CN115261982B - Method for growing large-size monocrystalline diamond based on side bonding and splicing - Google Patents
Method for growing large-size monocrystalline diamond based on side bonding and splicing Download PDFInfo
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- 239000010432 diamond Substances 0.000 title claims abstract description 94
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 135
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 238000005498 polishing Methods 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 11
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 11
- 238000007517 polishing process Methods 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000003746 surface roughness Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 241001632422 Radiola linoides Species 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 241001632427 Radiola Species 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000007704 transition Effects 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
- 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
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
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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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/06—Joining of crystals
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Abstract
A method for growing large-size single crystal diamond based on side bonding and splicing belongs to the field of diamond semiconductor growth. The monocrystalline diamond seed crystal is spliced through side bonding to form a mosaic spliced substrate, and CVD diamond is epitaxially grown on the substrate, and the process steps are as follows: a. polishing the monocrystalline diamond side to obtain a smooth vertical side; b. ar is carried out on the side face of the diamond seed crystal + Ion beam bombardment to remove side adsorbed gases and native oxides; c. plating a bonding metal film on the side surface of the seed crystal; d. seed crystal after plating or Ar after plating + The treated seed crystal is quickly bonded and pressed; e. polishing the spliced substrate on the same polished workpiece; f. and transferring the polished substrate into a chamber of a microwave plasma chemical vapor deposition device to perform epitaxial growth of diamond. The invention has the advantages of tight seed crystal combination, strong operability, small height difference after the substrate is polished, and similar surface state, thereby being beneficial to large-area growth.
Description
Technical Field
The invention belongs to the technical field of single crystal diamond semiconductor material growth; in particular to a method for realizing tight splicing among a plurality of monocrystalline diamond substrates by utilizing side bonding, and realizing large-size monocrystalline diamond through integrated polishing processing and epitaxial growth. The method is characterized by tighter seed crystal combination, strong operability, small height difference after polishing the substrate and similar surface state, and is beneficial to large-area growth.
Technical Field
The diamond, the hardest substance in nature composed of carbon elements, has very excellent physical and chemical properties because of the special atomic and electronic arrangement structure, and has wide application prospect in the fields of electrons, optical windows, heat sinks, machining and the like.
Generally, natural diamond is small in size, and in order to obtain diamond of a large size, diamond may be synthesized by an artificial method. Today, there are two methods for preparing artificial single crystal diamond: high temperature High Pressure (HPHT), chemical Vapor Deposition (CVD). The conditions of the high-temperature high-pressure method are extreme, the equipment load is large, and the size is difficult to break through greatly; in the chemical vapor deposition method, the diameter of the diamond based on heteroepitaxial growth can reach 92mm, but the defects are more, the dislocation density is high, and the preparation method based on homoepitaxial growth can obtain high-quality diamond single crystals, but the increase of the single crystal area is influenced due to the existence of edge effect, so that the size of the homoepitaxial diamond is limited by the size of the substrate. Currently, the maximum size of reported homoepitaxially grown diamond is 13×13mm (diap. Relay. Mate.18 (2009) 1258), with a substrate size of 8×8mm. It is difficult to meet the demands of semiconductor applications. Therefore, the searching of a preparation method of large-size high-quality single crystal diamond is very necessary, the large-size high-quality single crystal diamond can be obtained by a splicing mode, and the Japanese Yamada team finishes the splicing of 2-inch mosaics in 2014, so that the method is the maximum single crystal diamond mosaic splicing size reported at present. Some patents on splicing methods are reported at present, and CN 108754600A proposes to cut two single crystal surfaces into mutually parallel inclined planes for splicing; CN108977880 a describes a method of cross-stitching to grow large area single crystal diamond, starting from the intersection point to grow a microstructure connecting two single crystals of diamond; patent CN108677246 a proposes a method for growing large-area single crystal diamond by bridging and splicing, where two single crystals grow a bridging connection at the joint, and continue epitaxial growth to obtain a complete large-area single crystal diamond layer.
Numerous studies have shown that the height differential and surface condition of mosaic spliced diamond substrate seed crystals can affect the quality of the grown diamond. Therefore, the substrate seed crystal is polished to ensure good surface morphology and small height difference, the seed crystal forming the spliced substrate is treated by polishing respectively, and then the treated seed crystals are spliced together to form the mosaic substrate for deposition growth. One significant challenge faced in this process is: in the deposition process, adhesion between the substrate seed crystals is not tight enough, dislocation is possible due to external disturbance, and in addition, when single seed crystals are polished, the seed crystal sheets with similar heights cannot be obtained.
Disclosure of Invention
In order to solve the problems, the basic idea of the invention is to use side bonding to make the substrate connection composed of seed crystals more compact. The mosaic substrates spliced together can be polished by bonding the side surfaces of the seed crystals in advance instead of polishing the seed crystals independently, so that the height difference between the seed crystals of the substrates is controlled within a certain range. The problem that the height of each seed crystal after polishing cannot be accurately controlled is solved, and the mosaic spliced substrate formed by the mosaic spliced substrate is ensured to be positioned on a plane as much as possible. In addition, the side bonding is carried out on the spliced substrate in advance, so that the influence of disturbance on the substrate from the outside in the substrate moving and substrate deposition growth processes is effectively reduced. The phenomenon that edge polycrystal is generated at the splice joint caused by the factors of loose connection, dislocation, height difference and the like of the substrates is inhibited to a great extent, and the subsequent processing is facilitated.
A method for growing diamond based on side bonding and splicing is characterized in that the side bonding is utilized to carry out the splicing step in advance, then the spliced substrates are polished together, the spliced substrates with similar seed crystal height difference can be obtained, and the dislocation phenomenon caused by the fact that seed crystals are not tightly connected in the substrate moving and deposition growing processes can be avoided. The specific process steps are as follows:
(1) Side polishing
5-20 single crystal diamonds with the side length of 4-10 mm and the thickness of 0.3-5 mm are selected, and the side surface of the seed crystal is ground and polished, so that the roughness can be controlled within 10nm to ensure better combination of the metal film and the diamonds.
(2) Seed crystal cleaning and side argon ion beam bombardment
And ultrasonically cleaning the seed crystal with acetone, ethanol and deionized water after the side surface is polished. Subsequently using Ar + The ion beam bombards the sides of the diamond, removing adsorbed gases and native oxides.
(3) Deposition of metal films
Before bonding, a transition metal/bond metal layer (3-20)/(50-100) nm thick was deposited on the side of the diamond seed at room temperature in a plating system.
(4) Mosaic substrate side bonding
And after the film deposition is finished, taking out the seed crystal, splicing the side surfaces of the seed crystal together, and compacting to finish the side bonding of the mosaic substrate. Or directly carrying out Ar without depositing a metal film + And (5) performing side bonding on the bombarded diamond seed crystal.
(5) Substrate polishing
And placing the obtained substrate on a polished workpiece, so that the substrate spliced by all seed crystals can be polished under the same polishing process conditions, and the polished surface is ensured to have a slightly different height difference and surface state. The height difference of the substrate seed crystal after polishing is controlled within 10 mu m, and the surface roughness is controlled within 0.1 nm.
(6) Epitaxial growth of single crystal diamond
After the cleaning is completed, large-size epitaxial growth of single crystal diamond on the surface of the substrate is realized by utilizing a Microwave Plasma Chemical Vapor Deposition (MPCVD) method.
Further, the polishing process parameters in step 1 are as follows: the load is 100-800, the time is 10-60 min, and the roughness can be controlled within 1 mu m.
Further, the seed crystal is subjected to side polishing, and Ar is obtained after ultrasonic cleaning + The side surface of the diamond is bombarded to remove adsorbed gas and natural oxides, and the bombardment parameters of the argon ion beam in the step 2 are as follows: bias power source 40-100V, cavity pressure: 0.5-5 Pa, time: 5-10 min.
Further, the metal film is deposited in the step 3, a Ti/Au transition metal/bonding metal film is plated on the side face of the cleaned seed crystal by utilizing a film plating device for side face bonding, the transition layer metal is Ti/Ta/Cr/W/Mo, the bonding layer metal is Au, the transition metal layer is deposited to be 3-20 nm, and the bonding metal layer is deposited to be 50-100 nm.
Further, after the plating is completed, the seed crystal is quickly spliced and pressed, and the mosaic substrate is spliced in step 4, which includes two cases, one is to bond the diamond seed crystal after the plating and the other is to Ar + After bombardment, the diamond seed crystals are directly bonded, the side surfaces of the diamond seed crystals are completely bonded under the conditions of both bonding conditions, the bonding pressure is usually 10-50 MPa, and the bonding temperature is 100-300 ℃.
Further, the polishing of the substrate in step 5, before the growth of the substrate, requires polishing the substrate to obtain a good surface state and a small seed crystal height difference, and the parameters of the polishing machine are as follows: the load is 200-800, and the time is 10-90 min. Note that the polishing process is performed in the order of "low load slow speed-high load slow speed-low load high speed" to achieve fine polishing so that the height difference of the substrate seed crystal after polishing is controlled within 10 μm and the surface roughness is controlled within 0.1 nm.
Further, the substrate is placed in a micro-scaleIn the chamber of the wave plasma device, epitaxial growth of diamond is carried out, and the growth parameters in step 6 are as follows: into which CH is introduced 4 (2-10%), the growth power is 2000-3800W, the pressure is 15-25 kPa, the growth temperature is 700-1000 ℃, and the growth time is 50-200 h.
Further, the bonding metal is Au and Pt noble metal or alloy meeting the growth temperature, oxidation resistance and oxidation resistance.
The key of the implementation process of the invention is as follows:
1. in order to ensure good bonding of the metal layer to the diamond, the side roughness is controlled to be within 10 nm. Not only can ensure high enough bonding strength, but also does not influence the growth of diamond. The roughness can be controlled by changing the diamond granularity of the polishing disk and increasing the rotation speed of the polishing disk.
2. The argon beam bombardment not only can play a cleaning role, but also can change the roughness to ensure that the metal film has better adhesive force, and if only the surface pollution layer is considered for cleaning, the high-energy Ar can be ignored + The impact of surface damage caused by bombardment, however, in order to ensure good quality of the subsequent diamond substrate, serious damage to the surface of the diamond and excessive change of the physicochemical properties of the surface need to be avoided, namely, the surface of the diamond is safely cleaned, and the bias voltage is not excessively high. At bias power 40-100V, cavity pressure: cleaning for 5-10 min under the condition of 0.5-5 Pa.
3. The bonding process can be divided into two types of direct bonding of diamond and film plating bonding, and good bonding force is needed between diamond seed crystals, and film plating bonding is selected if the bonding force needs to be met by a single bonding metal layer. At this time, a transition metal layer is introduced, the thickness of the transition metal layer is 3-20 nm, and the thickness of the bonding metal layer is 50-100 nm, so that the seed crystal can have good bonding force while having a small splicing gap.
4. The bonding metal is usually a noble metal such as Au, pt, etc., in view of the fact that it is capable of both easy bonding and achieving the problems of no cracking, low stress, oxidation resistance, etc. at the diamond deposition temperature. The alloy coating can also be used for adjusting the melting point of the bonding metal.
5. In the mosaic substrate splicing process, the bonding of the side face of the seed crystal is rapidly completed, the adhesion of impurities is reduced, and in order to ensure that the bonding layer has larger bonding force in the subsequent polishing process, the bonding pressure is 10-50 MPa, and the bonding temperature is 100-300 ℃.
6. In the polishing process of the substrate, in order to obtain a good surface of the substrate, the surface roughness of the substrate is usually controlled to be 0.1nm, the height difference of seed crystals is controlled to be within 10 mu m, the seed crystals forming the substrate are required to be polished simultaneously, in the process, the substrate seeds possibly break in the polishing process due to insufficient bonding force at the spliced part and infirm splicing, therefore, firstly, the lower load is selected to carry out trial polishing slowly, then the load is gradually increased, the rotating speed is increased, the load parameters of the polishing machine are usually selected to be 200-800, and the polishing time is 10-90 min. Note that the polishing process is performed in the order of "low load slow-high load slow-low load high speed" to achieve finish polishing.
7. In the growth process, the temperature has obvious influence on the growth of the CVD single crystal diamond, the temperature is increased, the corresponding growth rate is increased, but the defect density is increased due to the excessively high temperature, and in order to ensure that the high-quality diamond crystal grows at a higher speed, the growth temperature interval is selected to be 700-1000 ℃. Under the condition of the same temperature, the high cavity pressure can obviously improve the growth rate, and the pressure is selected to be 15-25 kPa. The influence of microwave power on the growth process is mainly related to the ionization rate of a carbon source, and high ionization rate of carbon atoms can be obtained by high power, so that sp is more easily used in the deposition process 3 Form alignment and epitaxial growth, and high power to raise atomic H concentration for sp 2 The amorphous carbon phase etching action of the form is enhanced, but the excessively high energy input can be that the seed crystal substrate is overheated, and the crystal quality is affected, so that the power selection range is 2000-3800W. The increase of the carbon source concentration can effectively improve the growth rate, but the quality of the grown crystal is also affected correspondingly, and CH is introduced to ensure that a higher-quality CVD growth layer is obtained in the growth process and a higher growth rate is obtained at the same time 4 The concentration is selected to be 2-10%. In summary, the growth process parameters were as follows: introducing CH 4 (2-10%) the growth power is 2000-5000W, the pressure is 15-25 kPa,the growth temperature is 700-1000 ℃ and the growth time is 50-200 h.
The invention has the beneficial effects as follows:
(1) According to the invention, the seed crystals are spliced in advance by utilizing side bonding to obtain the mosaic substrate, and the large-size diamond is epitaxially grown, so that the polished seed crystals have similar surface states and height differences, the surface of the substrate is basically maintained on the same plane, and the problems that the height differences of the seed crystals are difficult to control and the surface states are uneven in the traditional splicing method are solved.
(2) The method for splicing and growing based on side bonding is more convenient to operate in the process of transferring and depositing and growing the substrate because the seed crystals are spliced in advance, greatly inhibits the phenomenon that the seed crystals are misplaced due to external disturbance in the process, reduces the occurrence of polycrystal at the edge of a spliced seam, and effectively improves the quality of growing diamond.
(3) The invention relates to a method for splicing and growing based on side bonding, which can control the size of a spliced seam to be very small and even reach nano-scale by the side bonding, and is beneficial to connecting the spliced seam together as soon as possible.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly described below. The following drawings are merely a brief description of the present invention.
FIG. 1 is a schematic illustration of a single crystal diamond seed sputter coated in a method of the present invention;
FIG. 2 is a schematic illustration of a side bonding process for a coated seed crystal in accordance with the present invention;
fig. 3 is a schematic view of a single crystal diamond grown by microwave plasma chemical vapor deposition after a substrate is composed of a plurality of seed crystals in the method of the present invention.
Wherein: 1. a single crystal diamond seed; 2. a transition metal layer; 3. a bonding metal layer; 4. epitaxially grown large-size diamond; 5. a splice joint; w (W) 1 The thickness of the transition metal layer; w (W) 2 Thickness of bonding metal layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention performs splicing treatment on diamond monocrystal seed crystals in advance by using side bonding, then precisely polishes all seed crystals on a substrate together, and then performs epitaxial growth of monocrystal diamond on the spliced substrate by using a Microwave Plasma Chemical Vapor Deposition (MPCVD) method. The method for growing diamond based on side bonding and splicing comprises the following steps:
example 1
10 single crystal diamonds with large surface orientation of (100) and sizes of 4×4×1mm are selected 3 Polishing the side surface, controlling the roughness of the side surface at 7nm, and ultrasonically cleaning 10 polished seed crystals by using acetone, ethanol and deionized water. Ar is carried out on the side surface of the seed crystal + Ion beam bombardment, bias voltage of 50V, cavity pressure of 3.5Pa, bombardment duration of 5min, and then plating Ti/Au film on the side of seed crystal by magnetron sputtering, wherein the film thickness is controlled at 5/52nm, as shown in figure 1; after the seed crystal is taken out, the seed crystal is subjected to side splicing at 250 ℃, and is compressed, and the bonding pressure is 10MPa, so that the side surface of the seed crystal is bonded as shown in figure 2; polishing the substrate produced after splicing, wherein the substrate formed by all seed crystals is placed on a polished workpiece to be polished together under the same process condition, so that the seed crystals have similar height difference and surface state after surface polishing; firstly, adopting a load of 200 and a time of 10min, then raising the load to 500, polishing for 15min, and finally adopting a load of 300 and polishing for 10min, wherein the height difference after polishing is 5 mu m, and the surface roughness is 0.3nm; respectively ultrasonically cleaning the sample with acetone and absolute ethyl alcohol for 10min; placing the processed monocrystalline diamond substrate into microwave plasmaIntroducing 300sccm hydrogen and 2% methane into a chamber of the equipment, controlling the growth power to 3800W, the pressure to 23KPa and the growth temperature to be about 750 ℃, and performing a single crystal diamond splicing growth test under the process for 100h; after the growth, the length and width are 10.4X4.5X4.6 mm 3 Large size diamond.
Example 2
15 single crystal diamonds with large surface orientation of (100) and sizes of 8×8×1mm are selected 3 Polishing the side surface, controlling the roughness of the side surface at 9nm, and ultrasonically cleaning 15 polished seed crystals by using acetone, ethanol and deionized water. Ar is carried out on the side surface of the seed crystal + Ion beam bombardment, bias voltage of 60V, cavity pressure of 1.5Pa, bombardment duration of 5min, and then plating Ti/Au film on the side of seed crystal by magnetron sputtering, wherein the film thickness is controlled at 15/100nm, as shown in figure 1; after the seed crystal is taken out, the seed crystal is subjected to side splicing at 200 ℃, and is compressed, and the bonding pressure is 12MPa, so that the side surfaces of the seed crystal are bonded, as shown in fig. 2; polishing the substrate produced after splicing, wherein the substrate formed by all seed crystals is placed on a polished workpiece to be polished together under the same process condition, so that the seed crystals have similar height difference and surface state after surface polishing; firstly, adopting a load of 200 for 10min, then raising the load to 700, polishing for 20min, and finally adopting the load of 200, polishing for 10min, wherein the height difference after polishing is 4 mu m, and the surface roughness is 0.2nm; respectively ultrasonically cleaning the sample with acetone and absolute ethyl alcohol for 10min; placing the treated monocrystalline diamond substrate into a chamber of microwave plasma equipment, introducing 300sccm hydrogen and 5% methane, controlling the growth power to 3000W, the pressure to 20kPa, controlling the growth temperature to about 800 ℃, and performing monocrystalline diamond splicing growth test under the process for 150 hours; after the growth, the length and width are 15.6X8.5X8.7 mm 3 Large size diamond.
Example 3
Selecting 20 single crystal diamond with large surface orientation of (100) and size of 10×10×1mm 3 Polishing the side surface with roughness of 5nm, and using 20 polished seed crystalsAnd carrying out ultrasonic cleaning on the acetone, the ethanol and the deionized water. Ar is carried out on the side surface of the seed crystal + Ion beam bombardment, bias voltage 80V, cavity pressure 4.0Pa, bombardment duration 5min, then plating Ti/Pt/Au film on the side of seed crystal by magnetron sputtering, film thickness being controlled at 5/15/100nm, as shown in figure 1; after the seed crystal is taken out, the seed crystal is subjected to side splicing at 300 ℃, and is compressed, and the bonding pressure is 20MPa, so that the side surfaces of the seed crystal are bonded, as shown in fig. 2; and polishing the substrates generated after splicing, wherein the substrate formed by all seed crystals is placed on a polished workpiece to be polished together under the same process condition, so that the seed crystals have similar height difference and surface state after surface polishing. Firstly, adopting a load of 300 for 5min, then raising the load to 800, polishing for 20min, and finally adopting the load of 300, polishing for 10min, wherein the height difference after polishing is 5 mu m, and the surface roughness is 0.6nm; respectively ultrasonically cleaning the sample with acetone and absolute ethyl alcohol for 10min; placing the treated monocrystalline diamond substrate into a chamber of microwave plasma equipment, introducing 300sccm hydrogen and 5% methane, controlling the growth power to 2700W, controlling the growth temperature to be about 800 ℃ and performing monocrystalline diamond splicing growth test under the process, wherein the growth time is 200 hours; after the growth, the length and width are 20.5X10.4X10.7 mm 3 Large size diamond.
Example 4
10 single crystal diamonds with large surface orientation of (100) and sizes of 8×8×1mm are selected 3 Polishing the side surface, controlling the roughness of the side surface to be 6nm, and ultrasonically cleaning 10 polished seed crystals by using acetone, ethanol and deionized water; ar is carried out on the side surface of the seed crystal + Ion beam bombardment, bias voltage 70V, cavity pressure 3.5Pa, bombardment duration 5min; after the seed crystal is taken out, directly bonding the side surface of the seed crystal at 350 ℃, compacting, and bonding under the pressure of 15MPa to bond the side surface of the seed crystal, as shown in figure 2; polishing the substrate produced after splicing, wherein the substrate formed by all seed crystals is placed on a polished workpiece to be polished together under the same process condition, so that the seed crystals have similar height difference and surface state after surface polishing; the load 250 is used first and then,the time is 15min, the load is increased to 800, the polishing is carried out for 20min, finally, the polishing is carried out for 10min by adopting the load of 200, the height difference after polishing is 5 mu m, and the surface roughness is 0.3nm; respectively ultrasonically cleaning the sample with acetone and absolute ethyl alcohol for 15min; placing the treated monocrystalline diamond substrate into a chamber of microwave plasma equipment, introducing 300sccm hydrogen and 4% methane, controlling the growth power to 3800W, the pressure to 22kPa, controlling the growth temperature to about 850 ℃, and performing monocrystalline diamond splicing growth test under the process, wherein the growth time is 150h; after the growth, the length and width are 15.2×7.9×8.2mm 3 Large size diamond.
Claims (2)
1. The method for splicing and growing diamond based on side bonding is characterized in that a plurality of single crystal diamond seed crystals are spliced into a mosaic substrate in advance by using side bonding, the substrate is subjected to the same polishing process treatment, and single crystal diamond epitaxial growth is carried out by microwave plasma chemical vapor deposition; the method specifically comprises the following steps:
(1) Side polishing
Selecting single-crystal diamond as seed crystal, and grinding and polishing the side surface of the seed crystal; the polishing process parameters are as follows: the load is 100-800, the time is 10-60 min, and the roughness can be controlled within 10 nm;
(2) Seed crystal cleaning and side argon beam bombardment
Side polishing the seed crystal, and after ultrasonic cleaning, ar + The bombardment of the side of the diamond removes adsorbed gas and natural oxide, and the bombardment parameters of the argon ion beam are as follows: bias power source 40-100V, cavity pressure: 0.5-5 Pa, time: 5-10 min;
(3) Deposition of metal films
Depositing a transition metal/bond metal layer on the side of the diamond seed crystal at room temperature in a coating system before bonding;
preparing a transition metal/bonding metal film on the side surface of the cleaned seed crystal by using a coating device, wherein the transition metal is Ti/Ta/Cr/W/Mo, the bonding layer metal is Au, the deposition transition metal layer is 3-20 nm, and the deposition bonding metal layer is 50-100 nm;
(4) Mosaic substrate side bonding
After the deposition of the film is completed, the seed crystal is taken out, the side surfaces of the seed crystal are spliced together and pressed in the room temperature atmosphere to complete the side bonding of the mosaic substrate, or the deposition of the metal film is not carried out, ar is used + The diamond seed crystal after bombardment treatment is directly bonded on the side surface;
the bonding metal is Au and Pt noble metal or alloy which accords with growth temperature, oxidation resistance and oxidation resistance;
the mosaic substrate splicing comprises two cases, one is bonding diamond seed crystals after coating, and the other is bonding Ar + Directly bonding diamond seed crystals after bombardment, wherein the two bonding conditions need to ensure that the side surfaces are completely bonded, the bonding pressure is 10-50 MPa, and the bonding temperature is 100-300 ℃;
(5) Substrate polishing
Placing the obtained substrate on a polished workpiece, so that the substrate spliced by all seed crystals can be polished under the same polishing process conditions, thereby ensuring that the polished surface has a slightly different height difference and surface state; the height difference of the substrate seed crystal after polishing is controlled within 10 mu m, and the surface roughness is controlled within 0.1 nm;
before the substrate is polished and grown, in order to obtain a good surface state of the substrate and a small seed crystal height difference, the substrate needs to be polished, and the polishing machine uses the following parameters: the load is 200-800, and the time is 10-90 min; note that the polishing process is performed in the order of "low load slow speed-high load slow speed-low load high speed" to achieve fine polishing, so that the height difference of the substrate seed crystal after polishing is controlled within 10 μm, and the surface roughness is controlled within 0.1 nm;
(6) Epitaxial growth of single crystal diamond
After the cleaning is finished, large-size epitaxial growth of the monocrystalline diamond on the surface of the substrate is realized by utilizing a Microwave Plasma Chemical Vapor Deposition (MPCVD); the growth parameters were as follows: into which CH is introduced 4 (2-10%), the growth power is 2000-3800W, the pressure is 15-25 kPa, and the growth temperature is 700-1The growth time is 50-200 h at 000 ℃.
2. The method for splicing and growing diamond based on side bonding as claimed in claim 1, wherein a plurality of seed crystals are spliced together in advance by side bonding, 5-20 single crystal diamonds with the side length ranging from 4 mm to 10mm and the thickness ranging from 0.3 mm to 5mm can be selected, and the single crystal diamonds are spliced into substrates for epitaxial growth, thereby realizing the preparation of large-size single crystal diamonds.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474021A (en) * | 1992-09-24 | 1995-12-12 | Sumitomo Electric Industries, Ltd. | Epitaxial growth of diamond from vapor phase |
| CN110079860A (en) * | 2019-03-29 | 2019-08-02 | 郑州磨料磨具磨削研究所有限公司 | A kind of splicing growing method of large size single crystal diamond epitaxial wafer |
| CN110541199A (en) * | 2019-10-11 | 2019-12-06 | 山东大学 | Preparation method of high-quality SiC seed crystal with diameter of 8 inches or more |
| CN112391680A (en) * | 2020-11-16 | 2021-02-23 | 物生生物科技(北京)有限公司 | Splicing growth process for large-size single crystal diamond |
| CN113463192A (en) * | 2021-07-02 | 2021-10-01 | 吉林大学 | Method for splicing and growing diamond single crystal |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474021A (en) * | 1992-09-24 | 1995-12-12 | Sumitomo Electric Industries, Ltd. | Epitaxial growth of diamond from vapor phase |
| CN110079860A (en) * | 2019-03-29 | 2019-08-02 | 郑州磨料磨具磨削研究所有限公司 | A kind of splicing growing method of large size single crystal diamond epitaxial wafer |
| CN110541199A (en) * | 2019-10-11 | 2019-12-06 | 山东大学 | Preparation method of high-quality SiC seed crystal with diameter of 8 inches or more |
| CN112391680A (en) * | 2020-11-16 | 2021-02-23 | 物生生物科技(北京)有限公司 | Splicing growth process for large-size single crystal diamond |
| CN113463192A (en) * | 2021-07-02 | 2021-10-01 | 吉林大学 | Method for splicing and growing diamond single crystal |
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