CN110970363A - Preparation method of heterogeneous integrated single crystal diamond film - Google Patents
Preparation method of heterogeneous integrated single crystal diamond film Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 134
- 239000010432 diamond Substances 0.000 title claims abstract description 134
- 239000013078 crystal Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 131
- 238000000034 method Methods 0.000 claims abstract description 88
- 230000007547 defect Effects 0.000 claims abstract description 59
- 239000010408 film Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000005468 ion implantation Methods 0.000 claims abstract description 24
- 239000010409 thin film Substances 0.000 claims abstract description 19
- 238000004381 surface treatment Methods 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims description 34
- 238000000137 annealing Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 238000010884 ion-beam technique Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 6
- 238000000678 plasma activation Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
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- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000009304 pastoral farming Methods 0.000 claims description 4
- 238000001020 plasma etching Methods 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- -1 SOI Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
- H01L21/7806—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices involving the separation of the active layers from a substrate
- H01L21/7813—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices involving the separation of the active layers from a substrate leaving a reusable substrate, e.g. epitaxial lift off
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
- H01L21/26506—Bombardment with radiation with high-energy radiation producing ion implantation in group IV semiconductors
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/76—Making of isolation regions between components
- H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
- H01L21/7624—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology
- H01L21/76251—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques
- H01L21/76254—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques with separation/delamination along an ion implanted layer, e.g. Smart-cut, Unibond
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
- H01L2021/26573—Bombardment with radiation with high-energy radiation producing ion implantation in diamond
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Abstract
The invention relates to a preparation method of a heterogeneous integrated single crystal diamond film, which at least comprises the following steps: providing a diamond substrate, carrying out ion implantation on the upper surface of the diamond substrate, forming a defect layer at a preset depth, and setting the diamond substrate on the defect layer as a substrate thin layer; growing a homoepitaxial diamond thin film layer on the surface of the substrate thin film layer; forming a first bonding medium layer on the surface of the diamond film layer; providing a heterogeneous substrate, and forming a second bonding medium layer on the upper surface of the heterogeneous substrate; bonding the first bonding medium layer and the second bonding medium layer to form a bonding structure; stripping the bonding structure along the defect layer to form a heterostructure; and carrying out surface treatment on the stripping surface of the heterostructure to remove the residual defect layer and the substrate thin layer. The homoepitaxial monocrystal diamond film is integrated on the heterogeneous substrate through ion implantation and bonding processes to obtain a large-area high-quality diamond film, and an advanced material platform is provided for application of photon and quantum sensing devices.
Description
Technical Field
The invention belongs to the field of functional material preparation, and particularly relates to a preparation method of a heterogeneous integrated single crystal diamond film.
Background
Diamond is a wide bandgap semiconductorThe forbidden band width reaches 5.47eV at normal temperature, and the glass has high refractive index, high thermal conductivity and excellent mechanical and chemical properties. The single crystal diamond has a Mohs hardness of 10, which is the hardest material known to be formed in the existing natural world and has a density of 3.52g/cm2The refractive index was 2.41. The single crystal diamond has a face-centered cubic structure, and each C atom is sp3Hybridization forms covalent bonds with 4 other adjacent C atoms, each 4C atoms constituting a regular tetrahedron, so that the natural diamond on a macroscopic scale tends to be octahedral. The diamond has strong C-C bonds and no free electrons, so that the diamond has high hardness and high chemical stability, and the melting point of the diamond is 3815 ℃. However, diamond is relatively easy to ignite, with an ignition point of 800 ℃ in pure oxygen and 1000 ℃ in air. Meanwhile, the diamond also has good biocompatibility. On the other hand, diamond can achieve high conductivity by doping with N. Diamond is therefore one of the ideal materials for optical, thermal and electronic devices.
Single crystal diamond is unique in that it has been developed with over 500 color centers, the wavelengths covering the various bands from ultraviolet to infrared, many of which have sufficient brightness to function as a single photon source, while some of which, especially the negatively charged nitrogen vacancy color center (NV-), exhibit highly desirable quantum properties. In general, when a device is fabricated by utilizing the above characteristics of diamond, a high-quality single crystal diamond submicron thin film material is generally required, including electronic, optical, and quantum devices. The diamond film grown by homoepitaxy has a large processing difficulty due to the over-thick substrate because the growth substrate is a diamond material, and has a series of problems of poor light field mode locking effect and the like due to the homogeneity of the film and the substrate. Due to lattice mismatch and thermal matching, the epitaxial growth based on the heterogeneous substrate has the disadvantages of more defects of the grown diamond film, poor crystal quality and serious influence on the performance of the device.
Aiming at the defects of the prior art, the invention provides a preparation method of a high-quality heterogeneous substrate integrated single crystal diamond film.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a method for preparing a high quality single crystal diamond thin film and to integrate it with a foreign substrate. The technology can break through the limit of the traditional method, obtain a large-area high-quality submicron-micron-thickness diamond film, and provide an advanced material platform for application of photon and quantum sensing devices.
In order to achieve the above and other related objects, the present invention provides a method for preparing a heterogeneous integrated single crystal diamond thin film, comprising at least the following steps:
providing a diamond substrate, carrying out ion implantation on the upper surface of the diamond substrate, wherein the ion implantation energy is used for enabling implanted ions to reach a preset depth in the diamond substrate, forming a defect layer at the preset depth, and setting the diamond substrate positioned above the defect layer as a substrate thin layer;
growing a homoepitaxial monocrystal diamond thin film layer on the surface of the substrate thin film layer;
forming a second bonding medium layer on the surface of the single crystal diamond film layer;
providing a heterogeneous substrate, and forming a first bonding medium layer on the upper surface of the heterogeneous substrate;
bonding one surface of the diamond substrate, which is covered with the first bonding medium layer, with one surface of the heterogeneous substrate, which is covered with the second bonding medium layer, to form a bonding structure;
peeling the bonding structure along the defect layer, and removing the diamond substrate to form a heterostructure;
and carrying out surface treatment on the stripping surface of the heterostructure to remove the residual defect layer and the substrate thin layer.
The invention also provides a preparation method of the heterogeneous integrated single crystal diamond film, which at least comprises the following steps:
providing a diamond substrate, carrying out ion implantation on the upper surface of the diamond substrate, wherein the ion implantation energy is enough to enable implanted ions to reach a preset depth in the diamond substrate, forming a defect layer at the preset depth, and setting the diamond substrate positioned above the defect layer as a substrate thin layer;
forming a first bonding medium layer on the upper surface of the substrate thin layer;
providing a heterogeneous substrate, and forming a second bonding medium layer on the upper surface of the heterogeneous substrate;
bonding one surface of the substrate thin layer covered with the first bonding medium layer with one surface of the heterogeneous substrate covered with the second bonding medium layer to form a bonding structure;
peeling the bonding structure along the defect layer, and removing the diamond substrate to form a heterostructure;
carrying out surface treatment on the stripping surface of the heterostructure to remove the residual defect layer;
and growing a homoepitaxial single crystal diamond film on one surface of the heterogeneous structure with the substrate thin layer.
Optionally, the bonding step further includes, before bonding, activating the first bonding medium layer and the second bonding medium layer by using a plasma activation method, where the gas used in the plasma activation method includes oxygen, nitrogen, and argon.
Optionally, the step of peeling further comprises the step of annealing the bonded structure at a high temperature before peeling.
Optionally, the high-temperature annealing temperature range is 500-1600 ℃, the annealing time is 1 minute to 24 hours, and the annealing atmosphere comprises nitrogen, argon, hydrogen and vacuum.
Optionally, the implanted ions are H ions or He ions.
Optionally, the energy range of the implanted ions is 20KeV to 2MeV, and the dose range of the implanted ions is 1E16ions/cm2～1E18inos/cm2。
Optionally, the preparation method of the homoepitaxial diamond film comprises a chemical vapor deposition method and a microwave plasma chemical vapor deposition method.
Optionally, the material of the foreign substrate comprises silicon, SOI, sapphire, silicon carbide, SiCOI.
Optionally, the first bonding base dielectric layer and the second bonding dielectric layer are made of silicon oxide, aluminum oxide and silicon nitride, the thickness of the first bonding base dielectric layer and the second bonding base dielectric layer is 0 nm-5 μm, and the growth method of the bonding dielectric layers comprises a thermal oxidation method and a vapor deposition method.
Optionally, the bonding temperature range is room temperature to 800 ℃, and the bonding environmental conditions include normal temperature and pressure, a vacuum environment, and a nitrogen atmosphere.
Optionally, the surface treatment method comprises a high temperature annealing method, a chemical mechanical polishing method, a reactive ion etching method, an ion beam etching method and an ion beam grazing incidence polishing method.
As described above, the method forms the defect layer on the diamond substrate by the ion implantation method through the ion implantation and bonding process, and the homoepitaxial monocrystal diamond film is bonded and peeled to the heterogeneous substrate to obtain the heterogeneous integrated monocrystal diamond film, so that the blank of growing a large-area diamond film on the heterogeneous substrate in the world at present is filled, the high monocrystal quality of the diamond film is ensured, and a material platform is provided for the micro-nano processing, optics and quantum application of the diamond film.
Drawings
FIG. 1 is a schematic view of a method for preparing a heterogeneous integrated single crystal diamond thin film according to an embodiment.
Fig. 2 to 9 are schematic structural diagrams corresponding to steps of a method for heterozygously integrating single-crystal diamond thin films according to an embodiment.
FIG. 10 is a schematic view of the method for preparing a heterogeneous integrated single crystal diamond thin film according to the second embodiment.
Fig. 11 to 18 are schematic structural diagrams corresponding to steps of the method for heterozygously integrating single-crystal diamond thin films according to the second embodiment.
Description of the element reference numerals
11 diamond substrate
111 defective layer
112 thin layer of substrate
113 single crystal diamond film layer
114 first bonding dielectric layer
12 heterogeneous substrate
121 second bonding dielectric layer
13 heterostructure
21 diamond substrate
211 defective layer
212 substrate thin layer
213 first bonding dielectric layer
214 single crystal diamond film layer
22 heterogeneous substrate
221 second bonding dielectric layer
23 heterostructure
1 bonding structure
2 bonding structure
d depth
depth of d
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 18. It should be noted that the drawings provided in the present embodiment are only schematic and illustrate the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, the form, quantity and proportion of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Example one
As shown in fig. 1 to 9, the present embodiment provides a method for preparing a hetero-integrated single-crystal graphene film.
Referring to fig. 1, the method for preparing a hetero-integrated single-crystal graphene film provided in this embodiment at least includes the following steps:
s1: providing a diamond substrate, carrying out ion implantation on the upper surface of the diamond substrate, wherein the ion implantation energy is enough to enable implanted ions to reach a preset depth in the diamond substrate, forming a defect layer at the preset depth, and setting the diamond substrate above the defect layer as a substrate thin layer;
s2: growing a homoepitaxial monocrystal diamond thin layer on the surface of the diamond substrate thin layer;
s3: forming a first bonding medium layer on the surface of the single crystal diamond thin film layer;
s4: providing a heterogeneous substrate, and forming a second bonding medium layer on the upper surface of the heterogeneous substrate;
s5: bonding one surface of the diamond substrate, which is covered with the first bonding medium layer, with one surface of the heterogeneous substrate, which is covered with the second bonding medium layer, to form a bonding structure;
s6: peeling the bonded structure along the defect layer, removing the diamond substrate, and forming a peeled heterostructure;
s7: and carrying out surface treatment on the stripping surface of the heterostructure to remove the residual defect layer and the substrate thin layer.
The technical solution of the present embodiment is further described in detail with reference to the accompanying drawings.
As shown in fig. 2, a diamond substrate 11 is provided, ion implantation is performed on the upper surface of the diamond substrate by ion implantation, a defect layer 111 is formed at a depth d of the diamond substrate, and the diamond substrate on the defect layer 111 is set as a substrate thin layer 112.
The ion species for the ion implantation can be selected from H ions or He ions, and other suitable ion types can be selected according to technical requirements. The ion beam with energy is incident into the material, the ion beam and the atoms or molecules in the material will have a series of physical or chemical interactions, the incident ions gradually lose energy and finally stay in the material, and some lattice defects are generated in the material, and a defect layer is formed. In the present embodimentThe energy of the H ions or the He ions is 20 KeV-2 MeV, and the implantation dose is 1E16ions/cm2～1E18ions/cm2The defect layer 111 is formed to a depth d of 10nm to 50 μm. The depth and defect concentration of the defect layer 111 are related to the energy and dose of the implanted ions, and specific technical parameters can be set according to actual needs.
As shown in fig. 3, a single crystal diamond thin film layer 113 is homoepitaxially grown on the upper surface of the substrate thin layer 112.
The preparation method of the homogeneous epitaxial diamond film comprises high-temperature vapor phase epitaxy methods such as a chemical vapor deposition method (CVD), a microwave plasma chemical vapor deposition Method (MPCVD) and the like. In this embodiment, the MPCVD method is used for epitaxial growth, the growth temperature range is 900-1500 ℃, the growth pressure range is 10 kPa-50 kPa, the growth environment is carbon-containing gas such as CH4 gas, and the like, and the auxiliary gas such as H2、O2Etc. shielding a gas such as N2、Ar2And the vacuum degree and the gas flow rate need to be accurately controlled in the growth process.
As shown in fig. 4, a first bonding medium layer 114 is formed on the surface of the single crystal diamond thin film layer 113.
As shown in fig. 5, a foreign substrate 12 is provided, and a first bonding medium layer 121 is formed on the upper surface of the foreign substrate 12.
The heterogeneous substrate is made of materials such as Si, SOI, sapphire, SiC, SiCOI and the like. In the present embodiment, Si is selected as the foreign substrate material.
The first bonding dielectric layer and the second bonding dielectric layer are made of silicon oxide, aluminum oxide and silicon nitride, the thickness range is 0 nm-5 mu m, and the growth method comprises a thermal oxidation method, a vapor deposition method and the like. The bonding medium layer has the main functions of enhancing bonding strength, absorbing gas released by bonding of a bonding surface and ensuring flatness of the film.
As shown in fig. 6, the first bonding medium layer 114 and the second bonding medium layer 121 are bonded to form a bonded structure 1.
The first bonding layer 114 and the second bonding dielectric layer 121 may also be activated prior to bonding using a plasma activation process using gases including oxygen, nitrogen, argon, or other gases. In the bonding process, the bonding temperature range is from room temperature to 800 ℃, and the bonding environmental conditions comprise normal temperature and normal pressure, a vacuum environment, a nitrogen atmosphere and the like.
As shown in fig. 7 and 8, the bonded structure 1 is peeled off along the defect layer 111, and the diamond substrate 11 is removed to form the heterostructure 13.
Before the peeling, the bonded structure 1 may be subjected to a high temperature annealing to facilitate the peeling step. The temperature range of high-temperature annealing can be 500-1600 ℃, the annealing time can be 1 minute to 24 hours, and the annealing atmosphere can be nitrogen, argon, hydrogen, vacuum or other atmospheres. During annealing, the concentration of implanted ions increases the pressure inside the defect, resulting in the breaking of chemical bonds and the propagation of defects, resulting in the formation of flat-type defects at the defect layer and, ultimately, in the delamination of the diamond substrate.
As shown in fig. 9, the heterostructure 13 is subjected to a surface treatment to remove the remaining defect layer 111 and remove the thin substrate layer 112, resulting in a hetero-integrated single crystal diamond thin film structure.
After the lift-off, the surface of the heterostructure 13 formed after the lift-off is also treated to remove the remaining defect layer 111 and the thin substrate layer 112. The surface treatment method comprises a high-temperature annealing method, a chemical mechanical polishing method, a reactive ion etching method, an ion beam grazing incidence polishing method and the like. In this embodiment, the heterostructure is surface treated by ion beam etching. The energy range of ion beams in the ion beam etching is 1 eV-10 keV, the environmental temperature is 0-600 ℃, the incident angle of the ion beams is 0-90 ℃, and the process time is 1-120 min.
In the embodiment, the homoepitaxial monocrystal diamond film is integrated on the heterogeneous substrate through ion implantation and bonding processes, the technology breaks through the limit of the traditional method, the large-area high-quality submicron-micron-thickness diamond film is obtained, and an advanced material platform is provided for application of photon and quantum sensing devices.
Example two
As shown in fig. 10 to 18, the present embodiment provides a method for preparing a hetero-integrated single-crystal graphene film,
referring to fig. 10, the present embodiment provides a method for preparing a heterogeneous integrated single crystal diamond thin film, including the following steps:
s1: providing a diamond substrate, carrying out ion implantation on the upper surface of the diamond substrate, wherein the ion implantation energy is enough to enable implanted ions to reach a preset depth in the diamond substrate, forming a defect layer at the preset depth, and setting the diamond substrate above the defect layer as a substrate thin layer;
s2: forming a first bonding medium layer on the upper surface of the diamond substrate;
s3: providing a heterogeneous substrate, and forming a second bonding medium layer on the upper surface of the heterogeneous substrate;
s4: bonding one surface of the diamond substrate, which is covered with the first bonding medium layer, with one surface of the heterogeneous substrate, which is covered with the second bonding medium layer, to form a bonding structure;
s5: peeling the bonded structure along the defect layer, removing the diamond substrate, and forming a peeled heterostructure;
s6: carrying out surface treatment on the stripping surface of the heterostructure to remove the residual defect layer and the substrate thin layer;
s7: and growing a homoepitaxy monocrystal diamond film on one surface of the heterogeneous structure with the substrate thin layer to obtain a heterogeneous integrated monocrystal diamond film structure.
As shown in fig. 11, a diamond substrate 21 is provided, ion implantation is performed on the upper surface of the diamond substrate 21 by ion implantation, a defect layer 211 is formed at a depth d' of the diamond substrate, and the diamond substrate located above the defect layer 211 is set as a substrate thin layer 212.
The ion species for the ion implantation can be selected from H ions or He ions, and other suitable ion types can be selected according to technical requirements. The ion beam with energy is incident into the material, the ion beam and the atoms or molecules in the material will produce a series of physical or chemical interactions, the incident ions gradually lose energy and finally stay in the material, and some crystal lattices are generated in the materialAnd a defect, i.e., a defective layer is formed. In this embodiment, the energy of the H ion or He ion is 20KeV to 2MeV, and the implantation dose is 1E16ions/cm2～1E18ions/cm2The depth d' of forming the defect layer 211 is 10nm to 50 μm. The depth and defect concentration of the defect layer 211 are related to the energy and dose of the implanted ions, and specific technical parameters can be set according to actual needs.
As shown in fig. 12, a first bonding medium layer 213 is formed on the surface of the diamond substrate.
As shown in fig. 13, a foreign substrate 22 is provided, and a second bonding medium layer 221 is formed on the upper surface of the foreign substrate 22.
The heterogeneous substrate is made of materials such as Si, SOI, sapphire, SiC, SiCOI and the like. In the present embodiment, Si is selected as the foreign substrate material.
The materials of the first bonding dielectric layer and the second bonding dielectric layer comprise silicon oxide, aluminum oxide and silicon oxide, the thickness of the first bonding dielectric layer and the second bonding dielectric layer is 0-5 nm, and the growth method of the bonding dielectric layers comprises a thermal oxidation method and a vapor deposition method. The bonding medium layer has the main functions of enhancing bonding strength, absorbing gas released by bonding of a bonding surface and ensuring flatness of the film.
As shown in fig. 14, the first bonding dielectric layer 213 and the second bonding dielectric layer 221 are bonded to form a bonding structure 2.
The first bonding layer 213 and the second bonding dielectric layer 221 may also be activated using a plasma activation method using a gas including oxygen, nitrogen, argon, or other gas before bonding. In the bonding process, the bonding temperature range is from room temperature to 800 ℃, and the bonding environmental conditions comprise normal temperature and normal pressure, a vacuum environment, a nitrogen atmosphere and the like.
As shown in fig. 15 and 16, the bonded structure 2 is peeled off along the defect layer 211, and the diamond substrate 21 is removed to form the heterostructure 23.
The bonded structure 2 may be subjected to a high temperature anneal prior to the stripping step to facilitate the stripping step. The temperature range of high-temperature annealing can be 500-1600 ℃, the annealing time can be 1 minute to 24 hours, and the annealing atmosphere can be nitrogen, argon, hydrogen, vacuum or other atmospheres. During annealing, the concentration of implanted ions increases the pressure inside the defect, resulting in the breaking of chemical bonds and the propagation of defects, resulting in the formation of flat-type defects at the defect layer and, ultimately, in the delamination of the diamond substrate.
As shown in fig. 17, the heterostructure 23 is subjected to a surface treatment to remove the remaining defect layer 211.
After the lift-off, the surface of the heterostructure formed after the lift-off is also treated to remove the remaining defect layer 211. The surface treatment method comprises a high-temperature annealing method, a chemical mechanical polishing method, a reactive ion etching method, an ion beam grazing incidence polishing method and the like. In this embodiment, the heterostructure 23 is treated by ion beam etching. The ion beam energy range of the ion beam etching is 1 ev-10 kev, the environment temperature is 0-600 ℃, the ion beam incidence angle is 0-90 degrees, and the process time is 1-120 min.
As shown in fig. 18, a single crystal diamond film 214 is homoepitaxially grown on the top surface of the substrate thin layer 212.
The preparation method of the homogeneous epitaxial diamond film comprises high-temperature vapor phase epitaxy methods such as a chemical vapor deposition method (CVD), a microwave plasma chemical vapor deposition Method (MPCVD) and the like. In this embodiment, the MPCVD method is used for epitaxial growth, the growth temperature range is 900-1500 ℃, the growth pressure range is 10 kPa-50 kPa, the growth environment is carbon-containing gas such as CH4 gas, and the like, and the auxiliary gas such as H2、O2Etc. shielding a gas such as N2、Ar2And the vacuum degree and the gas flow rate need to be accurately controlled in the growth process.
According to the embodiment, the homoepitaxial monocrystal diamond film is integrated on the heterogeneous substrate, the technology breaks through the limit of the traditional method, the large-area high-quality submicron-micron-thickness diamond film is obtained, and an advanced material platform is provided for application of photon and quantum sensing devices.
In summary, the preparation method of the heterogeneous integrated single crystal diamond film of the invention forms a defect layer on the diamond substrate by using the ion implantation method, and bonds and peels the homoepitaxial single crystal diamond film on the heterogeneous substrate to obtain the heterogeneous integrated single crystal diamond film, fills the blank of growing large-area diamond films on the current international heterogeneous substrate, ensures the high single crystal quality of the diamond film, and provides a material platform for micro-nano processing, optics and quantum application of the diamond film.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (12)
1. A method for preparing a heterogeneous integrated single crystal diamond film is characterized by at least comprising the following steps:
providing a diamond substrate, carrying out ion implantation on the upper surface of the diamond substrate, wherein the ion implantation energy is used for enabling implanted ions to reach a preset depth in the diamond substrate, forming a defect layer at the preset depth, and setting the diamond substrate positioned above the defect layer as a substrate thin layer;
growing a homoepitaxial monocrystal diamond thin film layer on the surface of the substrate thin film layer;
forming a first bonding medium layer on the surface of the single crystal diamond thin film layer;
providing a heterogeneous substrate, and forming a second bonding medium layer on the upper surface of the heterogeneous substrate;
bonding one surface of the diamond substrate, which is covered with the first bonding medium layer, with one surface of the heterogeneous substrate, which is covered with the second bonding medium layer, to form a bonding structure;
peeling the bonding structure along the defect layer, and removing the diamond substrate to form a heterostructure;
and carrying out surface treatment on the stripping surface of the heterostructure to remove the residual defect layer and the substrate thin layer.
2. A method for preparing a heterogeneous integrated single crystal diamond film is characterized by at least comprising the following steps:
providing a diamond substrate, carrying out ion implantation on the upper surface of the diamond substrate, wherein the ion implantation energy is used for enabling implanted ions to reach a preset depth in the diamond substrate, forming a defect layer at the preset depth, and setting a part of the diamond substrate positioned above the defect layer as a substrate thin layer;
forming a first bonding medium layer on the upper surface of the substrate thin layer;
providing a heterogeneous substrate, and forming a second bonding medium layer on the upper surface of the heterogeneous substrate;
bonding one surface of the substrate thin layer covered with the first bonding medium layer with one surface of the heterogeneous substrate covered with the second bonding medium layer to form a bonding structure;
peeling the bonding structure along the defect layer, and removing the diamond substrate to form a heterostructure;
carrying out surface treatment on the stripping surface of the heterostructure to remove the residual defect layer;
and growing a homoepitaxial single crystal diamond film on one surface of the heterogeneous structure with the substrate thin layer.
3. The method for preparing a hetero-integrated single-crystal diamond film according to claim 1 or 2, wherein the bonding step further comprises the step of activating the first bonding medium layer and the second bonding medium layer by a plasma activation method before bonding, wherein the gas used in the plasma activation method comprises oxygen, nitrogen and argon.
4. The method of claim 1 or 2, wherein the step of peeling further comprises a step of annealing the bonded structure at a high temperature before peeling.
5. The method for preparing a hetero-integrated single-crystal diamond film according to claim 4, wherein the high-temperature annealing temperature is 500-1600 ℃, the annealing time is 1 minute to 24 hours, and the annealing atmosphere comprises nitrogen, argon, hydrogen and vacuum.
6. The method of claim 1 or 2, wherein the implanted ions are H ions or He ions.
7. The method of claim 6, wherein the implanted ions have an energy ranging from 20KeV to 2MeV and a dose ranging from 1E16ions/cm2～1E18 ions/cm2。
8. The method for preparing a hetero-integrated single-crystal diamond film according to claim 1 or 2, wherein the method for growing the homoepitaxial diamond film comprises Chemical Vapor Deposition (CVD) or microwave plasma CVD.
9. The method of claim 1 or 2, wherein the heterogeneous substrate comprises silicon, SOI, sapphire, SiC, SiCOI.
10. The method for preparing a hetero-integrated single-crystal diamond film according to claim 1 or 2, wherein the materials of the first bonding medium layer and the second bonding medium layer comprise silicon oxide, aluminum oxide and silicon nitride, the thickness range is 0 nm-5 μm, and the growth method of the bonding medium layers comprises a thermal oxidation method and a vapor deposition method.
11. The method for preparing a hetero-integrated single-crystal diamond film according to claim 1 or 2, wherein the bonding temperature is in a range from room temperature to 800 ℃, and the bonding environment conditions include a vacuum environment, normal temperature and pressure, and a nitrogen atmosphere.
12. The method for preparing a hetero-integrated single crystal diamond film according to claim 1 or 2, wherein the surface treatment method comprises a high temperature annealing method, a chemical mechanical polishing method, a reactive ion etching method, an ion beam etching method and an ion beam grazing incidence polishing method.
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