preferably, the concentration of hydrogen is less than 15 atomic % of 
the carbon concentration. It is understood that the material of the 
invention can comprise three-component, four-component, as well as more 
complicated combinations of the alloying elements, depending on the 
specific technical requirements required of the material. The alloying 
combination SiO.sub.x (Fe,Ni,Cr).sub.y, wherein the ranges of x and y 
comprise 0.5.ltoreq..times.1.0 and 1.ltoreq.y.ltoreq.3 can provide Quasam 
having properties of electrical conductivity and resistance against high 
temperature oxidation, while maintaining its magnetic and catalytic 
properties. In order to characterize the material of the invention, 
because the material is neither crystalline nor pure amorphous solid 
matter, no one method alone can be used for structure characterization. It 
is necessary to utilize a group of methods for identifying such 
characteristics. Such methods can be selected from the any know method for 
characterization of the requisite property. For example, such methods 
include Auger spectroscopy, XAFS (X-Ray Absorption Fine Structure), XPS 
(X-Ray Photoelectron Spectroscopy), Raman Spectroscopy, etc. 
High-Resolution X-Diffraction based on the synchrotron light source does 
not expose any long-range order that corresponds to an absolutely pure 
amorphous solid matter, even in the very thick, free-standing Quasam 
specimens. However, at the same time, High-Resolution X-Diffraction 
reveals a strong evidence of short-range order due to the graphite-like 
layered structure. The chemical structure of the material studied by 
NEXAFS (Near-Edge x-Ray Absorption Fine Structure), XPS and also by 
Infra-Red Spectroscopy may or may not reveal evidence of carbide bondings 
between the carbon structure and the alloying elements. Carbide bondings 
depends on the material synthesis conditions and can be controlled during 
growth, as described hereinafter. However NEXAFS and XPS indicate an 
evidence of C-O-Si and C-O-Me bondings between the carbon-based structure 
and the alloying element. Also XAFS reveals an unusual shift of oxygen 
peak that apart of Quasam is observed only in high-temperature 
superconductors that are also highly anisotropic and intrinsically 
disordered layered materials. XPS reveals a similar behavior of the 
characteristic oxygen features in Quasam. Mechanical testing revealed a 
layered structure of the material. 
With reference to FIG. 3A and 3B, there is shown results obtained using 
1000 indentations of diamond pyramid (by Vickers) with 115N load in the 
same point of a 50 mm thick Quasam sample. The curves represent the plots 
of the Imprint Diagonal vs. Number of imprints. Curves "i" shows the 
imprinted area, while curves "e" are plots of the maximum contact area 
(including both, plastic and elastic deformation). Critical points of the 
tests are indicated with numbers: I=2.5 hours relaxation; II=8 mm internal 
crack; III-V=shallow splits. Maximum final indented depth was about 10 
.mu.m, e.g. 20% of the material thickness. One of the important features 
exposed during these and other mechanical tests of Quasam is a strong 
stratified character of the Quasam fracture, as is demonstrated in the 
figures. In the material tested in FIGS. 3A and 3B, after the first 250 
indentations a shallow 8 mm long crack was observed. However no crack 
propagation was forced thereafter. After 300 indentations a 
micro-splitting was observed and a fresh stratum was exposed. Only after 
730 indentations was a new shallow crack initiated. After the 750 
indentations in sum, a new micro-splitting took place. A new stratum was 
exposed, which withheld without any new crack up to the 1000.sup.th 
indentation when tests were finished. Such behavior is typical for the 
Quasam. Thus, the present invention provides a new class of materials 
exhibiting extremely high fracture toughness similar to that of high 
quality steel. With reference to Table 1, there is shown the hardness and 
fracture toughness of Quasam along with other materials for purposes of 
illustration of the superior features of the present material. 
TABLE 1 
______________________________________ 
Modules Hardness Fracture Toughness 
Material MPa MPa MPa V m 
______________________________________ 
Quasam 
minimum 120 12 40 
typical 200 25 45 
maximum 550 60 55 
Ultrahigh-strength 
200-220 about 1.0 20 to 120 
steels 
Soda-lime glass 
70 5.5 0.70 
Fused Quartz 
72 8.9 0.58 
Silicon 168 9.3 0.70 
Sapphire 403 21.6 2.2 
Si.sub.3 N.sub.4 
300 16.3 4.0 
Diamond films 
about 1000 about 100 2.2 
______________________________________ 
The cracking threshold of Quasam is correspondingly high. For a Vickers 
indenter, the cracking threshold of Quasam typically exceeds 2N, and in 
some samples has been shown to exceed 4N. Also, less than 2% of the 2000 
tests exposed cracks under loads 0.65N. In contrast, in most ceramics 
cracking thresholds typically are about 0.25N. It has been determined that 
the stratified fracture and novel mechanical properties of Quasam are due 
to the fundamental structure of this new class of materials which 
integrates features of both carbon solid forms, graphite and diamond. 
Illustrative novel properties of Quasam include, without limitation, 
diamond-like hardness and graphite-like stratification. Furthermore, while 
diamond is a brittle material with high, three dimensional mechanical 
strength, the diamond fracture toughness is relatively low. Also, graphite 
possesses even higher than diamond strength in plane, however, theoretical 
strength cannot be exposed in bulk graphite due to a very weak interaction 
between the layers of graphite structure. In contrast, the graphite layers 
in Quasam are bonded by a diamond-like framework and possess a hardness of 
up to about 55-60 Gpa which corresponds to the crystalline diamond 
hardness in relatively soft &lt;100&gt;direction. Yet, the fracture toughness of 
Quasam much exceeds the diamond value and thus cannot be compared to 
common graphite. 
Quasam exhibits a strong cleavage fracture, and yields the atomically 
smooth straits. However, opposite to graphite, the fracture of Quasam 
occurs with very high loads and never expends in an area over a few 
microns width or depth. As a result, the fractured specimen does not 
experience a destructive damage apart from a shallow trace of indent or 
scratching at the tip of the material. 
Quasam's fundamental structure comprises isotropic mechanical properties in 
planes while it may be slightly one-axis anisotropic with a special axis 
along the growth direction (i.e., the Vickers hardness values measured by 
indentation of two perpendicular cross-fractures of a typical Quasam 
sample were virtually identical: 25.+-.1 GPa, the hardness measured by 
indentation of the growth plane was about 30 Gpa). 
Another novel feature of Quasam is that it exhibits a low density in the 
range of from about 1.35 to about 2.0 g.cm.sup.-3 and, preferably, in the 
range of from about 1.5 to about 1.7 g.cm.sup.-3. This is much lower than 
graphite density (i.e., 2.25 g.cm.sup.-3). In comparison, the density of 
Diamond-Like Atomic-Scale Nanocomposite (DLN) disclosed in U.S. Pat. Nos. 
5,352,493 and 5,466,431 to Dorfman et al., is in the range of from about 
1.9 to about 2.5 g.cm.sup.-3 (the Vickers hardness of DLN is in the range 
of from about 8 to about 22, and typically in the range of from about 10 
to about 12); and Diamond-Like Carbon (DLC) is in the range of from about 
1.8 to about 2.9, although the lower value correspond to a relatively soft 
material. Also, DLC hardness is directly proportional to its density and 
intrinsic stress. 
In contrast, Quasam exhibits a density unlike the density of any known hard 
material. The lowest density hard material believed known is cubic boron 
nitride (c-BN) which comprises a specific density of 2.25 g.cm.sup.-3. 
Silicon carbide (SiC) comprises a specific density of 3.35 g.cm.sup.-3. 
The low limit of the Quasam density (1.35 g.cm.sup.-3) corresponds to the 
density of common coal and to the anthracite density (1.5 to 1.7 
g.cm.sup.-3). However, such materials (coal), unlike Quasam, are very soft 
material. Consequently Quasam is believed to represent a novel 
carbon-based solid matter, as well as a new class of the hard materials. 
The thermal expansion coefficient of Quasam is in the range of 
1.6.multidot.10.sup.-6, K.sup.-1 to 1.7.multidot.10.sup.-6 K.sup.-1. This 
is close to diamond and graphite thermal expansion "in plane" (about 
1.5.10.sup.-6, K.sup.-1), while in the perpendicular direction the 
graphite thermal expansion is over one order of magnitude higher 
(28.10.sup.-6, K.sup.-1). What one must take into consideration is that 
the thermal expansion of Quasam is not dependent on temperature up to 
700.degree. K., while the thermal expansion of diamond and graphite is 
strongly dependent on temperature. 
Another important feature of the graphite-like layered structure of Quasam 
is the smoothness of this new material which is typical for the graphite 
cleavage planes. Table 2 shows the material surface roughness in the range 
of thickness varied over 4 orders of magnitude, from 0.005 .mu.m to 160 
.mu.m and areas of measurements varied almost in 11 orders of magnitude, 
from 0.1 .mu.m.sup.2 to 75 cm.sup.2, e.g. in nano (Ra.sub.n), micro 
(Ra.mu.), and macro (Ra) scales. The measurements were realized by Atomic 
Force Microscopy in the areas of measurements 0.1, 1. 0, 100, and 2500 
.mu.m.sup.2 and by Micro-profilometry in the areas of measurements 10 
mm.sup.2 and in the whole substrate range (75 cm.sup.2). It is 
demonstrated by the Ra.sub.n parameter measurements, in the micro-scale 
areas an atomic-scale smoothness is preserved at least up to 50 .mu.m 
thickness. Such a result is in conformity with the fundamental structure 
of this new class of materials, as shown in FIG. 1. At the thickness over 
100 .mu.m the Ra.sub.n parameter slowly increases but still in nano-scale 
range. This increase is mainly because of the micro-droplets from the 
plasma and microparticles from the ceramic head. Future improvements of 
the present technology can expand the atomic-scale smoothness over wide 
range of new materials thickness. 
TABLE 2 
______________________________________ 
The Quasam surface roughness in nano (Ra.sub.n), micro (Ra.mu.), and 
macro (Ra) scales 
Ra.sub.n (nm) in areas: 
Ra.mu. (.mu.m) in areas: 
Ra (.mu.m) in areas: 
Film 0.1 1.0 100 2500 10 75 
thickness 
.mu.m.sup.2 
.mu.m.sup.2 
.mu.m.sup.2 
.mu.m.sup.2 
mm.sup.2 
cm.sup.2 
______________________________________ 
0.005 .mu.m 
&lt;0.2 &lt;0.2 .ltoreq.0.2 
.ltoreq.0.2 
&lt;0.02 &lt;0.02 
nm nm nm nm .mu.m .mu.m 
0.05 .mu.m 
&lt;0.2 &lt;0.2 .ltoreq.0.2 
.ltoreq.0.2 
&lt;0.02 &lt;0.02 
0.5 .mu.m 
&lt;0.2 &lt;0.2 .ltoreq.0.2 
.ltoreq.0.2 
&lt;0.02 &lt;0.02 
1.0 .mu.m 
&lt;0.2 &lt;0.2 .ltoreq.0.2 
.ltoreq.0.2 
&lt;0.02 &lt;0.02 
5.0 .mu.m 
&lt;0.2 0.20 6 10 0.02 0.03 
20 .mu.m 
.ltoreq.0.2 
.ltoreq.0.2 
&lt;1.0 20 0.1 0.1 
50 .mu.m 
.ltoreq.0.2 
.ltoreq.0.4 
1.5 25 0.07 0.1 
160 .mu.m 
1.25 2.4 73 165 1.1 1.5 
______________________________________ 
The specific density of Quasam containing a high concentration of the 
alloying metals, particularly heavy metals like W, can increase up to 
about 3 to about 6 g.cm.sup.-3. However, the higher values corresponds to 
specific applications of these materials which usually are not essential 
to the specific weight (e.g. protective coatings, supported catalyst, 
etc.). The dielectric Quasam materials typically comprise a specific 
weight below 2.0 g.cm.sup.-3 and electric conductive material of about 
2.5-3.5 g.cm.sup.-3. Such a low density, in conjunction with elastic 
modules of 100 to over 500 GPa, provides the new class of materials of the 
invention having high specific values for some mechanical parameters, as 
shown in FIG. 4, 
According to the present invention, it is possible to synthesize the 
materials wherein the nanocrystals or clusters of diamond, and/or 
carbides, silicides, oxides, and/or metals are embodied in the 
predominantly amorphous layer(s) and/or structure. Such materials have 
mechanical application in fields requiring high abrasion resistance, as 
well as electronic and photo-electronic applications where the 
nanocrystals can be used as the electronic microdevice. 
Also in accordance with the present invention, it is possible to synthesize 
the materials wherein the layers of stabilizing elements and/or their 
compounds are embodied in the predominantly amorphous structure. The 
thickness of the embodied stabilizing layers is in the range of from about 
1 nm to about 1,000 nm. Such a structure provides stabilization to the 
Quasam during the synthesis process. Also, such a structure comprising 
dielectric matrix layers and thin metallic layers has application for 
multi-level electronic packaging. 
The material (Quasam) can be fabricated in the form of very thin films 
(i.e., 1.0 nm in thickness) to bulk material (i.e., 1.0 inch thick layered 
composite materials). While the present technology allows for a material 
deposition area over 0.7 m.sup.2, no limit appears to exist for the 
deposition area or the thickness of the deposited material such that it is 
possible to develop a very light material that can be used in the 
aerospace industry, such as for aircraft. 
The principles of the present technology are based on a shift of the carbon 
phase equilibrium using alloying elements, as shown in FIG. 5, and on a 
combination of electrical-magnetic energizing and thermal activation of 
the precursor species during material synthesis. This process (i.e., 
thermal activation of the surface growth; and activation by kinetic energy 
of the incident particles), creates quasi-equilibrium growth conditions 
whereby the material formed comprises a structure having an optimum 
sp.sup.2 :sp.sup.3 ratio. In this structure, almost all the sp.sup.2 
bondings are oriented in the growth plane only, while the sp.sup.3 
bondings form a three-dimensional network. This because of the principle 
distinction between the nucleation mechanism of the graphite-like matter 
and diamond-like matter. The graphite layers formation is promoted by a 
stabilizing surface, where the tetrahedral diamond-like network formation 
is activated by kinetic energy of the incident particles and by the 
point-like centers of nucleation upon the growth surface and, 
particularly, by free bondings of the formed sp.sup.3 network. 
During formation of the materials, the carbon and alloying elements valence 
bonds can initially remain free in the growing structure. In this regard, 
it is important that at the optimum deposition temperature, that moderate 
thermal activation promote the mutual saturation of such free bonds (i.e., 
C-O, Si-O, C-Si, etc.), while these atoms occupy positions upon the 
surface, or few top surface, layers. In any event, during this period in 
the process, each carbon (or alloying atom) can form bonding with other 
atoms without essential deformation of the solid material. Also, such 
saturation does not create any additional stress in the material 
structure. 
Furthermore, if the temperature during synthesis is too low, too many free 
bonds are freezing in the growing structure and the resultant material is 
not stable due to high stress. If the temperature during synthesis is too 
high, the graphite-like structure transforms into micro-crystalline 
graphite. If the incident particles energy is too low, the concentration 
of sp.sup.3 bondings decrease and the material may not be formed. If the 
incident particles energy is too high, accidental orientation of sp.sup.2 
and sp.sup.3 bondings occurs, and the material may not form. 
At optimum growth conditions, a hybrid carbon based structure is formed 
comprising two solid matters, diamond and graphite, in a single material, 
thereby providing the material of the invention with novel properties. The 
technology of the invention can be described as formation of 
thermodynamically stable graphite layers using thermally activated 
processes, while simultaneous "sewing" these layers together with 
diamond-like filaments of atomic scale. Optimum growth conditions comprise 
(1) electrical-magnetic energizing of the initial gas species; (2) surface 
thermal activation at a particular temperature range; and (3) shifting the 
carbon phase equilibrium using alloying elements in order to support the 
continuous quasi-equilibrium growth conditions which are necessary for 
synthesis of the material of the invention. Important parameters to 
control during material synthesis include the type and energy of the 
incident ions and charged radicals upon the growing material surface and 
the temperature of the material during its growth. 
The range of the incident particles energy during Quasam growth is 
preferably from about 10 to about 500 eV, more preferably from about 25 to 
about 250 eV and most preferably from about 50 to about 200 eV. In the 
above range of energy, the incident ions and charged radicals form the 
necessary bondings to impart the material of the invention with novel 
features such as high mechanical properties (i.e., hardness, elastic 
modules, fracture toughness) between known materials having a specific 
gravity below 2 g./cm.sup.3, very low thermal expansion, high chemical 
resistance, high thermal stability and pore free structure. The range of 
the growth temperature during Quasam growth is preferably from about 
200.degree. C. to about 1000.degree. C., more preferably from about 
250.degree. C. to about 650.degree. C. and most preferably, from about 
300.degree. C. to about 500.degree. C. As shown in FIG. 6, in this 
temperature range, both material hardness, and the ratio between hardness 
and intrinsic stress are high. 
In a preferred embodiment of the growth process of the invention, the 
particles energy range comprises from about 50 to about 200 eV and growth 
temperature ranges from about 300.degree. C. to about 500.degree. C. The 
materials formed in accordance with these parameters comprise high 
hardness and elastic modules, in combination with the lowest specific 
density, intrinsic stress, and thermal expansion coefficient. Although the 
synthesized material is neither an equilibrium solid matter nor an 
equilibrium chemical compound, the material comprises a very high 
stability (i.e., close to crystalline diamond). Like crystalline diamond, 
the material of the invention is thermodynamically unstable at common 
conditions, but possesses an extremely high actual stability. 
The preferred method of synthesis of the material of the invention 
comprises: (1) generating an initial plasma discharge in low pressure 
vapor or gas of selected precursors; the initial plasma generation is 
realized in a D.C. or r.f. electrical field and with applying the magnetic 
field in the cross direction to the electrical field; (2) applying a 
secondary D.C. or r.f. electrical field cross-directed to the primary 
electrical field and parallel to the magnetic field thereby additionally 
activating the initial plasma; (3) field acceleration (and direction) of 
the ion and charged radicals from plasma to the material deposition 
surface; and (4) thermally activating certain surface chemical processes 
on the growth front of the depositing material. 
Optimizing the geometry of the plasma generator, which facilitates, as well 
as holds, material growth is also important. The optimum energy range of 
the incident particles (e.g., range of effective bias potential of the 
substrate during Quasam growth) preferably is about -20 to about -200 V, 
more preferably the range is between about -25 to about -100 V and most 
preferably the range is from about -50 to about -100 V. The low energy 
range is an important feature of the synthesis of the material of the 
invention because it provides a process which is simpler and necessary 
equipment is less expensive. The optimum range for the bias potential for 
synthesis of the materials of the invention is dependent on the following 
conditions: real pressure and its space distribution in the reactor, the 
reactor geometry, selected precursor, plasma generation conditions and 
effectiveness of the initial molecules fragmentation in plasma. Thus, the 
range of the bias potential should be defined for the specific reactor and 
synthesis conditions used to fabricate the materials of the invention, and 
the above indicated ranges of the bias potential are for purposes of 
illustration only, and not limitation. 
One embodiment of the process of the invention is shown at FIGS. 7A and 7B. 
A vacuum chamber, generally shown at 1 comprises conventional diffusion 
and mechanical pumps (not shown), the arrow indicating the pumping outlet 
of the chamber. The initial vacuum of chamber 1 is in the range of from 
about 3.times.10.sup.-4 to about 3.times.10.sup.-3 Pa. While the pressure 
in the area of material deposition is not critical for synthesis. That is, 
it is possible to deposit the material under standard (about 1 atmosphere) 
pressure conditions. However, sophisticated and expensive equipment is be 
necessary to provide high energy particles under such conditions. 
Likewise, high vacuum conditions (i.e.,. 10.sup.-3 to about 10.sup.-5 Pa) 
are more feasible, but under such conditions the growth rate is limited, 
the productivity is relatively low and material cost high. Preferably, the 
pressure of the plasma discharge is in the range of from about 
5.times.10.sup.-2 Pa to about 10 Pa and, more preferably in the range of 
from about 2.times.10.sup.-1 to about 2.0 Pa. Although the pressure in the 
area of material deposition should not exceed the pressure in the area of 
plasma discharge, it is not limited with any lower value, and depends on 
the technical design of the vacuum system, particularly in the case of a 
differential pumping system. Most preferably, the pressure in the chamber 
during the deposition process is in the range of from about 
1.times.10.sup.-2 to about 1.0 Pa.. 
Existing plasma chambers comprise turbo-molecular pumps for fast starting 
the process. The turbo-molecular pumps can facilitate synthesis of the 
hierarchical Quasam based structures of the invention comprising 
hard-melting transition metals like Ti, Zr, etc., which metals are 
sensitive to the vacuum environment during sputtering. Although the 
turbo-molecular pumps facilitate synthesis of a wide range of Quasam 
structures, the turbo-molecular pumps are only optional for Quasam 
synthesis. 
With reference to FIGS. 7A and 7B, the key features of the system include 
plasmatrons 2 having been installed on major flange 3, while super, high 
speed rotating substrate holders 4-12 essentially improve the technology 
performance, productivity and available properties range of Quasam 
materials. The super high-speed inlet for the substrate holders (4-12) is 
insulated from the chamber 1 and has an independent bias potential. The 
super high-speed inlet consists of the electrically insulated rotating 
holder 7, carrying substrates 6, stator 4, 5 and 12, vacuum-tight magnetic 
clutch 8, mechanical clutch 9, and electrical motor 10. Both the magnetic 
clutch 8 and mechanical clutch 9, as well as motor 10 are installed in a 
special section 11. The holder rotation speed may be varied from 0 to 1500 
rotations/minute. The holder bias potential can be varied in the range of 
from about 0 to about -1000 V DC or r.f. 
The plasmatrons are fully insulated from the chamber, and the potentials of 
the hot filament cathodes are independent from the chamber ground 
potential and substrate holder bias potential. Therefore, an effective 
accelerating potential between each individual plasma source on one hand, 
and the substrates holder and substrates on other hand, can be different 
for each individual plasmatron during one deposition process. While 
rotating, each substrate passes in turn each plasmatron wherein different 
accelerating voltage is applied, and correspondingly different particles 
of energy is realized. The preferred conditions of the graphite-like 
layers and diamond-like framework can be realized in turn upon each 
substrate during the substrates rotation. 
For example, low energy plasmatrons with an effective accelerating voltage 
of from about 20 to about 100 V, and high energy plasmatrons with an 
effective accelerating voltage selected from the range of from about 200 
to about 1000 V are alternated such that the total number N of plasmatrons 
installed in each side of the reactor is even. The rotation speed w 
(s.sup.-1) corresponds to the synthesis of integer number (n) of 
monolayers of the depositing material during the slew of the substrate 
holder on the angle corresponding to one couple of plasmatron. Integer 
number (n) is preferably less than 10. The preferred rotation speed is 
w.apprxeq.2V/Nn, s.sup.-1. 
Where V=15 .mu.m/h, N=2, n=1, the rotation speed w=900 revolution/minute. 
In the more intensive deposition process, wherein V=25 .mu.m/h, N=2, n=1, 
and the optimum rotation speed w=1500 revolution/minute, which corresponds 
to the maximum value available in the existing equipment. Alternatively, a 
low rotation speed can be used. For example, V=10 .mu.m/h, N=6, n=10 and 
w=20 revolution/minute. Such control of the rotation speed and the plasma 
beams energetic parameters makes it possible to grow the material 
hierarchical structures during one continuous process in the same chamber. 
Also, side installation of the plasmatron is an optional feature of the 
invention, however such a design doubles system productivity and 
compensates the growing structures intrinsic stress while minimizing 
strain. 
Any plasmatron providing a well focused plasma beam and effective 
conversion of the precursors vapors in the low molecular ions and radical 
can be used to synthesize the material of the invention. Such plasmatron 
designs are illustrated for purposes of example only and, not limitation, 
in FIGS. 7A and 7B. As shown in the figures, plasmatron 2 comprises a 
precursor vapor injector 13, hot filament 14 and hot high current 
electrical magnetic coil 15. Hot filament 2 and hot high current 
electrical magnetic coil 15 are the series elements of the same high 
current line. Internal screens 16 and 19 are manufactured from tungsten or 
W-Mo alloy. External screen 17 is manufactured from a high-temperature 
ceramic. Water cooling screen 18 and filament holder 20 are manufactured 
from tungsten or molybdenum. Insulated inlets are shown at 21. The typical 
filament current is in the range of from about 60 to about 100 A. The 
filament potential relative to screens 17, 18 is in the range of from 
about 100 to about 160 V, while the screens potential relatively to the 
ground potential (e.g. the chamber body potential) is in the range of from 
about 0 to about 1500 V and preferably, in the range of from about 0 to 
about 500 V. The substrate holder can be biased with DC potential in the 
range of from about 50 to about 200 relative to the ground potential, or 
with an equal r.f potential in the frequency range of from about 100 KHz 
to about 13.56 Mhz. 
Although many different precursors and methods of their supply to the 
plasma discharge can be used for material synthesis, selection of optimal 
precursors provides lower cost production and high material effectiveness. 
Gaseous, liquid or solid precursors, including separate precursors for 
carbon and each of the alloying elements are contemplated by the 
invention. Different methods of precursor introduction into the plasma 
include a simple inlet of the gaseous precursors, an inject of the liquid 
precursor, evaporation of the liquid or solid precursors and/or sputtering 
of the solid precursors. The preferred alloying elements for stabilization 
include silicon and oxygen. Examples of such elements include 
silicon-organic compounds, particularly siloxanes. Examples of siloxanes 
within the scope of the invention, without limitation, include: 
cycloheptasiloxane C.sub.14 H.sub.42 O.sub.7 Si.sub.7 (molecular weight M 
519; melting point T.sub.m -26.degree. C.; boiling point T.sub.b 
=154.degree. C.), cyclotrisiloxane C.sub.9 H.sub.24 O.sub.3 Si.sub.3 
(M=265; T.sub.m -3; T.sub.b =199), cycloheptasiloxanes C.sub.14 H.sub.42 
O.sub.7 Si.sub.7 (M 519; T.sub.m -26; T.sub.b 154), cyclotetrasiloxanes 
C.sub.9 H.sub.24 O.sub.4 Si.sub.4 (M 308; T.sub.m &lt;0, T.sub.b =84), 
C.sub.4 H.sub.16 O.sub.4 Si.sub.4 (M=240,5; T.sub.m =-65; T.sub.b =134.5), 
C.sub.7 H.sub.22 O.sub.4 Si.sub.4 (M 283; T.sub.m -27; T.sub.b 165), 
C.sub.8 H.sub.24 O.sub.4 Si.sub.4 (M 297; T.sub.m 17,5; T.sub.b 175), 
C.sub.28 H.sub.32 O.sub.4 Si.sub.4 (M=545; T.sub.m =-99; T.sub.b =237), 
C.sub.12 H.sub.24 O.sub.4 Si.sub.4 (M=345; T.sub.m =-43.5; T.sub.b =224), 
C.sub.12 H.sub.32 O.sub.4 Si.sub.4 (M=353; T.sub.m =-43.5; T.sub.b =245), 
phenilmethylsiloxane C.sub.27 H.sub.42 O.sub.4 Si.sub.5 (M=571; T.sub.m 
&lt;0; T.sub.b =297). Any of the above elements can be introduced as vapors 
directly into the plasma generation zone of the reactor from an external 
source, while cyclotrisiloxanes and cyclotetrasiloxanes C.sub.6 H.sub.18 
O.sub.3 Si.sub.3 (M=222; T.sub.m =64.5; T.sub.b =134), C.sub.24 H.sub.30 
O.sub.3 Si.sub.3 (M=451; T.sub.b =166), C.sub.21 H.sub.24 O.sub.3 Si.sub.3 
(M=409; T.sub.m =100; T.sub.b =190), C.sub.32 H.sub.40 O.sub.4 Si.sub.4 
(M=601; T.sub.m =106; T.sub.b =212) C.sub.20 H.sub.48 O.sub.4 Si.sub.4 
(M=465; T.sub.b =291), C.sub.48 H.sub.40 O.sub.4 Si.sub.4 (N 793; T.sub.m 
=200; T.sub.b =330) have to be evaporated into the reactor directly in the 
area of plasma generation. Cyclotetrasiloxanes C.sub.28 H.sub.32 O.sub.4 
Si.sub.4 (M=545; T.sub.m =-99; T.sub.b =237), C.sub.48 H.sub.40 O.sub.4 
Si.sub.4 (M 793; T.sub.m =200; T.sub.b =330), and C.sub.32 H.sub.40 
O.sub.4 Si.sub.4 (M=601; T.sub.m =106; T.sub.b =212) are characterized by 
having a high ratio of C:H, wherein C.sub.48 H.sub.40 O.sub.4 Si.sub.4 (M 
793; T.sub.m =200; T.sub.b =330) comprises the highest value of C:H&gt;1. 
The preferred precursors for Quasam synthesis the silicon-organic compounds 
of trisiloxanes and tetrasiloxanes groups, particularly cyclotetrasiloxane 
C.sub.28 H.sub.32 O.sub.4 Si.sub.4 (M=545; T.sub.m =-99; T.sub.b =237) and 
phenilmethylsiloxane C.sub.27 H.sub.42 O.sub.4 Si.sub.5 (M=571; T.sub.m&lt;0 
; T.sub.b =297). 
To date, the material of the invention has been synthesized to about 0.1 to 
1.0 mm in thickness. In addition, 2 cm thick structures comprising about 
hundred layers of Quasam have been manufactured. The maximum area of 
deposition manufactured to date is about 7,000 cm.sup.2 per camera having 
a mass productivity of about 5 to about 10 cm.sup.3 /day/camera, although 
it is important to note that a limit does not exist and processes are 
under way to produce material having even greater thickness. 
The material of the invention exhibits very high mechanical properties 
(hardness, fatigue, specific modules, fracture toughness, fracture 
threshold, tribological characteristics, etc.), variable electrical 
properties, thermal stability, corrosion resistance, wear resistance, low 
specific weight, an excellent biocompatibility, high adhesion to virtually 
any substrate, and can be deposited upon metals, ceramics, composites, 
glasses and plastics including Teflon. The material of the invention can 
be used as protective coatings for various applications, as a structural 
material for the precise mechanic and, particularly, for micromechanical 
devices, as micro electrical-mechanical systems (MEMS), and also as a high 
heat conductive insulated substrate. Material containing metallic alloying 
elements can be used as a heat and electrical conductive substrate. The 
materials of the invention can be used as constructive materials for 
aerospace and automotives, and have orthopedic application. 
The following Examples are provided to further illustrate the synthesis, 
properties, and applications of the carbon materials (Quasam) of the 
present invention. While metallic alloying metals are not illustrated in 
the Examples, the following metals have been successfully used to 
manufacture electrically conductive Quasam and hierarchical multilayer 
composite materials of the invention: Be, Se, Ti, Zr, Al, Nb, Ta, Cr, W, 
Fe, Co, N and Re. Also, the following metals from the second group of 
alloying elements were particularly preferred to grow the Quasam material 
of the invention: Be in the range of from about 6 to about 15 atomic %; Al 
in the range of from about 5 to about 20 atomic %; Ti, Zr, Hf, Nb, Ta and 
Re in the range of from about 5 to about 40 atomic % weight each element; 
Cr, Mo and W in the range of from about 5 to about 50 atomic % each 
element; Fe, Co and Ni in the range of from about 5 to about 50 atomic % 
each element; Cr, Fe, Ni anc Co alloys in the range of from about 10 to 
about 55 atomic % in total; and W, Cr and Ti embodied layers in the range 
of from about 10 nm to about 1000 nm. 
EXAMPLE 1 
The material of the invention was deposited under the following process 
conditions: 
______________________________________ 
Maximum particles energy 
90 eV 
Accelerated field r.f., 1.75 Mhz 
Cathode current 66 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 O.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
8 cm 
Substrate temperature 
300.degree. C. 
Precursor flow rate 
7 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
8 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
40 cm 
Process time 0.5 hour 
The material was grown as follows: 
Thickness 4 .mu.m 
Specific density 1.45 g.cm.sup.-3 
Hardness 18 GPa 
Elastic modules 140 Gpa 
Roughness, Ra &lt;0.02 .mu.m 
Thermal expansion 1.6 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.75 cm.sup.2 s.sup.-1 
Electrical resistivity 
10.sup.12 Ohm.cm 
______________________________________ 
One application of the material shown in Example 1 is for use as insulating 
coatings (e.g. steel membrane for automotive sensors). The active sensor 
structure (thin film strain transducer) can be formed upon the carbon 
material of Example 1. Such a sensor structure is believed to exhibit the 
following characteristics: excellent adhesion both between the steel 
membrane and hard carbon, as well as between the steel membrane and active 
sensor structure; atomically smooth surface; flexibility and high fatigue. 
EXAMPLE 2 
The material of the invention was deposited under the following process 
conditions: 
______________________________________ 
Maximum particles energy 
90 eV 
Accelerated field DC 
Cathode current 65 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 P.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
6 cm 
Substrate temperature 
385.degree. C. 
Precursor flow rate 
7 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
10 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
30 cm 
Process time 0.5 hour 
The material was grown as follows: 
Thickness 5 .mu.m 
Specific density 1.96 g.cm.sup.-3 
Hardness 38 GPa 
Elastic modules 512 Gpa 
Roughness, Ra 0.02 .mu.m 
Thermal expansion 1.6 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.75 cm.sup.2 s.sup.-1 
Electrical resistivity 
5 .times. 10.sup.12 Ohm.cm 
______________________________________ 
The material of Example 2 exhibits high strength and elastic modules. Areas 
of applications of material fabricated in accordance with Example 2 
include hard protective coatings, in particular, protective coating for 
steel tools. 
EXAMPLE 3 
The material was deposited under similar conditions to Example 1, except 
the energy of the particles was lower, while the substrate temperature 
higher. Also, the distance between the plasmatron and substrate was less, 
and the growth rate was correspondingly higher in contrast to Example 1. 
The material was deposited under the following process conditions: 
______________________________________ 
Maximum particles energy 
75 eV 
Accelerated field r.f., 1.75 MHZ 
Cathode current 70 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 O.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
5.5 cm 
Substrate temperature 
470.degree. C. 
Precursor flow rate 
8 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
14 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
25 cm 
Process time 0.25 hour 
The material was grown as follows: 
Thickness 3.5 .mu.m 
Specific density 1.56 g.cm.sup.-3 
Hardness 25 GPa 
Elastic modules 160 Gpa 
Roughness, Ra 0.0025 .mu.m 
Thermal expansion 1.6 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.8 cm.sup.2 s.sup.-1 
Electrical resistivity 
10.sup.9 Ohm.cm 
______________________________________ 
This material can be used for protective coating for cutting tools, in 
particular, protective coating for high-speed steel cutting tools. Mills 
with different diameters and shape manufactured in different countries 
(U.S.A., Japan, Israel) were coated with material from Example 3 and 
tested under standard conditions of steel cutting. The tests (data not 
shown) showed a 62 to 65% increase of mill life when coated with the 
material of the invention. 
EXAMPLE 4 
The material was deposited under similar conditions to Example 1, except 
that: the particle energy was 50 eV, the substrate temperature was 
530.degree. C., the distance between the plasmatron and substrate was 4 
cm, the growth rate was 20 .mu.m hours and the process time was 15 hours. 
The material was deposited under the following process conditions: 
______________________________________ 
Maximum particles energy 
50 eV 
Accelerated field r.f., 1.75 MHZ 
Cathode current 65 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane 
Distance "filament-substrate" 
4 cm 
Substrate temperature 
530.degree. C. 
Precursor flow rate 8 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
20 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
20 cm 
Process time 15 hour 
The material was grown as follows: 
Thickness 300 .mu.m 
Specific density 1.5 g.cm.sup.-3 
Hardness 28 GPa 
Elastic modules 180 Gpa 
Roughness, Ra 2.1 .mu.m 
Thermal expansion 1.7 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.8 cm.sup.2 s.sup.-1 
Electrical resistivity 
8 .times. 10.sup.8 Ohm.cm 
______________________________________ 
The silicon substrate was scratched from back to side using a diamond tip. 
The 2.times.2 cm.sup.2 pieces were then fabricated. Thereafter, the 
substrates were etched out from the pieces and free-standing material was 
bonded with a high-temperature compound having a composition similar to 
the deposited materials composition. 2.times.2.times.2 cm.sup.3 bulk 
material was obtained having a total thickness of 63 compound interlayers 
(about 800 em). This material can be used for protective coatings, as well 
as heat-conductive insulated substrates for electronic devices. The 
material can also be used as a basic constructive material for 
micro-mechanics and micro electrical mechanical devices. 
EXAMPLE 5 
The material was deposited under similar conditions to Example 4, except 
that the growth conditions were under higher temperature. The material was 
deposited under the following process conditions: 
______________________________________ 
Maximum particles energy 
50 eV 
Accelerated field r.f., 1.75 MHZ 
Cathode current 65 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 P.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
2 cm 
Substrate temperature 
955.degree. C. 
Precursor flow rate 
7 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
17 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
10 cm 
Process time 2 hour 
The material was grown as follows: 
Thickness 34 .mu.m 
Specific density 1.6 g.cm.sup.-3 
Hardness 31 GPa 
Elastic modules 220 Gpa 
Roughness, Ra 0.7 .mu.m 
Thermal expansion 1.7 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.7 cm.sup.2 s.sup.-1 
Electrical resistivity 
5 .times. 10.sup.8 Ohm.cm 
______________________________________ 
The general characteristics of this material are similar to the material 
grown in Example 4, although this material exhibits somewhat lower 
electrical resistivity and higher thermal stability. 
EXAMPLE 6 
The material was grown at a high temperature with different types of 
accelerating fields. The material was deposited under the following 
process conditions: 
______________________________________ 
Maximum particles energy 
50 eV 
Accelerated field r.f., 1.75 MHZ 
Cathode current 65 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 O.sub.4 Si.sub.5 
Distance "filament-substrate" 
3 cm 
Substrate temperature 
685.degree. C. 
Precursor flow rate 
7 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
15 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
15 cm 
Process time 6 hour 
The material was grown as follows: 
Thickness 90 .mu.m 
Specific density 1.55 g.cm.sup.-3 
Hardness 32 GPa 
Elastic modules 260 Gpa 
Roughness, Ra 0.3 .mu.m 
Thermal expansion 1.7 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.8 cm.sup.2 s.sup.-1 
Electrical resistivity 
10.sup.8 Ohm.cm 
______________________________________ 
The general characteristics of this material are high thermal stability. In 
an oxygen-free environment, material grown in accordance to Example 6 can 
be used for periods of time at temperatures of at least 685.degree. C. 
EXAMPLE 7 
The material was grown at conditions similar to Example 6 except at a 
different accelerating field. The material was deposited under the 
following process conditions: 
______________________________________ 
Maximum particles energy 
100 eV 
Accelerated field DC 
Cathode current 70 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 P.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
2 cm 
Substrate temperature 
1095.degree. C. 
Precursor flow rate 
8 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
12 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
10 cm 
Process time 1.0 hour 
The material was grown as follows: 
Thickness 12 .mu.m 
Specific density 1.96 g.cm.sup.-3 
Hardness 30 GPa 
Elastic modules 220 Gpa 
Roughness, Ra 0.04 .mu.m 
Thermal expansion 1.7 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.8 cm.sup.2 s.sup.-1 
Electrical resistivity 
5 .times. 10.sup.7 Ohm.cm 
______________________________________ 
This material exhibits even higher thermal stability than the material 
grown in Example 6, and can be used under sever (extremely high) 
temperature conditions, such as, for example, a sensor membrane for such 
conditions. 
EXAMPLE 8 
The material was deposited under the following process conditions: 
______________________________________ 
Maximum particles energy 
-100 eV 
Cathode current 65 A 
Number of plasmatrons 
2 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 P.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
6 cm 
Substrate temperature 
385.degree. C. 
Precursor flow rate 
2 .times. 8 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
20 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
30 cm 
Process time 20 hour 
The material was grown as follows: 
Thickness 400 .mu.m 
Specific density 1.56 g.cm.sup.-3 
Hardness 28 GPa 
Elastic modules 195 Gpa 
Roughness, Ra 3 .mu.m 
Thermal expansion 1.6 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 8.5 cm.sup.2 s.sup.-1 
Electrical resistivity 
5 .times. 10.sup.7 Ohm.cm 
______________________________________ 
This material was deposited into a reactor as illustrated in FIG. 7A and 
7B. 
EXAMPLE 9 
The material was deposited under the following process conditions: 
______________________________________ 
Low energy 50 eV, r.f., 1.75 MHz 
High accelerated voltage 
250 eV, DC 
Cathode current 65 A 
Number of plasmatrons 
6 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 P.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
6 cm 
Substrate temperature 
400.degree. C. 
Precursor flow rate 
8 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
15 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
80 cm 
Rotation 300 min.sup.-1 
Process time 10 hour 
The material was grown as follows: 
Thickness 150 .mu.m 
Specific density 1.57 g.cm.sup.-3 
Hardness 18 GPa 
Elastic modules 170 Gpa 
Roughness, Ra 1 .mu.m 
Thermal expansion 1.7 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.8 cm.sup.2 s.sup.-1 
Electrical resistivity 
5 .times. 10.sup.9 Ohm.cm 
______________________________________ 
This material was deposited into a reactor as illustrated in FIG. 7A and 
7B. 
EXAMPLE 10 
The material was deposited under the following process conditions: 
______________________________________ 
Maximum particles energy 
90 eV 
Accelerated field r.f., 1.75 MHz 
Cathode current 66 A 
Number of plasmatrons 
1 
Precursor phenilmethylsiloxane C.sub.27 H.sub.42 P.sub.4 Si.sub.5 
(M = 571; T.sub.m &lt; 0; T.sub.b = 297) 
Distance "filament-substrate" 
8 cm 
Substrate temperature 
300.degree. C. 
Precursor flow rate 
7 cm.sup.3 hour.sup.-1 
Hard graphite-like material 
7 .mu.m hour.sup.-1 
growth rate 
Effective deposition area (diameter) 
40 cm 
Process time 1 hour 
The material was grown as follows: 
Thickness 7 .mu.m 
Specific density 1.8 g.cm.sup.-3 
Hardness 15 GPa 
Elastic modules 120 Gpa 
Roughness, Ra &lt;0.02 .mu.m 
Thermal expansion 1.6 .times. 10.sup.-7 K.sup.-1 
Thermal diffusity 0.75 cm.sup.2 s.sup.-1 
Electrical resistivity 
3 .times. 10.sup.12 Ohm.cm 
______________________________________ 
This material was deposited into a reactor as illustrated in FIG. 7A and 
7B. 
From the foregoing, it will be obvious to those skilled in the art that 
various modifications in the above-described invention and Examples can be 
made without departing from the spirit and scope of the invention. 
Accordingly, the invention can be embodied in other specific forms without 
departing from the spirit or essential characteristics thereof, including 
the specific design of the plasmatron and process conditions. Present 
embodiments and Examples, therefore, are to be considered in all respects 
as illustrative and not restrictive, the scope of the invention being 
indicated by the appended claims rather than by the foregoing, and all 
changes which come within the meaning and range of equivalency of the 
claims are therefore intended to be embraced therein.