CN113628956A - Composite aperture film and preparation method thereof - Google Patents
Composite aperture film and preparation method thereof Download PDFInfo
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- CN113628956A CN113628956A CN202110678808.5A CN202110678808A CN113628956A CN 113628956 A CN113628956 A CN 113628956A CN 202110678808 A CN202110678808 A CN 202110678808A CN 113628956 A CN113628956 A CN 113628956A
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 73
- 239000010703 silicon Substances 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 25
- 238000009792 diffusion process Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- 238000005468 ion implantation Methods 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000001312 dry etching Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000001039 wet etching Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 229910021426 porous silicon Inorganic materials 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000110 cooling liquid Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/0203—Making porous regions on the surface
-
- 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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a composite aperture film, which comprises a first doped silicon layer and a second doped silicon layer which are stacked, wherein through holes with nanoscale are distributed on the first doped silicon layer, through holes with microscale are distributed on the second doped silicon layer, and the doping concentration of the first doped silicon layer is greater than that of the second doped silicon layer. The invention also relates to a preparation method of the composite aperture film. The composite aperture film has the characteristic of changing the aperture across the micro-nano scale in the thickness direction, and has improved performance in the fields of biosensing, optics, heat transfer and the like. The preparation method solves the technical situation that the conventional micro-nano processing technology is difficult to realize the preparation of the cross-scale variable-aperture porous film, changes the doping concentration of the surface of the substrate through the surface doping technology, and prepares the porous silicon film with the cross-micron to nano-scale variable-aperture characteristic in the thickness direction through the electrochemical corrosion technology.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a composite aperture film and a preparation method thereof.
Background
The variable-aperture porous film structure has gradient aperture distribution in the thickness direction, and has important application value in the research fields of biosensing, optics, heat transfer and the like. However, the pore diameters of the existing variable-pore-diameter thin film are mostly distributed in the same dimension, taking a porous silicon thin film as an example, the pore diameter regulation in the thickness direction can be realized on the same substrate by changing preparation conditions such as parameters of etching current, electrolyte solution ratio and the like, but the regulation is carried out in a small range under the same dimension, so that the further improvement of the performance of the variable-pore-diameter porous silicon thin film in the application fields is limited. Therefore, there is a need to develop a porous silicon thin film with a cross-scale variable pore size.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a composite aperture film which has the characteristic of changing the aperture across the micro-nano scale in the thickness direction and has improved performance in the fields of biosensing, optics, heat transfer and the like.
The invention also aims to provide a preparation method of the composite aperture film, which has simple and efficient process steps.
In order to achieve the above object, the present invention provides the following technical solutions.
A composite aperture film comprises a first doped silicon layer and a second doped silicon layer which are stacked, through holes with nanoscale are distributed on the first doped silicon layer, through holes with microscale are distributed on the second doped silicon layer, and the doping concentration of the second doped silicon layer is greater than that of the first doped silicon layer.
The preparation method of the composite aperture film comprises the following steps:
pretreating the moderately doped silicon substrate;
doping the shallow surface layer of the moderately doped silicon substrate to convert the shallow surface layer into a heavily doped silicon layer;
after obtaining the heavily doped silicon layer, carrying out electrochemical corrosion on the whole substrate; and
and thinning the surface of the substrate far away from the heavily doped silicon layer.
Compared with the prior art, the invention achieves the following technical effects:
1. the composite aperture film has the characteristic of changing the aperture across the micro-nano scale in the thickness direction, and has improved performance in the fields of biosensing, optics, heat transfer and the like.
2. The preparation method of the invention can simply and efficiently prepare the composite aperture film. The preparation method solves the technical situation that the conventional micro-nano processing technology is difficult to realize the preparation of the cross-scale variable-aperture porous film, changes the doping concentration of the surface of the substrate through the surface doping technology, and prepares the porous silicon film with the cross-micron to nano-scale variable-aperture characteristic in the thickness direction through the electrochemical corrosion technology.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic cross-sectional view of a composite pore size membrane of the present invention.
FIG. 2 is a flow chart of the method of making the composite pore size film of the present invention.
Description of the reference numerals
100 is a composite aperture film, 101 is a first doped silicon layer, and 102 is a second doped silicon layer.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. It should be understood that the description is illustrative only and is not intended to limit the scope of the present disclosure. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure.
Various structural schematics according to embodiments of the present disclosure are shown in the figures. The figures are not drawn to scale, wherein certain details are exaggerated and possibly omitted for clarity of presentation. The shapes of various regions, layers, and relative sizes and positional relationships therebetween shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and a person skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions, as actually required.
In the context of the present disclosure, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present. In addition, if a layer/element is "on" another layer/element in one orientation, then that layer/element may be "under" the other layer/element when the orientation is reversed.
Because the pore size distribution of the existing variable-pore-size porous membrane is in the same size, the further improvement of the performance of the variable-pore-size porous membrane in many application fields is limited. To this end, the present invention provides an improved porous membrane, and will be further described with reference to the accompanying drawings.
As shown in fig. 1, the composite aperture thin film 100 of the present invention includes a first doped silicon layer 101 and a second doped silicon layer 102 stacked, wherein through holes with nanometer scale are distributed on the first doped silicon layer 101, through holes with micrometer scale are distributed on the second doped silicon layer 102, and a doping concentration of the first doped silicon layer 101 is greater than a doping concentration of the second doped silicon layer 102.
The first doped silicon layer 101 is a heavily doped silicon layer and has a resistivity of 0.01 Ω · cm or less. The second doped silicon layer 102 is a moderately doped silicon layer having a resistivity in the range of 1-30 Ω -cm, preferably 1-10 Ω -cm. The resistivity directly reflects the doping level of the silicon layer. The heavily doped silicon layer and the moderately doped silicon layer may be p-type silicon substrates doped with boron, aluminum, gallium, or indium elements. The aperture of the through hole with the nanoscale is less than 50nm, and the depth of the through hole with the nanoscale is less than 5 mu m; the aperture of the through hole with the micron scale is more than 2 mu m, and the depth is less than 495 mu m.
The composite aperture membrane 100 is a unitary structure.
The composite aperture film has the characteristic of changing the aperture across the micro-nano scale in the thickness direction, can be used in the field of heat dissipation, and when cooling liquid evaporates, the aperture of the nano scale at an evaporation interface can provide strong capillary pressure difference as liquid supply power to realize the spontaneous flow of the cooling liquid, so that the whole cooling device does not need an external pumping system, the occupied space of a heat dissipation system is reduced, the power consumption is reduced, and the heat dissipation of a chip in a limited space is easy to realize. The second doped silicon layer 102 is used for supporting the first doped silicon layer 101, which is beneficial to reducing the flow resistance and ensuring the efficient transportation of the cooling liquid.
The composite pore diameter film of the present invention can be prepared by the process shown in fig. 2, which is specifically described below.
And preprocessing the moderately doped silicon substrate.
The moderately doped silicon substrate has a resistivity in the range of 1-30 Ω -cm, preferably 1-10 Ω -cm. The moderately-doped silicon substrate may be a p-type silicon substrate doped with a boron element, an aluminum element, a gallium element, or an indium element.
The pretreatment comprises the following steps: the surface of the moderately-doped silicon substrate is chemically treated with acid, alkali and ultrapure water. The acid includes hydrofluoric acid, hydrochloric acid, phosphoric acid, nitric acid, and the like. The alkali includes sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and the like.
And doping the shallow surface layer of the moderately doped silicon substrate to convert the shallow surface layer into a heavily doped silicon layer.
The doping is a diffusion process or an ion implantation process.
The diffusion process includes pre-deposition and drive-in. In the pre-deposition process, the diffusion temperature is set to 800-. The diffusion temperature was set at 1000-. Different doping concentrations and doping layer depths can be obtained by controlling the diffusion temperature and diffusion time during the drive-in process.
The process parameters of the ion implantation process comprise: the dopant amount is 1X 1015cm-2-10×1015cm-2The energy of the ion implanter is 50-200 keV. Different surface doping concentrations and surface doping layer depths can be obtained by controlling the doping amount and the energy of the ion implanter.
Preferably, before the ion implantation process, a thermal oxidation process is used to grow a silicon dioxide layer on the surface of the substrate, and the thickness of the silicon dioxide layer can be
In the present invention, the resistivity of the heavily doped silicon layer is 0.01 Ω · cm or less, and the thickness of the heavily doped silicon layer is 5 μm or less.
The impurity source of the doping process is a boron source, an aluminum source, a gallium source or an indium source. The impurity source is the same as the doping element of the doped silicon substrate itself.
And after the heavily doped silicon layer is obtained, carrying out electrochemical corrosion on the whole substrate.
The corrosion solution adopted by the electrochemical corrosion is a mixed solution of hydrofluoric acid solution and ethanol. The volume ratio of the hydrofluoric acid solution to ethanol in the present invention is not particularly limited, and may be any value greater than 0 and less than 100, for example, 1: 1. The corrosion current is 1-100mA/cm2Preferably 10 to 50mA/cm2。
The aperture of the composite aperture structure prepared by the electrochemical corrosion process is mainly influenced by the current density of the electrochemical corrosion process and the doping degree of the substrate. The size of the aperture is positively related to the current density and negatively related to the doping level of the substrate. Under the same electrochemical corrosion reaction conditions, a heavily doped substrate portion corresponds to the creation of a porous structure with nanometer-scale pore sizes, while a moderately doped substrate portion generally corresponds to the creation of a porous structure with micrometer-scale pore sizes.
And thinning the surface of the substrate far away from the heavily doped silicon layer.
The method for thinning is not particularly limited, and the surface of the substrate far away from the heavily doped silicon layer can be thinned by chemical mechanical polishing, mechanical grinding, wet etching, dry etching or combination of the processes and the like until the porous structure obtained by the electrochemical corrosion step is released.
The preparation method of the invention can simply and efficiently prepare the composite aperture film. The preparation method solves the technical situation that the conventional micro-nano processing technology is difficult to realize the preparation of the cross-scale variable-aperture porous film, changes the doping concentration of the surface of the substrate through the surface doping technology, and prepares the porous silicon film with the cross-micron to nano-scale variable-aperture characteristic in the thickness direction through the electrochemical corrosion technology.
The invention will be further illustrated with reference to two specific examples, but the invention is not limited thereto.
Example 1
A5 omega cm P-type silicon substrate is selected and is pretreated. Then, a layer is grown on the surface of the substrate by adopting a thermal oxidation process
The silicon dioxide layer of (1). And then, regulating and controlling the doping concentration of the shallow layer on the surface of the substrate by adopting an ion implantation process, wherein the process parameters are set as follows: the dopant amount ranges from 5X 1015cm-2The doping type is boron, and the energy range is 150 KeV. Then, preparing a cross-scale porous structure on the surface of the substrate by adopting an electrochemical corrosion process, wherein the corrosion solution is formed by mixing hydrofluoric acid solution and absolute ethyl alcohol solution in a volume ratio of 1:1, and the corrosion current is set to be 10mA/cm2. And finally, thinning the back of the silicon substrate by adopting a chemical mechanical polishing process until the blind holes become through holes, thereby forming the composite aperture film.
Example 2
A5 omega cm P-type silicon substrate is selected and is pretreated. After that, the pre-deposition diffusion of the surface source was carried out, with the diffusion temperature set at 900 ℃ and the diffusion time 20 minutes. Subsequently, boron is selected as a diffusion impurity source for carrying out the drive diffusion, and different surface doping concentrations and surface doping layer depths are obtained by controlling the diffusion temperature (1000-1250 ℃) and the diffusion time. Then, preparing a cross-scale porous structure on the surface of the substrate by adopting an electrochemical corrosion process, wherein the corrosion solution is formed by mixing hydrofluoric acid solution and absolute ethyl alcohol solution in a volume ratio of 1:1, and the corrosion current is set to be 10mA/cm2. And finally, thinning the back of the silicon substrate by adopting a chemical mechanical polishing process until the blind holes become through holes, thereby forming the composite aperture film.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The composite aperture film is characterized by comprising a first doped silicon layer and a second doped silicon layer which are stacked, through holes with nanoscale are distributed on the first doped silicon layer, through holes with microscale are distributed on the second doped silicon layer, and the doping concentration of the first doped silicon layer is greater than that of the second doped silicon layer.
2. The composite aperture membrane of claim 1, wherein the composite aperture membrane is a unitary structure; the first doped silicon layer is a heavily doped silicon layer, and the resistivity of the first doped silicon layer is less than 0.01 omega cm; the second doped silicon layer is a moderately doped silicon layer, and the resistivity of the second doped silicon layer ranges from 1 to 30 omega cm.
3. The composite aperture film of claim 2, wherein the heavily doped silicon layer and the moderately doped silicon layer are p-type silicon substrates doped with boron, aluminum, gallium, or indium.
4. The composite aperture membrane according to claim 1 or 2, wherein the nano-scale through-holes have an aperture of 50nm or less and a depth of 5 μm or less; the aperture of the through hole with the micron scale is more than 2 mu m, and the depth is less than 495 mu m.
5. The method for preparing a composite pore size membrane according to any one of claims 1 to 4, comprising:
pretreating the moderately doped silicon substrate;
doping the shallow surface layer of the moderately doped silicon substrate to convert the shallow surface layer into a heavily doped silicon layer;
after obtaining the heavily doped silicon layer, carrying out electrochemical corrosion on the whole substrate; and
and thinning the surface of the substrate far away from the heavily doped silicon layer.
6. The method of manufacturing according to claim 5, wherein the pre-treatment comprises: and chemically treating the surface of the moderately-doped silicon substrate by acid, alkali and ultrapure water.
7. The method according to claim 5 or 6, wherein the doping is a diffusion process or an ion implantation process.
8. The method according to claim 5 or 6, wherein the electrochemical etching process uses an etching current of 1-100mA/cm2。
9. The preparation method according to claim 8, wherein the electrochemical etching process uses an etching current of 10-50mA/cm2。
10. A method of manufacturing as claimed in claim 5 or 6, characterized in that the thinning is performed by chemical mechanical polishing, mechanical grinding, wet etching, dry etching or a combination thereof.
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| Title |
|---|
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