Patent ID: 12234570

DETAILED DESCRIPTION

Positively charged substitutional nitrogen (Ns+) is indicative of the presence of defects such as vacancy clusters, distorted spa bonding and extrinsic defects such as NVH. These defects significantly contribute to an observed brown colour in single crystal diamond. On the other hand, the Ns0defect is not typically associated with defects that give rise to a brown colour. However, as higher levels of nitrogen are incorporated into the diamond crystal lattice, the concentration of defects that give rise to the undesirable brown colour also increases. As mentioned above, it is desirable to reduce the brown colour in order to limit the reduction of the coherence time (T2/T2*) of produced NV in such material. Furthermore, increased brown colour leads to higher optical absorption, making light pass less efficiently through the diamond in order to excite an NV centre in the diamond due to absorption of the exciting light source. Similarly, increase brown colour makes it more difficult to detect an optical signal passing through the CVD diamond material due to absorption of that optical signal.

It is desirable to have a high concentration of substitutional nitrogen in the diamond lattice because subsequent annealing gives rise to migration of vacancies towards substitutional nitrogen to form NV centres as discussed above. The inventors have addressed the competing requirements of high nitrogen concentration and low brown colour and produced a high nitrogen CVD diamond material that has improved colour properties.

Referring toFIG.1, there is provided a flow diagram showing exemplary steps for making single crystal CVD diamond. The following numbering corresponds to that ofFIG.1:

S1. A single crystal diamond substrate is located on a substrate holder and then located in a CVD reactor. Note that in a typical process, a plurality of single crystal diamond substrates are located on the substrate holder.

S2. Process gases are fed into the CVD reactor. The process gases comprise between 60 ppm and 200 pm nitrogen, a carbon-containing gas and hydrogen. The ratio of carbon atoms in the carbon-containing gas to hydrogen atoms in the hydrogen gas is between 0.5% and 1.5%. This ratio may be lower than 1.0%

S3. A plasma of the process gases is formed within the reactor and single crystal CVD diamond material is grown on a surface of the single crystal diamond substrate.

Such a process gives rise to a single crystal CVD diamond material that has a total nitrogen concentration of at least 5 ppm and a neutral single substitutional nitrogen, Ns0, to total single substitutional nitrogen, Ns, ratio of at least 0.7. It has surprisingly been found that this gives a material with low brown colouration but a high degree of nitrogen incorporation.

Four exemplary single crystal CVD diamond runs were carried out in an 896 MHz microwave CVD reactor fraction using methane as a carbon process gas and hydrogen, and in the absence of oxygen. The ratio of methane to hydrogen was varied while the pressure and power density was kept at the same level for each run to give a nominal substrate temperature of around 1000° C. It was found that the incorporation efficiency of nitrogen into the diamond matrix was increased with increasing ratio of hydrogen to methane. It was also found that increasing ratio of hydrogen to methane gave rise to an increase in the ratio of neutral single substitution nitrogen)(Ns0compared to total single substitution nitrogen (Ns) which, in turn produced diamond with a decrease in brown colouration.

The substrates were carefully prepared to minimise any defects that could grow into the CVD single crystal diamond using techniques described in WO 2011/076643. The substrates were mounted on a tungsten substrate carrier before placing the substrate carrier in the CVD reactor and growing CVD single crystal diamond. The concentrations of the gases in the synthesis environment were controlled by altering the concentration of the gases in the process gas before inputting the source gas into the CVD reactor. Therefore, the ratios given herein for gas concentrations in the process gas have been determined by the process gas composition before it is inputted into the CVD reactor and have not been measured in the synthesis environment in situ. Growth temperatures and microwave power conditions were similar to those described in WO2010/010352.

Table 1 shows the conditions under which the four exemplary single crystal CVD diamonds were grown at substrate carrier temperatures above 850° C.:

TABLE 1Exemplary single crystal CVD diamond growth conditions.ComparativeExample 1Example 2Example 3Example 4CH4/H2ratio %4.32.21.801.3C in CH4to H2.151.100.900.65in H2ratioN2gas ppm155656565

After growth of the CVD synthetic diamond material, the samples were processed to remove the substrate and create freestanding diamond plates to facilitate optical examination and characterisation of the material.

The ratio of carbon in the carbon-containing gas to hydrogen in the hydrogen containing is given above. Note that the ratio of carbon containing gas to hydrogen will change depending on which carbon containing gas is used and the number of carbon atoms in a molecule of that carbon-containing gas.

It has been found that reducing the CH4to H2ratio in the process gas increases the amount of substitutional nitrogen incorporated in the diamond lattice.

Referring toFIG.2, there is shown a graph showing a relationship between the ratio of CH4and H2in the process gas and the amount of substitutional nitrogen in the resultant synthetic CVD diamond.

The concentration of Ns0present in the synthetic CVD diamond material may be measured using the 270 nm peak using UV-visible absorption spectroscopy at room temperature. Alternatively, the concentration of NV centres, in both neutral and negative charge states, may be quantified by evaluating the integrated intensity under their zero-phonon-lines at 575 nm and 637 nm, respectively when measurements are performed at 77 K. The technique of UV-visible absorption spectroscopy is well-known in the art.

The concentration of Ns0in synthetic CVD diamond material may be found using Fourier-Transform Infrared (FTIR) spectroscopy by measuring infrared absorption peaks at wavenumbers of 1332 cm−1and 1344 cm−1. Using a spectrometer with a resolution of 1 cm−1, the conversion factors between the absorption coefficient values in cm−1for the peaks at 1332 cm−1and 1344 cm−1and the concentrations of single nitrogen in the positively-charged and neutral states respectively are 5.5 and 44. However, it must be noted that the value derived from the 1332 cm−1peak is only an upper limit. FTIR can therefore be used to measure both Ns0and Ns+.

Alternatively, the total concentration of nitrogen may be determined using secondary ion mass spectroscopy (SIMS). SIMS has a lower detection limit for nitrogen in diamond of approximately 0.1 ppm and its use is well-known in the art. For synthetic diamond produced by a CVD method, the vast majority of nitrogen present in the solid is in the form of neutral single substitutional nitrogen, Ns0, and therefore, whilst SIMS measurements of the total nitrogen concentration inevitably provide an upper limit to the concentration of Ns0, they typically also provide a reasonable estimate of its actual concentration.

Alternatively, the amount of Ns0may be determined using electron paramagnetic resonance (EPR). In measurements conducted using EPR, the abundance of a particular paramagnetic defect (e.g. the neutral single-substitutional nitrogen defect, Ns0) is proportional to the integrated intensity of all the EPR absorption resonance lines originating from that centre. This permits the concentration of the defect to be determined by comparing the integrated intensity to that which is observed from a reference sample, provided care is taken to prevent or correct for the effects of microwave power saturation. Since continuous wave EPR spectra are recorded using field modulation, double integration is required to determine the EPR intensity and hence the defect concentration. To minimise the errors associated with double integration, base line correction, finite limits of integration, etc., especially in cases where overlapping EPR spectra are present, a spectral fitting method is employed to determine the integrated intensity of the EPR centres present in the sample of interest. This entails fitting the experimental spectra with simulated spectra of the defects present in the sample and determining the integrated intensity of each from the simulation. In the case of low nitrogen concentrations, it is often necessary to use modulation amplitudes approaching or exceeding the line width of the EPR signals to achieve a good signal/noise ratio, which allows the Nsconcentration to be determined with a reproducibility of better than ±5%. The concentration of NV centres may also be determined using EPR.

Example 2 contained 14 ppm Ns, example 3 contained 16 ppm Nsand example 4 contained 22 ppm Ns. These values were obtained using a combination of Ns0and Ns+concentrations measured by FTIR, as described above on the assumption that other forms of Nswould be present in very low amounts.

It has been found that reducing the CH4to H2ratio in the process gas increases the ratio of neutral single substitutional nitrogen, Ns0, to total single substitutional nitrogen, Ns. In other words, as the CH4to H2ratio reduces, the relative amount of Ns0as a fraction of total Nsincreases.

FIG.3shows a relationship between the ratio of CH4and H2in the process gas and the ratio of neutral single substitutional nitrogen, Ns0, to total single substitutional nitrogen, Ns. Example 2 had a ratio of 0.73, Example 3 had a ratio of 0.81 and example 4 had a ratio of 0.85. Comparative Example 1 had a ratio of around 0.55. For applications where it is desirable to convert substitutional nitrogen into NV centres, a high ratio of Ns0to total Nsis required. Comparative example 1 had a much lower ratio than examples 2 to 4.

It has been found that the higher the amount of Ns0as a fraction of the total amount of Ns, the better the colour of the synthetic CVD diamond material is. ‘Better colour’ is used here to mean that the amount of brown colouration is reduced. This assists with reducing absorption, which means that an NV−centre in a device can be better interrogated without loss of information. Furthermore, a higher fraction of Ns0as a fraction of the total amount of Nsis thought to contribute to a good T2* for an NV centre. It is possible that this is because there are fewer defects that have paramagnetic charge states, and so do not reduce the decoherence time as much.

Turning now to colour, the perceived colour of an object depends on the transmittance/absorbance spectrum of the object, the spectral power distribution of the illumination source and the response curves of the observer's eyes. The CIE L*a*b* chromaticity coordinates (and therefore hue angles) referred to below have been derived in the way described below. Using a standard D65 illumination spectrum and standard (red, green and blue) response curves of the eye, CIE L*a*b* chromaticity coordinates of a parallel-sided plate of diamond have been derived from its transmittance spectrum using the relationships below, between 350 nm and 800 m with a data interval of 1 nm:

Sλ=transmittance at wavelength λ

Lλ=spectral power distribution of the illumination

xλ=red response function of the eye

yλ=green response function of the eye

zλ=blue response function of the eye
X=Σλ[SλxλLλ]/Y0
Y=Σλ[SλyλLλ]/Y0
Z=Σλ[SλzλLλ]/Y0
Where Y0=ΣλyλLλ

L* = 116 (Y/Y0)1/3− 16 = Lightness(for Y/Y0> 0.008856)a* = 500[(X/X0)1/3− (Y/Y0)1/3](for X/X0> 0.008856, Y/Y0>0.008856)b* = 200[(Y/Y0)1/3− (Z/Z0)1/3](for Z/Z0> 0.008856)C* = (a*2+ b*2)1/2= saturationhab= arctan (b*/ a*) = hue angle
L*, the lightness, forms the third dimension of the CIE L*a*b* colour space. The lightness and saturation vary as the optical path length is changed for diamond with particular optical absorption properties. This can be illustrated on a colour tone diagram in which L* is plotted along the y-axis and C* is plotted along the x-axis. The method described in the preceding paragraph can also be used to predict how the L*C* coordinates of diamond with a given absorption coefficient spectrum depend on the optical path length.

The C* (saturation) numbers can be divided into saturation ranges of 10 C* units.

It was observed that the L* values are independent of Ns0over the ranges measured, but L* decreases with increasing Ns+. As the total Nsis typically made of up Ns0with the bulk of the balance being Ns+, it has been observed that L* increases with increasing ratio of Ns0to Ns, as shown inFIG.4. A higher L* value is indicative of a lighter material, hence the diamond with a higher ratio of Ns0to Nsis less brown than diamond material with a lower ratio of Ns0to Ns.

A strong relationship was also observed between e and the ratio of Ns0to Ns, as shown inFIG.5. A lower c* value is indicative of reduced brownness. It can be seen that this relationship did not hold for comparative example 1 (points surrounded by a dashed line) but did hold for values of Ns0to Nsabove 0.70.

The material produced as described above can be treated to convert a proportion of the Ns0centres to N-V centres, which are useful in applications such as sensing or quantum computing. N-V centres are typically formed by irradiation and annealing. The annealing may be performed during or after irradiation. NV centres attracted a lot of interest as a useful quantum spin defect because it has several desirable features including:(i) Its electron spin states can be coherently manipulated with high fidelity owing to an extremely long coherence time (which may be quantified and compared using the transverse relaxation time T2);(ii) Its electronic structure allows the defect to be optically pumped into its electronic ground state allowing such defects to be placed into a specific electronic spin state even at non-cryogenic temperatures. This can negate the requirement for expensive and bulky cryogenic cooling apparatus for certain applications where miniaturization is desired. Furthermore, the defect can function as a source of photons which all have the same spin state; and(iii) Its electronic structure comprises emissive and non-emissive electron spin states, which allows the electron spin state of the defect to be read out through photons. This is convenient for reading out information from synthetic diamond material used in sensing applications such as magnetometry, spin resonance spectroscopy and imaging. Furthermore, it is a key ingredient towards using the NV− defects as qubits for long-distance quantum communications and scalable quantum computation. Such results make the NV−defect a competitive candidate for solid-state quantum information processing (QIP).

A problem in producing materials suitable for quantum applications is preventing quantum spin defects such as NV−from decohering, or at least increasing the time a system takes to decohere (i.e. lengthening the “decoherence time”). A long T2time is desirable in applications such as quantum computing as it allows more time for the operation of an array of quantum gates and thus allows more complex quantum computations to be performed. A long T2time is also desirable for increasing sensitivity to changes in the electric and magnetic environment in sensing applications. T2* is the inhomogeneous spin-spin relaxation time and is shorter than T2as it includes interactions with the environment. For sensing applications, T2* is the coherence time relevant for DC magnetic-field sensing, whereas methods that measure/utilize T2only detect AC contributions.

One way to increase the decoherence time of quantum spin defects is to ensure that the concentration of other point defects within the synthetic diamond material is low so as to avoid dipole coupling and/or strain resulting in a decrease in decoherence time of the quantum spin defects. However, for thin plates of material (for example, plates of material with a thickness below 100 μm), it has been found that this is still insufficient to achieve very high decoherence times.

Reducing the concentration of the quantum spin defects themselves can increase decoherence times of individual quantum spin defects. However, while this will increase the sensitivity of each individual quantum spin defect, a reduction in the number of quantum spin defects will reduce the overall sensitivity of the material. What is considered important for many quantum sensing applications is the product of the NV−defect concentration and the decoherence time T2* of the NV−defects. Preferably, this product should be at least 2.0 ppm μs at room temperature. A higher ratio of Ns0to Nsgives an improved product value. While the inventors are unaware of a theoretical maximum value for the product, it is currently thought that a product of around 10 ppm·μs is achievable.

Further samples were prepared in order to measure the product of [NV−] and T2*. Sample 5 contained 14.2 ppm [Ns0] post synthesis. This was electron irradiated and annealed to create 2.5 ppm [NV−] and had a T2* (measured at room temperature using a Ramsey method as described below) of 1.0 μs. Thus the [NV]·T2* product was 2.5 ppm·μs for example 5.

Example 6 contained 12.7 ppm [Ns0] post synthesis. This was electron irradiated and annealed to create 2.6 ppm [NV−] and had a T2* (measured at room temperature using a Ramsey method as described below) of 1.1 μs. Thus the [NV]·T2* product was 2.9 ppm·μs for example 6.

Values for T2* have been determined via a Ramsey pulse sequence. The simplest on-resonance decay in the NV luminescence (free-induction-decay or “FID”) would be single exponential with the desired characteristic decay time T2*. However, in order to improve the visibility of the decay from the background noise it is typical to detune the microwave frequency slightly away from the resonant NV frequency (the line position as observed in an ODMR frequency scan). This introduces additional oscillations, which are more easily discriminated from the shot-noise background. However for NV, depending on the chosen RF power level, multiple resonance lines for a single NV− defect (or a group of commonly-aligned NV− defects) may be observed, due to the14N hyperfine interaction (14N has nuclear spin 1).

The experimentally observed FID is therefore commonly fitted to a decay given by the following expression:
I=exp[−(τ/T*2)∈]Σm=−1m=+1βmcos[2π(δ+mAN)τ]
where τ is the free procession time interval, ε is a factor to permit the quality of the fit to be improved (ε=1.0 is ideal), βmis the weighting of each hyperfine contribution (β1,2,3=⅓ is ideal) and δ is the detuning away from the central NV line position.

By least-square fitting the determined FID curve to the expression in the above equation, the optimum value of T2* can be determined. This is taken to be the NV−T2* value, with an uncertainty defined by the quality of fit.

It is known that different irradiating and annealing regimes can lead to an increased concentration of [NV−] in diamond, and it is likely that further irradiation and annealing of similar materials to examples 5 and 6 would increase [NV−] without reducing T2*, and so an [NV]·T2* product with such recipes is higher.

For sensing applications where the NV−centre is used, the single crystal synthetic CVD diamond material may be grown with a thickness of anywhere from around 100 nm to around 4 mm, although it might typically be grown to a thickness of between 500 nm and 50 μm.

Furthermore, where the single crystal synthetic CVD diamond material is to be used in sensing applications, it may be overgrown onto a further diamond material with a much lower concentration of solid substitutional nitrogen, as shown inFIG.6.FIG.6shows a composite diamond 1 having a first layer 2 of diamond grown as described above with a total nitrogen concentration of at least 5 ppm and a neutral single substitutional nitrogen, Ns0, to total single substitutional nitrogen, Ns, ratio of at least 0.70, and a second layer 3 of diamond with a total nitrogen concentration lower than that of the first layer 2. This may be achieved by growing one layer on top of the other, or altering the source gases in the microwave reactor to create layers with different concentrations of nitrogen. An advantage of this is that the second layer of diamond 3 is not grown under the same conditions as the first layer, and so a less expensive growth regime may be used for the second layer that grows diamond that is less pure or grows more quickly. This composite diamond 1 therefore has a high nitrogen layer in which irradiated and annealed NV−centres can be used, but has an overall thickness that allows for easier handling and mechanical strength. A further advantage of this technique is that making the first layer sufficiently thin allows generated NV− centres to be effectively isolated when viewed throughout the thickness of the composite diamond 1.

Similarly, overgrowth techniques using masking can be used to give a material with a first surface region of diamond with a total nitrogen concentration of at least 5 ppm and a neutral single substitutional nitrogen, Ns0, to total single substitutional nitrogen ratio of at least 0.70, and an adjacent second surface region with a total nitrogen concentration lower than that of the first surface region. For example, the second layer described can be grown, a mask placed over the second layer, and the first layer overgrown so that the first layer only grows on the second layer in a region exposed by the mask. Further masking can be used to build more complicated layers with different types of diamond on different parts of the surface.

Owing to the low number of defects, the optical birefringence of the material is typically such that at a temperature of 20° C., in a sample measured over an area of at least 3 mm×3 mm, for 98% of the area analysed, the sample remains in first order (δ does not exceed π/2), and the maximum value of Δn[average], the average value of the difference between the refractive index for light polarised parallel to the slow and fast axes averaged over the sample thickness does not exceed 5×10−5. A description of this measure of birefringence may be found in WO 2004/046427.

For some applications where NV−centres are required, the presence of13C can be detrimental to the properties of the diamond as it has a non-zero nuclear spin. It therefore may be preferred to use a carbon containing gas in the source gas that in which at least 99% of the carbon is12C, at least 99.9% of the carbon is12C or at least 99.99% of the carbon is12C.

This allows synthetic CVD diamond to be produced with a high level of incorporated nitrogen but still acceptable levels of brown colouration for use in sensing applications where the NV−centre is used. It has been found that the brown colouration can be controlled by controlling the ratio of carbon in a carbon-containing source to hydrogen atoms in the hydrogen gas, which in turn affects the ratio of Ns0to total Nsincorporated in the resultant CVD synthetic diamond. The ratio of Ns0to total Nsaffects the colour of the diamond and a higher ratio leads to less brown colouration.

Turning back toFIG.6, and as described above, an issue comes when growing the first layer on a second layer of very low nitrogen diamond (as known in the art, for example https://doi.orq/10.1088/1361-6463/ab81d1), because strain from the second layer will also be present in the first layer, and be deleterious to the sensing properties of the first layer. Additionally, attempting to grow a thin-layer (of <100 μm) of the first layer directly on the second layer prohibits the use of long etches that are typically used to mitigate interface-induced strain, as these have a detrimental effect on the morphology and smoothness of the final surface.

The inventors have realised that by growing a first diamond layer and treating it to form NV−centres, and subsequently overgrowing a second layer with a lower concentration of NV−centres, the strain in the first layer can be greatly reduced compared to overgrowing a first layer on a low nitrogen substrate. In this manner, the inventors have recognised that the strain in the second, lower-concentration NV−region of the composite material is unimportant as this is merely used to collect NV−emission or act as a supporting medium for the first layer. Moreover, the substrate used for growth of the first layer described above may have a higher Nsconcentration, as this is removed in the process of creating a substrate from the first-layer material.

FIG.7shows exemplary steps to form a composite diamond, with the following numbering corresponding to that ofFIG.7.

S4. A first layer of single crystal diamond is provided that contains nitrogen and has a uniform strain such that over an area of at least 1×1 mm, at least 90 percent of points display a modulus of strain-induced shift of NV resonance of less than 200 kHz, wherein each point in the area is a resolved region of 50 μm2(see below for further discussion of the strain measurement). Strain uniformity is important as strain gradients are a source of decoherence for NV ensembles spin properties. The easiest way to achieve a uniform strain is to reduce it to as low a value as possible over the whole sample area. The modulus of strain-induced shift of NV resonance may be selected from any of less than 150 kHz, less than 100 kHz, less than 50 kHz, and less than 25 kHz.

The first layer, in one embodiment, is CVD single crystal diamond material that is grown on a diamond substrate that has a low defect density at the surface to ensure that intrinsic strain in the first layer is minimised. After growth of the first layer, it is removed from the substrate by any conventional means. The first layer has a relatively high nitrogen content (typically of the order of 1 ppm or higher) to ensure that it has enough nitrogen for subsequent conversion to NV−centres. Alternatively, the first layer may be HPHT single crystal.

S5. The first single crystal diamond layer is treated to convert at least some of the nitrogen to form nitrogen-vacancy, NV−, centres, such that after treatment the first single crystal diamond body has an NV−concentration of at least 0.3 ppm. The treatment typically comprises irradiating and subsequently annealing the first single crystal diamond layer, as is known in the art. Note that in the case where the first layer is single crystal CVD diamond, this treatment can take place before or after removal of the substrate. Depending on the starting concentration of nitrogen, and the conditions of irradiation and annealing, the NV−concentration may be selected from any of at least 0.5 ppm, at least 0.8 ppm and at least 1.0 ppm.

S6. A CVD process is used to grow a second single crystal diamond body on a surface of the first single crystal diamond body. The second single crystal diamond body has an NV−concentration less than or equal to 10 times lower than the NV−concentration in the first single crystal diamond body, thereby forming the diamond composite body comprising a first layer of the first single crystal diamond body and a second layer of the second single crystal diamond body.

This second layer may be low luminescence material such as the very low nitrogen containing diamond that is used conventionally. However, it is also possible to use a second layer that has a higher nitrogen content, which can be used to increase growth rates, provided the NV−concentration remains much lower than that of the first layer. As the treatment to convert nitrogen to NV−centres has been carried out before the second layer is grown, the high nitrogen content in the second layer will consist mostly of single substitutional nitrogen, and the concentration of NV−centres is still much lower than that of the first layer. Depending on the NV− concentration in the first and second layers, the second single crystal diamond layer may have an NV−concentration selected from less than 20 times, less than 50 times and less than 100 times lower than the NV−concentration in the first diamond layer.

S7. As an option, an exposed surface (which will ultimately be a sensing surface in a device) of the first layer is deterministically processed to provide any of a desired thickness profile, a desired surface profile and a desired surface pattern. Whether or not deterministic processing is applied the first single crystal diamond layer may have a thickness selected from any of 100 nm to 100 μm, 200 nm to 80 μm, and 500 nm to 50 μm.

The low strain in the first layer has an effect on the birefringence. At a temperature of 20° C., the first layer has an optical birefringence such that in a sample measured over an area of at least 3 mm×3 mm, for 98% of the area analysed, the sample remains in first order (δ does not exceed π/2), and the maximum value of Δn[average], the average value of the difference between the refractive index for light polarised parallel to the slow and fast axes averaged over the sample thickness does not exceed 5×10−5.

As described above, a product of a concentration of NV−defects and decoherence time T2* in the first diamond layer may be selected from any of at least 2.0 ppm·μs, at least 2.5 ppm·μs, at least 3 ppm·μs, and at least 5 ppm·μs. The presence of non-uniform strain would otherwise had a deleterious effect on these numbers. It is known that higher strains reduce the T2* values.

In order to measure the strain in the first layer, a technique is used as described in “Imaging crystal stress in diamond using ensembles of nitrogen-vacancy centers”, Kehayias et. al., Phys. Rev. B 100, 174103. This paper describes a micrometer-scale-resolution quantitative stress imaging method with millimeter-scale field-of-view for diamonds containing a thin surface layer of nitrogen-vacancy (NV) centres, such as those described above. Stress tensor elements are reconstructed over a two-dimensional field of view from NV optically detected magnetic resonance (ODMR) spectra to study how stress inhomogeneity affects NV magnetometry performance.

A portion of the surface of the first layer is imaged over an area of at least 1×1 mm. Within this area, at least 90 percent of points display a modulus of strain-induced shift of NV resonance of less than 200 kHz. Each point in the area is a resolved region of 50 μm2. This gives an indication of the uniformity of the strain.

On the surface of the first layer, there may be discontinuities or damage that could cause local region of strain. In an embodiment, the 2 mm×2 mm area is located within a central 70% of the area of the surface in order to avoid high strain regions that might be found toward the edges of a single crystal sample. Within this area, there are no series of more than 1000 contiguous points having a modulus of strain-induced shift of NV resonance lines exceeding 150 kHz. In a further embodiment, there may be no series of more than 500 contiguous points having a modulus of strain-induced shift of NV resonance lines exceeding 150 kHz. An example of a region of contiguous points is illustrated inFIG.8, in which a map of the strain shift over a 2×2 mm area has a small region of higher strain shift, as shown by contiguous darker points.

By obtaining a first layer with a uniform strain before applying another layer to form a composite single crystal diamond, the problems associated with growing the first layer by a CVD process on a substrate such as a low nitrogen substrate are avoided.

The invention as set out in the appended claims has been shown and described with reference to embodiments. However, it will be understood by 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 appended claims, and while exemplary methods have been described, it may be that other methods may be used to obtain the diamond material of the appended claims.