Illustrative embodiments of the invention generally relate to growing diamond and, more particularly, illustrative embodiments relate to removing defects from grown diamond.
Imperfections in the crystal lattice of diamond are common. Such defects may be the result of lattice irregularities or extrinsic substitutional or interstitial impurities, introduced during or after the diamond growth. The defects affect the material properties of diamond and determine to which type a diamond is assigned; the most dramatic effects are on the diamond color and electrical conductivity, as explained by the electronic band structure.
The defects can be detected by different types of spectroscopy, including electron paramagnetic resonance (EPR), x-ray diffraction, Raman spectroscopy, luminescence induced by light (photoluminescence, PL) or electron beam (cathodoluminescence, CL), and absorption of light in the infrared (IR), visible and UV parts of the spectrum. The absorption spectrum is used not only to identify the defects, but also to estimate their concentration; it can also distinguish natural from synthetic or enhanced diamonds.
In accordance with one embodiment of the invention, a method grows diamond by providing an initial substrate having a growth surface. A first layer of diamond growth inhibitor is positioned over a first area of the growth surface. Diamond is grown on the growth surface using chemical vapor deposition. Growing the diamond includes growing a first lateral overgrowth region over the diamond growth inhibitor. After growing the first lateral overgrowth region, a second layer of diamond growth inhibitor is positioned over a second area of the growth surface that is at least partially offset from the first area.
In various embodiments, the second layer of diamond growth inhibitor is positioned at a height that is equal to or greater than the first lateral overgrowth region. The first layer of diamond growth inhibitor and the second layer of diamond growth inhibitor may be formed from the same material.
The steps of positioning diamond growth inhibitor over an offset area of the growth surface and growing diamond on the growth surface using chemical vapor deposition may be repeated until threading defect density is reduced by at least 50% relative to the initial substrate in a reduced defect area. The reduced defect area may have a maximum dimension of at least 2 inches.
In various embodiments, diamond is grown on the growth surface using chemical vapor deposition, and the grown diamond may include a second lateral overgrowth region over the diamond growth inhibitor. The lateral overgrowth region and the second lateral overgrowth region may be on different layers.
A third diamond growth inhibitor may be positioned over a third area of the growth surface that is at least partially offset from the first area and the second area. Diamond may be grown on the growth surface using chemical vapor deposition, and the grown diamond may include a third lateral overgrowth region over the diamond growth inhibitor. In various embodiments, the first area of the growth surface, the second area of the growth surface, and the third area of the growth surface may not overlap.
The method may repeat the steps of: positioning diamond growth inhibitor over an area of the growth surface, and growing diamond on the growth surface using chemical vapor deposition, such that the grown diamond includes an additional overgrowth region over the diamond growth inhibitor, until substantially all of the growth surface of the diamond is defect free and/or high-quality.
Some embodiments may be used to grow a large-area high-quality grown diamond region. The large-area high-quality grown diamond region may be removed from the remainder of the grown diamond. The substrate may be a single-crystal diamond substrate. Alternatively, the substrate may be formed from a non-diamond material. The diamond may be grown heteroepitaxially. The grown diamond may be single crystal.
In various embodiments, non-diamond deposits over the diamond growth inhibitor. The non-diamond may be a form of carbon, such as amorphous carbon. In various embodiments, the diamond growth inhibitor may be formed from gold. Additionally, or alternatively, the diamond growth inhibitor may be formed from aluminum oxide.
Some embodiments may etch the growth surface to form etched regions. The diamond growth inhibitor may function as a mask that prevents or reduces the formation of etched regions beneath the diamond growth inhibitor. The method may deposit a first doped diamond portion using chemical vapor deposition. The diamond growth inhibitor may be removed. The diamond growth inhibitor may be positioned over a second area of the growth surface. The growth surface may be etched to form second etched regions. The diamond growth inhibitor may function as a mask that prevents or reduces the formation of the second etched regions beneath the diamond growth inhibitor. The method may deposit a second doped diamond portion using chemical vapor deposition. The second doped diamond portion may have a different doping concentration from the first doped diamond portion.
In some embodiments, the doped diamond portion includes boron, nitrogen, silicon, and/or phosphorous as dopants. Some embodiments may include an adherence portion between the diamond growth inhibitor and the diamond growth surface.
Some embodiments include a diamond grown using any of the aforementioned methods.
In accordance with another embodiment, a diamond includes a reduced-defect region grown above a higher defect single-crystal diamond region. A non-diamond substrate having a top surface area. The reduced-defect single-crystal diamond region may have an area that is at least 50% of the top surface area of the non-diamond substrate.
In some embodiments, the reduced-defect single-crystal diamond region has an area that is at least 90% of the top surface area of the non-diamond substrate. In some embodiments, the reduced-defect single-crystal diamond region is a sum of a plurality of disjointed regions. Alternatively, in some embodiments, the reduced-defect single-crystal diamond region may be a single continuous region. The reduced-defect single-crystal diamond region may take a variety of shapes, including but not limited to a rectangular shape.
In accordance with another embodiment, a system includes a reduced-defect single-crystal diamond region, a diamond growth inhibitor, and a growth substrate.
Among other things, the growth substrate may be a non-diamond substrate. The growth substrate may be a polycrystalline diamond substrate. The system may include a lateral overgrowth diamond region over the diamond growth inhibitor. Among other shapes, the diamond growth inhibitor may be in the shape of a bar, a hexagon, a circle, a pentagon, or a rectangle.
In some embodiments, the diamond growth inhibitor may cover at least 50% of the growth surface. The diamond growth inhibitor may include a micro-pattern diamond growth inhibitor. The micro-pattern DGI may include an array of micro-pores. The micro-pores may have a given shape. The shape may be rectangular or hexagonal. The micro-pores may be configured to be aligned with the crystal lattice orientation.
The diamond growth inhibitor may be configured to prevent or inhibit formation of single-crystal and polycrystalline diamond at a surface of the DGI when depositing diamond using a chemical vapor deposition growth process. Accordingly, diamond bonds may be unmeasurable by X-ray diffraction.
In various embodiments, the diamond growth inhibitor may be configured to cause formation of non-diamond carbon as diamond is deposited in a CVD diamond growth process thereon, when depositing diamond using a chemical vapor deposition growth process.
Removing the DGI may form a void in the diamond. The DGI may cover at least about 90% and less than 100% of the substrate surface. The DGI may have a pore size. The pore size may be less than 500 microns, less than 50 microns, and/or less than 5 microns. In some embodiments, the pore size may be greater than 1 nm.
In various embodiments, defect density is reduced uniformly across the reduced defect area. The substrate surface may have a maximum dimension that is at least 40 mm. In some embodiments, the substrate surface has a maximum dimension that is at least 20 mm.
Those skilled in the art should more fully appreciate advantages of various embodiments of the invention from the following “Description of Illustrative Embodiments,” discussed with reference to the drawings summarized immediately below.
Illustrative embodiments include a process of using selective deposition and lateral overgrowth to produce high quality diamond by removing defects in epitaxially grown diamond. Diamond growth inhibitor (“DGI”, e.g., gold) patterns are selectively deposited on diamond material (e.g., using the selective deposition methods described in U.S. Patent Application No. 63/453,378, which is incorporated herein by reference in its entirety). However, in this case, the diamond is allowed to grow out over the areas where the DGI is positioned, using a lateral growth technique. Growth over areas where DGI is deposited is unconstrained by the substrate below and diamond can be grown with very low defects. This process can then be repeated, plating gold on areas of high defects as many times as desired to produce a single crystal surface demonstrating low defects across the entire region, or across a desired region (e.g., where devices are fabricated on the surface).
As shown in
Single crystal diamond 10 demonstrates a number of properties that are greatly advantageous for electronics and other applications. However, size limitations, quality, and availability make it difficult to fully utilize diamond 10 for some applications, particularly in the realm of electronics and quantum uses. Illustrative embodiments use a CVD approach to grow diamond 10. Moreover, by use of heteroepitaxy, CVD diamond 10 may be produced in larger sizes than is commonly available. Up to 4-inch wafers have been produced using this method. Unfortunately, CVD diamond 10 tends to be high in crystal defects 9 and it often is not of sufficiently high quality for some applications where the material would be useful. When heteroepitaxy is utilized, achieving sufficient quality may be even more challenging than through homoepitaxy.
Epitaxial lateral overgrowth has been used for single-crystal diamond, but is cumbersome, expensive, and produces challenges for large-scale manufacturing. Furthermore, epitaxial lateral overgrowth generally requires etching. Various embodiments can provide epitaxial lateral overgrowth 14 without requiring etching, which is a significant advantage.
A problem solved by the process described above is the growth of large high-quality diamond 10. It is difficult to grow large high-quality diamond 10 using CVD. Generally, this requires growing diamond 10 on large substrates 8 using heteroepitaxy. But heteroepitaxial processes generally lead to low quality diamond 10. Alternatively, CVD diamond 10 can be homoepitaxially grown on a diamond substrate 8, which is limited by the size of the diamond substrate 8 that the process begins with. It is difficult to obtain high quality large diamond 10 substrates 8. Therefore, the size of a high-quality grown diamond 10 is generally constrained by the size of the high-quality diamond 10 substrate 8 available.
On the other hand, the problem with large non-diamond substrates 8 is that the quality is very poor because of lattice mismatch. The crystal structure of the non-diamond substrate is different (only by a few %, or it would not be possible to grow sp3 diamond on it at all), and those differences add up over distance, leading to increasing stress and subsequent dislocations or cracking—and the grown diamond 10 is highly defective. The process described below helps with reducing/removing defects 9. The process may be used to heteroepitaxially or homoepitaxially grow high quality diamond 10.
The process begins at step 202 by providing the substrate 8. In some embodiments, the process may be a homoepitaxial process, and thus the substrate 8 may be diamond 10, such as single-crystal or polycrystalline diamond 10. In some embodiments, the process may be a heteroepitaxial process, and therefore, the substrate 8 may be formed from some other suitable material (e.g., iridium film on sapphire, silicon, and/or MgO (for single crystal), e.g., 2″, 4″ diameter, square/rectangular, circular).
At step 204, the process positions diamond growth inhibitor 20 over a first portion of the diamond substrate 8.
Furthermore, for the sake of discussion,
In various embodiments, certain materials function as diamond growth inhibitor 20 when epitaxially growing diamond 10 using CVD. The diamond growth inhibitor 20 (“DGI 20”) offers a surface that prevents single crystal or polycrystalline diamond 10 growth under CVD growth conditions. In various embodiments, diamond 10 growth is inhibited such that no more than a negligible amount of diamond bonds to the DGI, such that diamond bonds are not detectable using X-ray diffraction.
Instead, the deposited carbon forms an amorphous carbon deposit on the DGI 20 (instead of diamond 10), which is relatively easily removed (e.g., blown away) and/or wiped away. In particular, gold 20 and/or aluminum oxide may be used as diamond growth inhibitor 20. Accordingly, diamond growth inhibitor 20 may be placed over portions of the growth surface 11 to selectively prevent diamond 10 growth.
Because gold 20 has preferable properties as a diamond growth inhibitor 20, it will be referred to throughout various embodiments. However, illustrative embodiments may include the use of aluminum oxide, or any other diamond growth inhibitor 20, in addition to or instead of gold 20. For the sake of discussion, various embodiments may refer to gold 20 and DGI 20 interchangeably. However, it should be understood that any reference to gold 20 is intended to apply to DGI 20 generally, and is not limited to DGI 20 formed from gold.
It can be challenging to deposit gold 20 directly on carbon or other substrates 8. Thus, various embodiments may include a small layer of adherence material/an adhesion layer (e.g., angstrom-nanometer scale of chrome, molybdenum, and/or titanium) between the gold 20 and the substrate 8 (not shown). Various embodiments may include an adherence layer of between about 10 nanometers and about 20 nanometers in thickness. Some embodiments may include an adherence material that is up to 1 micron in thickness. As used herein, DGI 20 is considered to be deposited on or over the substrate 8 even when an adherence material is added therebetween.
The process proceeds to step 206, which epitaxially grows diamond 10 in a CVD chamber.
At step 208, the process positions diamond growth inhibitor 20 over a different portion of the grown diamond 10 from step 206.
At step 210, diamond 10 is grown in the CVD chamber such that a second epitaxial lateral overgrowth 14 diamond region is grown.
As in
The process then proceeds to step 212, which asks whether there are more no defect/reduced defect regions to be grown. If yes, then process returns to step 208, and more diamond growth inhibitor 20 may be provided over a different portion of the diamond 10. This process may be repeated multiple times until a high-quality diamond 10 of desirable size is grown. Thus, illustrative embodiments may use one, two, three, or more layers of DGI 20 to achieve a desirable reduction in defects 9 and to produce a large reduced-defect region 18. After the high-defect regions in the diamond 10 have been reduced, the process proceeds to step 214, which grows high-quality diamond 10 over the large defect-free/reduced defect grown region 18.
Although not mentioned previously, in some embodiments, the growth may be interrupted after sufficient growth time (e.g. sufficient time to deposit several hundred nanometers of diamond 10) and the metal films may be removed either by a wet etch technique, or using dry etch-the latter may be done in-situ in the CVD chamber. Diamond 10 growth may then resume, at least until such time that lateral overgrowth 14 occurs and overtakes the ridges or pits remaining from where gold 20 had been deposited. Again, this process may be repeated to further reduce the density of crystalline defects 9 and stress along the crystal surface.
It should be reiterated various embodiments may achieve the same or similar outcomes to the process described above. For example, various embodiments may have 50% of the growth surface 11 covered with gold 20 on a given layer, 60% of the growth surface 11 covered with the gold 20 on a given layer, etc. It should further be understood that direct growth over gold 20 is suppressed, but lateral overgrowth 14 occurs. Thus, the gold 20 areas on a lower layer become high quality diamond 10 areas in a subsequent layer. The process may be repeated until the entire top layer, or substantially all of the top layer becomes high quality diamond 10 (e.g., high-quality single-crystal diamond 10).
In the CVD process, diamond 10 can be said to be grown vertically. Illustrative embodiments achieve large drops in defect density by providing the first layer of DGI 20A over a first area 26A, and by providing a second layer of DGI 20B over a second area 26B that is at least partially offset horizontally from the first area 26A. As shown in
When considering stress/strain, in a well ordered crystal, all of the atoms are evenly spaced. In a poorly ordered crystal/stressed crystal, the atoms are not evenly spaced. The ELO area allows for better order of the atoms, and therefore, reduces the overall stress. Accordingly, illustrative embodiments allow for the formation of reduced stress diamond 10.
Various embodiments refer to defect 9 reduction, but those skilled in the art will understand that various embodiments may improve strain/stress in grown diamond 10. Reduced stress can provide useful applications in optics (e.g., as a diffraction crystal) and electrical applications.
As shown in
It should be understood that various embodiments may use a homo-epitaxial process or hetero-epitaxial process. Semiconductor devices (e.g., transistors) may be grown using the methods described herein, and defects 9 may advantageously be reduced in the regions where semiconductor devices are grown using the methods described herein.
Furthermore, some embodiments may use multiple substrates 8 placed in contact or spaced apart (e.g., a mosaic approach). In some embodiments, DGI 20 may be positioned over the interfaces between the multiple substrates.
As used in this specification and the claims, the singular forms “a,” “an,” and “the” refer to plural referents unless the context clearly dictates otherwise. For example, reference to “the first doped portion” in the singular includes a plurality of first doped portions, and reference to “the second doped portion” in the singular includes one or more second doped portions and equivalents known to those skilled in the art. Thus, in various embodiments, any reference to the singular includes a plurality, and any reference to more than one component can include the singular.
While various inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the inventive teachings is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific inventive embodiments described herein.
It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Illustrative embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure. Disclosed embodiments, or portions thereof, may be combined in ways not listed above and/or not explicitly claimed. Thus, one or more features from variously disclosed examples and embodiments may be combined in various ways. For example, it is to be understood that the present disclosure contemplates that, to the extent possible, one or more features of any embodiment can be combined with one or more features of any other embodiment.
Various inventive concepts may be embodied as one or more methods, of which examples have been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.
Although the above discussion discloses various exemplary embodiments of the invention, it should be apparent that those skilled in the art can make various modifications that will achieve some of the advantages of the invention without departing from the true scope of the invention.
This patent application claims priority from provisional U.S. patent application No. 63/453,401, filed Mar. 20, 2023, entitled, “DEFECT REDUCTION IN DIAMOND,” the disclosure of which is incorporated herein, in its entirety, by reference.
This invention was made with government support under HR0011-23-9-0105 awarded by DARPA. The government has certain rights in the invention.
Number | Date | Country | |
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63453401 | Mar 2023 | US |