CONTROLLING DOPING OF SYNTHETIC DIAMOND MATERIAL
Field of Invention
The present invention relates to a method of controlling the concentration and
uniformity of dopants in synthetic diamond material manufactured using a chemical
vapour deposition (CVD) technique.
Background of Invention
CVD processes for manufacture of synthetic diamond material are now well known in
the art. Useful background information relating to the chemical vapour deposition of
diamond materials may be found in a special issue of the Journal of Physics:
Condensed Matter, Vol. 21, No. 36 (2009) which is dedicated to diamond related
technology. For example, the review article by R.S Balmer et al. gives a
comprehensive overview of CVD diamond materials, technology and applications
(see "Chemical vapour deposition synthetic diamond: materials, technology and
applications" J . Phys.: Condensed Matter, Vol. 21, No. 36 (2009) 364221).
Being in the region where diamond is metastable compared to graphite, synthesis of
diamond under CVD conditions is driven by surface kinetics and not bulk
thermodynamics. Diamond synthesis by CVD is normally performed using a small
fraction of carbon (typically <5%), typically in the form of methane although other
carbon containing gases may be utilized, in an excess of molecular hydrogen. If
molecular hydrogen is heated to temperatures in excess of 2000 K, there is a
significant dissociation to atomic hydrogen. In the presence of a suitable substrate
material, diamond can be deposited.
Atomic hydrogen is believed to be essential to the process because it selectively
etches off non-diamond carbon from the substrate such that diamond growth can
occur. Various methods are available for heating carbon containing gas species and
molecular hydrogen in order to generate the reactive carbon containing radicals and
atomic hydrogen required for CVD diamond growth including arc-jet, hot filament,
DC arc, oxy-acetylene flame, and microwave plasma.
Methods that involve electrodes, such as DC arc plasmas, can have disadvantages due
to electrode erosion and incorporation of material into the diamond. Combustion
methods avoid the electrode erosion problem but are reliant on relatively expensive
feed gases that must be purified to levels consistent with high quality diamond
growth. Also the temperature of the flame, even when combusting oxy-acetylene
mixes, is insufficient to achieve a substantial fraction of atomic hydrogen in the gas
stream and the methods rely on concentrating the flux of gas in a localized area to
achieve reasonable growth rates. Perhaps the principal reason why combustion is not
widely used for bulk diamond growth is the cost in terms of kWh of energy that can
be extracted. Compared to electricity, high purity acetylene and oxygen are an
expensive way to generate heat. Hot filament reactors while appearing superficially
simple have the disadvantage of being restricted to use at lower gas pressures which
are required to ensure relatively effective transport of their limited quantities of
atomic hydrogen to a growth surface.
In light of the above, it has been found that microwave plasma is the most effective
method for driving CVD diamond deposition in terms of the combination of power
efficiency, growth rate, growth area, and purity of product which is obtainable.
A microwave plasma activated CVD diamond synthesis system typically comprises a
plasma reactor vessel coupled both to a supply of source gases and to a microwave
power source. The plasma reactor vessel is configured to form a resonance cavity
supporting a standing microwave. Source gases including a carbon source and
molecular hydrogen are fed into the plasma reactor vessel and can be activated by the
standing microwave to form a plasma in high field regions. If a suitable substrate is
provided in close proximity to the plasma, reactive carbon containing radicals can
diffuse from the plasma to the substrate and be deposited thereon. Atomic hydrogen
can also diffuse from the plasma to the substrate and selectively etch off non-diamond
carbon from the substrate such that diamond growth can occur.
A range of possible microwave plasma reactors for diamond film growth via a
chemical vapour deposition (CVD) process are known in the art. Such reactors have a
variety of different designs. Common features include: a plasma chamber; a substrate
holder disposed in the plasma chamber; a microwave generator for forming the
plasma; a coupling configuration for feeding microwaves from the microwave
generator into the plasma chamber; a gas flow system for feeding process gases into
the plasma chamber and removing them therefrom; and a temperature control system
for controlling the temperature of a substrate on the substrate holder.
A useful overview article by Silva et al. (Paris University's LIMHP group)
summarizing various possible reactor designs is given in the previous mentioned
Journal of Physics (see "Microwave engineering of plasma-assisted CVD reactors for
diamond deposition" J . Phys.: Condensed Matter, Vol. 21, No. 36 (2009) 364202).
Having regard to the patent literature, US6645343, EP0480581 and US20 10/0 189924
disclose various reactor designs including systems in which process gas is injected
into the plasma chamber at high velocity to establish convective transfer of activated
gas species from the plasma to the substrate in order to increase growth rate of a CVD
diamond film and/or improve thickness uniformity of the CVD diamond film.
Doping of synthetic diamond material during CVD synthesis is also known in the art.
Common dopants in diamond material which may have some desirable use include
boron, nitrogen, silicon, sulphur, phosphorous, lithium and beryllium. Synthetic
boron doped diamond material is of particular interest as boron doping can, for
example, make the synthetic diamond material semi-conductive or, at high doping
levels, full metallic conduction can be achieved. Synthetic boron doped diamond
material finds applications that range from mechanical applications to electronics and
sensors.
There is a need to grow synthetic diamond material which contains a uniform
concentration of dopant to maintain consistency of product. For example, in boron
doped polycrystalline diamond it is desirable to grow large area (e.g. greater than 120
mm diameter), thick (e.g. great than 0.5 mm), free-standing polycrystalline diamond
wafers which can be processed using electric discharge machining (EDM) methods.
In order to achieve this, the boron concentration needs to be high enough to ensure a
reasonable and viable cutting rate, but not so high that it begins to degrade the
material properties. Furthermore, the boron concentration must be within these limits
over the majority volume of the disk.
A similar argument applies to single crystals, for example wherein a plurality of
single crystals might be homoepitaxially grown in a single growth run. Specifications
on the boron set by applications that include electronics require all of these single
crystal diamonds to contain similar boron concentrations.
There is also a need in some methods (particularly in single crystal {100} oriented
growth) to find routes to achieve higher boron concentrations necessary for example,
for metallic conduction.
A significant amount of work has been performed in this field in relation to boron
doped polycrystalline and single crystal diamond material. For example, EP 0 822
269 Bl discloses the basic CVD chemistry required for achieving boron doping.
EP1463849 teaches how to achieve uniform boron doping over a single crystal of
synthetic CVD diamond material by utilizing a diamond substrate having a surface
substantially free of crystal defects.
J . Achard, F. Silva et al. also discuss boron doping of CVD diamond material using a
reactor as described in the previous discussed Silva et al. paper (see "Thick boron
doped diamond single crystals for high power electronics", Diamond & Related
Materials (2010), doi: 10.1016/j.diamond.2010.1 1.014). Here, the effect of boron
concentration in the reaction gases and microwave power density is discussed in
relation to boron doping of single crystal CVD diamond material. It is described that
in order to increase the level of boron incorporation into a single crystal CVD
diamond film it is necessary to increase the amount of diborane added to the reaction
gases but for [B]/[C]gas ratios above 5000 ppm the plasma is unstable due to formation
of soot that accumulates and prevents deposition longer than a couple of hours, and
thus prevents the growth of thick films. It is also described that high microwave
power densities are desirable for rapid growth of CVD diamond films but that higher
microwave power densities result in lower boron incorporation. As such, it is
concluded that a compromise must be reached by using a mid-range microwave
power density (specifically disclosed as 60 Wcm ) and a [B]/[C]gas ratio of 5000 ppm
to grow a 300 mih-thick heavily boron-doped film (102 cm 3 ) from which a
freestanding plate can be formed.
It is an aim of certain embodiments of the present invention to provide a method and
apparatus which is capable of achieving more uniform doping of CVD diamond
material over large areas of, for example, polycrystalline diamond material and/or
over a large number of single crystal diamonds grown in a single growth run. It is
also an aim of certain embodiments to achieve higher levels of doping such as high
boron doping concentrations for electronic and sensor applications. It is a further aim
to achieve uniform and/or higher levels of doping while simultaneous achieving good
growth rates given that some dopants such as boron have a tendency to reduce growth
rates.
Summary of Invention
While it was previously known that growth rate and thickness uniformity of a
synthetic CVD diamond film are sensitive to gas flow rate and geometry, the present
inventors have now surprisingly found that incorporation of dopants is also very
sensitive to gas flow rate and geometry of gas flow. In particular, it has been found
that it is advantageous to: select a microwave plasma reactor configured to inject
process gases towards a growth surface of a substrate (i.e. a gas flow configuration
which is oriented axially with respect to the plasma chamber so that process gases are
injected directly towards the substrate); operate the configuration at high velocity gas
flow; and introduce a dopant such as boron into the process gases at a suitable
concentration. It has been found that this combination of features enables uniform
doping to be achieved over larger areas of polycrystalline diamond material and/or
over a larger number of single crystal diamonds grown in a single growth run and/or
for achieving very high levels of doping such as high boron doping concentrations in
synthetic single crystal CVD diamond material while maintaining good growth rates
and good material quality. For example, following the teachings of J . Achard, F.
Silva et al. the present inventors consider that it is not possible to achieve boron
incorporation into certain synthetic single crystal CVD diamond materials, e.g. {100}
oriented synthetic single crystal CVD diamond materials, significantly over 10 cm .
In contrast, by using an axially oriented gas flow arrangement and operating at high
velocity gas flow it has been possible to significantly exceed 102 cm 3 boron
concentrations and access the metallic conduction regime in high quality single crystal
CVD diamond material produced using a microwave plasma activated CVD
technique. Previously, while such levels of boron incorporation were possible in thin,
lower quality single crystal films and polycrystalline diamond material, such a high
level of boron incorporation into high quality single crystal CVD diamond material
formed using a microwave plasma, particularly using a substrate having a desirable
crystallographic orientation for high quality single crystal CVD diamond growth, was
not achievable. In addition, using an axially oriented gas flow arrangement and
operating at high velocity gas flow, particularly when using multiple inlet nozzles, it
is possible to uniformly incorporate boron into both single crystal and polycrystalline
synthetic CVD diamond material over large areas.
In light of the above, according to a first aspect of the present invention there is
provided a method of manufacturing synthetic CVD diamond material, the method
comprising:
providing a microwave plasma reactor comprising:
a plasma chamber;
one or more substrates disposed in the plasma chamber providing a
growth surface area over which the synthetic CVD diamond material is to be
deposited in use;
a microwave coupling configuration for feeding microwaves from a
microwave generator into the plasma chamber; and
a gas flow system for feeding process gases into the plasma chamber
and removing them therefrom,
injecting process gases into the plasma chamber;
feeding microwaves from the microwave generator into the plasma chamber
through the microwave coupling configuration to form a plasma above the growth
surface area; and
growing synthetic CVD diamond material over the growth surface area,
wherein the process gases comprise at least one dopant in gaseous form,
selected from a one or more of boron, silicon, sulphur, phosphorous, lithium and
beryllium, the or each dopant present at a concentration equal to or greater than 0.01
ppm, and/or a nitrogen dopant at a concentration equal to or greater than 0.3 ppm,
wherein the gas flow system includes a gas inlet comprising one or more gas
inlet nozzles disposed opposite the growth surface area and configured to inject
process gases towards the growth surface area, and
wherein the process gases are injected towards the growth surface area at a
total gas flow rate equal to or greater than 500 standard cm3 per minute and/or
wherein the process gases are injected into the plasma chamber through the or each
gas inlet nozzle with a Reynolds number in a range 1 to 100.
The aforementioned method may be utilized to grow a large synthetic polycrystalline
CVD diamond wafer having a substantially uniform concentration of dopant
throughout the wafer or for growing a larger number of single crystal diamonds grown
in a single growth run, the plurality of single crystal diamonds having substantially
the same dopant concentration. Further still, the method can be utilized to achieving
very high levels of doping (e.g. equal to or greater than 2 x 102 cm 3 ) while
maintaining good growth rates and good material quality. When uniform doping over
large areas is desired, the provision of multiple gas inlet nozzles is preferred.
However, when a high level of doping over a relatively small area is required a single
gas inlet nozzle may be utilized.
According to a second aspect of the present invention there is provided a synthetic
polycrystalline CVD diamond wafer, said wafer having a longest dimension equal to
or greater than 140 mm and comprising at least one dopant having a concentration
which varies by no more than 50% of a mean concentration over at least 70% of the
volume of the synthetic polycrystalline CVD diamond wafer.
According to a third aspect of the present invention there is provided a layer of
synthetic single crystal CVD diamond material, said layer having a thickness greater
than 50 m and comprising boron dopant having a concentration equal to or greater
than 2 x 1020 cm 3 .
According to a fourth aspect of the present invention there is provided a synthetic
single crystal CVD diamond comprising a doped layer and an adjacent undoped layer,
wherein an interface between the doped and undoped layer is substantially free of
impurities and wherein the dopant concentration varies by at least a factor of 3 over a
thickness of no more than 10 mih across the interface between the doped and undoped
layers.
Embodiments of the present invention use gas flow to control incorporation of
dopants such as nitrogen, boron, silicon, phosphorous, lithium and beryllium.
Embodiments may also control the concentration and distribution of other defects
such as dangling bonds and vacancy clusters. Particularly useful embodiments use
gas flow to control the concentration and distribution of boron in synthetic CVD
diamond material to meet the needs previously described in the background section of
this specification. For example: free-standing polycrystalline diamond wafers which
can be reliably and consistently processed using electric discharge machining (EDM)
methods, e.g. to form mechanical tool and wear parts; free-standing polycrystalline
diamond wafers with consistent and uniform conduction characteristics for use as
electrodes, e.g. in water treatment and ozone generation applications; highly boron
doped, uniform, high quality single crystal diamond components for use in sensing
and electronic applications, e.g. electrochemical sensing applications which require
very high boron concentrations and electronic components such as diamond diode and
transistor structures; gems having a reliable, uniform, consistent, and reproducible
colour, e.g. blue boron doped gems and colourless or near colourless gems formed by
co-doping using boron and another dopant such as nitrogen; and quantum grade
synthetic diamond material comprising a uniform distribution of nitrogen dopant in
the form of nitrogen-vacancy (NV ) defects. Further embodiments enable the
formation of doped layers which have high purity, well defined interfaces with
adjacent undoped layers within a synthetic single crystal CVD diamond.
Brief Description of the Drawings
For a better understanding of the present invention and to show how the same may be
carried into effect, embodiments of the present invention will now be described by
way of example only with reference to the accompanying drawings, in which:
Figure 1 shows a cross-sectional view of a microwave plasma reactor configured to
deposit a synthetic CVD diamond film using a single axially disposed gas inlet nozzle
arranged to inject process gases towards a growth surface of a substrate;
Figure 2 shows a cross-sectional view of a microwave plasma reactor configured to
deposit a synthetic CVD diamond film using a plurality of gas inlet nozzles arranged
to inject process gases towards a growth surface of a substrate;
Figure 3 shows a plan view of a gas inlet nozzle array;
Figure 4 shows a cross-sectional view of a portion of the gas inlet nozzle array
illustrated in Figures 2 and 3;
Figure 5 shows a plot indicating the relationship between resistivity of a synthetic
CVD diamond film and boron concentration - the metallic conduction regime is
reached at a boron concentration of approximately 4 x 102 cm 3 ;
Figure 6 shows a plot indicating how boron uptake varies as a function of the quantity
of boron in the reaction gases - increasing boron in the reaction gases leads to a linear
increase in the concentration of boron in a synthetic CVD diamond film up until
approximately 4 x 10 19 cm 3 after which no significant increase in concentration of
boron in a synthetic CVD diamond film is observed unless process gas flow velocity
is increased to achieve metallic conduction as indicated by the ringed graph points;
Figure 7 shows a plot indicating how boron uptake varies as a function of carbon
containing gas flow;
Figure 8 shows a plot indicating how boron uptake varies as a function of boron
containing gas flow;
Figure 9 illustrates how increasing flow rate can be used to access higher operating
pressures without onset of arcing;
Figure 10 illustrates how increasing flow rate can be used to access higher operating
pressures without onset of arcing and how the range of suitable flow rates narrows at
higher pressures;
Figure 11 illustrates how changing gas flow Reynolds number can be used to access
higher operating pressures without onset of arcing and how the range of suitable
Reynolds numbers narrows at higher pressures;
Figure 1 illustrates that growth rate can increase with flow rate and with an increase
in the number of gas inlet nozzles;
Figures 13 to 16 show resistivity maps for synthetic polycrystalline CVD diamond
wafers illustrating that doping uniformity can be improved by tailoring gas inlet
nozzle diameter and spacing; and
Figure 17 illustrates how growth rate of a plurality of synthetic single crystal CVD
diamonds increases with process gas flow rate.
Detailed Description of Certain Embodiments
Reactor Hardware and Gas Inlet Configurations
Figure 1 shows a cross-sectional view of a microwave plasma reactor configured to
deposit a synthetic CVD diamond film using a single axially disposed gas inlet nozzle
arranged to inject process gases towards a growth surface of a substrate as a directed
jet of high velocity process gas.
The microwave plasma reactor comprises the following basic components: a plasma
chamber 102; a substrate holder 104 disposed in the plasma chamber for holding a
substrate 105; a microwave generator 106 for forming a plasma 108 within the plasma
chamber 102; a microwave coupling configuration 110 for feeding microwaves from
the microwave generator 106 into the plasma chamber 102 via a coaxial waveguide
and through an annular dielectric window 119; a gas flow system 112, 122 for feeding
process gases into the plasma chamber 102 and removing them therefrom; and a
substrate coolant system 114 for controlling the temperature of a substrate 105.
The plasma chamber 102 may have a number of different configurations suitable for
supporting a standing microwave. However, it is found that this invention is best
utilized in conjunction with simple modal synthesis chambers, for instance the TM0n
mode is advantageous as it has been found to be the most compact (small) mode
which can be practicably used in a diamond CVD plasma reactor. Its compactness
means that the impact of gas flow aspects on the near gas phase chemistry are
maximized, however, this invention is not limited to this modal geometry. The use of
a small plasma chamber having a compact microwave cavity is made possible by the
flow characteristics of the gas inlet according to embodiments of the present invention
which ensures that process gas flows through a central portion of the plasma chamber
without undue circulation of gases within the plasma chamber contaminating walls of
the chamber which will be relatively close to the gas flow in a compact cavity
arrangement.
The gas flow system 112 comprises source gas containers 117 and a gas inlet coupled
to the source gas containers and positioned in a top portion of the plasma chamber 102
axially disposed above the substrate holder 104 and substrate 105 for directing
process gases towards the substrate 105 in use. In the illustrated embodiment the
process gas is fed from the source gas containers 117 to the gas inlet through a central
conductor of the microwave coupling configuration 110. However, other
configurations are also possible for feeding the process gases to the gas inlet 120.
The microwave window 119 for feeding microwaves from the microwave generator
into the plasma chamber is preferably disposed at an opposite end of the plasma
chamber to the substrate holder. Furthermore, the gas inlet is preferably disposed
closer to the substrate holder than the microwave window. Such an arrangement can
minimize the possibility of the microwave window being contaminated with process
gases while also ensuring that the process gas is injected at a location relatively close
to the substrate.
In the arrangement shown in Figure 1, the gas inlet comprises a single gas injection
nozzle located on a central rotational axis of the plasma chamber so as to direct a jet
of process gas in an axial direction towards the substrate holder. The gas injection
nozzle may be formed by a portion of the microwave/vacuum wall such that the
nozzle form part of the microwave cavity wall of the plasma chamber, rather than
being outside the mesh that defines the microwave cavity wall.
One or more gas outlets 122 are provided in a base of the plasma chamber 102. The
gas outlets 122 are preferably located in a ring around the substrate holder 104 and
most preferably form a uniformly spaced array around the substrate holder 104 to
enhance continuous gas flow from the gas inlet 120 towards the substrate 105, around
the substrate 105, and out of the gas outlets 122 while minimizing turbulence and gas
recirculation back up the plasma chamber 102. For example, it may be preferable to
provide at least 6, 12, 18, or 30 gas outlets disposed around the substrate holder 104,
preferably in a uniformly spaced array. In this regard, it should be noted that while
embodiments of the present invention may function to reduce uncontrolled gas r e
circulation within the plasma chamber, this does not preclude the possibility of using
a controlled gas re-circulation system outside the plasma chamber for re-using process
gas which is extracted from the plasma chamber through the gas outlets.
Figure 2 shows a similar microwave plasma reactor to that shown in Figure 1. The
arrangement shown in Figure 2 differs in that the gas inlet comprises a plurality of gas
inlet nozzles arranged in a gas inlet nozzle array 124 to inject process gases towards a
growth surface of a substrate in an axial direction. In other respects like reference
numerals are used for like parts.
The gas inlet nozzle array 124 comprises a plurality of gas inlet nozzles disposed
opposite the substrate holder 104 for directing process gases towards the substrate
holder 104. The gas inlet nozzle array 124 comprises a plurality of gas inlet nozzles
disposed in a substantially parallel orientation relative to the central axis of the plasma
chamber 102. The gas inlet array 124 also comprises a housing 128 defining a cavity
130 for receiving process gases from one or more gas inlet pipes. The housing 128
also defines the plurality of inlet nozzles for injecting process gases from the cavity
130 into the plasma chamber 102 and towards the substrate holder 104. For example,
the housing may comprise metallic walls in which the inlet nozzles are integrally
formed.
The housing 128 and cavity 130 can function as a mixing chamber for mixing source
gases prior to injection into the plasma chamber. Such a pre-mixing chamber has
found to be useful to ensure efficient gas mixing prior to injection into the plasma
chamber. Furthermore, a pre-mixing chamber is useful to ensure that there is a
uniform gas flow over the entirety of the array of gas nozzles. The pre-mixing
chamber may include a diffuser or an array of holes disposed prior to the gas inlet
nozzle array to encourage gas mixing and/or provide an even flow of gas to the gas
inlet nozzle array.
The housing 128 can also extend into the plasma chamber allowing gases to be
injected closer to the substrate. The distance between the gas inlet nozzle array and
the substrate where diamond growth occurs affects the thickness of a boundary layer
over the substrate. Reducing the distance between the gas inlet nozzle array and the
substrate had been found to reduce the thickness of such a boundary layer and lead to
an increase in diamond deposition rate.
The present inventors have found that in contrast to the teachings of
US20 10/0 189924, it is advantageous to provide a gas inlet configuration in which gas
inlet nozzles are not angled inwardly to interact above the substrate and constrain the
plasma in a lateral direction. Furthermore, US20 10/0 189924 discloses a relatively
small number of gas inlets. One problem with providing a single axially positioned
gas inlet arrangement or one which uses a relatively small number of gas inlets is that
at very high velocity flows, the gas stream can penetrate through the plasma,
essentially punching a hole in the plasma discharge and pushing the plasma outwards
towards the sides of the substrate, leading to non-uniform diamond film formation.
The present inventors have found that instead of providing a relatively small number
of gas inlet nozzles, problems associated with the process gas stream punchingthrough
a central region of the plasma discharge at very high gas stream velocities can
be reduced by providing a higher number of inlet nozzles. The inlet nozzles may be
oriented so as to be substantially parallel or divergent in orientation.
In addition, it has been found that the relatively high number of nozzles may be
closely spaced to ensure a relatively uniform flow of gas. It has been found that
providing a relatively high number density of nozzles in an array improves the
uniformity of gas flow towards the substrate in use and allows the plasma to be
uniformly flattened and shaped relative to the substrate to achieve uniform diamond
film formation at high rates over a relatively large area.
It has also been found to be useful to provide relatively small area nozzles such that
the area of the nozzle array is largely made up of the space in-between the nozzles
rather than the area of the nozzle outlets themselves. As such, whereas it has been
found to be advantageous to provide a relatively large number density of nozzles in
relation to the area of the nozzle inlet array, it has also been found to be advantageous
to provide an array in which the ratio of the area of the nozzle inlets divided by the
area of the nozzle array as a whole is low. It has been found that small nozzles are
advantageous for providing high velocity directed gas flows. However, it is also
desired to have a relatively uniform gas flow over a relatively large area for uniform
deposition of a diamond film over a relatively large area. Accordingly, a combination
of relatively small inlet nozzle size and a relatively high number density of such
nozzles has been found to be advantageous to achieve a balance between high velocity
directed gas flows and uniformity of gas flow over a relatively large area.
In light of the above findings, it has been found to be advantageous to provide a gas
inlet nozzle array comprising at least six gas inlet nozzles disposed in a substantially
parallel or divergent orientation relative to a central axis of the plasma chamber (by
substantially parallel we mean at least within 10°, 5°, 2°, or 1° of a perfect parallel
arrangement). Preferably, the gas inlet nozzle array comprises a gas inlet nozzle
number density equal to or greater than 0.1 nozzles/cm2, wherein the gas inlet nozzle
number density is measured by projecting the nozzles onto a plane whose normal lies
parallel to the central axis of the plasma chamber and measuring the gas inlet number
density on said plane. Furthermore, the gas inlet nozzle array may comprise a nozzle
area ratio of equal to or greater than 10, wherein the nozzle area ratio is measured by
projecting the nozzles onto a plane whose normal lies parallel to the central axis of the
plasma chamber, measuring the total area of the gas inlet nozzle area on said plane,
dividing by the total number of nozzles to give an area associated with each nozzle,
and dividing the area associated with each nozzle by an actual area of each nozzle.
The aforementioned arrangements capture four features which are advantageously
provided: (i) a relatively high number of gas inlet nozzles (in the most simple
embodiment, six nozzles arranged in a hexagonal arrangement, but preferably many
more nozzles are provided for certain applications); (ii) the orientation of the nozzles
may be substantially parallel or divergent; (iii) the gas inlet nozzle number density
may be high (at least 0.1 nozzles/cm2 but preferably much higher for certain
applications); and (iv) the ratio of the area associated with each nozzle relative to the
actual area of each nozzle should be high (at least 10 but preferably much higher for
certain applications).
It has been found that a gas inlet nozzle array comprising these four characteristics
can be utilized to form a relatively solid curtain of process gas flowing towards the
substrate. By "solid" we mean that the plurality of individual gas streams are so
densely packed that they may be approximated to a single uniform mass of gas
flowing towards the substrate. The solid gas stream may comprise a dense curtain of
individual gas flows or an essentially continuous (in a radial direction) uniform flow
of process gas. The nozzles may be configured such that individual gas streams are
aimed at the substrate but do not significantly interact with each other before the
substrate to cause unwanted turbulence. While the individual gas streams may merge
to form a single "plug" of gas flowing towards the substrate, the streams are not
configured to significantly cross each other above the substrate. This is advantageous
to provide good gas flow characteristics creating a more laminar flow of the gas
streams and preventing or at least reducing turbulence.
Such an arrangement can provide a relatively uniform flow of gas over a relatively
large area. Furthermore, such an arrangement can reduce gas entrainment such that
the majority, or preferably substantially all, the gas flows in a direction towards the
substrate and out of outlets in a base of the chamber with reduced, or preferably
substantially no, gas re-circulating within the chamber. It has been found that by
preventing gas entrainment, the concentration of species in the activated plasma
region is more controllable by direct control of the concentration of gases injected
through the inlet nozzles. Furthermore, by limiting the possibility of gases r e
circulating within the plasma chamber, it is possible to minimize the possibility of
contaminating the walls of the chamber even when relatively large area plasmas are
formed. That is, a high density of closely spaced high velocity gas streams functions
both to prevent any gas flowing back towards the inlet nozzles via convection and can
also provide a relatively even distribution of pressure on the plasma discharge to
flatten it in an even manner and allow the possibility for very large area, flat, even
plasmas to be achievable at very high flow rates.
For example, for flat substrate configurations it is has been found to be advantageous
to provide a gas inlet configuration comprising a high density of inlet nozzles which
are oriented in a direction substantially perpendicular to the substrate so as to provide
a substantially uniform curtain of gas propagating towards the substrate and
impinging upon the plasma discharge disposed between the gas inlet and the substrate.
Such an arrangement has been found to flatten the plasma discharge and increase the
concentration of activated gas species in close proximity to the substrate surface.
Furthermore, the substantially uniform curtain of gas formed by a high density of the
nozzles has been found to provide a substantially uniform deposition of reactive gas
species from the plasma to the substrate via convection transport over large areas
without unduly constricting the plasma in a lateral direction by angling the inlet
nozzles inwardly as is suggested in US20 10/0 189924.
In some arrangements, it has actually been found to be advantageous to angle at least
some of the gas inlet nozzles outwardly in a divergent configuration to achieve more
uniform diamond film formation. For example, one central nozzle and six
surrounding nozzles which are oriented to form divergent gas streams. This
arrangement has been found to be particularly useful when a non-planar substrate is
utilized. In one arrangement, a convex substrate is provided with a central portion
which is closer to the gas inlet arrangement than side edge portions. The divergent
nozzles are then useful to aid in pushing the plasma around towards the side edge
portions of the substrate to achieve relatively uniform diamond film formation over
the convex substrate. Such an arrangement is useful for forming non-planar diamond
films.
While the aforementioned description specifies that at least six gas inlet nozzles may
be provided to achieve more uniform diamond film formation over larger areas and/or
over non-planar substrates, it has been found that for certain applications a much
larger and more dense array of gas inlet nozzles is advantageous for many
applications. For example, in certain applications it may be preferable to provide a
gas inlet configuration comprising equal to or greater than 6, 7, 9, 10, 15, 20, 30, 40,
60, 90, 120, 150, 200, 300, 500, 700, 1000, 1200, 1500 or more gas inlet nozzles.
Particularly preferred arrangements comprise a close-packed array of gas inlet
nozzles, for example, a hexagonal close-packed array of gas inlet nozzles has been
found to be particularly advantageous in achieving uniform diamond film formation
over large areas and at a high rate of deposition. As such, hexagonal close-packed
nozzle configurations comprising 6, 7, 19, 37, 61, 91, 127, 169, 217, 271, 331, 397,
469, 547, 631, 721, 817, 919, 1027, 1141, 1261, 1387, 1519 or more nozzles may
provide preferable arrangements.
Figure 3 shows a plan view of the gas inlet nozzle array 124. The array comprises a
hexagonal close-packed array of gas inlet nozzles 126. The array may comprise a gas
inlet nozzle number density much greater than 0.1 nozzles/cm 2, wherein the gas inlet
nozzle number density is measured by projecting the nozzles onto a plane whose
normal lies parallel to a central axis of the plasma chamber and measuring the gas
inlet number density on said plane. The gas inlet nozzle number density is measured
in this way because the array may not necessarily be disposed in a plane. For
example, the array may be disposed in a wall which is curved or otherwise angled
relative to a plane whose normal lies parallel to a central axis of the plasma chamber.
However, in the illustrated embodiment it will be noted that the array is disposed in a
plane whose normal lies parallel to a central axis of the plasma chamber.
The gas inlet nozzle array 120 may have a nozzle area ratio much greater than 10,
wherein the nozzle area ratio is measured by projecting the nozzles onto a plane
whose normal lies parallel to a central axis of the plasma chamber, measuring the total
area A of the gas inlet nozzle array on said plane, dividing by the total number of
nozzles to give an area associated with each nozzle, and dividing the area associated
with each nozzle by an actual area of a nozzle a . Where the nozzles have different
areas, an average nozzle area can be used for the area a . If the total area A of the gas
inlet array is delineated by a line passing through the centre of each of the nozzles in
an outer ring of nozzles in the array, it will be noted that half the area associated with
the outer ring of nozzles will be outside this area. This can be corrected for by
dividing the number of nozzles in the outer ring by two when calculating the total
number of nozzles and then using this corrected value in the aforementioned
calculation so as to correctly calculate the area associated with each nozzle. The
actual area of each nozzle may be calculated as an average nozzle area by summing
the actual area of every nozzle in the array and dividing by the total number of
nozzles in the array. Alternatively, if all the nozzles have the same area then the area
of a single nozzle may be used for the actual area of each nozzle.
Each gas inlet nozzle 126 may have an outlet diameter in the range 0.1 mm to 5 mm,
0.2 mm to 3.0 mm, 2.0 mm to 3 mm, 0.2 mm to 2 mm, 0.25 mm to 2 mm, or 0.25 mm
to 1.5 mm. The diameter of the gas inlet nozzles may be configured to achieve good
laminar flow of the individual gas streams injected through and out of the nozzles into
the plasma chamber 102. The dimensions of the gas inlet nozzles 126 also affect the
Reynolds number Re for gas injection. The Reynolds number is a dimensionless
number that gives a measure of the ratio of inertial forces to viscous forces acting in a
gas stream and consequently quantifies the relative importance of these two types of
forces for given flow conditions. When calculating Reynolds numbers for a nozzle, a
characteristic length scale may be taken to be a cross sectional dimension of the
nozzle. The Reynolds number may be used to characterize different flow regimes,
such as laminar or turbulent flow. Laminar flow occurs at low Reynolds numbers,
where viscous forces are dominant, and is characterized by smooth, constant fluid
motion, while turbulent flow occurs at high Reynolds numbers and is dominated by
inertial forces, which tend to produce chaotic eddies, vortices and other flow
instabilities. In accordance with certain embodiments of the present invention it is
preferable to operate at low Reynolds number to minimize turbulence. The effect of
providing an array of smaller nozzles compared to a small number of larger ones is to
decrease the Reynolds number (if the mean velocity of the gas stream is maintained).
This reduces the "inertial" component of gas injection, in comparison to the viscous
forces operating. Accordingly, it is preferred that the dimensions of the gas inlet
nozzles 126 are selected to give a Reynolds number for gas injection equal to or less
than 100, 80, 50, 40, or 35. Furthermore, the Reynolds number for gas injection may
be equal to or greater than 1, 5, 10, 15, 20, or 25. The most preferred Reynolds
number for operation will depend to some extent on the specific nozzle inlet array
which is utilized.
Figure 4 shows a vertical cross-sectional view of a portion of the gas inlet nozzle
array 124 shown in Figures 2 and 3 . In the illustrated arrangement, each gas inlet
nozzle 126 has an inlet portion 134 having a first diameter di and an outlet portion
136 having a second diameter d2, the first diameter di being larger than the second
diameter d2. Such an arrangement can be advantageous as the fine bore of the outlet
portion which is advantageous for operating in a low Reynolds number regime is only
required to be formed at a minimum length for achieving good gas flow
characteristics. As such, for a wall thickness which is larger than a minimum length
required for achieving good gas flow characteristics, the remainder of the wall
thickness can be drilled out at a larger diameter. For example, the inlet portion 134
may have a length and the outlet portion 136 may have a length 12 with the sum of
and 12 being equal to a wall thickness. Furthermore, this design aids in achieving
clean laminar flow as a converging nozzle profile causes a parabolic velocity profile
to develop more quickly. Of course, it is also possible to provide a gas inlet nozzle in
a wall portion of the gas inlet nozzle array which consists only of a single continuous
bore which may have a constant diameter along its length or a continuously varying
taper.
The present invention has thus far been described with reference to an embodiment as
illustrated in Figures 1 to 4 . However, it is envisaged that various modification can be
made within the scope of the invention. For example, certain embodiments of the
present invention may conform to one or more general design principles for an array
of gas inlet nozzles as discussed below.
Each nozzle in the array can be characterised by its lateral spacing (radius) away from
a central axis of the plasma chamber. A central nozzle, if it exists, may be disposed
down a central axis of the plasma chamber. Nozzles at the same radius (lying on a
ring centred on the central axis) may show periodic rotational symmetry around the
central nozzle, although the rotational angle may vary for different rings of nozzles.
Nozzles positioned at a particular radius from the central axis may be parallel to the
central axis, or may be divergent from it. The nozzles at any particular radius may be
at least as divergent as any nozzles lying on a smaller radius. That is not to say that a
minority of nozzles which do not follow this principle, or even are directed at a
convergent angle, are not permitted.
The nozzles may all be retained parallel to the central axis until some radius Rp, and
then start to become divergent out to a maximum radius on which the nozzles are
placed, Rm. In the region between Rp and Rm, the divergence of the nozzles may vary
as a function of the radius, or the angle of divergence may be fixed.
The spacing of the nozzles may be uniform across the surface through which they
emerge. Preferably the nozzles are in a consistent geometric arrangement, most
preferably in a hexagonal array. While not being bound by theory, it is believed that
such arrangements are advantageous as the gas jets from individual nozzles converge
such that their velocity profiles are well matched. This allows the gas jets to converge
with little or no disturbance. Alternatively, the spacing of the nozzles may increase
with radius, such that the density of nozzles reduces towards the outer edge of the
array. The nozzles may be arranged in discrete rings, with little obvious correlation in
the position of nozzles lying in adjacent rings. It is indeed possible to have a random
array of nozzles which provides some reasonably uniform average density of nozzles
to perform an adequate performance and realise some of the benefits of this invention,
although the best arrangement is one of a regular array.
The diameter of each nozzle is optionally the same, particularly for large nozzle
arrays (e.g. greater than 100 nozzles), or at least particularly for the majority (e.g.
greater than 50% of) the nozzles in such an array.
Projecting all the nozzles onto a plane whose normal lies parallel to the central axis,
the density of nozzles in the nozzle array, particularly for large nozzle arrays (e.g.
greater than 100 nozzles), given in nozzles/cm 2, is preferably equal to or greater than
0.1, 0.2, 0.5, 1, 2, 5, or 10 and equal to or less than 100, 50, or 10.
Projecting all the nozzles onto a plane whose normal lies parallel to the central axis,
the total area of the nozzles in the array (that is the sum of the areas of each nozzle
outlet in the array), given in mm2, may be in a range 1 to 5000, 5 to 3000, 10 to 3000,
20 to 2750, 30 to 2750, or 50 to 2700. The total area of the array over which the
nozzles are spaced, given in mm2, may be in a range 100 to 15000, 200 to 15000, 400
to 10000, 800 to 10000, or 1000 to 8000. The actual total area of the nozzles and the
total area of the array will depend on the number of nozzles provided in the array and
the area over which they are distributed, which will also be dependent on the area of
CVD diamond to be grown. For example, a simple six nozzle array may have a
nozzle diameter in the range 2 to 3 mm, a total nozzle area of 20 to 50 mm2, and a
total array area of approximately 450 mm2. In contrast, a 9 1 nozzle array may have a
nozzle diameter of approximately 0.5 mm, a total nozzle area of approximately 18
mm2, and a total array area of approximately 1000 mm2. Further still, a 1519 nozzle
array may have a nozzle diameter in the range 0.25 to 1.5 mm, a total nozzle area of
75 to 2700 mm2, and a total array area of approximately 8000 mm2.
A ratio of the total nozzle area / area of the nozzle array should preferably be
relatively low, for example, equal to or less than 0.5, 0.35, 0.3, 0.2, 0.1, 0.05, 0.02,
0.01, or 0.007. The ratio of the total nozzle area / area of the nozzle array may be
equal to or greater than 0.001, 0.004, 0.007, 0.01, or 0.02. The actual ratio provided
will depend on the number of nozzles provided in the array and the area over which
CVD diamond is to be grown. For example, a simple six nozzle array may have a
ratio in the range 0.05 to 0.1, a nine nozzle array may have a ratio of approximately
0.007, a 721 nozzle array may have a ratio in the range 0.004 to 0.2, and a 1519
nozzle array may have a ratio in the range 0.01 to 0.35.
A ratio of the area of the nozzle array to an array of the growth surface of the
substrate may be in the range 0.05 to 2, 0.1 to 1.5, 0.5 to 1.25, 0.8 to 1.1, or 0.9 to 1.1.
For arrays which comprise a large number of nozzles (e.g. greater than 100, 500, or
1000), the area of the array may be set to be substantially equal to the area of the
growth surface. For arrays which have a lower number of nozzles, the area of the
array is preferably less than the area of the growth surface of the substrate.
Projecting all the nozzles onto a plane whose normal lies parallel to the central axis,
the total area of the nozzle array, 7 (Rm)2, divided by the total number of nozzles gives
the area associated with each nozzle. A ratio of the associated area of each nozzle
divided by an actual area of each nozzle is preferably equal to or greater than 10, 30,
100, 300, 1000, or 3000 and equal to or less than 100000, 30000, or 10000.
Embodiments of the present invention provide inlet nozzle configurations which
ensure: a relatively even flow of process gas towards the substrate thus improving
diamond film uniformity; relatively little gas entrainment compared to the gas flow
through the nozzles thus improving control of plasma chemistry; the possibility of
plasma formation outside a region of interest near the substrate for diamond film
formation is lowered; the possibility of plasma punch-through is lowered thus
allowing higher velocities of gas flow and thus an increased rate of uniform diamond
film formation over potentially larger areas; the nozzles are adapted to provide
directed gas flow streams at high gas flow velocities and suitable operating pressures;
the possibility of reactive species flowing towards the walls of the reactor by diffusion
or convection is lowered thus lowering contamination during use and improving
diamond film purity; and higher gas flow rates and operating pressures can be utilized
without arcing occurring within the plasma chamber, enabling higher power densities
to be achieved facilitating increased growth rates and improved quality of CVD
diamond product.
It should be noted that while terms such as "top portion" and "base" are used in this
specification when describing the plasma reactor, it is possible to invert the reactor so
that in use the gas flow is in an upwards direction. As such, the terms "top portion"
and "base" refer to the location of the reactor components relative to each other and
not necessarily their location relative to the earth. In standard usage, the gas flow will
be in a downwards direction such that the gas streams from the gas inlet nozzle array
flow downwards with gravity. However, it is possible to invert the reactor such that
the gas streams from the gas inlet nozzle array flow upwards against gravity. In the
inverted orientation the gas flow will be parallel to principle thermally driven
convection currents (which are in an upwards direction due to the large amount of
heat generated in the plasma which is below the substrate in an inverted arrangement).
This inverted arrangement may have some benefits for certain applications.
It should also be noted that while the microwave plasma reactor illustrated in Figures
1 and 2 has a separate substrate holder disposed in the plasma chamber, the substrate
holder may be formed by the base of the plasma chamber. The use of the term
"substrate holder" is intended to cover such variations. Furthermore, the substrate
holder may comprise a flat supporting surface which is the same diameter (as
illustrated) or larger than the substrate. For example, the substrate holder may form a
large flat surface, formed by the chamber base or a separate component disposed over
the chamber base, and the substrate may be carefully positioned on a central region of
the flat supporting surface. In one arrangement, the flat supporting surface may have
further elements, for example projections or grooves, to align, and optionally hold, the
substrate. Alternatively, no such additional elements may be provided such that the
substrate holder merely provides a flat supporting surface over which the substrate is
disposed.
A variety of modifications to the gas inlet array may be envisaged. For example, the
gas inlet array may be configured to transport different gas compositions though
different nozzles. Furthermore, a plurality of gas inlet nozzles may have a non
uniform spacing and/or comprise non-uniform nozzle diameters. This may be
advantageous as different gases will have different flow characteristics and so each of
the nozzles, or a group of nozzles, can be optimized for injection of a particular source
gas. In this case, the mixing cavity should be segregated to prevent mixing of source
gases and configured to direct each source gas to one or more nozzles which have
been specifically adapted for injecting the associated source gas. For example, one or
more central nozzles may be configured to inject carbon and dopant containing gas
species and optionally hydrogen gas while a plurality of outer nozzles may be
configured to inject hydrogen with less or no carbon and dopant containing gas
species. Such an arrangement can prevent or at least reduce contamination of the
reactor walls by carbon and dopant containing species.
An alternative to the provision of a metallic housing in which the inlet nozzles are
integrally formed is to form the nozzles in a microwave window which extends over a
central region in an upper portion of the plasma chamber or even located closer to the
substrate in a central portion of the plasma chamber. For example, the microwaves
may be coupled into the chamber via a plate of microwave window material (e.g.
quartz) in which the inlet nozzles are integrally formed. In such an arrangement, the
high velocity laminar flow produced by a gas inlet nozzle array according to
embodiments of the present invention will aid in keeping the plasma away from the
microwave window. Using high gas flows will result in less contaminants being
deposited near the injection nozzles and the microwave window therefore reducing
the problem of contaminants falling onto the substrate and causing problems such as
black spots, inclusions, and nuclei for defect formation in the CVD diamond material.
Each nozzle is preferably of a sufficiently large diameter to allow sufficient gas flow
volumes at reasonable operating pressures. Accordingly, the nozzles should not be
made too small and this size limitation will limit the density of nozzles which can be
provided over the area of the nozzle array. Conversely, each nozzle should be made
small enough to achieve a highly directed gas stream with good flow characteristics.
As such, the diameter of each gas inlet nozzle is preferably in the range 0.1 mm to 5
mm, 0.2 mm to 3.0 mm, 2.0 mm to 3 mm, 0.2 mm to 2 mm, 0.25 mm to 2 mm, or
0.25 mm to 1.5 mm.
The array of nozzles is preferably formed into a surface which itself is rotationally
symmetric around the central axis of the chamber. This surface may be planar, or it
may curve, preferably in some smoothly varying manner. Preferably it is planar,
particularly for large nozzle arrays (e.g. greater than 100 nozzles), or at least
particularly for the majority (greater than 50% of) the nozzles in such an array.
The surface in which the nozzles lie is preferably reasonably close to the growth
surface area, with a distance D from the central nozzle (or where the central axis
intersects the plane of the first ring of nozzles) which is less than or equal to 6RS, 4RS,
or 2RS, where Rs is the radius of the growth surface area. Preferably the central
nozzle, or a plane defining the first ring of nozzles, is at least as close, or in some
arrangements preferably closer, to the growth surface area as the plane defined by the
next ring of nozzles out from the central axis. Optionally, the plane defining the outer
ring of nozzles is also no more than 6RS, 4RS, or 2RSfrom the growth surface area.
The arrangement of nozzles can be thought to fit into one of three example
configurations as discussed below, although in practice the three example
configurations all lay along a continuous spectrum of possible configurations.
A first example configuration is one which comprises at least six nozzles. The
nozzles form a rotationally symmetric pattern and are either parallel to or divergent
from (more particularly are divergent from) the central axis of the chamber. This
configuration seeks to obtain the benefits of providing a plurality of nozzles while
limiting to a relatively low number of nozzles, simplifying the fabrication of the
nozzle array and simplifying use of additional elements such as interchangeable
nozzle bores to vary the nozzle diameter for different applications and flow rates. The
technique can achieve substantially higher uniformity in deposition than a single
nozzle, particularly in relation to processes involving doping with boron.
A second example configuration comprises a central disc of nozzles which are all
essentially parallel to the central axis of the plasma chamber and disposed in some
regular array out to a radius Rp, outside of which are one or more rings of increasingly
divergent nozzles to 'soften' the edge of the nozzle array. This configuration seeks to
achieve a balance of the benefits from the example discussed above and the example
discussed below.
A third example configuration is one in which Rp = Rm and all, or substantially all, of
the nozzles are parallel to the central axis. Ideally the nozzles lie in a close packed
hexagonal array, and the maximum radius of the nozzle array Rm meets the criteria Rm
x Fm is greater than or equal to Rs, where Fm is preferably equal to or greater than 0.5,
0.6, 0.7, 0.8, 0.9, or 1 and preferably equal to or less than 1.5, 1.3, 1.2, or 1.1. This
configuration provides a dense column of flow from the surface containing the
nozzles to the substrate, and which covers the entire substrate, and which permits
essentially no intermixing of the existing gases in the chamber such that whilst there
may be some convective currents in the peripheral regions of the chamber the
substrate only sees gases which have just been injected ('fresh' gases).
The aforementioned design criteria may provide one or more advantages for certain
applications as discussed below.
The position and uniformity of the plasma with respect to the substrate can easily be
optimised by optimising the total flow. The solid gas stream of process gas towards
the substrate can apply a substantially uniform 'pressure' across the plasma region.
Due to minimal gas flow outside of the solid gas stream between the nozzle array and
the substrate, wall contaminants do not enter the depositing gas stream, so that the
purity of the deposited diamond is improved.
Furthermore, the solid gas stream ensures that no activated gases re-circulate within
the plasma chamber and come into contact with the surface comprising the nozzles, so
that this surface stays free of deposits. This avoids any risk of such deposits breaking
free and being pushed onto the substrate, which can be a source of defective growth.
Further still, minimizing gas re-circulation within the plasma chamber by providing a
solid gas flow of densely packed gas streams enables the nozzles to be formed in a
material which may be eroded by the plasma activated species, such as a quartz plate,
without the plate becoming eroded or coated. Such a quartz plate providing the
nozzles may also be used as the entry point into the cavity of the microwave power,
with its performance undiminished by the formation of coatings. Alternatively it is
advantageous for the end of the microwave cavity in which the gases are introduced
through the nozzles to be proximal to the region where the microwaves are
introduced, with the substrate in the distal region of the cavity.
Process Gas Composition and Effect of Gasflow on Dopant Uptake
By using a microwave plasma reactor comprising a gas inlet configuration as
described in the previous section it is possible to achieve a high level of control in
relation to the level and distribution of dopant uptake in a synthetic CVD diamond
film. In order to achieve such control a dopant containing gas must be provided at a
suitable concentration within the process gas fed through the gas inlet and the flow
rate of the process gas must be high. As such, according to an aspect of the present
invention the process gases comprise at least one dopant at a concentration equal to or
greater than 0.01 ppm and the process gases are injected towards the growth surface
area at a total gas flow rate equal to or greater than 500 standard cm3 per minute.
The dopant may comprise one or more of nitrogen, boron, silicon, sulphur,
phosphorous, lithium or beryllium provided in gaseous form. The dopant may
intentionally be added into the process gas at a desired concentration and controlled to
maintain the dopant at a desired level within the plasma reactor chamber. The type
and concentration of dopant provided in the process gases will vary according to the
desired product. For example, to achieve metallic conduction in synthetic CVD
diamond material it is required to provide a high concentration of boron containing
gas, such as diborane, in the process gases. In contrast, to achieve semi-conductive
synthetic CVD diamond material a lower concentration of boron within the process
gas is needed. Low boron concentrations can also be utilized to achieve attractive
blue coloured gems. Alternatively, the concentration and distribution of nitrogen
dopant may be controlled to achieve, for example, synthetic CVD diamond material
suitable for quantum applications. For example, synthetic CVD diamond material
having a relatively low and uniform nitrogen concentration forming NV defects
which can be optically addressed for sensing and information processing applications.
For example, at least one dopant may be provided in gaseous form into the process
gases at a concentration equal to or greater than 0.01 ppm, 0.05 ppm, 0.1 ppm, 0.3
ppm, 0.5 ppm, 0.7 ppm, 1 ppm, 3 ppm, 5 ppm, 10 ppm, 20 ppm, 50 ppm, 100 ppm,
200 ppm, 300 ppm, 500 ppm, 700 ppm, or 1000 ppm. The concentration of dopant
and carbon in the process gas may be such that a ratio of dopant concentration /
carbon concentration is equal to or greater than 1 x 10 6 , 10 x 10 6 , 100 x 10 6 , or 1000
x 10 6 . Dopant concentrations are quoted as atomic concentrations of dopant to
account for different possible molecular gas species comprising the dopant and carbon
atoms, e.g. if a boron containing gas dopant species comprises two boron atoms, such
as diborane, then the concentration of diborane in the process gas is multiplied by two
to yield the atomic concentration of boron.
The one or more dopants may be injected into the plasma chamber in a controlled
manner either separately or added to one or more source process gases prior to
controlled injection into the plasma chamber.
For certain applications it may be desirable to have substantially no nitrogen dopant
while in certain other applications it may be desirable to have substantially only
nitrogen dopant. Accordingly, the at least one dopant may comprise: one or more of
boron, silicon, sulphur, phosphorous, lithium and beryllium with the process gases
comprising less than 0.3 ppm nitrogen or substantially no nitrogen other than minor
background impurities, i.e. no nitrogen intentionally added; or nitrogen at a
concentration of equal to or greater than 0.3 ppm with the process gases comprising
less than 0.01 ppm of boron, silicon, sulphur, phosphorous, lithium and beryllium or
substantially none of these dopant, i.e. only nitrogen intentionally added into the
process gas as a dopant.
The total gas flow fed through the gas inlet may be equal to or greater than 500, 750,
1000, 2000, 5000, 10000, 15000, 20000, 25000, 30000, 35000, or 40000 standard cm3
per minute. The total gas flow fed through the gas inlet may be equal to or less than
60000, 50000, 30000, 20000, or 10000 standard cm3 per minute depending on the
specific gas inlet configuration which is utilized. For example, for certain nozzle
arrays a typical operating flow rate may lie in a range 500 to 40000, 1000 to 40000, or
2500 to 40000 standard cm3 per minute depending on the desired growth rate, growth
surface area, and target dopant concentration.
The total gas flow fed through the gas inlet is preferably equal to or greater than 3, 10,
20, 50, 100, 200, 500, or 1000 standard cm3 per minute per cm2 of the substrate area
(i.e. growth surface area of the substrate) and equal to or less than 50000, 20000,
10000, or 5000 standard cm3 per minute per cm2 of the substrate area. The growth
surface area may be defined as the useful deposition area, with radius Rs, achieved in
the reactor. This may correspond to a substrate (e.g. for polycrystalline diamond
growth over a single substrate) or a substrate carrier (e.g. for single crystal diamond
growth where the substrate carrier comprises a plurality of individual substrates) or
the diameter of a table on which individual substrates may be placed (e.g. for coating
loose components).
It has been found that operating using a high velocity, axially oriented gas flow
enables higher dopant uptake than previously possible. In addition, using an axially
oriented gas flow arrangement and operating at high velocity gas flow, particularly
when using multiple inlet nozzles, it is possible to uniformly incorporate dopants such
as boron into both single crystal and polycrystalline synthetic CVD diamond material
over large areas.
Optionally, the atomic partial pressure of dopant within the plasma reactor is equal to
or greater than: 20 Pa, 100 Pa, 200 Pa, 400 Pa, 800 Pa, 1200 Pa or 1600 Pa at a
microwave frequency in a range 2300 to 2600 MHz ; 10 Pa, 50 Pa, 100 Pa, 200 Pa,
400 Pa, 600 Pa, 800 Pa, or 1000 Pa at a microwave frequency in a range 800 to 1000
MHz; 5 Pa, 25 Pa, 50 Pa, 100 Pa, 200 Pa, 300 Pa, 400 Pa, or 500 Pa at a microwave
frequency in a range 400 to 500 MHz. It has been found that increasing the atomic
partial pressure of dopant within the plasma reactor can lead to an increase in the
concentration of dopant which is incorporated into synthetic CVD diamond material
to achieve high levels of doping. Here, the partial pressure of the dopant is calculated
as the partial pressure of the dopant containing gaseous species multiplied by the
number of dopant atoms per molecule of the dopant containing gaseous species.
Optionally, the flow rate of carbon containing gas in the process gases is equal to or
greater than 5, 10, 15, 20, 30, or 40 seem. It has been found that increasing the flow
rate of carbon containing gas increases the uptake of dopants such as boron in the
solid phase.
Figure 5 shows a plot indicating the relationship between resistivity of a synthetic
CVD diamond film and boron concentration. The metallic conduction regime is
reached at a boron concentration of approximately 4 x 102 cm 3 . Figure 6 shows a
plot indicating how boron uptake varies as a function of the quantity of boron in the
reaction gas (5% CH4 in H2) using a single axially oriented gas inlet nozzle and a
microwave frequency of 2450 MHz. A total gas flow rate of approximately 600 seem
was utilized and boron containing species were introduced into the gas phase leading
to a linear increase in boron uptake with boron concentration in the reaction gas until
approximately 4 x 10 19 cm 3 . However, further increasing boron in the reaction gas
had no significant further impact on boron uptake as deduced using SIMS. The
desired metallic conduction regime as indicated by the points in the red circle
(approximately 4 x 102 cm 3 boron atoms in the solid phase) was only achieved by
reducing the gas inlet nozzle diameter while maintaining a high total gas flow rate so
as to increase the gas flow velocity.
Figures 7 and 8 illustrate the relative dependencies of carbon and boron containing
gas flow on solid boron concentration in synthetic CVD diamond material.
Experiments were conducted with certain process conditions kept fixed (including 2
mm inlet nozzle diameter, 2.75 kW microwave generator power, a microwave
frequency of 2450 MHz, and 90 torr process pressure). For a fixed boron containing
gas flow and increasing carbon containing gas flow, the solid boron concentration as
measured by secondary ion mass spectrometry (SIMS) increases from 2 1020 cm 3 to
3xl0 2 1 cm 3 as illustrated in Figure 7 . Correspondingly, the resistivity of the synthetic
boron doped CVD diamond material decreases from 8.6 c 10 2 W-cm to 7.7 c 10 4 W-
cm. Furthermore, for a fixed carbon containing gas flow and increasing boron
containing gas flow, the solid boron concentration as measured by SIMS increases
from 20 3 2 x 10 cm to 2 x 2 1 cm 3 as illustrated in Figure 8 . Correspondingly, the
resistivity of the synthetic boron doped CVD diamond material decreases from
1.9xlO 2 Q-cm to l.l xlO 3 W-cm.
PressurePower Density and Substrate Temperature
In addition to the above, it has been found that providing a gas inlet as previously
described enables higher gas flow rates and operating pressures to be utilized within
the plasma chamber without arcing occurring within the plasma chamber. Higher
operating flow rates and pressures enable higher power densities which equates to a
more reactive plasma, i.e. more atomic hydrogen is generated to facilitate increased
growth rates and improved quality of CVD diamond product.
It has surprisingly been found that the usable ranges for the synthesis parameters of
pressure and power density for the manufacture of synthetic CVD diamond material
can be altered by changes in the gas dynamics (flow, geometry etc) for a given gas
composition. Typically the upper limit for uniform diamond synthesis in terms of the
parameters pressure and power is determined by the onset of mono-polar arcs. Those
skilled in the art will know that this mono-polar arc limit is affected by experimental
factors such as the operating frequency, pressure/power ratio and also the geometry
(diameter/thickness) of the substrate.
The present inventors found it surprising that manipulating the gas flow can have a
dramatic effect on increasing the operating parameter space in terms of pressure and
power while simultaneously not reducing the area of CVD diamond deposition or the
uniformity of said deposition. An often encountered limitation in the pressure/power
parameter space for growing CVD diamond is the onset of arcing. Embodiments of
this invention allow growth of CVD diamond material at higher power densities and
pressures than in a conventional synthesis system. In practise the inventors have
found that the maximum pressure for operation is increased by >5%, >10%, >15%,
>20%, >25%, >30%, or >35% over that which would normally be possible with
alternative gas inlet geometries/flows. Furthermore this increase in operating pressure
is not at any expense of uniform deposition area. For example, in the case of an
operating frequency in a range 800 to 1000 MHz, uniform growth may be achieved to
form a disk of CVD diamond having uniform thickness over a diameter in the range
70 to 160 mm. Thickness uniformity may be calculated by measuring the thickness of
the CVD diamond disk at various points and calculating the percentage deviation
from a mean thickness. For example, at least 10, 15, 17 or 20 measurement points
may be taken over at least 70% of a total area of the disk. In accordance with certain
embodiments of the present invention the maximum growth thickness variation may
be equal to or less than 30%, 25%, 20%, 15%, 10%, 5%, or 2% of a mean thickness of
the synthetic CVD diamond disk.
Using embodiments of the present invention it is possible to avoid the problem of
arcing within the plasma chamber at operating pressures equal to or greater than: 100,
200, 220, 240, 260, 280, 300, 320, 340, 360, 380, or 400 Torr at a microwave
frequency in a range 2300 to 2600 MHz; 120, 140 160, 180, 200, 220, 240, or 260
Torr at a microwave frequency in a range 800 to 1000 MHz; or 60, 70, 80, 100, 120,
140, or 150 Torr at a microwave frequency in a range 400 to 500 MHz. The operating
pressure may be equal to or less than 550, 450, 400, 350, or 300 Torr depending on
the specific reactor design. For example, a typical operating pressure using a gas inlet
nozzle array according to certain embodiments of the present invention may be in the
range 200 to 330 Torr for a microwave frequency in a range 2300 to 2600 MHz, 160
to 220 Torr for a microwave frequency in a range 800 to 1000 MHz, or 80 to 140 Torr
for a microwave frequency in a range 400 to 500 MHz. Using embodiments of the
present invention it has been found that it is possible to achieve a uniform stable
plasma at these pressures and uniform CVD diamond growth.
Figure 9 shows how the threshold for formation of monopolar arcs can be a very
sensitive function of gas flow. In the example shown, the arcing threshold for
substantially uniform growth of synthetic CVD diamond material on a 120 mm
substrate in an 896 MHz microwave plasma reactor increased from 228 Torr to 262
Torr for a total gas flow change from 3 to 6.0 slpm (standard litres per minute)
through six 3 mm diameter gas inlet nozzles arranged in a circular geometry having
an array diameter of 37 mm.
Figure 10 illustrates a similar trend showing that substantially uniform synthetic CVD
diamond growth over large areas and at high pressure operation is only achievable by
using high gas flow rates. As in the previously described example, a 120 mm
substrate was with a process gas composition comprising 4% CH4 diluted in H2.
However, in this case a hexagonal array of 19 gas inlet nozzles was utilized, each
nozzle having a diameter of 0.5 mm. Figure 10 also illustrates that the gas flow
operating window for limiting arc formation decreases in size as the operating
pressure increases. As such, the gas flow rate may be carefully selected and
controlled so as to be maintained within the stability window for a particular gas inlet
nozzle configuration to achieve substantially uniform synthetic CVD diamond growth
over large areas and at high operating pressure without the onset of arcing.
Figure 11 illustrates how the threshold for formation of monopolar arcs varies with
Reynolds number. The experimental conditions were as described for Figure 10.
This Figure shows that the Reynolds number operating window for limiting arc
formation decreases in size as the operating pressure increases. As such, the Reynolds
number may be carefully selected and controlled so as to be maintained within the
stability window for a particular gas inlet nozzle configuration to achieve substantially
uniform synthetic CVD diamond growth over large areas and at high operating
pressure without the onset of arcing.
Figure 12 illustrates how growth rate of synthetic CVD diamond material varies with
flow rate and number of gas inlet nozzles up to a limit at which arcing occurs. The
left hand line in Figure 12 is for a gas inlet nozzle array comprising 19 nozzles
whereas the right hand line is for a gas inlet nozzle array comprising 9 1 nozzles. In
both cases, the diameter of each nozzle was 0.5 mm. The Figure shows that growth
rate increases with flow rate for both nozzle configurations but that a higher flow rate
and a higher growth rate is achievable prior to onset of arcing using a larger number
of nozzles.
The flow characteristics of embodiments of the present invention also allow the
plasma reactor to be operated at high power while constraining the plasma to avoid
damaging the walls of the chamber and/or the microwave window. The high velocity,
highly uniform gas flow within the plasma chamber achieved by embodiments of the
present invention allows more power to be introduced at high pressures without the
plasma arcing.
Power densities which can be delivered to the substrate may be equal to or greater
than 0.05, 0.1, 0.5, 1, 1.5, 2.0, 2.5, 2.75, 3.0, 3.2, or 3.5 W/mm2 of the substrate
growth surface. The power density may be equal to or less than 6.0, 5.0, or 4.0
W/mm2 of the substrate growth surface depending on the specific reactor design. For
example, a typical operating power density using a gas inlet nozzle array according to
certain embodiments of the present invention may be in the range 3.0 to 4.0 W/mm2
of the substrate growth surface.
The power delivered to the substrate also increases with high velocity, highly uniform
gas flow, increasing efficiency. That is, a fraction of the total power which is
delivered to a substrate is increased. Typically this enables at least 45%, 50%, 55%,
60%, 6 5%, or 70% of power fed into the plasma chamber to be transmitted through
the base of the chamber (opposite to the gas inlet). It has been found that the power
transmitted through the base of the chamber approximately equates to hydrogen flux
towards the base of the chamber. Accordingly, increasing the power fed through the
base of the chamber increases the hydrogen flux to the substrate over the base of the
chamber which leads to better quality diamond material being formed over the
substrate. It has also been found that utilizing high axial gas flows helps improve the
stability of the plasma, leading to more uniform deposition in terms of both growth
thickness and quality.
While J . Achard, F. Silva et al. have described that increasing the microwave power
density leads to a decrease in boron uptake during CVD diamond growth, the present
inventors have found that high boron uptake levels can be achieved at high microwave
power densities by using high velocity axial gas flow. This allows better quality
doped CVD diamond material to be produced. It may also be noted that the
advantageous technical effects of increased pressure and/or power can be applied to
plasma chemistries which do not require the dopant as specified in certain aspects of
this invention.
In addition to the above, during CVD diamond growth it is advantageous to maintain
the substrate on which the CVD diamond material is growing at a temperature in the
range 600 to 1300°C, 700 to 1300°C, or 750 to 1200°C. Combining the gas flow
conditions as described herein with such substrate growth temperatures allows
relatively thick, high quality CVD diamond material to be formed which contrasts
with lower temperature thin CVD diamond coatings of metal tools and the like.
Products
Using the previously described apparatus and methods it has been possible to provide
more efficient and consistent ways of producing existing products and also produce
new products which have not previously been achievable.
According to one aspect of the present invention it is possible to produce large
synthetic polycrystalline CVD diamond wafers have a high dopant uniformity. For
example, synthetic polycrystalline CVD diamond wafers having a longest dimension
equal to or greater than 70 mm, 80 mm, 90 mm, 100 mm, 110 mm, 120 mm, 130 mm,
135 mm, 140 mm, 145 mm or 150 mm may be produced comprising a dopant having
a concentration which varies by no more than 50%, 40%, 30%, 20%, 10%, or 5% of a
mean value over at least 70% 80%, 90%, or 95% of the volume of the synthetic
polycrystalline CVD diamond wafer. In this regard, it should be noted that individual
concentration measurements are taken over multiple grains of the polycrystalline
material. That is, the measurements are taken on a macroscopic, multi-grain scale. At
a scale approach the size of individual grains, concentration variations will occur, for
example due to different crystallographic faces having different concentrations of
dopant. As such, the technique used for individual measurements must be broad
enough to provide a local average over multiple grains. A plurality of such
measurements may then be taken at different positions across the wafer. Preferably at
least 70%, 80%, 90%, or 95% of the measurements fall within the previously stated
concentration ranges. Secondary Ion Mass Spectroscopy (SIMS) may be utilized for
measuring dopant concentrations. A spot size area typically 60 mih in diameter may
be used for single crystal measurements. For polycrystalline samples, the spot size
may be increased to 250 mih in diameter and the average of 4 separate measurements
may be taken to obtain a local average.
The synthetic polycrystalline CVD diamond wafer may have a thickness of at least
0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.75 mm, 1 mm, 1.25 mm, 1.5 mm, or 2
mm. Furthermore, the synthetic polycrystalline CVD diamond wafer may have a
thickness variation equal to or less than 30%, 25%, 20%, 15%, 10%, 5%, or 2% of a
mean thickness. Variations/uniformity values can be calculated as [(max-min)/mean]
x 100.
The methods described herein are particularly useful for manufacturing large area
wafers, e.g. equal to or greater than 140 mm in diameter. However, embodiments also
allow better quality smaller diameter wafers to be made when compared with other
methods.
Depending on the desired application the dopant may be selected from one of
nitrogen, boron, silicon, sulphur, and phosphorous and may be incorporated into the
synthetic polycrystalline CVD diamond wafer at a concentration of at least 10 14 cm 3 ,
10 15 cm 3 , 10 16 cm 3 , 1017 cm 3 , 1018 cm 3 , 1019 cm 3 , 1020 cm 3 , 2 x 1020 cm 3 , 4 x 1020
cm 3 , 6 x 1020, 8 x 1020 cm 3 , 102 1 cm 3 , 2 x 102 1 cm 3 , 4 x 102 1 cm 3 , 6 x 102 1, 8 x 102 1
cm 3 , or 1022 cm 3 .
Due to the high operating powers achievable using embodiments of the present
invention it is possible to produce very high quality material with low levels of
graphite and other undesirable impurities.
Figures 13 and 14 illustrate how boron uniformity may vary in synthetic
polycrystalline CVD diamond material as a function of gas inlet nozzle diameter. The
Figures show contour plots indicating variations in resistivity across a wafer of
polycrystalline CVD diamond material. The resistivity will vary with a variation in
boron concentration within the wafer. Figure 13 illustrates the results for a wafer
formed using larger nozzle diameters (six 3.0 mm nozzles in this particular
configuration) indicating some variation in resistivity and thus boron concentration.
In contrast, Figure 14 illustrates the results for a wafer formed in an analogous manner
but using a gas inlet configuration with smaller nozzle diameters (six 2.5 mm nozzles
in this particular configuration) indicating substantially uniform resistivity and thus
boron concentration across the wafer. Furthermore, it may be noted that the resistivity
of the wafer formed using narrower diameter gas inlet nozzles is low indicating high
boron uptake across the entire wafer.
Figures 15 and 16 illustrate how boron uniformity may vary in synthetic
polycrystalline CVD diamond material as a function of gas inlet nozzle spacing.
Again, the Figures show contour plots indicating variations in resistivity across a
wafer of polycrystalline CVD diamond material. Figure 15 illustrates the results for a
wafer formed using relatively closely spaced nozzles (six nozzles disposed in a
circular array having an array diameter of 25 mm in this particular configuration)
indicating some variation in resistivity and thus boron concentration. In contrast,
Figure 16 illustrates the results for a wafer formed in an analogous manner but using a
gas inlet configuration with less closely spaced nozzles (six nozzles disposed in a
circular array having an array diameter of 37 mm in this particular configuration)
indicating substantially uniform resistivity and thus boron concentration across the
wafer.
The previously described resistivity measurements were made using a four point
probe technique. Four point probe measurements are routinely used in assessing the
resistivity of doped silicon wafers in the semiconductor industry. The four point
probe technique removes the effects of any contact resistances encountered. The
probe itself has four tungsten carbide pins arranged in a line. The four probes are
placed in contact with the material to be measured and a current is applied between
the two outer pins. The voltage is then measured between the two inner pins. The
distance between the pins on the four point probe are large relative to the thickness of
the material, for example the thickness of the wafer may be less than 40% of the
spacing between each contact probe, and the polycrystalline wafer is assumed to be
semi-infinite in lateral dimensions. These two conditions allow a limiting case to be
considered where the sheet resistivity is first calculated. This sheet resistivity is given
by:
Where:
• V is the measured voltage across the two inner pins of the four point probe
• I is the current applied to the two outer pins of the four point probe
• k is a geometric factor which in this case is equal to
In 2
This sheet resistivity (Rs) is then multiplied by the thickness of the material to give the
resistivity of the material (p).
For each wafer, 17 points were measured using the four point probe. This consisted
of one centre point, 8 points around the edge of the wafer and a further 8 points
located on a circle midway between the centre and edge of the wafer. These same 17
points were used to measure the thickness of the wafer. Thus each point on the wafer
has a thickness and an associated resistance measurement. Contour plots representing
the resistivity of the wafer were then produced using these 17 measured points.
Synthetic polycrystalline diamond wafers may have a mean resistivity equal to or less
than 10 Ohm-cm, 1 Ohm-cm, 10 1 Ohm-cm, or 10 2 Ohm-cm. Furthermore, the wafers
may have a resistivity which varies by no more than ±30%, ±20%, ±10%, or ±5% of a
mean resistivity for at least 70%, 80%>, 90%, or 95% of at least 17 measurement
points taken across at least 70% 80%, 90%, or 95% of an area of the synthetic
polycrystalline diamond wafer. Preferably, the measurement method is as previously
described above.
It may be noted that when the dopant is boron, it is often easier to measure dopant
uniformity indirectly using the aforementioned resistivity measurement technique
rather than directly measure the concentration uniformity of boron atoms within the
synthetic polycrystalline CVD diamond wafer. Accordingly, a further aspect of the
present invention provides a synthetic polycrystalline CVD diamond wafer, said wafer
having a longest dimension equal to or greater than 135 mm, 140 mm, or 145 mm and
comprising boron dopant, wherein said wafer has a resistivity which varies by no
more than ±30%, ±25%, ±20%, ±15%, ±10%, or ±5% of a mean resistivity for at least
70%, 80% , 90%, or 95% of at least 17 measurement points taken across at least 70%
80% , 90%, or 95% of an area of the synthetic polycrystalline diamond wafer. For
example, at least 90% of the measurement points may fall with ±25% of the mean
resistivity, at least 80% or 90% of the measurement points may fall within ±20% of
the mean resistivity, at least 60%, 70%, 80% or 90% of the measurement points may
fall with ± 15% of the mean resistivity, and most preferably at least 60%, 70%, 80% or
90% of the measurement points may fall with ±10% of the mean resistivity.
For smaller diameter polycrystalline CVD diamond wafers an even higher degree of
uniformity can be obtained. Accordingly, another aspect of the present invention
provides a synthetic polycrystalline CVD diamond wafer, said wafer having a longest
dimension equal to or greater than 70 mm, 80 mm, or 90 mm and comprising boron
dopant, wherein said wafer has a resistivity which varies by no more than ±20%,
±15%, ±10%, or ±5% of a mean resistivity for at least 70%, 80%, 90%, or 95% of at
least 17 measurement points taken across at least 70% 80%, 90%, or 95% of an area
of the synthetic polycrystalline diamond wafer. For example, at least 90% of the
measurement points may fall with ±20% of the mean resistivity, at least 80% or 90%
of the measurement points may fall within ±15% of the mean resistivity, at least 70%,
80% or 90% of the measurement points may fall with ±10% of the mean resistivity,
and most preferably at least 60%, 70%, 80% or 90% of the measurement points may
fall with ± 5% of the mean resistivity.
According to another aspect of the present invention it is possible to produce a layer
of synthetic single crystal CVD diamond material, said layer having a thickness
greater than 50 m i, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.75 mm, 1 mm, 1.25
mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 5mm, 8mm, or 10 mm and comprising a dopant
having a concentration equal to or greater than 2 1020 cm 3, 4 x 1020 cm 3, 5 x 1020
cm 3, 7 x 1020 cm 3, 1 x 102 1 cm 3, or 2 x 102 1 cm 3 . Preferably, the concentration of
dopant varies by no more than 50%, 30%, 20%, 10%, or 5% of a mean concentration
over at least 70% 80%, 90%, or 95% of the volume of the layer of synthetic single
crystal CVD diamond material.
Again, due to the high operating powers achievable using embodiments of the present
invention it is possible to produce very high quality material with low levels of
graphite and other undesirable impurities. As such, the synthetic single crystal CVD
diamond material may comprise a dopant ratio x / y equal to or greater than 2, 5, 10,
20, 50, 100, 500, or 1000, where x is an intentional dopant which may be added to the
process gas in a controlled manner to a desired concentration and y is unintentional
dopant which may be present as an impurity in the process gas.
Further still, the dopant can be introduced into the synthetic single crystal CVD
diamond material while maintaining low levels of extended defects such as
dislocations. As such, the single crystal layer may comprise a concentration of
dislocation features no more than 105, 104, 103 cm and a birefringence no more than
4xl0 4 , lxlO 5 , 5xl0 5 , lxlO 6 .
The layer of synthetic single crystal CVD diamond material is grown on a substrate
having a growth surface oriented substantially in a { 111}, { 1 13}, { 1 10}, or {100}
crystallographic plane (e.g., at least within 15°, 10°, or 5° of said crystallographic
plane) so as to produce a doped single crystal layer orientated in a { 111}, { 1 13},
{ 1 10}, or {100} crystallographic plane. Furthermore, the layer of synthetic single
crystal CVD diamond material at the thickness grown shows no, or substantially no,
twins or large doping non-uniformities characteristic of defective growth.
In one particular example, the layer of synthetic single crystal CVD diamond material
is grown on a substrate having a growth surface oriented substantially in a {100}
crystallographic plane (e.g., at least within 15°, 10°, or 5° of a {100} crystallographic
plane) so as to produce a doped single crystal layer orientated in a {100}
crystallographic plane. In this regard, it should be noted that the uptake of dopant
varies according to the crystallographic orientation of the growing CVD diamond
layer. Conventionally, most synthetic single crystal CVD diamond material is grown
in a {100} crystallographic orientations for reasons of growth rate, morphology, and
low uptake of dopants. However, it has not previously been possible to incorporate
high levels of dopant into this orientation of synthetic single crystal CVD diamond
material. In contrast, using the apparatus and methods described herein it has been
found to be possible to achieve high dopant levels in this crystallographic orientation,
e.g. equal to or greater than 2 x 1020 cm 3 , 4 x 1020 cm 3 , 5 x 1020 cm 3 , 7 x 1020 cm 3 , 1
x 102 1 cm 3 , or x 102 1 cm 3 .
In addition to the above, it is possible to vary the concentration of dopant during a
growth run to form a synthetic CVD diamond material comprising doped and
undoped layers and/or layers having different concentrations of dopant. For example,
conductive and semi-conductive component features may be formed within a
synthetic single crystal CVD diamond to achieve electronic device structures such as
diodes and transistors. While such structures have been proposed in the art,
embodiments of the present invention allow a higher degree of dopant control so as to
achieve better functional performance. For example, a layered synthetic single crystal
CVD diamond may be formed having a dopant concentration, for example boron,
which varies by at least a factor of 3, 10, 30, 100, 300, 1000, 30000, or 100000 over a
thickness of no more than 10 m , 3 m , 1 m , 0.3 mp , 0.1 mp , 0.03 mp , 0.01 mp ,
0.003 mp , or 0.001 mih. Embodiments thus allow the concentration of dopant to be
changed quickly through a thickness of as grown CVD diamond material while
maintaining dopant uniformity across a specific layer within the CVD diamond
material. For example, the dopant level in the CVD diamond material may be ramped
up very quickly from undoped material to form a doped layer or ramped down quickly
to move from a doped layer to an undoped layer over a short distance within the CVD
diamond material. The later has been found to be particularly problematic using prior
art methods. That is, doped layers within a CVD diamond material can be formed
with well defined boundaries using high flow rates directed towards a growth surface
of the CVD diamond material. Furthermore, such well defined layers can be formed
in a single growth run. This can be very important in electronic applications using
boron doped layers. Previous attempts to form very well defined layers have involved
growing a doped layer in one growth run and then transferring the material into
another reactor to grow undoped material thereon as is was found to be difficult to
sharply cut off the dopant being taken up by the synthetic CVD diamond material
during a single growth run. However, this technique inevitably results in impurities,
typically nitrogen or silicon, being incorporated at the interface between the doped
layer and the overlying layer. This problem can be solved by using the methods
described herein to form a sharply defined doped layer in a single growth run. That
is, using high velocity gas flows and/or a suitable Reynolds number can allow the
formation of a synthetic single crystal CVD diamond comprising a doped layer and an
adjacent undoped layer, wherein an interface between the doped and undoped layer is
substantially free of impurities and wherein the dopant concentration varies by at least
a factor of 3, 10, 30, 100, 300, 1000, 30000, or 100000 over a thickness of no more
than 10 mp , 3 mp , 1 mp , 0.3 mp , 0.1 mp , 0.03 mp , 0.01 mp , 0.003 mp , or 0.001 m
across the interface between the doped and undoped layers.
An interface substantially free of impurities may be defined as an interface where, in a
region either side of the interface extending to 20%, 50%, or 100% of a thickness of
the doped layer, the impurity concentration does not exceed 10 14, 3 x 10 14, 1015, 3 x
10 15, 1016, 3 x 10 16, or 101 , and does not vary in concentration by more than a factor
of 2, 3, 5, 10, 30, 100, 300, or 1000. Multiple profile measurements may be taken
across an interface to show that this criteria is met across substantially all the
interface, e.g. a measurement may be made 1, 2, 3, 5, or 10 times at 1 mm spacings
along a line across the interface with all measurements meeting the required criteria.
The layered synthetic single crystal CVD diamond may comprise a doped layer which
has one or more of the characteristics of the layer of synthetic single crystal CVD
diamond material previous described. However, the doped layer may also by made
thinner than the previously described layer of synthetic single crystal CVD diamond
material. For example, the doped layer may have a thickness of at least 1 nm, 5 nm,
10 nm, 20 nm, 50 nm, 100 nm, 500 nm, or 1 m and thus be less thick than the 50 m
limit previous described. Alternatively, a thicker doped layer of at least 50 mih or
more may be provided as previously described. The required thickness will depend
on the desired application. For some electronic applications very thin layers of boron
doped material are desirable. The present invention allows such layers to be made
with well defined upper and lower interfaces, with substantially no interface
impurities, and with high uniformity of dopant in the plane of the layer
In addition to the above, embodiments of the present invention allow a plurality of
synthetic single crystal CVD diamonds to be synthesised at a high growth rate and
doped with a high degree of uniformity in a single CVD growth run. For example, at
least 10, 20, 30, 40, 50, or 60 synthetic single crystal CVD diamonds may be grown in
a single growth run, the synthetic single crystal CVD diamonds having a thickness
which varies by no more than 20%, 10%, or 5% of a mean thickness. In measuring
thickness variations, at least 20, 40, 60, 80, or 100 samples may be measured, e.g. 20
randomly selected single crystals across an array of as grown samples. The
measurements may be such that 100% of the measurements fall within ±10% of a
mean value, at least 90%, more preferably 95%, fall within ±5% of a mean value, at
least 80% , more preferably 85%, fall within ±3% of a mean value, at least 60%, more
preferably 70%, fall within ±2% of a mean value, and at least 30%, more preferably
3 5%, fall within ±1% of a mean value. Furthermore, greater than 80% of the
measured as-grown samples can have a morphology consistent with an alpha
parameter of 2±0.3. Further still, the measured room temperature absorption
coefficient for all of more than 20 randomly selected samples may be one or more of:
equal to or less than 2.5 cm 1 at 270 nm (characteristic of a single substitutional
nitrogen concentration equal to or less than 0.15 ppm); equal to or less than 1.5 cm 1
at 350 nm; and equal to or less than 0.7 cm 1 at 510 nm.
In this regard, Figure 17 illustrates that growth rate of the plurality of single crystals
increases substantially uniformly with an increase in total process gas flow rate. In
this example, the process gas comprises 0.5 ppm added N2 gas in 5% CH4:H2. Sixty
type lb substrates were arranged symmetrically onto a 120 mm substrate. Post growth
analysis shows that their morpology corresponded to an alpha parameter of 2±0.2.
The growth rate of the plurality of synthetic single crystal CVD diamonds varies by
no more than about 3%. As such, a high degree of thickness uniformity (e.g. less than
10%) can be achieved for a total thickness of, for example, 3.3 mm. The nitrogen
concentration as measured using transmission measurement sampling of
approximately 40% of the stone was 0.10±0.05 ppm. As such, uniform nitrogen
uptake in the plurality of single crystals was achieved. Such a process may be used to
form high quality optical CVD diamond material, e.g. for diamond window or Raman
laser applications. The methods described herein can achieve a high degree of
uniformity in terms of optical properties across a plurality of single crystals grown in
a single growth run.
Summary
In light of the above, it will be evident that embodiments of the present invention
enable uniform doping to be achieved over large areas of, for example, polycrystalline
diamond material and/or over a large number of single crystal diamonds grown in a
single growth run. Furthermore, very high levels of doping can be achieved for
electronic and sensor applications.
Embodiments of the present invention have also been able to achieve uniform and
consistent product at high growth rates and over large areas. Furthermore,
embodiments of the present invention have enabled the synthesis of products which
have not been possible to produce using prior art methods such as high boron
concentration single crystal diamond material, particularly {100} oriented single
crystal material.
In addition to improve dopant uniformity in synthetic CVD diamond material, certain
embodiments of the present invention can also improve uniformity of other material
parameters. For example, improvement in uniformity can be measured by one or
more of the following parameters: thickness uniformity of a CVD diamond film
(across the deposition area as defined by Rs) ; uniformity of one or more quality
parameters of the diamond material (e.g. colour, optical properties, electronic
properties); in polycrystalline diamond material, uniformity of texture, surface
morphology, grain size, etc . or in single crystal diamond material where growth
takes place on an array of single crystal diamond substrates on a substrate carrier,
uniformity of thickness, morphology, edge twinning, lateral growth, etc ., between
each single crystal.
The key parameters chosen for assessing uniformity depend on the synthesis process,
the economics of fabricating the final product from the synthesis product, and the
requirements of the final product itself. For example, for an array of single crystal
diamonds, consistent morphology between adjacent crystals enabling efficient
material utilisation may be more important than minor variations in colour,
particularly when the material is used in cutting applications. Conversely, in boron
doped material the uniformity of boron uptake may be the critical factor. The
behaviour of boron in a synthesis reactor is of note here. The tendency is for boron
containing gases to deplete rapidly to adjacent surfaces once the gas is broken down.
Accordingly, achieving uniformity in boron incorporation in a diamond film may be
quite different to achieving uniformity in growth rate or morphology in intrinsic
diamond where depletion of carbon containing species occurs much less quickly.
While this invention has been particularly shown and described with reference to
preferred embodiments, it will be understood to those skilled in the art that various
changes in form and detail may be made without departing from the scope of the
invention as defined by the appendant claims.
Claims
1. A method of manufacturing synthetic CVD diamond material, the method
comprising:
providing a microwave plasma reactor comprising:
a plasma chamber;
one or more substrates disposed in the plasma chamber providing a
growth surface area over which the synthetic CVD diamond material is to be
deposited in use;
a microwave coupling configuration for feeding microwaves from a
microwave generator into the plasma chamber; and
a gas flow system for feeding process gases into the plasma chamber
and removing them therefrom,
injecting process gases into the plasma chamber;
feeding microwaves from the microwave generator into the plasma chamber
through the microwave coupling configuration to form a plasma above the growth
surface area; and
growing synthetic CVD diamond material over the growth surface area,
wherein the process gases comprise at least one dopant in gaseous form,
selected from a one or more of boron, silicon, sulphur, phosphorous, lithium and
beryllium, the or each dopant present at a concentration equal to or greater than 0.01
ppm, and/or nitrogen at a concentration equal to or greater than 0.3 ppm,
wherein the gas flow system includes a gas inlet comprising one or more gas
inlet nozzles disposed opposite the growth surface area and configured to inject
process gases towards the growth surface area, and
wherein the process gases are injected towards the growth surface area at a
total gas flow rate equal to or greater than 500 standard cm3 per minute and/or
wherein the process gases are injected into the plasma chamber through the or each
gas inlet nozzle with a Reynolds number a Reynolds number in a range 1 to 100.
2 . A method according to claim 1, wherein the at least one dopant is injected into
the plasma chamber in a controlled manner or added to one or more source process
gases prior to injection into the plasma chamber.
3 . A method according to claim 1 or 2, wherein the at least one dopant
comprises: one or more of boron, silicon, sulphur, phosphorous, lithium and beryllium
and wherein the process gases comprise less than 0.3 ppm nitrogen; or nitrogen at a
concentration of equal to or greater than 0.3 ppm and wherein the process gases
comprise less than 0.01 ppm of boron, silicon, sulphur, phosphorous, lithium and
beryllium.
4 . A method according to any preceding claim, wherein the at least one dopant is
provided in the process gases at a concentration equal to or greater than 0.05 ppm, 0 .1
ppm, 0.3 ppm, 0.5 ppm, 0.7 ppm, 1 ppm, 3 ppm, 5 ppm, 10 ppm, 20 ppm, 50 ppm,
100 ppm, 200 ppm, 300 ppm, 500 ppm, 700 ppm, or 1000 ppm.
5 . A method according to any preceding claim, wherein the process gases
comprise a ratio of dopant concentration / carbon concentration equal to or greater
than 1 x 10 6 , 10 x 10 6 , 100 x 10 6 , or 1000 x 10 6 .
6 . A method according to any preceding claim, wherein the total gas flow rate
fed through the gas inlet is equal to or greater than 750, 1000, 2000, 5000, 10000,
15000, 20000, 25000, 30000, 35000, or 40000 standard cm3 per minute.
7 . A method according to any preceding claim, wherein the total gas flow fed
through the gas inlet is equal to or greater than 3, 10, 20, 50, 100, 200, 500, or 1000
standard cm3 per cm2 of the growth surface area and equal to or less than 50000,
20000, 10000, or 5000 standard cm3 per cm2 of the growth surface area.
8 . A method according to any preceding claim, wherein the or each gas inlet
nozzle has an outlet diameter in the range 0.1 mm to 5 mm, 0.2 mm to 3.0 mm, 2.0
mm to 3 mm, 0.2 mm to 2 mm, 0.25 mm to 2 mm, or 0.25 mm to 1.5 mm.
9 . A method according to any preceding claim, wherein a minimum distance D
between the gas inlet and the growth surface area is less than or equal to 6RS, 4RS, or
2RS, where Rs is a radius of the growth surface area.
10. A method according to any preceding claim, wherein the process gases are
injected into the plasma chamber through the or each gas inlet nozzle with a Reynolds
number equal to or less than 100, 80, 50, 40, or 35 and at least 1, 5, 10, 15, 20, or 25.
11. A method according to any preceding claim, wherein an operating pressure
within the plasma chamber is equal to or greater than: 100, 200, 220, 240, 260, 280,
300, 320, 340, 360, 380, or 400 Torr at a microwave frequency in a range 2300 to
2600 MHz; 120, 140 160, 180, 200, 220, 240, or 260 Torr at a microwave frequency
in a range 800 to 1000 MHz; or 60, 70, 80, 100, 120, 140, or 150 Torr at a microwave
frequency in a range 400 to 500 MHz.
12. A method according to any preceding claim, wherein at least 45%, 50%, 55%,
60%, 6 5%, or 70% of power fed into the plasma chamber is transmitted through a
base of the plasma chamber disposed opposite to the gas inlet.
13. A method according to any preceding claim, wherein a power density
delivered to the growth surface area is equal to or greater than 0.05, 0.1, 0.5, 1, 1.5,
2.0, 2.5, 2.75, 3.0, 3.2, or 3.5 W/mm2 of the growth surface area.
14. A method according to any preceding claim, wherein the gas inlet comprises
an inlet nozzle array comprising a plurality of gas inlet nozzles disposed opposite the
growth surface area and configured to inject process gases towards the growth surface
area.
15. A method according to claim 14, wherein the gas inlet nozzle array comprises
equal to or greater than 6, 7, 9, 10, 15, 20, 30, 40, 60, 90, 120, 150, 200, 300, 500,
700, 1000, 1200, 1500 gas inlet nozzles.
16. A method according to claim 14 or 15, wherein the gas inlet nozzle array
comprises:
a gas inlet nozzle number density equal to or greater than 0.1 nozzles/cm 2,
wherein the gas inlet nozzle number density is measured by projecting the nozzles
onto a plane whose normal lies parallel to the central axis of the plasma chamber and
measuring the gas inlet number density on said plane; and
a nozzle area ratio of equal to or greater than 10, wherein the nozzle area ratio
is measured by projecting the nozzles onto a plane whose normal lies parallel to the
central axis of the plasma chamber, measuring the total area of the gas inlet nozzle
area on said plane, dividing by the total number of nozzles to give an area associated
with each nozzle, and dividing the area associated with each nozzle by an actual area
of each nozzle.
17. A method according to claim 16, wherein the gas inlet nozzle number density
is equal to or greater than 0.2, 0.5, 1, 2, 5, or 10 nozzles/cm 2.
18. A method according to claim 16 or 17, wherein the gas inlet nozzle number
density is equal to or less than 100, 50, or 10 nozzles/cm 2.
19. A method according to any one of claims 16 to 18, wherein the nozzle area
ratio is equal to or greater than 30, 100, 300, 1000, or 3000.
20. A method according to any one of claims 16 to 19, wherein the nozzle area
ratio is equal to or less than 100000, 30000, or 10000.
21. A method according to any one of claims 16 to 20, wherein a ratio of total
nozzle area / area of the gas inlet nozzle array is equal to or less than 0.5, 0.35, 0.3,
0.2, 0.1, 0.05, 0.02, 0.01, or 0.007.
22. A method according to any one of claims 16 to 21, wherein a total area of
nozzles in the gas inlet nozzle array, given in mm2, is in a range 1 to 5000, 5 to 3000,
10 to 3000, 20 to 2750, 30 to 2750, or 50 to 2700.
23. A method according to any one of claims 16 to 22, wherein a total area of the
gas inlet nozzle array over which the gas inlet nozzles are spaced, given in mm2, is in
a range 100 to 15000, 200 to 15000, 400 to 10000, 800 to 10000, or 1000 to 8000.
24. A method according to any one of claims 16 to 23, wherein the gas inlet
nozzle array comprises a hexagonal close-packed array of gas inlet nozzles.
25. A method according to any one of claims 16 to 24, wherein the gas inlet
nozzles are disposed in a substantially parallel or divergent orientation relative to a
central axis of the plasma chamber.
26. A method according to any one of claims 16 to 25, wherein a maximum radius
of the gas inlet nozzle array Rm meets the criteria: Rm x Fm is greater than or equal to
Rs, where Rs is a radius of the growth surface area and Fm is equal to or greater than
0.5, 0.6, 0.7, 0.8, 0.9, or 1 and equal to or less than 1.5, 1.3, 1.2, or 1.1.
27. A method according to any preceding claim, wherein a synthetic
polycrystalline CVD diamond wafer is grown, the synthetic polycrystalline CVD
diamond wafer comprising the at least one dopant at a concentration which varies by
no more than 50%, 40%>, 30%>, 20%>, 10%>, or 5%> of a mean concentration over at least
70%, 80%, 90%, or 95% of the volume of the synthetic polycrystalline CVD diamond
wafer.
28. A method according to any on of claims 1 to 26, wherein at least 10, 20, 30,
40, 50, 60, 80 or 100 synthetic single crystal CVD diamonds are grown in a single
growth run, wherein the synthetic single crystal CVD diamonds having a thickness
which varies by no more than 20%>, 10%>, 5%>, 3%>, 2%, or 1%> of a mean thickness.
29. A method according to any preceding claim, wherein the atomic partial
pressure of dopant within the plasma reactor is equal to or greater than: 20, 100, 200
Pa, 400 Pa, 800 Pa, 1200 Pa or 1600 Pa at a microwave frequency in a range 2300 to
2600 MHz ; 10, 50, 100, 200 Pa, 400 Pa, 600 Pa, 800 Pa, or 1000 Pa at a microwave
frequency in a range 800 to 1000 MHz; 5 Pa, 25 Pa, 50 Pa, 100 Pa, 200 Pa, 300 Pa,
400 Pa, or 500 Pa at a microwave frequency in a range 400 to 500 MHz.
30. A synthetic polycrystalline CVD diamond wafer, said wafer having a longest
dimension equal to or greater than 140 mm and comprising at least one dopant having
a concentration which varies by no more than 50%> of a mean concentration over at
least 70% of the volume of the synthetic polycrystalline CVD diamond wafer.
31. A synthetic polycrystalline CVD diamond wafer according to claim 30,
wherein the concentration varies by no more than 40%, 30%>, 20%, 10%>, or 5% over
at least 70%, 80%, 90%, or 95% of the volume of the synthetic polycrystalline CVD
diamond wafer.
32. A synthetic polycrystalline CVD diamond wafer according to claim 30 or 31,
wherein the dopant is selected from one or more of nitrogen, boron, silicon, sulphur,
phosphorous, and lithium.
33. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 32, wherein the synthetic polycrystalline CVD diamond wafer comprises
said dopant at a concentration of at least 10 14 cm 3, 10 15 cm 3, 10 16 cm 3, 10 17 cm 3,
10 18 cm 3 , 10 19 cm 3 , 1020 cm 3 , 2 x 1020 cm 3 , 4 x 1020 cm 3 , 6 x 1020, 8 x 1020 cm 3 ,
102 1 cm 3 , 2 x 102 1 cm 3 , 4 x 102 1 cm 3 , 6 x 102 1, 8 x 102 1 cm 3 , or 1022 cm 3 .
34. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 33, wherein the synthetic polycrystalline CVD diamond wafer has a
thickness of at least 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.75 mm, 1 mm, 1.25
mm, 1.5 mm, or 2 mm.
35. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 34, wherein the synthetic polycrystalline CVD diamond wafer has a
longest dimension of at least 145 mm or 150 mm.
36. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 35, comprising a dopant ratio x / y equal to or greater than 2, 5, 10, 20,
50, 100, 500, or 1000, where x is said dopant and y is one or more different impurities
selected from the group consisting of boron, nitrogen and silicon.
37. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 36, having a resistivity equal to or less than 10 Ohm-cm, 1 Ohm-cm, 10 1
Ohm-cm, or 10 2 Ohm-cm.
38. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 37, having a resistivity which varies by no more than ±30%, ±20%,
±10%, or ±5% of a mean resistivity for at least 70%, 80%, 90%, or 95% of at least 17
measurement points taken across at least 70% 80%>, 90%, or 95% of an area the
synthetic polycrystalline diamond wafer.
39. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 38, having a thickness variation equal to or less than 30%, 25%, 20%,
15%, 10%, 5%, or 2% of a mean thickness.
40. A layer of synthetic single crystal CVD diamond material, said layer having a
thickness greater than 50 mih and comprising boron dopant having a concentration
equal to or greater than 2 x 102 cm 3 .
41. A layer of synthetic single crystal CVD diamond material according to claim
40, wherein the layer has a thickness of at least 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5
mm, 0.75 mm, 1 mm, 1.25 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 5mm, 8mm, or 10
mm.
42. A layer of synthetic single crystal CVD diamond material according to claim
40 or 41, wherein the dopant concentration is equal to or greater than 4 x 102 cm 3 , 5
x 1020 cm 3 , 7 x 1020 cm 3 , 1 x 102 1 cm 3 , or 2 x 102 1 cm 3 .
43. A layer of synthetic single crystal CVD diamond material according to any
one of claims 40 to 42, comprising a dopant ratio x / y equal to or greater than 2, 5,
10, 20, 50, 100, 500, or 1000, where x is said dopant and y is one or more different
impurities selected from the group consisting of boron, nitrogen and silicon.
44. A layer of synthetic single crystal CVD diamond material according to any
one of claims 40 to 43, wherein the layer has a birefringence equal to or less than
4xl0 4 , lxlO 5 , 5xl0 5 , or lxlO 6 .
45. A layer of synthetic single crystal CVD diamond material according to any
one of claims 40 to 44, the layer comprises a concentration of dislocation features no
more than 105, 104, or 103 cm 2 .
46. A layer of synthetic single crystal CVD diamond material according to any
one of claims 40 to 45, wherein the layer is orientated in a {100} crystallographic
plane.
47. A layer of synthetic single crystal CVD diamond material according to any
one of claims 40 to 46, wherein a concentration of said dopant varies by no more than
50%, 40%, 30%, 20%, 10%, or 5% of a mean value over at least 70%, 80%, 90%, or
9 5% of the layer of synthetic single crystal CVD diamond material.
48. A synthetic single crystal CVD diamond comprising a doped layer and an
adjacent undoped layer, wherein an interface between the doped and undoped layer is
substantially free of impurities and wherein the dopant concentration varies by at least
a factor of 3 over a thickness of no more than 10 mih across the interface between the
doped and undoped layers.
49. A synthetic single crystal CVD diamond according to claim 48, wherein the
dopant concentration varies by at least a factor of 10, 30, 100, 300, 1000, 30000, or
100000.
50. A synthetic single crystal CVD diamond according to claim 48 or 49, wherein
the thickness is no more than 3 m , 1 m , 0.3 m , 0 .1 m , 0.03 mi i, 0.01 mi i, 0.003
mih , or 0.001 mih .
51. A synthetic single crystal CVD diamond according to any one of claims 48 to
50, wherein the interface substantially free of impurities is an interface where, in a
region either side of the interface extending to 20%, 50%, or 100% of a thickness of
the doped layer, an impurity concentration does not exceed 10 14, 3 x 10 14, 10 15, 3 x
10 15, 1016, 3 x 10 16, or 101 , and does not vary in concentration by more than a factor
of 2, 3, 5, 10, 30, 100, 300, or 1000.
52. A synthetic polycrystalline CVD diamond wafer according to any one of
claims 30 to 39 made by a method according to any one of claims 1 to 29.
53. A layer of synthetic single crystal CVD diamond material according to any
one of claims 40 to 47 made by a method according to any one of claims 1 to 29.
54. A synthetic single crystal CVD diamond according to any one of claims 48 to
5 1 made by a method according to any one of claims 1 to 29.