Method for growing single crystal diamond assisted by polycrystalline diamond growth

Abstract

To provide a method for growing a single crystal diamond, supported by polycrystal diamond growth in order to improve the size and quality of the single crystal diamond.SOLUTION: A method for growing a single crystal diamond, supported by polycrystal diamond growth comprises thermally bonding a diamond seed on the upper surface of a substrate holder and providing a growth surface for combining the single crystal diamond and the polycrystal diamond. A predetermined temperature difference between the diamond seed and the substrate holder during treatment forms a single crystal diamond growth rate different by a predetermined amount from a polycrystal growth rate with plasma process conditions. Process gas is introduced in order to grow both the single crystal diamond and the polycrystal diamond on the growth surface to form plasma; and the polycrystal diamond grown to be adjacent to the single crystal diamond improves growth quality over the growing single crystal diamond by shielding the side surface of the growing single crystal diamond.SELECTED DRAWING: Figure 1

Description

[Background technology]

[0001] The headings used herein are for organizational purposes only and are not to be construed in any way as limiting the subject matter described herein.

[0002] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is a nonprovisional adaptation of U.S. Provisional Patent Application No. 62 / 945,180, entitled "Lateral Enlargement for Single Crystal Diamond Growth Using Plasma Chemical Vapor Deposition," filed December 8, 2019. The entire contents of U.S. Provisional Patent Application No. 62 / 945,180 are incorporated herein by reference.

[0003] (Introduction) The market for synthetic diamond is growing rapidly. This is at least in part due to diamond's many desirable material properties, such as excellent hardness, chemical stability, low thermal expansion, high thermal conductivity, wide electronic bandgap, and wide optical transmittance. Grown diamond material is currently used in a large and growing number of applications, including, for example, abrasives, electronics, optics, experimental physics, and jewelry. The increasing demand for grown diamond drives the need for improved equipment and methods that can efficiently produce high-quality, large-sized single-crystal diamonds. Summary of the Invention [Means for solving the problem]

[0004] The present specification also provides, for example, the following items: (Item 1) 1. A method for growing single crystal diamond assisted by polycrystalline diamond, comprising: a) thermally bonding a diamond seed onto a top surface of a substrate holder to provide a growth surface for a combined single crystal diamond and polycrystalline diamond substrate, wherein during processing there is a predetermined temperature difference between the diamond seed and the substrate holder, the temperature difference causing a single crystal diamond growth rate in a direction perpendicular to the top surface of the diamond seed to differ from a polycrystalline diamond growth rate in a direction perpendicular to the top surface of the diamond seed by a desired amount; b) providing a process gas and forming a plasma to grow both single crystal diamond and polycrystalline diamond on the growth surface, wherein the polycrystalline diamond grown adjacent to the single crystal diamond shields lateral surfaces of the growing single crystal diamond from the plasma and the process gas, thereby improving thermal uniformity across the growing single crystal diamond; A method comprising: (Item 2) 2. The method of claim 1, further comprising providing a spacer between the diamond seed and the substrate holder, the spacer adjusting the height of the diamond seed relative to the top surface of the substrate holder and changing the growth rate of the diamond seed in a direction perpendicular to the top surface of the diamond seed relative to the growth rate of the polycrystalline diamond in a direction perpendicular to the top surface of the diamond seed. (Item 3) Item 1. The method of claim 1, further comprising providing a spacer between the diamond seed and the substrate holder, the spacer adjusting the height of the diamond seed and changing the growth rate of the diamond seed in a direction perpendicular to the top surface of the diamond seed relative to the growth rate of the diamond seed in a lateral direction. (Item 4) 2. The method of claim 1, wherein the providing of the process gas and forming the plasma is provided such that there is a temperature difference of greater than 25°C across the growth surfaces of the combined single crystal diamond and polycrystalline diamond substrate during at least a portion of the growth. (Item 5) Item 10. The method of claim 1, wherein the diamond seed comprises a single crystal diamond. (Item 6) 2. The method of claim 1, wherein providing the process gas and forming the plasma to grow both the single crystal diamond and the polycrystalline diamond on the growth surface is carried out such that the single crystal growth rate in a direction perpendicular to the top surface of the diamond seed exceeds the polycrystalline growth rate in a direction perpendicular to the top surface of the diamond seed. (Item 7) Item 10. The method of item 1, wherein the substrate holder comprises molybdenum. (Item 8) Item 10. The method of item 1, wherein the substrate holder comprises tungsten. (Item 9) Item 10. The method of item 1, wherein the substrate holder comprises silicon. (Item 10) Item 10. The method of item 1, wherein the substrate holder comprises silicon carbide. (Item 11) Item 10. The method of item 1, wherein the substrate holder comprises diamond. (Item 12) Item 10. The method of item 1, wherein the top surface of the substrate holder comprises a recess for supporting the diamond seed. (Item 13) Item 10. The method of item 1, wherein the top surface of the substrate holder is formed with a polished surface. (Item 14) Item 10. The method of item 1, wherein the top surface of the substrate holder is formed with a textured finish. (Item 15) Item 10. The method of claim 1, further comprising attaching the diamond seed to the holder using a thermally conductive material. (Item 16) Item 10. The method of item 1, further comprising attaching the diamond seed to the holder using a material having a thermal expansion coefficient selected to reduce stress in the single crystal material during growth. (Item 17) Item 10. The method of item 1, further comprising mounting the diamond seed on the substrate holder such that a desired temperature difference exists between the diamond seed and the substrate holder during growth. (Item 18) 2. The method of claim 1, further comprising selecting an adhesive material for attaching the diamond seed to the substrate holder such that a desired temperature differential exists between the diamond seed and the substrate holder during growth. (Item 19) 2. The method of claim 1, wherein thermally bonding the diamond seed onto the top surface of the substrate holder is performed by bonding the seed to the holder using a material that reduces stress caused by thermal expansion. (Item 20) 2. The method of claim 1, wherein thermally bonding the diamond seed onto the top surface of the substrate holder is performed such that a temperature difference exists between the diamond seed and the polycrystalline material during growth. (Item 21) 2. The method of claim 1, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma comprises forming a pressure in the process chamber above 50 Torr. (Item 22) 2. The method of claim 1, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma comprises establishing a temperature at the growth surface in the range of 600°C to 1,400°C. (Item 23) 2. The method of claim 1, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma results in a final thickness of the polycrystalline material that is 20% to 150% of the final thickness of the single crystal material. (Item 24) Item 10. The method of item 1, further comprising changing the holder after a predetermined growth period. (Item 25) 2. The method of claim 1, further comprising varying process conditions during said growth to maintain a desired relative growth rate of said single crystal and polycrystalline materials. (Item 26) 2. The method of claim 1, further comprising modifying process conditions during the growth to maintain desired growth characteristics of the single crystal material. (Item 27) 10. The method of claim 1, further comprising producing a plate of single crystal diamond material by cutting the grown single crystal diamond. (Item 28) Item 14. The method of item 1, wherein the mass of the grown single crystal diamond is greater than 1 gram in a single process step. (Item 29) Item 1. The method of item 1, wherein the mass of the grown single crystal diamond is greater than 2 grams in a single process step. (Item 30) 2. The method of claim 1, wherein providing a process gas includes providing hydrogen, oxygen, and a carbon-containing gas. (Item 31) 31. The method of claim 30, further comprising providing argon proximate to the growth surface of the seed. (Item 32) 2. The method of claim 1, wherein thermally bonding the diamond seed onto the top surface of the substrate holder to provide the growth surface of the combined single crystal diamond and polycrystalline diamond substrate comprises thermally bonding a plurality of diamond seeds onto the top surface of the substrate holder to provide a plurality of growth surfaces of a plurality of combined single crystal diamond and polycrystalline diamond substrates. (Item 33) 1. A method for growing single crystal diamond assisted by polycrystalline diamond, comprising: a) thermally bonding a diamond seed onto a top surface of a substrate holder to provide a growth surface for a combined single crystal diamond and polycrystalline diamond substrate, wherein during processing there is a predetermined temperature difference between the diamond seed and the substrate holder, the temperature difference causing a desired relative growth rate of single crystal diamond in a direction lateral to the top surface of the diamond seed relative to the growth rate of single crystal diamond in a direction perpendicular to the top surface of the diamond seed; b) providing a process gas and forming a plasma to grow both single crystal diamond and polycrystalline diamond on the growth surface, wherein the polycrystalline diamond grown adjacent to the single crystal diamond shields lateral surfaces of the growing single crystal diamond from the plasma and the process gas, thereby improving thermal uniformity across the growing single crystal diamond; A method comprising: (Item 34) 34. The method of claim 33, further comprising providing a spacer between the diamond seed and the substrate holder, the spacer adjusting the height of the diamond seed relative to the top surface of the substrate holder to achieve the relative growth rate. (Item 35) 34. The method of claim 33, wherein the desired relative growth rate is less than two-fold. (Item 36) 34. The method of claim 33, wherein the desired relative growth rate is greater than one-half. (Item 37) 34. The method of claim 33, wherein providing the process gas and forming the plasma is provided such that there is a temperature difference of greater than 25° C. across the growth surface during at least a portion of the growth. (Item 38) Item 34. The method of item 33, wherein the diamond seed comprises a single crystal diamond. (Item 39) Item 34. The method of item 33, wherein the substrate holder comprises molybdenum. (Item 40) Item 34. The method of item 33, wherein the substrate holder comprises tungsten. (Item 41) Item 34. The method of item 33, wherein the substrate holder comprises silicon. (Item 42) Item 34. The method of item 33, wherein the substrate holder comprises silicon carbide. (Item 43) Item 34. The method of item 33, wherein the substrate holder comprises diamond. (Item 44) Item 34. The method of item 33, wherein the top surface of the substrate holder comprises a recess for supporting the diamond seed. (Item 45) Item 34. The method of item 33, wherein the top surface of the substrate holder is formed with a polished surface. (Item 46) Item 34. The method of item 33, wherein the top surface of the substrate holder is formed with a textured finish. (Item 47) Item 34. The method of item 33, further comprising attaching the diamond seed to the holder using a thermally conductive material. (Item 48) 34. The method of claim 33, further comprising attaching the diamond seed to the holder using a material having a thermal expansion coefficient selected to reduce stress in the single crystal material during growth. (Item 49) 34. The method of claim 33, further comprising mounting the diamond seed in the holder such that a desired temperature difference exists between the diamond seed and the polycrystalline material during growth. (Item 50) 34. The method of claim 33, further comprising selecting an adhesive material for attaching the diamond seed to the holder such that a desired temperature differential exists between the diamond seed and the polycrystalline material during growth. (Item 51) Item 34. The method of item 33, wherein thermally bonding the diamond seed onto the top surface of the substrate holder is performed by bonding the seed to the holder using a material that reduces stress due to thermal expansion. (Item 52) Item 34. The method of item 33, wherein thermally bonding the diamond seed onto the top surface of the substrate holder is performed such that a temperature difference exists between the diamond seed and the polycrystalline material during growth. (Item 53) 34. The method of claim 33, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma comprises forming a pressure in the process chamber above 50 Torr. (Item 54) 34. A method according to claim 33, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma comprises establishing a temperature at the growth surface in the range of 600°C to 1,400°C. (Item 55) Item 34. The method of item 33, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma results in a final thickness of the polycrystalline material that is 20% to 150% of the final thickness of the single crystal material. (Item 56) 34. The method of claim 33, further comprising changing the holder after a predetermined growth period. (Item 57) 34. The method of claim 33, further comprising varying process conditions during said growth to maintain desired relative growth rates of said single crystal and polycrystalline materials. (Item 58) 34. The method of claim 33, further comprising modifying process conditions during the growth to maintain desired growth characteristics of the single crystal material. (Item 59) 34. A method according to claim 33, further comprising producing a plate of single crystal diamond material by cutting the grown single crystal diamond. (Item 60) Item 34. The method of item 33, wherein the mass of the grown single crystal diamond is greater than 1 gram. (Item 61) Item 34. The method of item 33, wherein the mass of the grown single crystal diamond is greater than 2 grams. (Item 62) 34. The method of claim 33, wherein providing the process gas comprises providing hydrogen, oxygen, and a carbon-containing gas. (Item 63) 63. The method of claim 62, further comprising providing argon. (Item 64) 34. The method of claim 33, wherein thermally bonding the diamond seed onto the top surface of the substrate holder to provide the growth surface of the combined single crystal diamond and polycrystalline diamond substrate comprises thermally bonding a plurality of diamond seeds onto the top surface of the substrate holder to provide a plurality of growth surfaces of a plurality of combined single crystal diamond and polycrystalline diamond substrates. (Item 65) 1. A single crystal diamond material grown in a single uninterrupted step to a dimension equal to or greater than 6 millimeters, said single uninterrupted step comprising: a) thermally bonding a diamond seed onto a top surface of a substrate holder to provide a growth surface for a combined single crystal diamond and polycrystalline diamond substrate, wherein during processing there is a predetermined temperature difference between the diamond seed and the substrate holder, the temperature difference causing a single crystal diamond growth rate in a direction perpendicular to the top surface of the diamond seed to differ from a polycrystalline diamond growth rate in a direction perpendicular to the top surface of the diamond seed by a desired amount; b) providing a process gas and forming a plasma to grow both single crystal diamond and polycrystalline diamond on the growth surface, the polycrystalline diamond grown adjacent to the single crystal diamond shielding lateral surfaces of the growing single crystal diamond from the plasma and the process gas, thereby improving thermal uniformity across the growing single crystal diamond; 2. A single crystal diamond material made by a process including: (Item 66) Item 66. The method according to item 65, wherein the ratio of the growth rate of the polycrystalline diamond grown adjacent to the single crystal diamond to the growth rate of the single crystal diamond grown perpendicular to the upper surface of the diamond seed is within the range of 20% to 150%. (Item 67) 1. A single crystal diamond material grown in a single uninterrupted step to a weight equal to or greater than 2 grams, said single uninterrupted step comprising: a) thermally bonding a diamond seed onto a top surface of a substrate holder to provide a growth surface for a combined single crystal diamond and polycrystalline diamond substrate, wherein during processing there is a predetermined temperature difference between the diamond seed and the substrate holder, the temperature difference causing a single crystal diamond growth rate in a direction perpendicular to the top surface of the diamond seed to differ from a polycrystalline diamond growth rate in a direction perpendicular to the top surface of the diamond seed by a desired amount; b) providing a process gas and forming a plasma to grow both single crystal diamond and polycrystalline diamond on the growth surface, the polycrystalline diamond grown adjacent to the single crystal diamond shielding lateral surfaces of the growing single crystal diamond from the plasma and the process gas, thereby improving thermal uniformity across the growing single crystal diamond; 2. A single crystal diamond material made by a process including: (Item 68) Item 68. The method according to item 67, wherein the ratio of the growth rate of the polycrystalline diamond grown adjacent to the single crystal diamond to the growth rate of the single crystal diamond grown perpendicular to the upper surface of the diamond seed is within the range of 20% to 150%. BRIEF DESCRIPTION OF THE DRAWINGS The present teachings, in accordance with preferred exemplary embodiments, together with further advantages thereof, are more particularly described in the following detailed description and considered in conjunction with the accompanying drawings. Those skilled in the art will understand that the drawings described below are for illustrative purposes only. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the present invention. The drawings are not intended in any way to limit the scope of applicant's teachings. [Brief explanation of the drawings]

[0005] [Figure 1]FIG. 1 illustrates a sequence of growth steps using a known single crystal diamond growth substrate holder assembly.

[0006] [Figure 2] FIG. 2 illustrates a cross section of a diamond being grown on a substrate holder for one embodiment of a sequence of growth steps in the single crystal diamond growth apparatus and method of the present teachings.

[0007] [Figure 3] FIG. 3 illustrates a cross section of a seed diamond mounted on a substrate holder using a spacer in one embodiment of the single crystal diamond growth apparatus and method of the present teachings.

[0008] [Figure 4] FIG. 4 illustrates a cross section of a grown diamond used to produce a plate of single crystal diamond material having dimensions larger than a seed material using an embodiment of the single crystal diamond growth apparatus and method of the present teachings. DETAILED DESCRIPTION OF THE INVENTION

[0009] DESCRIPTION OF VARIOUS EMBODIMENTS The present teachings will now be described in more detail with reference to exemplary embodiments thereof, as illustrated in the accompanying drawings. While the present teachings will be described in conjunction with various embodiments and examples, it is not intended that the present teachings be limited to such embodiments. On the contrary, the present teachings encompass various alternatives, modifications, and equivalents, as will be understood by those skilled in the art. Those skilled in the art with access to the teachings herein will recognize additional implementations, modifications, and embodiments, as well as other fields of use, that are within the scope of the present disclosure described herein.

[0010] It should be understood that the individual steps of the methods of the present teachings may be performed in any order and / or simultaneously so long as the present teachings remain operable. Furthermore, it should be understood that the apparatus and methods of the present teachings can include any number or all of the described embodiments so long as the present teachings remain operable.

[0011] The present teachings relate to the growth of single-crystal diamond. Synthetic diamond material has been produced by various means for many years. Early synthetic diamond processing techniques used thermal torches and high-pressure, high-temperature reactors. In the early 1980s, researchers began exploring plasma-enhanced chemical vapor deposition (CVD) techniques to form synthetic diamond films. The deposited films were typically thin or thick films of diamond material deposited on substrates such as silicon, tungsten, and molybdenum. Much of the early development of plasma-enhanced CVD diamond deposition was carried out using microwave-based reactors operating in the general pressure range of 10 to 300 Torr. More recently, some diamond deposition has been carried out using lower-pressure plasma reactors and non-microwave generators. Generally, higher quality films and higher deposition rates have been obtained using higher-pressure microwave systems. See, for example, JE Butler, YA Mankelevich, A. Cheesman, Jie Ma and MNR Ashfold, “Understanding the Chemical Vapor Deposition of Diamond: Recent Progress,” Journal of Physics: Condensed Matter 21 (2009) 364201, IOP Publishing; and F. Silva, K. Hassouni, X. Bonnin and A. Gicquel, “Microwave Engineering of Plasma-Assisted CVD Reactors for Diamond Deposition,” Journal See, for example, J.E. Butler et al., of Physics: Condensed Matter 21 (2009) 364202, IOP Publishing. All references cited herein, including J.E. Butler et al. and F. Silva et al., are hereby incorporated by reference.

[0012] Plasma chemistries for depositing diamond, diamond-like carbon, graphene, and related materials primarily involve hydrogen chemistry with the addition of small amounts of carbon-containing gases (such as methane or acetylene). Other gases can also be added. For example, other gases containing carbon and hydrogen can be used. In addition, other gases such as nitrogen, oxygen, argon, and / or halogen species can be added. Gases containing one or more dopant materials (such as boron) can also be added in combination with other gases. The plasma dissociates a fraction of the hydrogen and carbon-containing species. Atomic hydrogen is a key ingredient because it adsorbs on the growing diamond surface and preferentially etches away non-diamond carbon bonds in favor of diamond bonds. One key to high deposition rates and high-quality film growth is having a high flux of atomic hydrogen at the workpiece surface, which favors the use of plasma systems as opposed to, for example, hot filament systems.

[0013] Generally, single crystal diamond material is grown on a starting substrate, which is itself single crystal diamond. Single crystal diamond material can also be grown on non-single crystal diamond substrates, such as iridium. For the growth of polycrystalline diamond material, a wide choice of substrates exists, including silicon, molybdenum, tungsten, and many other materials.

[0014] Typically, the starting substrate is at a temperature in the range of 600-1,400 °C during growth. To achieve high-rate growth of high-quality diamond material, it is essential that the plasma discharge be sufficiently intense to heat the gas in the core of the plasma discharge to above 2,000 °C. This high gas temperature is necessary to maintain a high degree of dissociation of hydrogen gas into atomic hydrogen, which is important for high-rate growth of high-quality material. Exemplary operating conditions that generate these high gas temperatures are typically a total gas pressure in excess of 20 Torr and a power of 50 W cm. -3 For a preferred high deposition rate, the power delivered into the plasma core is 100 W cm -3 and pressures can exceed 100 Torr, which can result in gas temperatures in the plasma core that can exceed 2,000°C, and in some processes even exceed 3,000°C.

[0015] Plasma discharges may be generated in several different ways. Traditionally, microwave power sources are used, typically at either 2.45 GHz or 915 MHz frequencies, with power levels ranging from as low as 1 kW to over 100 kW. These microwave frequencies are attractive because the energy travels in waves and the structure of the process chamber can allow the discharge to be concentrated near the substrate where deposition occurs, and away from the walls of the process chamber. Specific microwave frequencies can be higher or lower than these values, but these values ​​are typically used because they are reserved for industrial use by international agreements and components are widely available in the commercial market.

[0016] More recently, other frequencies for the power supply and other techniques for coupling power to the plasma discharge have been developed. One example is the toroidal plasma discharge, in which radio frequency (RF) power at 400 kHz is inductively coupled to a closed-loop discharge through a transformer structure. Other RF frequencies can also be utilized to form the toroidal discharge, from as low as 20 kHz to above 14 MHz. Another example is the use of a direct current (DC) discharge as the plasma source in a CVD diamond system.

[0017] One effective technique for CVD diamond deposition is a starting single-crystal diamond substrate, which provides a platform for the growth of diamond material. For some applications, it is desirable to grow the single-crystal diamond material not only perpendicular to the initial growth surface but also parallel to it. Parallel to the initial growth surface means laterally, or on a side of the initial growth surface. This allows the initial diamond "seed" to expand in both the perpendicular and parallel dimensions relative to the initial seed surface. Applications where this is beneficial include, for example, generating substrates for electronic devices and sensors, providing windows for various vacuum applications, producing materials for use in optical systems, producing lab-grown diamond gemstones, and generating diamond material for industrial applications such as cutting tools.

[0018] For some applications, it is desirable to grow thick single crystal diamond material primarily in a direction perpendicular to the initial seed surface. Some applications where this is beneficial include, for example, producing substrates for electronic devices and sensors, providing windows for various vacuum applications, producing materials for use in optical systems, producing lab-grown diamond gemstones, and producing diamond material for industrial applications such as cutting tools. This includes:

[0019] Known methods for growing large area substrates include, for example, co-locating multiple seeds and overlapping growth. These known methods typically result in visible mechanical defects that make the substrate undesirable for some applications.

[0020] Known methods for growing large area substrates include, for example, using cutting a single large seed from natural diamond, however, these known methods are typically very expensive and time consuming to implement.

[0021] It is known in the art that, absent lateral growth of diamond material using chemical vapor deposition, the mass of a finished diamond gem in grams cut from a chemical vapor deposition-grown diamond cannot exceed the maximum possible mass in grams, which can be determined by the formula M=0.002*A**1.5, where A is the area of ​​the seed in square millimeters. See, for example, Charles I. Carmona, Estimating Weights of Mounted Colored Gemstones, Gems and Gemology, Fall 1998. The present teachings relate, at least in part, to diamond substrate apparatus and growth methods that encourage material growth perpendicular to the growth plane and material growth parallel to or lateral to the growth plane. However, it has been determined that using the lateral growth method of the present teachings, there is no limit to the mass of the finished gem relative to the area of ​​the seed. This allows for optimization of the packing and cost of the initial diamond seed and allows for greater gem growth from chemical vapor deposition-grown diamond material than is possible with known methods. Thus, in contrast to known apparatus and methods for growing single crystal diamond, the present teachings allow for the deposition of large pieces of single crystal diamond using either single or multiple growth cycles.

[0022] One feature of the present teachings is that the quality of diamond material can be improved by using only a single or a few growth cycles, as opposed to using many growth cycles. Growth lines or other defects can occur due to stopping and starting the growth process or by significantly modifying growth process parameters during growth, but the reduced number of growth cycles according to the present teachings can eliminate or significantly reduce growth lines or other defects. Stopping and starting the growth process or significantly changing process parameters such as pressure, power, chemistry, or sample temperature can result in such growth lines or other defects that can be visible by eye, under optical magnification, or with other analytical instrumentation. Using a single or a few growth cycles also maximizes reactor utility and minimizes costs, allowing for overall savings in production costs.

[0023] Another feature of the methods and apparatus of the present teachings is that by varying process parameters and / or hardware associated with mounting the sample, the apparatus and methods of the present teachings can be used to reliably control growth in a direction parallel to (lateral to) the growing seed surface. In some embodiments, growth parallel to (lateral to) the initial seed surface can be varied from 0 mm to approximately 2 mm for every millimeter of growth perpendicular to the initial seed surface. In extreme cases, this results in a parallel-to-perpendicular growth ratio of 2.2:1. With additional optimization, the apparatus and methods can further extend the parallel-to-perpendicular growth ratio to greater values, such as 2.5:1 and even 3:1.

[0024] Figure 1 illustrates a growth sequence 100 using a known single crystal diamond growth substrate holder assembly 102. See, for example, U.S. Patent No. 9,732,440. The growing sample 104 is mounted in a holder assembly 102. The holder assembly 102 is used to both expand the growing single crystal diamond material parallel to the initial seed surface 106 of the growing sample 104 and to increase the size of the material perpendicular to the initial seed surface 106. The holder assembly 100 is typically made from molybdenum or another high temperature material to shield the outer edges of the sample 104 from the plasma discharge chemistry, thereby limiting the growth of unwanted polycrystalline diamond material at the edges.

[0025] At each successive step in the growth sequence 100 of the method of Figure 1, additional shielding material is added to the holder assembly 102, which allows the growing shape of the sample 104 to be maintained. However, this requires that each time the process is stopped, the sample 104 be removed, optionally cut and polished, and the holder assembly 102 be modified. The sample 104 must then be reloaded and the process restarted. Using this technique, an expansion of the diamond area by more than two times relative to the starting seed area has been demonstrated. Thus, this technique can provide up to about a 2:1 ratio of parallel to perpendicular growth.

[0026] However, a significant disadvantage of this known approach is that the growth step must be repeated multiple times using different sized holders to generate the area expansion. In addition, material processing between steps is typically required, which may include steps such as laser cutting followed by one or more polishing steps. These additional steps significantly add processing time and cost and increase the probability of damaging the sample 104. As an alternative to changing holders within a process chamber, users can have multiple chambers and sequentially move the sample between chambers, each with a holder optimized for a particular process step.

[0027] Another feature of the present teachings is that there is no requirement to use a substrate holder that must be changed periodically. However, periodically changing the substrate holder can still be used advantageously in the same manner as used in known methods. In particular, it should be understood that some embodiments of the methods and apparatus of the present teachings provide a greater ratio of parallel to perpendicular growth without the need to change the holder. It should also be understood that some embodiments of the methods and apparatus of the present teachings may include aspects of changing the holder to further increase growth and improve the economics of the process. For example, if a particularly large grown diamond sample is desired, it may be practiced to perform multiple holder changes during the growth process.

[0028] In some embodiments of the methods of the present teachings, the growth process is enhanced or optimized to achieve process goals other than achieving a greater ratio of parallel to perpendicular growth. For example, in some methods, rather than enhancing or optimizing the increase in physical size in at least one dimension of the individual growths, it is desirable to enhance or maximize seed packing. In such methods, the desired parallel growth may be zero or near zero.

[0029] In some embodiments of the present teachings, the single crystal diamond seed is thermally attached to a substrate holder, which can have a flat or textured surface or a surface with features to aid in mounting the starting seed. Also, in some embodiments, the single crystal diamond seed is thermally attached to the substrate holder using a material with high or low thermal conductivity and / or a material with a thermal expansion coefficient similar to that of the single crystal material. Various methods according to the present teachings use substrate holder materials in conjunction with adhesive materials to more closely match the coefficients of thermal conductivity.

[0030] In some embodiments, the holder is at a temperature below that of the diamond seeds during processing. The holder may be constructed from several different materials, including, for example, molybdenum, tungsten, silicon, high temperature ceramics, and other materials.

[0031] The holder must be capable of supporting the growth of polycrystalline diamond material at an average growth rate such that the polycrystalline material does not overwhelm the single crystal sample, but is large enough to support the growth of the single crystal material. That is, the holder geometry and temperature and plasma conditions are configured so that polycrystalline material that accumulates in areas not occupied by the seed does not grow significantly up to or beyond the single crystal diamond. The simultaneous growth of both polycrystalline and single crystal material allows the polycrystalline material to help maintain the temperature of the growing single crystal diamond material at a desired value. In addition, the system advantageously limits the growth of undesired polycrystalline material on the edges of the single crystal sample.

[0032] In some methods according to the present teachings, a non-diamond layer of carbon material is formed between single crystal and polycrystalline growth. Such a layer can be formed during some or all of the growth cycle. This can help reduce stresses that might otherwise be introduced by the polycrystalline material into the growing single crystal material.

[0033] FIG. 2 illustrates a cross section 200 of a diamond being grown on a substrate holder 202 for one embodiment of a series of growth steps in the single crystal diamond growth apparatus and method of the present teachings. The configuration of the holder 202 and seed 204 supports an increased surface area of ​​the CVD-grown diamond sample 206, 206′. The single crystal diamond (SCD) sample shown in the figure is the starting seed 204 for growth. The thickness shown in FIG. 2 is only one example of a growth cycle that may be achieved. The schematic cross section is not to scale.

[0034] As can be seen from FIG. 2 , an essential part of the present teachings is that the growth of polycrystalline diamond material on the sample holder 202 (shown as molybdenum in this example) must approximate, but not significantly exceed, the growth of single-crystal diamond in a direction perpendicular to the initial seed. It should be understood that, at certain times, the growth rate of the polycrystalline diamond material may be higher than that of the single-crystal material, as long as the total growth of the polycrystalline diamond material does not significantly exceed the total growth on the single-crystal growth surface during most of the growth process. During the latter part of the growth process, the polycrystalline diamond material may overgrow the single-crystal material. The relative growth rates of the single-crystal and polycrystalline materials 208, 208′ are controlled by at least one of the temperature of the sample exposed to the plasma, the temperature of the sample holder, and the process chemistry. The starting conditions of the sample holder 202 also affect the rate at which polycrystalline growth begins. This starting condition can be used, for example, to give the growth of the single-crystal material a “preferential start.” Thus, even if the growth rates of the polycrystalline material 208, 208' and the CVD grown diamond sample 206, 206' are similar, the single crystal growth will always be thicker than the polycrystalline growth, which may be desirable. The use of a thicker starting seed 204 of single crystal diamond material, or the use of an additional element to elevate the starting seed further above the sample holder 202, also provides a "prior start" for the single crystal growth. An embodiment of the elevated seed is not shown in Figure 2.

[0035] The temperature difference between the single crystal CVD grown diamond sample 206, 206' and the molybdenum holder 202, 304 can be controlled by how the single crystal material seed 204 is thermally bonded to the holder and the power density incident on the single crystal sample seed 204 from the plasma discharge chemistry. In one method, the seed 204 is placed on the surface of the holder 202, and the surface of the holder 202 may be textured to impart specific heat transfer characteristics. A finer texture (polished surface) for the holder 202 may be used. A surface (including a surface) generally provides better heat transfer between the single crystal diamond seed 204 and the holder 202. For example, the surface of the holder 202 can be machined to a finish within a range of 1 to 1,000 microinch radius. The surface of the holder 202 can be machined and / or polished by diamond turning to a finish of 0.2 microinch radius. In one embodiment, a surface holder finish of about 2 to 100 microinch radius is employed.

[0036] A roughened surface for the holder generally provides reduced heat transfer, which can be advantageously used in some processes. In some embodiments, the surface of the holder 202 is constructed with recesses for the seeds 204, which increases the thermal contact between the seeds 204 and the holder 202.

[0037] In some embodiments, the surface of the holder 202 is constructed with pillars or other elevation structures for the seeds 204, which increases the "preferential start" for single crystal growth versus polycrystalline growth. One or more surfaces of the holder may be constructed with texturing, pillars or other structures, cooling channels, recesses, etc.

[0038] Some embodiments of the methods and apparatus of the present teachings vary the temperature difference between the single crystal diamond sample and the holder by bonding the single crystal seed sample to a holder. In these embodiments, the bonding material must be able to withstand the temperature of the growing material and the temperature difference between the growing material and the holder. Examples of bonding materials include metal brazing materials with high thermal conductivity and other bonding materials containing fillers such as aluminum oxide, diamond, other oxides, nitrides, metals, and carbon. Varying the thickness of the bonding material and its composition affects the temperature difference and the difference in thermal expansion coefficients. Bonding the single crystal seed sample to a holder helps maintain consistent thermal contact throughout the duration of the process step and also helps prevent the single crystal seed sample from moving.

[0039] Some embodiments of the methods of the present teachings vary the temperature difference between the single crystal diamond sample seed and the holder by using an intermediate spacer element between the single crystal diamond sample seed and the holder, which adds an additional temperature difference between the holder and the seed.

[0040] 3 illustrates a cross section 300 of a seed diamond 302 mounted on a substrate holder 304 using a spacer 306 in one embodiment of the single crystal diamond growth apparatus and method of the present teachings. It should be understood that the cross section 300 is not to scale, but rather is presented to illustrate the present teachings. One aspect of the present apparatus and method using the spacer 306 is that it has the effect of providing an additional "first start" for the growth of the single crystal sample over polycrystalline diamond growth. Another aspect of the present apparatus and method using the spacer 306 is that it has the effect of increasing the temperature difference between the sample and the holder.

[0041] The volume and thickness of the spacer 306 and the material forming the spacer 306 are chosen to provide the desired temperature difference between the single crystal diamond sample and the sample holder, which therefore means that the single crystal sample has additional "preferential initiation" over polycrystalline growth, and potentially higher growth rates and improved growth metrics and properties.

[0042] The height of the single crystal diamond material is generally higher than the height of the polycrystalline material for most of the growth cycle, but it is possible that in some growth processes the polycrystalline material height may exceed the height of the single crystal sample near the latter part of the growth cycle. It is also possible that polycrystalline material may grow beyond the surface of the single crystal material in some cases. This limits the growth of the single crystal material, but does not necessarily damage the material or prevent its use.

[0043] As the polycrystalline material grows along with the single crystal growth, the temperature tends to equalize between the multiple single crystal growths and between the multiple single crystal growths and the sample holder. The polycrystalline growth rate can then increase over time as the temperature increases. Varying the process conditions over time can help maintain the relative growth rates of the single crystal and polycrystalline material at optimal values.

[0044] One feature of the single-crystal diamond growth method according to the present teachings is that the method can be used to grow specific crystal planes on a single crystal sample at different rates relative to other crystal planes, and these different rates can be precisely and reproducibly controlled by a process engineer. For example, the method and apparatus of the present teachings can be used to achieve lateral expansion of the upper (100) plane. As an example of this feature, consider the case of a starting seed having a (100)-oriented crystal plane. By carefully selecting various process parameters, such as the sample temperature at the growth surface, the pressure in the process chamber, the plasma power, the dimensions and configuration of the sample holder, and various process gas flow rates, the growth rates of the (110), (111), and (113) crystal planes relative to the (100) plane can be precisely and reproducibly controlled. The process parameters and the dimensions and configuration of the sample holder can also be selected to limit the development of stress within the material.

[0045] The growth rates of the (100), (110), (111), and (113) crystallographic planes depend on the temperature and concentration of various reactive gas species. In some methods according to the present teachings, the growth strategy controls the concentration and temperature of radical species across the growing surface. Such methods achieve high and uniform growth rates of single-crystal diamond material without the growth of polycrystalline diamond material on the edges of the growing sample due to the shielding provided by laterally positioned polycrystalline diamond material. Temperature and process chemistry can also be varied as needed during the growth cycle to achieve this.

[0046] The methods and apparatus of the present teachings can be used to fabricate plates of single crystal diamond material, which have parallel dimensions that significantly exceed the corresponding parallel dimensions of the starting seed material. There are numerous applications for such plates, including substrates for gem growth, electronics, sensors, quantum devices, windows for vacuum systems and many other applications, optics, and a variety of industrial applications, including cutting tools.

[0047] The methods and apparatus of the present teachings can be used to fabricate thick plates of single crystal material with little or no insignificant growth in the dimension parallel to the starting seed material. Numerous applications exist for such plates, including substrates for gem growth, electronics, sensors, quantum devices, windows for vacuum systems and many other applications, optics, and various industrial applications, including cutting tools.

[0048] FIG. 4 illustrates a cross section 400 of a grown diamond that is used to produce a plate of single crystal diamond material having dimensions larger than the seed material using certain embodiments of the single crystal diamond growth apparatus and methods of the present teachings. A starting seed 402 of single crystal material is grown to increase both the dimension parallel to the starting surface and the dimension perpendicular thereto. In some methods according to the present teachings, the diamond material is grown such that the dimension parallel to the initial growth surface is 1.5 to 3 times the growth of the dimension perpendicular to the initial growth surface. In one method, the material is grown such that the dimension parallel to the initial growth surface is 1.5 to 3 times the growth of the dimension perpendicular to the initial growth surface. The growth rate of the single crystal diamond material is increased by approximately two times the growth rate of the dimension perpendicular to the growth plane. Some methods according to the present teachings also produce plates of single crystal diamond material having dimensions parallel to the initial growth plane that exceed the dimensions of the starting seed.

[0049] In some methods, the resulting single crystal diamond material has a mass of more than 1 gram. In other methods, the resulting single crystal diamond material has a mass of more than 2 grams. In still other methods, the resulting single crystal diamond material has a mass of more than 5 grams. It has been experimentally determined that there is no inherent upper limit to the growth of single crystal diamond material using methods according to the present teachings other than the spacing between the growing surface of the diamond material and the plasma, and the spacing between multiple samples. In some methods, the substrate holder is retracted during the growth process to keep the growing surface in an ideal location.

[0050] Also, in some methods according to the present teachings, the single crystal diamond growth thickness that can be achieved in a single continuous growth cycle can exceed 6 mm. In other methods, the single crystal diamond growth thickness that can be achieved in a single continuous growth cycle can exceed 10 mm. In still other methods, the single crystal diamond growth thickness that can be achieved in a single continuous growth cycle can exceed 15 mm. It should be understood that there is no specific upper limit to the growth thickness that can be achieved in a single continuous growth cycle.

[0051] As a specific example of one implementation, as shown in Figure 4, seeds 402 had initial dimensions of about 7 x 7 mm in area and 0.3 mm thick, and were grown to a thickness of 4.5 mm with lateral dimensions of about 16 mm. It should be understood that plates 404 may be thicker or thinner than the example illustrated in Figure 4 depending on the particular application. It should be understood that the particular example illustrated in Figure 4 is not to scale.

[0052] After growth, the plate 404 is removed from the grown single crystal diamond. Some optional examples of post-growth steps are cutting the plate 404 into thin pieces, such as 1 mm thick pieces, using a laser or other suitable cutting device. Those skilled in the art will understand that the plate thickness can be greater or less than 1 mm. Alternatively, electrochemical etching can be used to cut the pieces of plate 404. Alternatively, strain induced by an embedded layer can be used to separate the pieces of plate 404 from the main growth.

[0053] Plate 404 can be used as a seed for further growth to larger dimensions. Multiple pieces can be removed from a single growth to generate multiple plates. Each section may form a plate having an area equal to or smaller than the previous plate. Plate 404 can also be used for a variety of applications, including, for example, electronics, optics, sensors, jewelry, and cutting tool applications.

[0054] In some methods according to the present teachings, the seed process and mounting conditions are adjusted so that plate 404 grows with little or no growth in a direction parallel to (lateral to) the seed surface. In these methods, pieces may still be cut from plate 404 for various uses.

[0055] Single crystal diamond can be grown in accordance with the present teachings using a plasma processing system that includes a vacuum chamber with gas injection, pumping, and pressure control. A microwave, DC, or RF generator creates the plasma to grow the single crystal diamond material. Typically, a holder for the diamond sample seed is used. The holder is , configured to support the growth of polycrystalline diamond material. In some embodiments, a molybdenum holder is used. The diamond seed may be thermally attached to the holder using a thermal adhesive material, which may be selected based on its thermal and mechanical properties. The diamond seed may also be placed on the surface of the holder without the use of a thermal adhesive material.

[0056] In some cases, it may be desirable to complete growth in one direction perpendicular to the seed surface, remove the sample from the CVD system, flip the sample over so that the growth surface now faces the holder, and resume growth on the seed side that previously faced the holder. This allows for increased perpendicular growth without increasing maximum growth parallel to (lateral to) the seed surface. In some cases, it may be desirable to clean or trim the grown material before resuming growth. In some cases, it may also be desirable to clean the holder and process chamber before resuming growth.

[0057] (Equivalent) While the applicant's teachings are described in conjunction with various embodiments, it is not intended that the applicant's teachings be limited to such embodiments. On the contrary, the applicant's teachings encompass various alternatives, modifications, and equivalents, which may be made therein without departing from the spirit and scope of the present teachings, as will be appreciated by those skilled in the art.

Claims

1. 1. A method for growing single crystal diamond assisted by polycrystalline diamond in a single continuous chemical vapor deposition growth cycle, the method comprising: a) thermally bonding a single crystal diamond seed onto a top surface of a substrate holder using an adhesive material to provide a combined single crystal diamond and polycrystalline diamond substrate growth surface that is not constrained by the substrate holder, wherein during processing of steps b) and c) there is a predetermined temperature difference between the single crystal diamond seed and the substrate holder that is determined at least in part by the adhesive material, the predetermined temperature difference causing a single crystal diamond growth rate in a direction perpendicular to the top surface of the single crystal diamond seed to differ from a polycrystalline growth rate in a direction perpendicular to the top surface of the single crystal diamond seed by a desired amount, and wherein the entire top surface of the substrate holder is flat; b) growing both single crystal diamond and polycrystalline diamond on the growth surface by providing a process gas and forming a plasma, wherein the polycrystalline diamond grown adjacent to the single crystal diamond shields lateral surfaces of the growing single crystal diamond from the plasma and the process gas, thereby improving thermal uniformity across the growing single crystal diamond during a single chemical vapor deposition; c) terminating chemical vapor deposition growth of the single crystal diamond without multiple growth cycles, thereby forming a diamond without growth lines and defects associated with multiple growth cycles while allowing lateral growth relative to the growth surface of the diamond seed unconfined by the substrate holder; A method comprising:

2. 2. The method of claim 1, further comprising providing a spacer between the diamond seed and the substrate holder, the spacer adjusting the height of the diamond seed relative to the top surface of the substrate holder to change the growth rate of the diamond seed in a direction perpendicular to the top surface of the diamond seed relative to the growth rate of the polycrystalline diamond in a direction perpendicular to the top surface of the diamond seed.

3. 2. The method of claim 1, wherein providing the process gas and forming the plasma is provided such that there is a temperature difference of greater than 25°C across the growth surfaces of the combined single crystal diamond and polycrystalline diamond substrate during at least a portion of the growth.

4. 2. The method of claim 1, wherein providing the process gas and forming the plasma to grow both the single crystal diamond and the polycrystalline diamond on the growth surface is performed such that the single crystal growth rate in a direction perpendicular to the top surface of the diamond seed is greater than the polycrystalline growth rate in a direction perpendicular to the top surface of the diamond seed.

5. The method of claim 1 , wherein the substrate holder comprises diamond.

6. The method of claim 1 , wherein the method further comprises forming the top surface of the substrate holder to have a recess for supporting the diamond seed.

7. The method of claim 1 , wherein the method further comprises forming the top surface of the substrate holder with a textured finish.

8. 10. The method of claim 1, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma comprises establishing a temperature at the growth surface in the range of 600°C to 1,400°C.

9. 10. The method of claim 1, wherein providing the process gas to grow both single crystal diamond and polycrystalline diamond on the growth surface and forming the plasma results in a final thickness of the polycrystalline material that is 20% to 150% of the final thickness of the single crystal material.

10. The method of claim 1 , wherein the method further comprises varying process conditions during the growth to maintain a desired relative growth rate of the single crystal and polycrystalline materials.

11. The method of claim 1 , wherein the method further comprises varying process conditions during the growth to maintain desired growth characteristics of the single crystal material.

12. 10. The method of claim 1, wherein the method further comprises producing a plate of single crystal diamond material by cutting the grown single crystal diamond.

13. 10. The method of claim 1, wherein the growth cycle continues until the mass of the grown single crystal diamond is greater than 2 grams in a single process step.

14. 2. The method of claim 1, wherein thermally bonding the diamond seed onto the top surface of the substrate holder to provide a growth surface for the combined single crystal diamond and polycrystalline diamond substrate comprises thermally bonding a plurality of diamond seeds onto the top surface of the substrate holder to provide a plurality of growth surfaces for a plurality of combined single crystal diamond and polycrystalline diamond substrates.

15. 1. A method for growing single crystal diamond assisted by polycrystalline diamond in a single continuous chemical vapor deposition growth cycle, the method comprising: a) Thermally bonding a diamond seed onto the top surface of the substrate holder using an adhesive material. and providing a growth surface of a combined single crystal diamond and polycrystalline diamond substrate that is not constrained by the substrate holder, wherein during processing of steps b) and c) there is a predetermined temperature difference between the diamond seed and the substrate holder, said predetermined temperature difference causing a desired relative growth rate of single crystal diamond material in a direction transverse to the top surface of the diamond seed relative to the growth rate of polycrystalline diamond in a direction perpendicular to the top surface of the diamond seed, and the entire top surface of the substrate holder is flat; b) performing a growth cycle by growing both single crystal diamond and polycrystalline diamond on the growth surface by plasma deposition by providing a process gas and forming a plasma, wherein the polycrystalline diamond grown adjacent to the single crystal diamond shields lateral surfaces of the growing single crystal diamond from the plasma and the process gas, thereby improving thermal uniformity across the growing single crystal diamond; c) obtaining a desired thickness by continuing the growth cycles described in step b) without interruption while continuously maintaining the single crystal diamond seed thermally bonded onto the top surface of the substrate holder, thereby preventing the formation of growth lines and defects during multiple growth cycles while allowing lateral growth relative to the growth surface of the diamond seed that is not limited by the substrate holder; A method comprising:

16. 16. The method of claim 15, wherein the desired relative growth rate of the single crystal material to the polycrystalline material is greater than one half.

17. 16. The method of claim 15, wherein providing the process gas and forming the plasma is provided such that there is a temperature difference across the growth surface greater than 25°C during at least a portion of the growth.

18. The method of claim 15 , wherein the method further comprises forming the top surface of the substrate holder with a textured finish.

19. The method of claim 15, wherein the method further comprises attaching the diamond seed to the holder with a thermally conductive material.

20. 16. The method of claim 15, wherein the method further comprises selecting an adhesive material to attach the diamond seed to the holder such that a desired temperature differential exists between the diamond seed and the polycrystalline material during growth.

21. 16. The method of claim 15, wherein thermally bonding the diamond seed onto the top surface of the substrate holder is performed such that a temperature differential exists between the diamond seed and the polycrystalline material during growth.

22. 16. The method of claim 15, wherein growing both single crystal diamond and polycrystalline diamond on the growth surface by providing the process gas and forming the plasma results in a final thickness of the polycrystalline material that is 20% to 150% of the final thickness of the single crystal material.

23. 16. The method of claim 15, wherein the method further comprises varying process conditions during the growth to maintain the desired relative growth rates of the single crystal and polycrystalline materials.

24. 16. The method of claim 15, wherein the method further comprises varying process conditions during the growth to maintain desired growth characteristics of the single crystal material.

25. 16. The method of claim 15, wherein thermally bonding the diamond seed onto the top surface of the substrate holder to provide a growth surface for the combined single crystal diamond and polycrystalline diamond substrate comprises thermally bonding a plurality of diamond seeds onto the top surface of the substrate holder to provide a plurality of growth surfaces for a plurality of combined single crystal diamond and polycrystalline diamond substrates.

26. 16. The method of claim 15, wherein the desired thickness is 6.0 mm or greater.

27. 16. The method of claim 15, wherein the desired thickness is 10.0 mm or greater.

28. 16. The method of claim 15, wherein the desired thickness is 15.0 mm or greater.

29. 2. The method of claim 1, wherein performing a growth cycle by providing the process gas and forming the plasma to grow both single crystal diamond and polycrystalline diamond on the growth surface by plasma enhanced chemical vapor deposition is carried out for a time that grows the polycrystalline diamond to a thickness of 4.5 mm or more.

30. The method of claim 1 , wherein the adhesive material comprises a metallic brazing material.

31. The method of claim 1 , wherein the adhesive material comprises a carbon material.

32. The method of claim 1 , wherein the adhesive material comprises a metallic material.

33. The method of claim 1 , wherein the adhesive material comprises a metal oxide material.

34. The method of claim 1 , wherein the adhesive material comprises a nitride material.

35. The method of claim 1 , wherein the adhesive material comprises a diamond material.

36. The method of claim 15 , wherein the adhesive material comprises a metallic braze material.

37. The method of claim 15 , wherein the adhesive material comprises a carbon material.

38. The method of claim 15 , wherein the adhesive material comprises a metallic material.

39. The method of claim 15 , wherein the adhesive material comprises a metal oxide material.

40. The method of claim 15 , wherein the adhesive material comprises a nitride material.

41. The method of claim 15 , wherein the adhesive material comprises a diamond material.

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