CN113193109A - Preparation method of composite film and composite film - Google Patents
Preparation method of composite film and composite film Download PDFInfo
- Publication number
- CN113193109A CN113193109A CN202110479316.3A CN202110479316A CN113193109A CN 113193109 A CN113193109 A CN 113193109A CN 202110479316 A CN202110479316 A CN 202110479316A CN 113193109 A CN113193109 A CN 113193109A
- Authority
- CN
- China
- Prior art keywords
- layer
- composite film
- thin film
- film layer
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000010409 thin film Substances 0.000 claims abstract description 144
- 239000010408 film Substances 0.000 claims abstract description 141
- 239000000758 substrate Substances 0.000 claims abstract description 118
- 238000002347 injection Methods 0.000 claims abstract description 40
- 239000007924 injection Substances 0.000 claims abstract description 40
- 238000005468 ion implantation Methods 0.000 claims abstract description 24
- 238000002513 implantation Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 77
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 62
- 230000008569 process Effects 0.000 claims description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 37
- 229910052710 silicon Inorganic materials 0.000 claims description 37
- 239000010703 silicon Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000137 annealing Methods 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 6
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 claims description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- WYOHGPUPVHHUGO-UHFFFAOYSA-K potassium;oxygen(2-);titanium(4+);phosphate Chemical compound [O-2].[K+].[Ti+4].[O-]P([O-])([O-])=O WYOHGPUPVHHUGO-UHFFFAOYSA-K 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 239000010410 layer Substances 0.000 description 268
- 235000012431 wafers Nutrition 0.000 description 71
- 235000012239 silicon dioxide Nutrition 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 14
- -1 hydrogen ions Chemical class 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000001307 helium Substances 0.000 description 8
- 229910052734 helium Inorganic materials 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 238000005498 polishing Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007943 implant Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000001994 activation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/072—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by laminating or bonding of piezoelectric or electrostrictive bodies
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/08—Shaping or machining of piezoelectric or electrostrictive bodies
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
Abstract
The application provides a preparation method of a composite film and the composite film. The preparation method comprises the steps of carrying out ion implantation on a first surface and a second surface of an original substrate to obtain a wafer implantation piece; the wafer injection sheet sequentially comprises a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer; bonding the first thin film layer and the first supporting substrate, and bonding the second thin film layer and the second supporting substrate to obtain a bonded body; the thermal expansion coefficient of the second supporting substrate is the same as that of the first supporting substrate; and heating the bonding body to a target temperature and preserving the temperature at the target temperature for a target time so as to separate the first thin film layer and the second thin film layer from the residual layer respectively to obtain a first composite film and a second composite film. By adopting the preparation method, the bonding body is prevented from being bent, the composite film is in a flat state, the composite film is prevented from being cracked, the yield of the composite film is improved, and the production cost of the composite film is reduced.
Description
Technical Field
The application relates to the technical field of semiconductors, in particular to a preparation method of a composite film and the composite film.
Background
The composite film made of piezoelectric material has the advantages of light weight, high voltage output, high dielectric strength, adjustable working frequency and the like, and plays an important role in functional conversion devices such as electricity, magnetism, sound, light, heat, humidity, gas, force and the like, so the composite film is more and more widely applied. Accordingly, the technology for preparing the composite film is also developing towards high efficiency, low cost and high quality.
The existing preparation of composite films usually adopts a direct bonding preparation technology. An original substrate is first processed by an ion implantation method to form a thin film layer and an excess layer and an implantation layer between the thin film layer and the excess layer. Then, an isolation layer is formed on one surface of the substrate base plate, and the surface of the thin film layer of the original base plate and the surface of the isolation layer of the substrate base plate are polished and cleaned to be in contact with each other to form a bonding body. And finally, heating the bonding body to perform annealing treatment. And in the annealing process, the injected ions in the injection layer are heated to form gas and generate bubbles, and the bubbles are connected with each other in the injection layer, so that the residual layer and the thin film layer are instantaneously and integrally separated to obtain the composite film.
However, because the thermal expansion coefficients of the composite film and the substrate are different greatly, and the expansion strength of the materials is in linear relation with the heating temperature, the higher the heating temperature is, the larger the expansion difference between the two materials with different thermal expansion coefficients is. When the bonding body is heated, acting force is generated between the original substrate and the substrate due to expansion difference, and the bonding body is bent. When the heating temperature reaches the separation temperature, the residual layer and the film layer are instantaneously and integrally separated, and the composite film can be restored to the flat state from the bent state in a short time. In the process of recovering the composite film to be in a flat state, the composite film is easy to crack due to larger force generated when the composite film is recovered to be flat, so that the yield of the composite film is reduced, and the production cost of the composite film is increased.
Disclosure of Invention
The application provides a preparation method of a composite film and the composite film, which aim to solve the problems that in the process of recovering the composite film to be in a flat state, the composite film is easy to crack due to large force generated when the composite film is recovered to be flat in the prior art, so that the yield of the composite film is reduced, and the production cost of the composite film is increased.
In a first aspect of the present application, there is provided a method for preparing a composite film, including:
performing ion implantation on the first surface and the second surface of the original substrate to obtain wafer implantation pieces; the wafer injection sheet sequentially comprises a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer, and injected ions are distributed in the first injection layer and the second injection layer;
bonding the first thin film layer of the wafer injection sheet with a first support substrate, and bonding the second thin film layer of the wafer injection sheet with a second support substrate to obtain a bonding body; the thermal expansion coefficients of the first supporting substrate and the second supporting substrate are different from the thermal expansion coefficient of the original substrate, and the thermal expansion coefficient of the second supporting substrate is the same as that of the first supporting substrate;
annealing the bonding body to separate the first thin film layer and the second thin film layer from the residual layer respectively to obtain a first composite film and a second composite film; the first composite film comprises a first support substrate and a first film layer, and the second composite film comprises a second support substrate and a second film layer.
Optionally, the thicknesses of the first thin film layer and the second thin film layer are both greater than or equal to 50nm and less than or equal to 3000 nm.
Optionally, a first intermediate layer is disposed between the first support substrate and the first thin film layer; and/or a second intermediate layer is arranged between the second support substrate and the second thin film layer; the first intermediate layer and the second intermediate layer each have a thickness of less than 5 μm.
Optionally, in the annealing process of the bonding body, a difference between a highest point and a lowest point of the bonding body is less than 1 mm.
Optionally, when the first thin film layer and the second thin film layer are separated from the remaining layer, a difference between a highest point and a lowest point of the first composite film is less than 1mm, and a difference between a highest point and a lowest point of the second composite film is less than 1 mm.
Optionally, the first support substrate and the second support substrate have the same structure.
Optionally, the original substrate is one of lithium niobate, lithium tantalate, silicon, gallium arsenide, quartz, rubidium titanyl phosphate, and potassium titanyl phosphate.
Optionally, in the annealing treatment process, the annealing temperature is greater than or equal to 100 ℃ and less than or equal to 600 ℃; the annealing time is more than or equal to 1min and less than or equal to 48 h.
Optionally, the energy of the ion implantation is greater than or equal to 50KeV and less than or equal to 1000 KeV; the ion implantation dosage is greater than or equal to 1 × 1015ions/cm2Is less than or equal to 1 x 1018ions/cm2。
In a second aspect of the present application, a composite film is provided, which is prepared by the preparation method of any one of the first aspect.
The application provides a preparation method of a composite film and the composite film. The preparation method of the composite film comprises the steps of carrying out ion implantation on a first surface and a second surface of an original substrate to obtain a wafer implantation piece; the wafer injection sheet sequentially comprises a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer, and injected ions are distributed in the first injection layer and the second injection layer; bonding the first thin film layer of the wafer injection sheet with a first support substrate, and bonding the second thin film layer of the wafer injection sheet with a second support substrate to obtain a bonding body; the thermal expansion coefficients of the first supporting substrate and the second supporting substrate are different from the thermal expansion coefficient of the original substrate, and the thermal expansion coefficient of the second supporting substrate is the same as that of the first supporting substrate; annealing the bonding body to separate the first thin film layer and the second thin film layer from the residual layer respectively to obtain a first composite film and a second composite film; the first composite film comprises a first support substrate and a first film layer, and the second composite film comprises a second support substrate and a second film layer.
By adopting the preparation method, after ion implantation is carried out on the first surface and the second surface of the original substrate, a wafer implantation piece is obtained, the first thin film layer of the wafer implantation piece is bonded with the first supporting substrate, the second thin film layer of the wafer implantation piece is bonded with the second supporting substrate, a bonding body is obtained, the thermal expansion coefficient of the first supporting substrate is the same as that of the second supporting substrate, in the heating process, the acting force generated between the wafer injection sheet and the first supporting substrate has the same magnitude and opposite direction with the acting force generated between the wafer injection sheet and the second supporting substrate, thereby avoiding the bending of the bonding body, when the first residual layer and the first film layer are instantly and integrally separated, the composite film is in a flat state, so that the composite film is prevented from being cracked, the yield of the composite film is improved, and the production cost of the composite film is reduced.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a method for preparing a composite film according to an embodiment of the present disclosure;
fig. 2 is a schematic flow chart of a method for manufacturing a composite film according to an embodiment of the present disclosure;
FIG. 3 is a schematic view of a first structure of a composite film according to an embodiment of the present disclosure;
FIG. 4 is a schematic diagram of a second structure of a composite film according to an embodiment of the present disclosure;
FIG. 5 is a schematic view of a third structure of a composite film according to an embodiment of the present disclosure;
fig. 6 is a schematic diagram of a fourth structure of a composite film according to an embodiment of the present disclosure.
Wherein, 110-original substrate; 120-wafer implant wafer, 1201-first thin film layer, 1202-first implant layer, 1203-residual layer, 1204-second implant layer, 1205-second thin film layer; 130-a first support substrate; 140-a second support substrate; 150-a first intermediate layer; 160 second intermediate layer.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
As described in the background of the present application, the direct bonding technique is commonly used to prepare composite films. An original substrate is first processed by an ion implantation method to form a thin film layer and an excess layer and an implantation layer between the thin film layer and the excess layer. Then, an isolation layer is formed on one surface of the substrate base plate, and the surface of the thin film layer of the original base plate and the surface of the isolation layer of the substrate base plate are polished and cleaned to be in contact with each other to form a bonding body. And finally, heating the bonding body to perform annealing treatment. And in the annealing process, the injected ions in the injection layer are heated to form gas and generate bubbles, and the bubbles are connected with each other in the injection layer, so that the residual layer and the thin film layer are instantaneously and integrally separated to obtain the composite film. However, because the thermal expansion coefficients of the composite film and the substrate are different greatly, and the expansion strength of the materials is in linear relation with the heating temperature, the higher the heating temperature is, the larger the expansion difference between the two materials with different thermal expansion coefficients is. When the bonding body is heated, acting force is generated between the original substrate and the substrate due to expansion difference, and the bonding body is bent. When the heating temperature reaches the separation temperature, the residual layer and the film layer are instantaneously and integrally separated, and the composite film can be restored to the flat state from the bent state in a short time. In the process of recovering the composite film to be in a flat state, the composite film is easy to crack due to larger force generated when the composite film is recovered to be flat, so that the yield of the composite film is reduced, and the production cost of the composite film is increased.
Therefore, in order to solve the above problems, embodiments of the present application provide a method for preparing a composite film, and referring to fig. 1, fig. 1 is a schematic structural diagram of the method for preparing the composite film.
Specifically, referring to fig. 2, the preparation method comprises the following steps:
step S11, performing ion implantation on the first surface and the second surface of the original substrate 110 to obtain wafer implanting pieces 120; the wafer implantation piece comprises a first thin film layer 1201, a first implantation layer 1202, a residual layer 1203, a second implantation layer 1204 and a second thin film layer 1205 in sequence, and implanted ions are distributed in the first implantation layer 1202 and the second implantation layer 1204.
The ion implantation method is not particularly limited in the present application, and any ion implantation method in the prior art may be used, the implanted ions may be ions that can generate gas by heat treatment, such as hydrogen ions, helium ions, argon ions, neon ions, and the like, and the ion implantation dose may be 1 × 1015ions/cm2-1×1018ions/cm2。
Optionally, in this step, the original substrate 110 may be one of lithium niobate, lithium tantalate, silicon, gallium arsenide, quartz, rubidium titanyl phosphate, and potassium titanyl phosphate. The material of the original substrate 110 may be selected according to the requirement, and the step is not particularly limited. Taking the original substrate 110 as a lithium niobate wafer and the implanted ions as helium ions as an example, the helium ions are implanted into both sides of the lithium niobate wafer, the implantation energy of the helium ions is not less than 50KeV and not more than 1000KeV, and the dosage is not less than 1 × 1016ions/cm2Is less than or equal to 1 x 1017ions/cm2(ii) a The thicknesses of the first thin film layer 1201 and the second thin film layer 1205 are adjusted by adjusting the ion implantation depth. Specifically, the greater the depth of ion implantation, the greater the thickness of the thin film layer produced; conversely, the smaller the depth of ion implantation, the smaller the thickness of the thin film layer produced. First thin film layer 1201 and second thin film obtained in this embodiment of the present applicationThe thickness of the film 1205 is greater than or equal to 50nm and less than or equal to 3000 nm. The thicknesses of first thin film layer 1201 and second thin film layer 1205 may be different, for example: the thickness of the first thin film layer 1201 is 900nm, and the thickness of the second thin film layer 1205 is 600 nm; preferably, first thin film layer 1201 and second thin film layer 1205 are the same thickness, for example: the thickness of the first thin film layer and the second thin film layer is 900 nm.
Step S12, bonding the first thin film layer 1201 of the wafer implantation piece 120 with the first support substrate 130, and bonding the second thin film layer 1205 of the wafer implantation piece 120 with the second support substrate 140 to obtain a bonded body; the first supporting substrate and the second supporting substrate have different thermal expansion coefficients from the original substrate, and the thermal expansion coefficient of the second supporting substrate is the same as that of the first supporting substrate.
The bonding method is not particularly limited in the present application, and any bonding method in the prior art, for example, surface activation bonding, may be used to obtain a bonded body. The surface activation method is not limited in the present application, and for example, plasma activation or chemical solution activation may be used.
Optionally, in this step, after ion implantation and before bonding, two contacting bonding surfaces generally need to be cleaned to enhance the bonding effect. The first and second support substrates 130 and 140 may be silicon, lithium niobate, lithium tantalate, silicon, gallium arsenide, quartz, silicon carbide, sapphire, or the like. Preferably, the first support substrate 130 and the second support substrate 140 are made of a single layer of silicon, for example. The first support substrate 130 and the second support substrate 140 have the same or similar thickness. For example, the thickness of each of the first and second support substrates 130 and 140 is 0.425 mm; the thickness of the first support substrate 130 is 0.4mm and the thickness of the second support substrate 140 is 0.425 mm; preferably, the thicknesses of the first and second support substrates 130 and 140 are the same.
Referring to fig. 3 and 4, optionally, a first intermediate layer 150 is disposed between the first support substrate 130 and the first thin-film layer 1201; and/or a second intermediate layer 160 is disposed between the second support substrate 140 and the second thin film layer 1205; the first intermediate layer 150 and the second intermediate layer 160 each have a thickness of less than 5 μm. The material of the first intermediate layer 150 and the second intermediate layer 160 may be silicon dioxide, silicon nitride, silicon oxynitride, tantalum pentoxide, quartz, aluminum oxide, diamond, or sapphire. Specifically, the first intermediate layer 150 and the second intermediate layer 160 may have a single-layer structure or a multi-layer structure, the number of layers of the first intermediate layer 150 and the second intermediate layer 160 and the material of each layer may be selected and set as required, and this step is not particularly limited.
Alternatively, the first intermediate layer 150 and the second intermediate layer 160 are each a single-layer structure. Silicon dioxide may be used as the first interlayer 150 and the second interlayer 160. A single layer of silicon is used as the first support substrate 130 and the second support substrate 140; preparing a first silicon dioxide layer, i.e., a first intermediate layer 150, on the first support substrate 130; preparing a second silicon oxide layer, i.e., a second intermediate layer 160, on the second support substrate 140; bonding the first thin film layer 1201 of the wafer implant 120 with the first silicon dioxide layer on the first support substrate 130, and bonding the second thin film layer 1205 of the wafer implant 120 with the first silicon dioxide layer on the second support substrate 140 to obtain a bonded body.
Alternatively, the first intermediate layer 150 and the second intermediate layer 160 are both multilayer structures, and the number of layers of the first intermediate layer 150 and the second intermediate layer 160 may be the same or different. A silicon dioxide layer and a polysilicon layer, which are sequentially stacked, may be used as the first intermediate layer 150 and the second intermediate layer 160; a single layer of silicon is used as the first support substrate 130 and the second support substrate 140; a first polysilicon layer and a first silicon dioxide layer are sequentially prepared on the first support substrate 130, a second polysilicon layer and a second silicon dioxide layer are sequentially prepared on the second support substrate 140, the first thin film layer 1201 of the wafer implantation piece 120 is bonded with the first silicon dioxide layer of the first intermediate layer 150 of the first support substrate 130, and the second thin film layer 1205 of the wafer implantation piece 120 is bonded with the second silicon dioxide layer of the second intermediate layer 160 of the second support substrate 140, so that a bonded body is obtained.
Step S13, annealing the bonding body to separate the first thin film layer 1201 and the second thin film layer 1205 from the residual layer 1203 respectively to obtain a first composite film and a second composite film; wherein the first composite film includes a first support substrate 130 and a first thin film layer 1201, and the second composite film includes a second support substrate 140 and a second thin film layer 1205. The first thin film layer 1201 in the first composite thin film and the second thin film layer 1205 in the second composite thin film have opposite crystal orientations.
Optionally, in the annealing process in this step, when the first thin film layer 1201 and the second thin film layer 1205 are separated from the residual layer 1203, a difference between a highest point and a lowest point of the first composite film is smaller than 1mm, and a difference between a highest point and a lowest point of the second composite film is smaller than 1 mm; and the difference value between the highest point and the lowest point of the bonding body is less than 1 mm. The annealing temperature is more than or equal to 100 ℃ and less than or equal to 600 ℃; the annealing time is more than or equal to 1min and less than or equal to 48 h. The bonding body needs to be insulated, and the purpose of the insulation is to improve the bonding force of the bonding body to be larger than 10MPa, and the damage of ion implantation to the first thin film layer 1201 and the second thin film layer 1205 can be recovered, so that the obtained properties of the first thin film layer 1201 and the second thin film layer 1205 are close to those of a lithium niobate wafer (functional thin film wafer). During the heat treatment, bubbles are formed in the first implanted layer 1202 and the second implanted layer 1204, for example, hydrogen ions form hydrogen gas, helium ions form helium gas, and the like, and as the heat treatment progresses, the bubbles in the first implanted layer 1202 and the second implanted layer 1204 are connected into one piece, and finally the first implanted layer 1202 and the second implanted layer 1204 are cracked, and the residual layer 1203 is separated from the first thin film layer 1201 and the second thin film layer 1205, respectively, so that the residual layer 1203 is peeled off from the bonded body. The thermal expansion coefficient of the first supporting substrate 130 is the same as that of the second supporting substrate 140, and in the heating process, the acting force generated between the wafer injection sheet 120 and the first supporting substrate 130 is the same as that generated between the wafer injection sheet 120 and the second supporting substrate 140, and the directions are opposite, so that the bonding body is prevented from being bent, the composite film is in a flat state when the residual layer 1203 is instantaneously and integrally separated from the first thin film layer 1201 and the second thin film layer 1205, and the composite film is prevented from being cracked. The first composite film and the second composite film obtained in the present application further need to be subjected to grinding and polishing treatment on the surface of the first thin film layer 1201 and the surface of the second thin film layer 1205. The present embodiment also provides a composite film, which is prepared by the preparation method steps S11-S13, referring to fig. 5 and 6, and includes the first support substrate 130 and the first film layer 1201, or includes the second support substrate 140 and the second film layer 1205. In the embodiment of the present application, the embodiment of the composite film structure portion and the embodiment of the preparation method portion may be referred to each other, and are not described herein again.
The preparation method disclosed by the embodiment of the application has the advantages that the process is simple, the operation is easy, the harsh conditions for preparing the nano-scale composite film are greatly improved, the preparation of two nano-scale composite films can be simultaneously realized, the requirement of large-scale industrial production is met, and the preparation method is suitable for large-scale popularization and application.
In order to make the scheme of the application clearer, specific examples are further disclosed in the embodiment of the application.
Example 1
1) Cleaning two 4-inch silicon wafers with a thickness of 0.5mm and smooth surfaces, and respectively depositing a layer of SiO 2.5 μm on the smooth surfaces of the two silicon wafers by PECVD (including but not limited to sputtering, evaporation and electroplating)2An intermediate layer, and a CMP process for planarization to improve SiO2The roughness is less than 0.5nm, and the surface flatness is less than 1 nm.
2) Preparing 4-inch lithium niobate wafer, and implanting helium ions into the lithium niobate wafer from the upper and lower surfaces of the lithium niobate wafer by ion implantation method at a dosage of 4 × 1016ions/cm2. And forming the lithium niobate wafer with a five-layer structure of a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer, wherein the thicknesses of the first thin film layer and the second thin film layer are both 1100 nm.
3) For SiO on a silicon wafer in step 1)2Cleaning the process surface of the middle layer and the process surface of the first thin film layer in the step 2), and bonding the process surface of the first thin film layer of the cleaned lithium niobate wafer by adopting a plasma bonding methodSiO with silicon wafer2Bonding the process surface of the middle layer; then SiO on the other silicon wafer in the step 1)2Cleaning the process surface of the middle layer and the process surface of the second thin film layer in the step 2), and bonding the process surface of the second thin film layer of the cleaned lithium niobate wafer and the SiO of the silicon wafer by adopting a plasma bonding method2And bonding the process surface of the middle layer to form a bonded body.
4) And (3) putting the bonding body in a nitrogen atmosphere for heat preservation at the temperature of 400 ℃ for 3h until the first thin film layer and the second thin film layer are separated from the rest layer respectively, polishing and thinning the first thin film layer and the second thin film layer to 900nm respectively, and simultaneously obtaining two identical first lithium niobate composite films and second lithium niobate composite films. The first lithium niobate composite film and the second lithium niobate composite film are both composed of laminated lithium niobate, silicon dioxide and silicon substrates.
The bonding body is basically not bent in the heat preservation process, and the difference value between the highest point and the lowest point of the bonding body is close to zero; when the first thin film layer and the second thin film layer are separated from the residual layer, the first lithium niobate composite film and the second lithium niobate composite film are basically not bent, and the difference value between the highest point and the lowest point of the first lithium niobate composite film and the second lithium niobate composite film is close to zero.
Example 2
1) Cleaning two 4-inch silicon wafers with the thickness of 0.5mm and smooth surfaces, and preparing SiO with the thickness of 500nm on one silicon wafer in a thermal oxidation mode2Intermediate layer of SiO2The roughness is less than 0.5nm, and the surface flatness is less than 1 nm;
2) preparing 4-inch lithium niobate wafer, and implanting helium ions into the lithium niobate wafer from the upper and lower surfaces of the lithium niobate wafer by ion implantation method at a dosage of 8 × 1016ions/cm2. And forming the lithium niobate wafer with a five-layer structure of a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer, wherein the thicknesses of the first thin film layer and the second thin film layer are both 900 nm.
3) For step 1) SiO on the silicon wafer prepared in (1)2Cleaning the process surface of the middle layer, the process surface of the other silicon wafer, the process surface of the first thin film layer and the process surface of the second thin film layer in the step 2), and bonding SiO on the cleaned silicon wafer by adopting a plasma bonding method2And bonding the process surface of the middle layer with the process surface of the first thin film layer, and bonding the process surface of the other silicon wafer with the process surface of the second thin film layer to form a bonded body.
4) And (3) putting the bonding body in an atmospheric environment for heat preservation at the temperature of 500 ℃ for 6h until the first thin film layer and the second thin film layer are separated from the residual layer respectively, polishing and thinning the first thin film layer and the second thin film layer to 700nm respectively, and obtaining a first lithium niobate composite film and a second lithium niobate composite film simultaneously.
The first lithium niobate composite film is composed of lithium niobate, silicon dioxide and a silicon substrate which are sequentially stacked; the second lithium niobate composite film is composed of lithium niobate and a silicon substrate which are sequentially laminated.
Wherein, the difference value between the highest point and the lowest point of the bonding body is less than 1mm in the heat preservation process; when the first thin film layer and the second thin film layer are separated from the residual layer respectively, the difference value between the highest point and the lowest point of the prepared first lithium niobate composite film is smaller than 1mm, and the difference value between the highest point and the lowest point of the second lithium niobate composite film is smaller than 1 mm.
Example 3
1) Preparing two 4-inch silicon wafers with a thickness of 0.5mm and smooth surfaces as a first supporting substrate and a second supporting substrate;
2) preparing 4-inch lithium niobate wafer, and implanting hydrogen ions into the lithium niobate wafer from the upper and lower surfaces of the lithium niobate wafer by ion implantation method at a dosage of 3 × 1017ons/cm2. And forming the lithium niobate wafer with a five-layer structure of a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer, wherein the thicknesses of the first thin film layer and the second thin film layer are both 600 nm.
3) Cleaning the process surface of one silicon wafer in the step 1) and the process surface of the first thin film layer in the step 2), and bonding the process surface of the first thin film layer of the cleaned lithium niobate wafer with the process surface of the silicon wafer by adopting a plasma bonding method; and cleaning the process surface of the other silicon wafer in the step 1) and the process surface of the second thin film layer in the step 2), and bonding the process surface of the second thin film layer of the cleaned lithium niobate wafer and the process surface of the silicon wafer by adopting a plasma bonding method to form a bonded body.
4) And (3) preserving the heat of the bonding body in an argon atmosphere at the temperature of 550 ℃ for 3h until the first thin film layer and the second thin film layer are separated from the rest layer respectively, polishing and thinning the first thin film layer and the second thin film layer to 500nm respectively, and simultaneously obtaining a first lithium niobate composite film and a second lithium niobate composite film which have the same structure.
The first lithium niobate composite film and the second lithium niobate composite film are both composed of laminated lithium niobate and silicon substrates.
The bonding body is basically not bent in the heat preservation process, and the difference value between the highest point and the lowest point of the bonding body is close to zero; when the first thin film layer and the second thin film layer are separated from the residual layer, the first lithium niobate composite film and the second lithium niobate composite film are basically not bent, and the difference value between the highest point and the lowest point of the first lithium niobate composite film and the second lithium niobate composite film is close to zero.
Example 4
1) Preparing two 4-inch silicon wafers with a thickness of 0.5mm and smooth surfaces as a first supporting substrate and a second supporting substrate;
2) preparing 4-inch lithium niobate wafers, and implanting hydrogen ions into the lithium niobate wafers from the upper and lower surfaces of the lithium niobate wafers by ion implantation at a dosage of 8 × 1016ions/cm2And 4X 1017ions/cm2. And forming the lithium niobate wafer with a five-layer structure of a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer, wherein the thicknesses of the first thin film layer and the second thin film layer are both 900nm and 1300 nm.
3) Cleaning the process surface of one silicon wafer in the step 1) and the process surface of the first thin film layer in the step 2), and bonding the process surface of the first thin film layer of the cleaned lithium niobate wafer with the process surface of the silicon wafer by adopting a plasma bonding method; and cleaning the process surface of the other silicon wafer in the step 1) and the process surface of the second thin film layer in the step 2), and bonding the process surface of the second thin film layer of the cleaned lithium niobate wafer and the process surface of the silicon wafer by adopting a plasma bonding method to form a bonded body.
4) And (3) preserving heat of the bonding body in the atmosphere, wherein the heat preservation temperature is 550 ℃, the heat preservation time is 3h, until the first thin layer and the second thin layer are respectively separated from the residual layer, polishing and thinning the first thin layer to 600nm, polishing and thinning the second thin layer to 900nm, and simultaneously obtaining a first lithium niobate composite film and a second lithium niobate composite film which have the same structure and different thicknesses.
The first lithium niobate composite film and the second lithium niobate composite film are both composed of laminated lithium niobate and silicon substrates.
Before the first thin film layer and the second thin film layer are separated from the residual layer respectively, the difference value between the highest point and the lowest point of the second bonding body is smaller than 1 mm; when the first thin film layer and the second thin film layer are respectively separated from the residual layer, the difference value between the highest point and the lowest point of the prepared first lithium niobate composite film is smaller than 1mm, and the difference value between the highest point and the lowest point of the second lithium niobate composite film is smaller than 1 mm.
In addition, on the basis of the above embodiments, other embodiments may also be derived, such as: on the basis of each embodiment, the functional thin film layer in the embodiment is replaced by lithium tantalate, gallium arsenide, quartz or silicon; that is, one skilled in the art can combine alternative materials and process parameters according to the above embodiments, and the application is not limited specifically.
The present application has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to limit the application. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the presently disclosed embodiments and implementations thereof without departing from the spirit and scope of the present disclosure, and these fall within the scope of the present disclosure. The protection scope of this application is subject to the appended claims.
Claims (10)
1. A method for preparing a composite film, comprising:
performing ion implantation on the first surface and the second surface of the original substrate to obtain wafer implantation pieces; the wafer injection sheet sequentially comprises a first thin film layer, a first injection layer, a residual layer, a second injection layer and a second thin film layer, and injected ions are distributed in the first injection layer and the second injection layer;
bonding the first thin film layer of the wafer injection sheet with a first support substrate, and bonding the second thin film layer of the wafer injection sheet with a second support substrate to obtain a bonding body; the thermal expansion coefficients of the first supporting substrate and the second supporting substrate are different from the thermal expansion coefficient of the original substrate, and the thermal expansion coefficient of the second supporting substrate is the same as that of the first supporting substrate;
annealing the bonding body to separate the first thin film layer and the second thin film layer from the residual layer respectively to obtain a first composite film and a second composite film; the first composite film comprises a first support substrate and a first film layer, and the second composite film comprises a second support substrate and a second film layer.
2. The method for preparing a composite film according to claim 1, wherein the thickness of each of the first film layer and the second film layer is 50nm or more and 3000nm or less.
3. The method for producing a composite film according to claim 1, wherein a first intermediate layer is provided between the first support substrate and the first film layer; and/or a second intermediate layer is arranged between the second support substrate and the second thin film layer; the first intermediate layer and the second intermediate layer each have a thickness of less than 5 μm.
4. The method for preparing the composite film according to claim 1, wherein the difference between the highest point and the lowest point of the bonding body is less than 1mm during the annealing treatment of the bonding body.
5. The method for preparing a composite film according to claim 1, wherein when the first film layer and the second film layer are separated from the residual layer, respectively, a difference between a highest point and a lowest point of the first composite film is less than 1mm, and a difference between a highest point and a lowest point of the second composite film is less than 1 mm.
6. The method of manufacturing a composite film according to claim 1, wherein the first support substrate and the second support substrate have the same structure.
7. The method of preparing a composite thin film according to claim 1, wherein the original substrate is one of lithium niobate, lithium tantalate, silicon, gallium arsenide, quartz, rubidium titanyl phosphate, and potassium titanyl phosphate.
8. The method for preparing the composite film according to claim 1, wherein in the annealing treatment process, the annealing temperature is not less than 100 ℃ and not more than 600 ℃; the annealing time is more than or equal to 1min and less than or equal to 48 h.
9. The method for preparing the composite film according to claim 1, wherein the energy of the ion implantation is 50KeV or more and 1000KeV or less; the ion implantation dosage is greater than or equal to 1 × 1015ions/cm2Is less than or equal to 1 x 1018ions/cm2。
10. A composite film, characterized in that it is produced by the process according to any one of claims 1 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110479316.3A CN113193109A (en) | 2021-04-30 | 2021-04-30 | Preparation method of composite film and composite film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110479316.3A CN113193109A (en) | 2021-04-30 | 2021-04-30 | Preparation method of composite film and composite film |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113193109A true CN113193109A (en) | 2021-07-30 |
Family
ID=76983249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110479316.3A Withdrawn CN113193109A (en) | 2021-04-30 | 2021-04-30 | Preparation method of composite film and composite film |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113193109A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI790002B (en) * | 2021-09-13 | 2023-01-11 | 新加坡商英幸創科有限公司 | Frequency tunable dielectric apparatus applied to building components and manufacturing method thereof |
CN115867107A (en) * | 2023-02-27 | 2023-03-28 | 青禾晶元(天津)半导体材料有限公司 | Method for synchronously preparing two composite piezoelectric substrates by using bonding technology |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104143497A (en) * | 2013-05-08 | 2014-11-12 | 上海华虹宏力半导体制造有限公司 | Method for manufacturing GaN epitaxial wafers or GaN substrates |
CN104868050A (en) * | 2014-06-09 | 2015-08-26 | 济南晶正电子科技有限公司 | Method of manufacturing thin film on substrate with different thermal expansion coefficient from original substrate |
CN107154450A (en) * | 2016-03-02 | 2017-09-12 | 映瑞光电科技(上海)有限公司 | A kind of multilayer bonding method for light emitting diode (LED) chip with vertical structure |
CN109671801A (en) * | 2017-10-13 | 2019-04-23 | 济南晶正电子科技有限公司 | Ultra-thin super optical flat plate base and preparation method thereof |
CN110880920A (en) * | 2018-09-06 | 2020-03-13 | 中国科学院上海微系统与信息技术研究所 | Preparation method of heterogeneous thin film structure |
CN112259678A (en) * | 2020-10-19 | 2021-01-22 | 济南晶正电子科技有限公司 | Method for improving burst of thin film layer and thin film material |
CN112382563A (en) * | 2020-11-13 | 2021-02-19 | 济南晶正电子科技有限公司 | Ion implantation thin film wafer separation method, single crystal thin film, and electronic component |
CN112420914A (en) * | 2020-11-23 | 2021-02-26 | 济南晶正电子科技有限公司 | Composite film, preparation method and electronic component |
-
2021
- 2021-04-30 CN CN202110479316.3A patent/CN113193109A/en not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104143497A (en) * | 2013-05-08 | 2014-11-12 | 上海华虹宏力半导体制造有限公司 | Method for manufacturing GaN epitaxial wafers or GaN substrates |
CN104868050A (en) * | 2014-06-09 | 2015-08-26 | 济南晶正电子科技有限公司 | Method of manufacturing thin film on substrate with different thermal expansion coefficient from original substrate |
CN107154450A (en) * | 2016-03-02 | 2017-09-12 | 映瑞光电科技(上海)有限公司 | A kind of multilayer bonding method for light emitting diode (LED) chip with vertical structure |
CN109671801A (en) * | 2017-10-13 | 2019-04-23 | 济南晶正电子科技有限公司 | Ultra-thin super optical flat plate base and preparation method thereof |
CN110880920A (en) * | 2018-09-06 | 2020-03-13 | 中国科学院上海微系统与信息技术研究所 | Preparation method of heterogeneous thin film structure |
CN112259678A (en) * | 2020-10-19 | 2021-01-22 | 济南晶正电子科技有限公司 | Method for improving burst of thin film layer and thin film material |
CN112382563A (en) * | 2020-11-13 | 2021-02-19 | 济南晶正电子科技有限公司 | Ion implantation thin film wafer separation method, single crystal thin film, and electronic component |
CN112420914A (en) * | 2020-11-23 | 2021-02-26 | 济南晶正电子科技有限公司 | Composite film, preparation method and electronic component |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI790002B (en) * | 2021-09-13 | 2023-01-11 | 新加坡商英幸創科有限公司 | Frequency tunable dielectric apparatus applied to building components and manufacturing method thereof |
CN115867107A (en) * | 2023-02-27 | 2023-03-28 | 青禾晶元(天津)半导体材料有限公司 | Method for synchronously preparing two composite piezoelectric substrates by using bonding technology |
CN115867107B (en) * | 2023-02-27 | 2023-12-08 | 青禾晶元(天津)半导体材料有限公司 | Method for synchronously preparing two composite piezoelectric substrates by using bonding technology |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9142448B2 (en) | Method of producing a silicon-on-insulator article | |
KR101828635B1 (en) | Semiconductor On Glass Substrate With Stiffening Layer and Process of Making the Same | |
RU2728484C2 (en) | Method of making composite substrate from sic | |
JP7522555B2 (en) | Method for transferring a thin layer to a supporting substrate having a different thermal expansion coefficient - Patents.com | |
CN110828298A (en) | Single crystal thin film composite substrate and method for manufacturing same | |
CN113193109A (en) | Preparation method of composite film and composite film | |
CN109166792B (en) | Method for preparing flexible single crystal film based on stress compensation and flexible single crystal film | |
TWI430339B (en) | Method for the preparation of a multi-layered crystalline structure | |
JP2013516767A5 (en) | ||
WO2021201220A1 (en) | Composite substrate and production method therefor | |
JP2019527937A (en) | Use of an electric field to peel a piezoelectric layer from a donor substrate | |
CN116669523A (en) | Preparation method of pyroelectric composite film | |
JP7262421B2 (en) | Piezoelectric composite substrate and manufacturing method thereof | |
JP5053252B2 (en) | Method for manufacturing a heterostructure comprising at least one thick layer of semiconductor material | |
US20240030883A1 (en) | Process for manufacturing a piezoelectric structure for a radiofrequency device and which can be used to transfer a piezoelectric layer, and process for transferring such a piezoelectric layer | |
WO2011074329A1 (en) | Method for manufacturing piezoelectric device | |
JP7515657B2 (en) | Composite substrate and method for manufacturing same | |
JP5643488B2 (en) | Manufacturing method of SOI wafer having low stress film | |
WO2022176689A1 (en) | Composite wafer and method for producing same | |
WO2021157218A1 (en) | Composite substrate and method for manufacturing same | |
CN117497477A (en) | Composite film and preparation method thereof | |
Radu | In memoriam Ulrich Gösele: wafer bonding á la carte | |
CN111510093A (en) | Piezoelectric film body for manufacturing bulk acoustic wave device and preparation method thereof | |
CN118173432A (en) | Low-warpage composite film and preparation method thereof | |
CN116065127A (en) | Composite film and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210730 |
|
WW01 | Invention patent application withdrawn after publication |