LARGE AREA SINGLE CRYSTAL DIAMOND
20220127751 · 2022-04-28
Inventors
Cpc classification
C30B25/186
CHEMISTRY; METALLURGY
International classification
C30B25/20
CHEMISTRY; METALLURGY
Abstract
A method includes positioning a designated rectangular single crystal diamond seed in a diamond growth reactor, the designated single crystal diamond seed having a (001) plane, with the edges being (001) planes and corners are pointed in the <110> direction, positioning a pair of blocking seeds on opposite edges of the designated seed, and growing diamond of the designated seed and blocking seeds, wherein lateral single crystal growth occurs laterally from the designated seed.
Claims
1. A method comprising: positioning a designated rectangular single crystal diamond seed in a diamond growth reactor, the designated single crystal diamond seed having a (001) plane, with the edges being (001) planes and corners are pointed in the <110> direction; positioning a pair of blocking seeds on opposite edges of the designated seed; and growing diamond of the designated seed and blocking seeds, wherein lateral single crystal growth occurs laterally from the designated seed.
2. The method of claim 1 and further comprising: separating the designated seed and lateral single crystal growth from the blocking seeds and other lateral growth to form a second designated seed having a first pair of opposite edges longer than a second pair of opposite edges; and repeating growth with new blocking seeds on opposite edges of the second designated seed along opposite longer edges.
3. The method of claim 2 and further comprising repeating the growth and separation of designated seeds until a desired size single crystal diamond substrate is obtained.
4. The method of claim 3 and further comprising: placing blocking seeds on all four edges of the single crystal diamond substrate; and growing single crystal diamond on the single crystal diamond substrate while blocking lateral growth.
5. The method of claim 1 wherein the designated seed has edges that are at least 3 mm in length.
6. The method of claim 1 wherein the top, back, and edges of the designated seed are all oriented in the (001) plane to within plus or minus five degrees.
7. The method of claim 1 wherein the designated seed has a thickness of at least 0.05 mm.
8. The method of claim 1 wherein the designated seed and blocking seeds are polished flat prior to growing diamond.
9. The method of claim 1 and further comprising: following growing, turning the designated seed and blocking seeds with growth over; and growing diamond on the turned over designated seed and blocking seeds, wherein lateral single crystal growth occurs laterally from the designated seed.
10. The method of claim 4 and further comprising: creating a nanowire mask the substrate; and reactive plasma etching the masked substrate to create nanowires as a function of the mask.
11. The method of claim 10 and further comprising: cleaning the substrate to remove the mask; growing single crystal diamond on top of the nanowires; and etching the nanowires to separate the grown single crystal diamond from the substrate.
12. The method of claim 10 wherein the nanowires have a diameter of 50 nanometers or more and a height of up to 1 micrometer.
13. The method of claim 4 and further comprising: obtaining a slab of polished polycrystalline diamond which is larger than the substrate; and attaching the slab to the substrate.
14. The method of claim 13 wherein the slab is attached to the substrate by one or more of optical contacting, metallization, or photoresist glue.
15. A method comprising: creating a nanowire mask on a single crystalline diamond substrate; and reactive plasma etching the masked substrate to create vertical nanowires as a function of the mask.
16. The method of claim 15 and further comprising: cleaning the single crystalline diamond substrate to remove the mask; growing single crystal diamond on top of the nanowires; and etching the nanowires to separate the grown single crystal diamond from the substrate.
17. The method of claim 15 wherein the nanowires have a diameter of 50 nanometers or more and a height of up to 1 micrometer.
18. The method of claim 17 and further comprising: obtaining a slab of polished polycrystalline diamond which is larger than the substrate; and attaching the slab to the substrate.
19. The method of claim 18 wherein the slab is attached to the substrate by one or more of optical contacting, metallization, or photoresist glue.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0048] In the following description, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific embodiments which may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural, logical and electrical changes may be made without departing from the scope of the present invention. The following description of example embodiments is, therefore, not to be taken in a limited sense, and the scope of the present invention is defined by the appended claims.
[0049] Various embodiments are directed to the growth of large area diamond substrates for semiconductor and quantum devices, cutting tools, optical devices, gemstones and other applications, as well as the handling and removal of such substrates from their original substrate. One method employs a series of lateral growth steps to produce single crystal diamond of large size, substrate removal, such as by nanowire production or other method, single crystal growth and subsequent removal combined with the use of polycrystalline diamond wafers to provide mechanical support to the single crystal diamond wafer during handling, polishing, device deposition and fabrication and packaging. The method is self-sustaining and removes the need for natural or high pressure high temperature (HPHT) diamonds for seed crystals.
[0050] In one embodiment, It can be appreciated that many of these composites of single crystal and polycrystalline diamond can be grown simultaneously in a large diamond growing chamber resulting in production of a large number of large single crystal diamond wafers per week. This would move single crystal diamond from a laboratory curiosity, to an industrial scale process which in turn would enable a robust diamond device manufacturing capability to develop. It should be noted that once a large area of homoepitaxial single crystal diamond is achieved, (since the vertical growth rate for both homoepitaxial single crystal and heteroepitaxial diamond will be the same or close) there is no cost advantage to heteroepitaxial diamond versus homoepitaxial diamond (and the crystal quality of homoepitaxial diamond is currently believed to always be higher).
[0051] The growth of large area diamond single crystals by the HPHT method is currently limited by the size of HPHT growers currently available and the time required to grow a diamond crystal to a suitable large size. CVD single crystal growth is currently limited by the size of HPHT or natural diamond seed crystals which are available and certain features of CVD growth.
[0052] Selective Lateral Growth.
[0053] In one embodiment, Selective Lateral Growth (SLG) is used to form a large area diamond substrate. At least three diamond seed crystals are placed end to end while touching each other, in a diamond growth reactor as shown in
[0054] The seed crystals are subjected to a temperature, pressure and gas composition commonly used for CVD diamond growth. Two of the three seeds are referred to as end or blocking seeds 210, 215, since they will block the growth of defective diamond onto a center seed 220. The center seed is called the designated seed 220 since it will be designated for expansion in size. This nomenclature shall be used throughout. The center seed 220 may have the same orientation and nomenclature as seed 100.
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[0057] The orientation of the adjacent blocking seeds is not critical since we are only concerned with the lateral extension of an individual crystal from the designated seeds to achieve increased area.
[0058] This process can be continued to further increase the single crystal area. In
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[0060] Crystal Separation:
[0061] It should be appreciated that any of the previous steps can be interrupted, a separation layer grown and a new single crystal layer grown and separated to form a new family of seeds, both blocking and designated, for future or parallel use in growing larger single crystal diamonds.
[0062] Seed Size Preservation
[0063] Seed size can be preserved by the application of blocking seeds on all four edges of the desired seed.
[0064] Dislocation Reduction:
[0065] Dislocations in CVD single crystal diamond usually originate from the original HPHT diamond seed or from polishing imperfections in the preparing the natural, HPHT or CVD diamond seeds.
[0066] Separation of New Growth from Substrate:
[0067] Separation of growth from substrate can be accomplished be several methods as described earlier. In this case we describe the use of diamond-nano-wires, however any of the other separation methods can be used as described previously. To form vertical diamond-nano-wires, a polished single crystal diamond wafer 700 is used as shown in
[0068] Device Substrate on Polycrystalline Diamond:
[0069] The newly separated, large area diamond substrate will be thin and fragile. The process steps involved in the production of diamond substrate wafers, and diamond devices such as semiconductor devices, quantum devices and others, may require handling and transport of diamond substrates in a wide range of operating environments. Holders for the diamond substrates may need to operate over the temperature range of the process while providing physical support and protection from corrosive gasses or plasma. Of particular concern is the need to avoid stress during processing due to chemical reaction or differential thermal expansion coefficient. This is particularly true when processing thin diamond films, whether devices or in-process single crystal substrates. Thin diamond films are fragile, especially in large areas, and it is important for their survival in processes chemicals, gasses and wafer handling equipment where accurate transport of wafers from one step to another is required. Some of the required attributes for a diamond substrate holder are:
[0070] Physical Strength, Chemical Resistance, Matching Thermal Expansion Coefficient Over the Processing Range, and Affordability.
[0071] Polycrystalline diamond: The material for a holder which meets all of the criteria for most of these applications is polycrystalline diamond. Polycrystalline diamond meets all the requirements of thermal expansion coefficients and chemical activity of single crystal diamond. Polycrystalline diamond can be used to hold, support and carry thin diamond films which are generated by implant and liftoff, diamond growth on nanowires, mechanical grinding and polishing, plasma etching or some other thinning process. The polycrystalline diamond can be made by CVD or by HPHT processes. Polycrystalline diamond would be strong enough to pass through conventional wafer handling equipment.
[0072] Fused Quartz: Fused quartz has a very low thermal expansion coefficient and would be suitable for use as a substrate for diamond in many applications. It should not be used at elevated temperatures where it would soften, or in plasma etching where etching would release silicon which might have harmful effects on device properties.
[0073] Improved substrate holders for diamond processing may be used to perform one or more of the following functions:
[0074] Hold a single crystal diamond during implantation and lift-off;
[0075] Hold a single crystal diamond after nanowire formation and single crystal growth;
[0076] Hold a single crystal diamond during fabrication, polishing or etching;
[0077] Hold a single crystal diamond during subsequent additional cvd growth, metallization, or other processing for device or circuit production;
[0078] Hold a single crystal diamond during subsequent growth of additional doped layers, including without limitation N, Si, .sup.13C, P or other elements; and
[0079] Hold a single crystal diamond during treatments involving heat, pressure, irradiation, annealing or other conditions.
[0080] This section describes a method for supporting and carrying the diamond substrate and devices throughout subsequent growth, separation, processing and device deposition.
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[0082] In the fulfillment of the process of growing large single crystal diamond substrates, the polycrystalline diamond can be grown by the CVD method or formed from diamond powder by the HPHT process. In addition, at the end of device fabrication, the polycrystalline diamond may be removed, left in place thinned, scribed or processed in a similar manner as other carrier materials in the processing of conventional semiconductor devices.
EXAMPLES
Example 1: Growth of Large Area Substrates by SLG
[0083] Start with a raw CVD, HPHT or natural diamond crystal
[0084] Fabricate a square or rectangular shape from the crystal such that the dimensions that the top, back and edges are all oriented in the (001) plane to within +−5 degrees
[0085] For ease of subsequent steps, the rectangular dimensions should be a minimum of 3 mm in length, or more preferably 5 mm, or preferably larger if available.
[0086] If the slab is less than 2 mm thick, it should be placed in a cvd reactor and grown to at least 2 mm in thickness. The cvd grower may be selected from among microwave plasma, DC plasma, hot filament and any other appropriate diamond grower.
[0087] The slab is laser trimmed so that has near vertical sides if it does not already.
[0088] The slab is sliced edgewise to produce a minimum of 3 slabs of a minimum of 100 um thickness
[0089] An accurate record is kept of the side and orientation of each slice
[0090] The slabs may be mounted on a polishing block and polished flat
[0091] The slabs are placed in a cvd grower and held so that they do not move during heating. The cvd grower may be selected from among microwave plasma, DC plasma, hot filament and any other appropriate diamond grower.
[0092] The grower with the seeds is heated to growth temperature of between 700 and 1250° C. The growth gas mixture can be from 1% to 10% methane in hydrogen. (or other hydrocarbon gasses giving the same free carbon content).
[0093] The nitrogen concentration is maintained between 0.1 and 500 ppm.
[0094] CVD diamond growth is carried out to a thickness of 50 to 500 micrometers or more
[0095] The slab is removed and inspected for defects. The slabs will be seen to be grown together on the top face and the edges
[0096] If the new enlarged slab has defects at the top and side seams. If these are holes or divots they must be removed by polishing, laser trimmed or slab discarded.
[0097] Optionally, the slab may be reintroduced to the grower and be grown on the reverse side. This will give additional strength to the slab for subsequent processing. The slab may be polished on both sides for more uniform contact to the grower surface. The edges of the slab may be laser trimmed to remove any defects at the seams.
[0098] The slab is then placed in the grower and diamond grown to a minimum of 1 to 2.5 mm thick or more, preferably more than 2.5 mm thick. In the configuration which has been chosen, the diamond crystal will grow laterally at the same rate as it grows perpendicular. Therefore, if the vertical growth was 2.5 mm, the combined lateral growth will be 5 mm. If we started with 5 mm square seeds, the new single crystal slab within the whole slab will be 5 mm×10 mm. It should be noted that this slab within the slab will be one single crystal with no seams!]. [the slabs which were at the ends, have corners which face in the <110> and will grow out of existence, leaving the final growth shape 6 sided with smooth (001) faces and rough (110) edges. Only the interior slab will be free of defective (110) growth. If we had chosen in the beginning, at stage (f), decided to make 4 or more slices, we would have additional single crystal slabs within the larger slab].
[0099] The single crystal (s) within the slab is cut out using a laser by cutting from the surface on the original seam. This will produce a thick single crystal slab with no seams.
[0100] This slab is sliced from the slab edge to produce a slab of 5 mm×10 mm×100 to 500 um.
[0101] This slab is grown to 2.5 mm or greater in thickness
[0102] The growth is laser trimmed and sliced as described above.
[0103] The new array is grown as described above.
[0104] The subsequent slab will contain single crystal slabs having dimensions of 10×10 mm.
[0105] This process may be continued to reach one or more inches square.
Example 2: Separation of Seed and Substrate
[0106] The procedure for separation is as follows
[0107] Start with a polished diamond crystal with the desired orientation and finish.
[0108] Convert the surface of the substrate to diamond nanowires by masking and reactive plasma etching using photolithographically produced masks or self-aligning mask materials. This method produces single crystal nanowires having heights of up to 1 micrometer or more and a diameter of 50 nanometers or more. The array covers the entire upper surface of the seed.
[0109] After cleaning, the wafer with the nanowire array is placed in a suitable diamond growing reactor. The cvd grower may be selected from among microwave plasma, DC plasma, hot filament and any other appropriate diamond grower.
[0110] With the nano-wire array facing up. The chamber is evacuated, the wafer is heated to the growing temperature and the growth gases introduced to the chamber. Conditions are typically between 900 and 1250° C. (or greater) and methane (or equivalent) concentrations from 1 to 10% (or more).
[0111] Growth begins from the tip of the nanowire and spreads linearly with the axis of the wire and laterally, perpendicular to the axis of the wire. Growth only occurs at the tip of the wire and not down the axis of the wire. Growth from adjacent wires meet and since the wires are of exactly the same orientation, form a new continuous single crystal surface. Since lateral growth only occurs at the wire tip. Since there is no lateral growth below the surface, the volume surrounding the wire is a void and only filled with reactor gas.
[0112] After growing to the desired thickness, the seed crystal with its new growth is removed from the growth chamber, cleaned and prepared for separation
[0113] The seed crystal with its new growth is placed in a furnace containing oxygen or air and heated to 600 to 1200° C. (or more) for 1 to 60 minutes (or more) depending on the temperature.
[0114] The oxygen/air penetrates the array of nanowires, which are covered by the single crystal overgrowth, and oxidizes the nanowires to CO and CO2. The wires are preferentially etched compared with the substrate, due the small diameter and large total surface area with respect to their volume.
[0115] Once the nanowires are completely etched away, the original seed crystal and the new growth separate.
[0116] Since only one micrometer of the original substrate is consumed, the substrate may be used for a repeated growths and replication.
Example 3: Separation Using Ion Implantation
Example 4: Separation Using Growth Through Silica Masks
Example 5: Handling Diamond Wafers
[0117] A slab of polycrystalline diamond is chosen which is larger in area than the CVD diamond seed or device slab to be processed. The slab may be CVD or HPHT pressed polycrystalline diamond.
[0118] The slab is polished on both sides to be flat, parallel and smooth. Thickness should be no less than 50 um thick and up to 500 um or greater.
[0119] The polycrystalline slab is attached to the surface of the single crystal seed by optical contacting, metallization, photoresist glue or any other suitable means.
[0120] The polycrystalline slab serves as a handle and carrier through subsequent steps of:
[0121] 1 Seed separation
[0122] 2 Device layer growth
[0123] 3 Heat Treatment
[0124] 4 Metallization
[0125] 5 Dicing and thinning
[0126] 6 Packaging note realignment
Example 6: Process of Enlarging Diamond Seed Wafer and Growing Device Layers
[0127] Produce enlarged diamond seed wafer according to example 1.
[0128] Remove large area seed wafer according to example 2 or 3 or 4.
[0129] Support and carry seed wafer and device layers according to examples 4 and 5.
[0130] Produce diamond layers having purity and doping levels required for the intended devices.
[0131] Fabricate and mount diamond devices.
Example 7: Fused Silica Holder
[0132] Method s of example 5 and 6 wherein the holder is fused silica
Example 8: Silicon Carbide Holder
[0133] Method s of example 5 and 6 wherein the holder is silicon carbide.
Example 9: Silicon Nitride Holder
[0134] Method of examples 5 and 6 wherein the holder is silicon nitride
Example 10: Annealing Diamond Layers
[0135] Method of 5 and 6 wherein the polycrystalline diamond substrate and the attached single crystal diamond layers are heat treated to a high temperature, with or without high pressure.
[0136] Although a few embodiments have been described in detail above, other modifications are possible. For example, the logic flows depicted in the figures do not require the particular order shown, or sequential order, to achieve desirable results. Other steps may be provided, or steps may be eliminated, from the described flows, and other components may be added to, or removed from, the described systems. Other embodiments may be within the scope of the following claims.