CN118147747B - Large-size high-quality diamond crystal and application thereof - Google Patents
Large-size high-quality diamond crystal and application thereof Download PDFInfo
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- 239000010432 diamond Substances 0.000 title claims abstract description 244
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 241
- 239000013078 crystal Substances 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000001069 Raman spectroscopy Methods 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 235000012431 wafers Nutrition 0.000 description 88
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 50
- 238000012360 testing method Methods 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 229910052786 argon Inorganic materials 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 238000005229 chemical vapour deposition Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000012876 topography Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 230000003746 surface roughness Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000001534 heteroepitaxy Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001657 homoepitaxy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
- C30B25/205—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer the substrate being of insulating material
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses a large-size high-quality diamond crystal and application thereof, and belongs to the technical field of diamond preparation. The diamond crystal is grown by a splicing method, the diameter of the diamond crystal is not smaller than 2 inches, the diamond crystal comprises a first surface and a second surface opposite to the first surface, the first surface and/or the second surface is/are provided with a plurality of atomic steps, the height of the atomic steps is 10-200 nm, and the width of the atomic steps is 2-60 mu m. The crystal surface can form stable step flow, the uniformity and the crystallization quality of the crystal atomic steps are high while the size is improved, and the stability of a device prepared by diamond can be improved.
Description
Technical Field
The application relates to a large-size high-quality diamond crystal and application thereof, and belongs to the technical field of diamond preparation.
Background
With the increasing demands of the industry for material properties, diamond, as a material with excellent physical properties, has shown a wide application prospect in various fields. However, the difficulty in expanding the diameter of diamond has been a great difficulty in the growth and preparation process, and the obtaining of large-size single crystal diamond is limited.
Conventional diamond growth methods mainly include two types, chemical Vapor Deposition (CVD) and high temperature high pressure synthesis (HPHT). Although these methods can achieve growth of diamond to some extent, it is difficult to control the size and quality of diamond crystals, especially to obtain large-sized single crystal diamond. In view of this problem, researchers have proposed various solutions, mainly heteroepitaxy and splicing.
The heteroepitaxy method mainly comprises depositing iridium or composite material thereof on the surface of a non-diamond substrate, and then growing diamond to realize the diameter expansion of diamond crystals. However, this method is limited by factors such as lattice matching and crystal quality, and it is often difficult to obtain high quality single crystal diamond.
In contrast, the splice growth is a method of attracting attention, mainly based on the homoepitaxy principle, by splicing together a plurality of small-sized diamond crystals, and growing again at the interface thereof, thereby achieving the enlargement of the crystal size. This method makes it easier to obtain high quality single crystal diamond relative to heteroepitaxy. However, some problems still exist in the current growth process of the splicing method, especially the quality problems of uneven crystallization quality, polycrystal, cracks and the like easily occur at the splicing seam, which is always a pain point in the growth process of the splicing method.
Some diamond splicing growth improvement growth methods are reported at present, for example, in CN115874282A, diamond seed crystals are firstly pre-grown, samples with the direction deviation within 10 degrees are selected for splicing by taking the step flow direction deviation as a reference basis, but the growth method does not pay attention to the quality of crystals at a splicing joint; in CN115261982A, a plurality of single crystal diamond seed crystals are spliced into mosaic substrates in advance by using side bonding, the substrates are subjected to the same polishing process treatment, and single crystal diamond epitaxial growth is carried out by microwave plasma and chemical vapor deposition, so that the method is difficult to effectively inhibit crystal mismatch at a splicing joint caused by mismatching of crystal orientations; before the splicing growth in CN113463192B, a layer of iridium film is sputtered at the splicing seam in advance by magnetron sputtering or vacuum coating to prepare the diamond monocrystal, and the method is basically similar to heteroepitaxy, which is unfavorable for obtaining high-quality diamond crystals. So at present, the problem that low-quality diamond generated at a splicing joint in the splicing growth of diamond is difficult to be solved is solved, so that large-size diamond crystals with stable step flow and high crystallization quality cannot be obtained.
Disclosure of Invention
In order to solve the above problems, a large-sized high-quality diamond crystal is provided, the crystal surface can form stable step flow, the uniformity and the crystallization quality of the crystal atomic steps are high while the size is improved, and the stability of a device prepared by diamond can be improved.
According to an aspect of the present application, there is provided a large-sized high-quality diamond crystal grown by a splicing method, the diamond crystal having a diameter of not less than 2 inches and comprising a first surface and a second surface opposite to the first surface, the first surface and/or the second surface having a plurality of atomic steps having a height of 10 to 200nm and a width of 2 to 60 μm.
Optionally, the atomic step has a height of 80-200 nm and a width of 20-60 μm.
Optionally, the difference in height of the plurality of atomic steps is not greater than 19nm, and the difference in width of the plurality of atomic steps is not greater than 4.1 μm;
preferably, the difference in height of the plurality of atomic steps is not more than 16nm, and the difference in width of the plurality of atomic steps is not more than 3.7 μm;
more preferably, the difference in height of the plurality of atomic steps is not more than 10nm, and the difference in width of the plurality of atomic steps is not more than 2.1 μm.
More preferably, the difference in height of the plurality of atomic steps is not more than 8nm, and the difference in width of the plurality of atomic steps is not more than 1.5 μm.
Optionally, the XRD half-widths at different locations of the first and second surfaces are no greater than 140arcsec, preferably the XRD half-widths at different locations of the first and second surfaces are no greater than 120arcsec;
preferably, the XRD half-widths at different positions of the first and second surfaces are no greater than 35arcsec; more preferably, the XRD half-widths at different locations of the first and second surfaces are each no greater than 15arcsec.
Optionally, the raman half-peak widths at different locations of the first surface and the second surface are no greater than 4.3cm -1; preferably, the raman half-peak widths at different positions of the first surface and the second surface are not more than 4.0 cm -1.
Preferably, the difference of the raman half-peak widths at different positions of the first surface and the second surface is not more than 1cm -1.
Optionally, the included angle between the first surface and/or the second surface and the (100) surface of the diamond crystal is 0-0.5 °, preferably 0-0.2 °.
Optionally, the included angle between the first surface and/or the second surface and the (311) surface is 0-0.5 °, preferably 0-0.2 °.
Optionally, the thickness of the diamond crystal is 200-1000 μm, preferably 300-600 μm.
Alternatively, the diameter of the diamond crystal is not less than 4 inches, preferably the diameter of the diamond crystal is not less than 6 inches, more preferably the diameter of the diamond crystal is not less than 8 inches.
According to another aspect of the present application there is provided the use of a large size high quality diamond crystal as described in any one of the above in semiconductor devices and quantum communications.
A method of producing large-size diamond crystals as claimed in any one of the preceding claims, comprising the steps of:
(1) Selecting a diamond wafer: six sides of the diamond wafer are (100) faces, the thickness difference of different diamond wafers is less than 5 mu m, the XRD rocking curve half-peak width of the diamond wafer growth face is less than or equal to 400arcsec, and the Raman half-peak width is less than or equal to 10cm -1;
And when the (100) surface and/or the (311) surface of the diamond wafer perform phi scanning and X scanning of XRD, the following conditions a and b are satisfied:
Individual diamond wafer orientation values: phi is less than 0 DEG and less than 90 DEG, beta is less than or equal to 0.5 DEG and less than or equal to 1|＜6°、|Χ2 DEG and less than 6 DEG,
Deviation values for each direction of different diamond wafers: ΔΦ < 2 °, Δ 1＜0.5°、ΔΧ2 < 0.5 °,
Wherein, beta 1 is the deviation of the orientation of the wire between test point 1 and test point 3 relative to the lattice, and beta 2 is the deviation of the orientation of the wire between test point 2 and test point 4 relative to the lattice;
(2) And arranging a plurality of diamond wafers to serve as splicing substrates, and performing diamond growth by a chemical vapor deposition method to obtain the large-size diamond.
According to the application, the thickness difference of different diamond wafers is less than 5 mu m, the consistency of the subsequent diamond crystal growth can be ensured, the diamond wafer with better crystal quality is selected as the seed crystal through XRD half-peak width and Raman half-peak width, and the diamond wafer with consistent crystal form is selected through phi, 1 and phi 2 values, so that the optimization of the seed crystal quality is realized, the crystal quality at the splicing seam of the diamond is improved, the overall quality and size of the diamond are improved, and the diamond crystal with large size, good crystal quality and uniform arrangement of atomic steps is obtained.
The number of diamond wafers in step (2) is two or more, and a person skilled in the art may select a suitable number according to the size of diamond crystal to be prepared and the size of diamond wafer (seed crystal).
The method comprises the steps that test points 1,2,3 and 4 are arranged at four corners of a crystal face of a diamond crystal, the test points 1 and 3 are distributed diagonally, the test points 2 and 4 are distributed diagonally, a connecting line of the test points 1 and 3 and a connecting line of the test points 2 and 4 intersect at the center of the diamond crystal, in phi scanning and X scanning of XRD, firstly, phi scanning is carried out on the crystal face of the diamond crystal, and the strongest diffraction peak is found; then rotating the diamond crystal to enable the phi value of the strongest diffraction peak to be placed between 0 and 90 degrees, and defining the test point 2 and the test point 4 which are respectively with the included angle smaller than 45 degrees with the connecting line in the X-ray direction at the moment; and finally, beta scanning the crystal face of the diamond crystal to obtain beta 1 and beta 2, selecting a plurality of diamond wafers meeting requirements according to the judgment standard of the numerical values of the directions of the single diamond wafer, and recording specific phi, beta 1 and beta 2 values of each diamond wafer.
And when the diamond is spliced and grown, selecting the diamond wafers meeting the numerical value requirements of each direction of a single diamond wafer so that the individual direction deviation values of different diamond wafers meet the requirements, and arranging a plurality of diamond wafers meeting the requirements to grow the diamond so as to obtain large-size high-quality diamond crystals.
The numerical values of each direction of the single diamond wafer are used for ensuring that the single diamond wafer can form stable step flow, the deviation values of each direction of different diamond wafers are used for ensuring that the stable step flow formed by different diamond wafers can be bridged at the splicing seam, and the problems of polycrystal, crack and the like at the splicing seam are avoided.
Optionally, the XRD rocking curve half-peak width of the growth surface of the diamond wafer is less than or equal to 200arcsec, and the Raman half-peak width is less than or equal to 6cm -1.
The index can further improve the quality of diamond crystals and optimize the quality of large-size diamond.
Alternatively, 30 DEG < phi < 60 DEG in the values of the directions of the individual diamond wafers.
Too large or too small phi can lead to too small included angle between the step flow direction of the diamond crystal and the periphery of the diamond wafer, which is unfavorable for bridging of the splice joint, so that the crystallization quality at the splice joint can be further improved when the phi is less than 30 degrees and less than 60 degrees, and the large-size diamond crystal without splice joint and with stable step flow can be obtained.
Optionally, the length of any side of the diamond wafer is more than or equal to 4mm.
If the same number of diamond wafers are used for crystal preparation, the side length is beneficial to improving the size of the final diamond crystal; if diamond crystals with the same size are prepared, the size can reduce the number of seed crystals, facilitate industrial production operation and improve the consistency of batch-produced diamond crystals.
Optionally, the thickness of the diamond wafer is 200-1000 μm.
Optionally, the surface roughness of the diamond wafer is less than or equal to 100nm, preferably, the surface roughness of the diamond wafer is less than or equal to 20nm.
Optionally, the TTV of the diamond wafer is less than or equal to 10 mu m.
The smaller the surface roughness or TTV of the diamond wafer is, the better the quality of the grown diamond crystal is, the more uniform the crystal quality is, the larger the available area of the diamond crystal is under the same size, and the utilization rate of the diamond crystal can be improved.
Optionally, the growth temperature of the chemical vapor deposition method is 850-1200 ℃, the growth pressure is 80-240 Torr, and the growth time is 10-50 h; preferably, the growth temperature of the chemical vapor deposition method is 1100-1150 ℃, and the growth pressure is 80-200 Torr, preferably 120-200 Torr.
Optionally, hydrogen, argon, oxygen, methane and nitrogen are introduced into the chemical vapor deposition method for diamond growth, the flow rate of the hydrogen is 200-1000 sccm, the flow rate of the argon is 1-100 sccm, the flow rate of the oxygen is 0.1-10 sccm, the flow rate of the methane accounts for 2-10% of the total volume of the flow rates of the hydrogen and the argon, and the flow rate of the nitrogen is 1-100 ppm of the total flow rate of the gas.
Optionally, before the chemical vapor deposition, vacuumizing the cavity to below 1×10 -6 Pa, maintaining the pressure for 20-30 min, adjusting the flow of hydrogen to 200-500 sccm, adjusting the flow of argon to 10-50 sccm, maintaining for 10-60 min, and then performing diamond growth.
The growth chamber of the diamond and the surface of the diamond can be cleaned by vacuumizing and introducing hydrogen and argon before chemical vapor deposition, so that impurities are prevented from affecting the growth of the diamond, and the quality of the diamond crystal is further improved.
The beneficial effects of the application include, but are not limited to:
1. The large-size high-quality diamond crystal can be used for bridging the splicing seam so that the crystal quality of the whole crystal is high, stable step flow can be formed, the atomic steps are uniformly arranged and have high uniformity, and the stability of a device prepared from diamond can be improved.
2. The large-size high-quality diamond crystal has the advantages that the quality of the crystal at the splicing joint and the quality of the crystal in other areas are always the same, the quality of the crystal in the radial direction and the axial direction are uniformly distributed, the problems of polycrystal and crack are avoided, the usable area of the crystal is increased, and the utilization rate of the diamond crystal is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute a limitation on the application. In the drawings:
FIG. 1 is a view showing the appearance and surface morphology of a diamond crystal according to example 3 of the present application, wherein (a) is a view showing the appearance of the diamond crystal and (b) is a view showing the surface morphology of the diamond crystal;
FIG. 2 is an XRD scan of a diamond crystal according to example 3 of the present application;
FIG. 3 is a surface topography of a diamond crystal according to example 8 of the present application;
FIG. 4 is a surface topography of a diamond crystal of comparative example 1 of the present application;
FIG. 5 is a surface topography of a diamond crystal of comparative example 2 of the present application;
FIG. 6 is a surface topography of a diamond crystal of comparative example 3 of the present application;
FIG. 7 is a surface topography of a diamond crystal of comparative example 4 of the present application;
FIG. 8 is a surface topography of a diamond crystal of comparative example 5 of the present application;
Fig. 9 is a graph showing the distribution of test points when the XRD is used to test the values of the diamond wafer in each direction.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The following examples and comparative examples were conducted on the diamond wafer in each direction by XRD measurement, and the following steps were carried out:
(1) Performing phi scanning on the (100) surface and/or the (311) surface of the diamond wafer with the surface roughness less than 100nm by adopting XRD, wherein the angle range is 0-360 degrees, the scanning step length is 0.3 degrees/s, the initial incident angle and the initial exit angle are 21+/-0.5 degrees and 71+/-0.5 degrees respectively, and the strongest diffraction peak is found;
(2) The method comprises the steps that a test point 1, a test point 2, a test point 3 and a test point 4 are arranged at four corners of a crystal face of a diamond wafer, the test point 1 and the test point 3 are diagonally distributed, the test point 2 and the test point 4 are diagonally distributed, a connecting line of the test point 1 and the test point 3 and a connecting line of the test point 2 and the test point 4 intersect at the center of the diamond crystal, a test point 5 is arranged at the intersection of the center, the diamond crystal is rotated so that the phi value of the strongest diffraction peak is placed between 0-90 degrees, and referring to FIG. 9, the test point 2 and the test point 4 are respectively defined that the included angle between the connecting line and the X-ray direction is less than 45 degrees;
(3) And performing beta scanning on the crystal face of the diamond wafer to obtain beta 1 and beta 2, wherein the beta scanning angle range is-10 degrees, the scanning step length is 0.05 degrees/s, the beta 1 is the orientation deviation of the connecting line of the test point 1 and the test point 3 relative to the crystal lattice, the beta 2 is the orientation deviation of the connecting line of the test point 2 and the test point 4 relative to the crystal lattice, and specific phi, beta 1 and 2 values of each diamond wafer are recorded.
The test results of the (100) crystal plane and the (311) crystal plane can be converted to each other when the above-mentioned numerical value measurement of each direction is performed on the same diamond wafer.
Example 1
The embodiment relates to a splicing growth method of large-size diamond, which comprises the following steps:
(1) Selecting a diamond wafer: six sides of the diamond wafer are all (100) planes, the thickness is 1000 mu m, the thickness difference of different diamond wafers is less than 5 mu m, any side length is 10mm, the surface roughness is 60nm, the TTV is 10 mu m, the XRD rocking curve half peak width of the diamond wafer growth plane is 400arcsec, and the Raman half peak width is 10cm -1;
And when performing phi scanning and X scanning of XRD on the (100) surface and the (311) surface of the diamond wafer, the following conditions are satisfied:
Individual diamond wafer orientation values: phi is less than 0 DEG and less than 90 DEG, beta is less than or equal to 0.5 DEG and less than or equal to 1|＜6°、|Χ2 DEG and less than 6 DEG,
Deviation values for each direction of different diamond wafers: ΔΦ < 2 °, Δ 1＜0.5°、ΔΧ2 < 0.5 °,
(2) Arranging 2 diamond wafers to serve as a splicing substrate, adsorbing diamond on the surface of a molybdenum support through ethanol, placing the molybdenum support carrying diamond seed crystals to be spliced into a Microwave Plasma Chemical Vapor Deposition (MPCVD) cavity, vacuumizing the cavity to be less than 1X 10 -6 Pa, maintaining the pressure for 20min, adjusting the hydrogen flow to be 200sccm, adjusting the argon flow to be 10sccm, maintaining for 60min, introducing hydrogen, argon, oxygen, methane and nitrogen to perform diamond growth, wherein the growth temperature is 1150 ℃, the growth pressure is 80Torr, the hydrogen flow is 1000sccm, the argon flow is 1sccm, the oxygen flow is 0.1sccm, the methane flow accounts for 2% of the total volume of the hydrogen flow and the argon flow, the nitrogen flow is 1ppm of the total volume of the gas, and growing for 50h, thus obtaining the large-size diamond.
Example 2
The embodiment relates to a splicing growth method of large-size diamond, which comprises the following steps:
(1) Selecting a diamond wafer: six sides of the diamond wafer are (100) planes, the thickness is 200 mu m, the thickness difference of different diamond wafers is less than 5 mu m, any side length is 5mm, the surface roughness is 100nm, the TTV is 10 mu m, the XRD rocking curve half peak width of the diamond wafer growth plane is 180arcsec, and the Raman half peak width is 5cm -1;
And when performing phi scanning and X scanning of XRD on the (100) surface and the (311) surface of the diamond wafer, the following conditions are satisfied:
Individual diamond wafer orientation values: phi is less than 30 degrees and less than 60 degrees, beta is less than or equal to 0.5 degrees and less than or equal to 1|＜6°、|Χ2 degrees and less than 6 degrees,
Deviation values for each direction of different diamond wafers: ΔΦ < 2 °, Δ 1＜0.5°、ΔΧ2 < 0.5 °,
(2) Arranging 2 diamond wafers to serve as splicing substrates, adsorbing the diamond on the surface of a molybdenum support through ethanol, placing the molybdenum support carrying diamond seed crystals to be spliced into a Microwave Plasma Chemical Vapor Deposition (MPCVD) cavity, vacuumizing the cavity to be less than 1X 10 -6 Pa, maintaining the pressure for 30min, adjusting the hydrogen flow to be 500sccm, adjusting the argon flow to be 50sccm, maintaining the pressure for 10min, introducing hydrogen, argon, oxygen, methane and nitrogen to perform diamond growth, wherein the growth temperature is 1150 ℃, the growth pressure is 200Torr, the hydrogen flow is 200sccm, the argon flow is 100sccm, the oxygen flow is 10sccm, the methane flow accounts for 10% of the total volume of the hydrogen flow and the argon flow, the nitrogen flow is 100ppm of the total volume of the gas flow, and growing for 10h, thus obtaining the large-size diamond.
Example 3
The embodiment relates to a splicing growth method of large-size diamond, which comprises the following steps:
(1) Selecting a diamond wafer: six sides of the diamond wafer are (100) planes, the thickness is 200 mu m, the thickness difference of different diamond wafers is less than 5 mu m, any side length is 4mm, the surface roughness is 10nm, the TTV is 8 mu m, the XRD rocking curve half peak width of the diamond wafer growth plane is 190arcsec, and the Raman half peak width is 5cm -1;
And when performing phi scanning and X scanning of XRD on the (100) surface and the (311) surface of the diamond wafer, the following conditions are satisfied:
Individual diamond wafer orientation values: phi is less than 30 degrees and less than 60 degrees, beta is less than or equal to 0.5 degrees and less than or equal to 1|＜6°、|Χ2 degrees and less than 6 degrees,
Deviation values for each direction of different diamond wafers: ΔΦ < 2 °, Δ 1＜0.5°、ΔΧ2 < 0.5 °,
(2) Arranging 2 diamond wafers as a splicing substrate, adsorbing diamond on the surface of a molybdenum support through ethanol, placing the molybdenum support carrying diamond seed crystals to be spliced into a Microwave Plasma Chemical Vapor Deposition (MPCVD) cavity, vacuumizing the cavity to below 1X 10 -6 Pa, maintaining the pressure for 30min, adjusting the hydrogen flow to 300sccm, adjusting the argon flow to 40sccm, maintaining the pressure for 20min, introducing hydrogen, argon, oxygen, methane and nitrogen for diamond growth, wherein the growth temperature is 1100 ℃, the growth pressure is 120Torr, the hydrogen flow is 500sccm, the argon flow is 50sccm, the oxygen flow is 4sccm, the methane flow accounts for 8% of the total volume of the hydrogen flow and the argon flow, the nitrogen flow is 40ppm of the total volume of the gas, and growing for 20h, thus obtaining the large-size diamond.
Example 4
The difference between this example and example 3 is that the diamond wafer has a roughness of 300nm, and the remaining parameters and steps are the same as in example 3, resulting in large-sized diamond.
Example 5
The difference between this example and example 3 is that the TTV of the diamond wafer is 15 μm, and the remaining parameters and steps are the same as those of example 3, to obtain a large-sized diamond.
Example 6
The difference between this example and example 3 is that the growth temperature in step (2) was 1200 ℃, and the remaining parameters and steps were the same as in example 3, to obtain a large-sized diamond.
Example 7
The difference between this example and example 3 is that the growth gas pressure in step (2) was 240Torr, and the remaining parameters and steps were the same as those in example 3, to obtain a large-size diamond.
Example 8
The difference between this example and example 3 is that the nitrogen flow rate in step (2) was 0.1ppm of the total gas flow rate, and the remaining parameters and steps were the same as those in example 3, to obtain a large-sized diamond.
Example 9
The embodiment relates to a splicing growth method of large-size diamond, which comprises the following steps:
(1) Selecting a diamond wafer: six sides of the diamond wafer are (100) planes, the thickness is 200 mu m, the thickness difference of different diamond wafers is less than 5 mu m, any side length is 4mm, the surface roughness is 10nm, the TTV is 8 mu m, the XRD rocking curve half peak width of the diamond wafer growth plane is 200arcsec, and the Raman half peak width is 4cm -1;
And when performing phi scanning and X scanning of XRD on the (100) surface and the (311) surface of the diamond wafer, the following conditions are satisfied:
Individual diamond wafer orientation values: phi is less than 30 degrees and less than 60 degrees, beta is less than or equal to 0.5 degrees and less than or equal to 1|＜6°、|Χ2 degrees and less than 6 degrees,
Deviation values for each direction of different diamond wafers: ΔΦ < 2 °, Δ 1＜0.5°、ΔΧ2 < 0.5 °,
(2) Arranging 2 diamond wafers to serve as a splicing substrate, adsorbing diamond on the surface of a molybdenum support through ethanol, placing the molybdenum support carrying diamond seed crystals to be spliced into a Microwave Plasma Chemical Vapor Deposition (MPCVD) cavity, vacuumizing the cavity to be less than 1X 10 -6 Pa, maintaining the pressure for 30min, adjusting the hydrogen flow to 300sccm, adjusting the argon flow to 10sccm, maintaining the pressure for 20min, adjusting the hydrogen, argon, oxygen, methane and nitrogen flow to perform diamond growth, wherein the growth temperature is 850 ℃, the growth pressure is 120Torr, the hydrogen flow is 200sccm, the argon flow is 1sccm, the oxygen flow is 0.1sccm, the methane flow accounts for 2% of the total volume of the hydrogen flow and the argon flow, the nitrogen flow is 1ppm of the total volume of the gas, and growing for 20h, thus obtaining the large-size diamond.
Example 10
The embodiment relates to a splicing growth method of large-size diamond, which comprises the following steps:
(1) Selecting a diamond wafer: six sides of the diamond wafer are (100) planes, the thickness is 200 mu m, the thickness difference of different diamond wafers is less than 5 mu m, any side length is 4mm, the surface roughness is 10nm, the TTV is 8 mu m, the XRD rocking curve half peak width of the diamond wafer growth plane is 200arcsec, and the Raman half peak width is 6cm -1;
And when performing phi scanning and X scanning of XRD on the (100) surface and the (311) surface of the diamond wafer, the following conditions are satisfied:
Individual diamond wafer orientation values: phi is less than 30 degrees and less than 60 degrees, beta is less than or equal to 0.5 degrees and less than or equal to 1|＜6°、|Χ2 degrees and less than 6 degrees,
Deviation values for each direction of different diamond wafers: ΔΦ < 2 °, Δ 1＜0.5°、ΔΧ2 < 0.5 °,
(2) Arranging 2 diamond wafers to serve as a splicing substrate, adsorbing the diamond on the surface of a molybdenum support through ethanol, placing the molybdenum support carrying diamond seed crystals to be spliced into a Microwave Plasma Chemical Vapor Deposition (MPCVD) cavity, vacuumizing the cavity to below 1X 10 -6 Pa, maintaining the pressure for 30min, adjusting the hydrogen flow to 800sccm, adjusting the argon flow to 10sccm, maintaining the pressure for 20min, introducing hydrogen, argon, oxygen, methane and nitrogen to perform diamond growth, wherein the growth temperature is 950 ℃, the growth pressure is 200Torr, the hydrogen flow is 800sccm, the argon flow is 100sccm, the oxygen flow is 5sccm, the methane flow accounts for 10% of the total volume of the hydrogen flow and the argon flow, the nitrogen flow is 100ppm of the total volume of the gas, and growing for 20h, thus obtaining the large-size diamond.
Comparative example 1
This comparative example differs from example 3 in that beta 1 of a single diamond wafer is less than 0.5 deg., and the remaining parameters and steps are the same as example 3, resulting in large-sized diamond.
Comparative example 2
This comparative example differs from example 3 in that beta 2 of a single diamond wafer is greater than 6 deg., and the remaining parameters and steps are the same as example 3, resulting in large size diamond.
Comparative example 3
This comparative example differs from example 3 in that the delta phi of the different diamond wafers was greater than 2 deg., and the remaining parameters and steps were the same as example 3, resulting in large-size diamond.
Comparative example 4
This comparative example differs from example 3 in that Δζ 1 of different diamond wafers is greater than 0.5 °, and the remaining parameters and steps are the same as example 3, resulting in large-sized diamond.
Comparative example 5
This comparative example differs from example 3 in that Δζ 2 of different diamond wafers is greater than 0.5 °, and the remaining parameters and steps are the same as example 3, resulting in large-sized diamond.
Test example 1
Atomic step tests were performed on the surfaces of the large-sized diamonds prepared in the above examples and comparative examples using an atomic force microscope, the results are shown in table 1 below, and the appearance and surface morphology of the diamond prepared in example 3 are shown in fig. 1 (a) and 1 (b), respectively, it can be seen that a stable and uniform step flow is formed, and the splice joint can be well closed, and the sample centers on both sides and the splice joint of the diamond crystal obtained in example 3 are scanned using the Omega scanning mode of XRD, and as a result, see fig. 2, it can be seen that the crystal quality at the splice joint is only slightly lower than that at the centers on both sides, indicating the formation of single crystal diamond at the splice joint.
The diamond surface topography prepared in example 8 is shown in fig. 3, it can be seen that polycrystal exists at the splice joint of diamond, and it is difficult to effectively bridge the splice joint even though some steps cross the splice joint; the surface topography of the diamond prepared in comparative example 1 is shown in fig. 4, and it can be seen that the step flow shape is not obvious and disordered due to the too small surface orientation, and it is difficult to form a stable step flow; the diamond surface topography prepared in comparative example 2 is shown in fig. 5, and it can be seen that the gap at the splicing position is obvious, which shows that although the step flow can be partially formed when the deflection angle is too large, the step flow is difficult to cross the splicing seam due to poor transverse expansibility; the diamond surface topography prepared in comparative example 3 is shown in fig. 6, and it can be seen that the difference in step flow direction is large when the difference in Φ angle of the splice pieces is excessive, resulting in difficulty in effective bridging at the splice joints; as shown in fig. 7, the diamond surface topography prepared in comparative example 4, when the angle difference of the angle of the beta 1 between the splice pieces is too large, results in too large step flow topography difference between the two pieces, and it is difficult to form stable step flow at the splice joint even if the directions are the same; the diamond surface topography prepared in comparative example 5 is shown in fig. 8, and it can be seen that although continuous step flow can be formed and polycrystals are substantially eliminated, deviation in orientation due to large beta 2 difference between splice pieces causes amorphous regions to be formed at the splice joints, making it difficult to efficiently bridge the splice joints.
Table 1 results of step flow test of diamonds prepared in examples and comparative examples
Note that: in the table "-" represents that no atomic step is formed.
Test example 2
XRD testing was performed on the surfaces of the large-sized diamonds prepared in the above examples and comparative examples using Omega-Rel mode, and Raman testing was performed using single spectrum scanning, and the test results are shown in Table 2.
Table 2 XRD and raman test results of diamond prepared in examples and comparative examples
The above description is only an example of the present application, and the scope of the present application is not limited to the specific examples, but is defined by the claims of the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The large-size high-quality diamond crystal is characterized in that the diamond crystal is grown by a splicing method, the diameter of the diamond crystal is not less than 2 inches, the diamond crystal comprises a first surface and a second surface opposite to the first surface, the first surface and the second surface are provided with a plurality of atomic steps, the atomic steps are 10-200 nm in height and 2-60 mu m in width;
the height difference of the plurality of atomic steps is not more than 19nm, and the width difference of the plurality of atomic steps is not more than 4.1 mu m;
The difference of XRD half-peak widths at different positions of the first surface and the second surface is not more than 35arcsec, and the difference of Raman half-peak widths at different positions of the first surface and the second surface is not more than 1cm -1.
2. The large-size high-quality diamond crystal according to claim 1, wherein the atomic step has a height of 80 to 200nm and a width of 20 to 60 μm.
3. The large scale high quality diamond crystal according to claim 1, wherein the XRD half widths at different locations of the first and second surfaces are no greater than 140arcsec.
4. The large scale high quality diamond crystal according to claim 1, wherein the raman half width at different locations of the first and second surfaces is no greater than 4.3cm -1.
5. The large-size high-quality diamond crystal according to claim 1, wherein the included angle between the first surface and/or the second surface and the (100) plane of the diamond crystal is 0-0.5 °.
6. The large-size high-quality diamond crystal according to claim 1, wherein the angle between the first surface and/or the second surface and the (311) surface of the diamond crystal is 0-0.5 °.
7. The large-size high-quality diamond crystal according to claim 1, wherein the thickness of the diamond crystal is 200 to 1000 μm.
8. The large-size high-quality diamond crystal according to claim 1, wherein the diameter of the diamond crystal is not less than 4 inches.
9. Use of the large-sized high-quality diamond crystal according to any one of claims 1 to 8 in a semiconductor device.
10. Use of the large-size high-quality diamond crystal according to any one of claims 1 to 8 in quantum communication.
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