CN114937602A - Method for wet etching of patterned gallium oxide - Google Patents
Method for wet etching of patterned gallium oxide Download PDFInfo
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- CN114937602A CN114937602A CN202210730245.4A CN202210730245A CN114937602A CN 114937602 A CN114937602 A CN 114937602A CN 202210730245 A CN202210730245 A CN 202210730245A CN 114937602 A CN114937602 A CN 114937602A
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- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 111
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000001039 wet etching Methods 0.000 title claims abstract description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 167
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 84
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 83
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 82
- 238000005530 etching Methods 0.000 claims abstract description 66
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- 238000005240 physical vapour deposition Methods 0.000 claims description 12
- 229910052594 sapphire Inorganic materials 0.000 claims description 10
- 239000010980 sapphire Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001259 photo etching Methods 0.000 claims description 9
- 238000005566 electron beam evaporation Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 5
- 238000004549 pulsed laser deposition Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000000206 photolithography Methods 0.000 claims description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 claims description 2
- 238000000059 patterning Methods 0.000 abstract description 9
- 238000001312 dry etching Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 22
- 238000000151 deposition Methods 0.000 description 14
- 238000010586 diagram Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000407 epitaxy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance 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
- H01L21/04—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
- H01L21/34—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 not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/465—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/467—Chemical or electrical treatment, e.g. electrolytic etching using masks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention relates to a method for patterning gallium oxide, in particular to a method for etching patterned gallium oxide by a wet method, and provides the method for etching the patterned gallium oxide by the wet method, which comprises the following steps: s1, preparing a gallium oxide layer; s2, preparing a photoresist mask pattern layer; s3, preparing an aluminum metal layer; s4, forming a patterned metal aluminum mask layer; s5, preparing a silicon dioxide mask layer; s6, preparing a patterned silicon dioxide mask layer; s7, wet etching the gallium oxide layer; and S8, removing the silicon dioxide mask layer by wet etching. The invention solves the technical problems of high mask layer silicon dioxide wet etching rate and difficult control in the existing gallium oxide wet etching and the problem of high cost of silicon dioxide dry etching.
Description
Technical Field
The invention relates to a method for patterning gallium oxide, in particular to a method for etching patterned gallium oxide by a wet method.
Background
In comparison with GaN and SiC material, gallium oxide (Ga) 2 O 3 ) The material has a larger band gap value (4.9eV), a critical breakdown electric field is as high as 8MV/cm, and the material shows an ultra-high BarlGau value, and is very suitable for high-power electronic equipment. In addition, gallium oxide has very high transmittance in the visible region and ultraviolet region (>80%) can be used as a transparent conductive material and is highly suitable for the production of ultraviolet emitting/detecting devices and solar blind sensors.
At present, the patterning method of gallium oxide mainly comprises dry etching and wet etching. The dry etching has the characteristics of adjustable etching rate, high patterning precision, good uniformity and repeatability and the like, but the dry etching equipment is expensive and high in cost, and has large damage to materials. In contrast, wet etching does not require expensive equipment, is convenient to operate, has low etching cost and high etching rate, and can be used for mass production. Currently, the wet etching of gallium oxide mostly uses silicon dioxide as a mask. Because the wet etching rate of the silicon dioxide is high and is not easy to control, the patterning of the silicon dioxide mask still uses the dry etching. Therefore, in order to save cost, it is necessary to develop an all-wet etching method to achieve the purpose of patterning gallium oxide.
Disclosure of Invention
The invention aims to solve the technical problems of high wet etching rate and difficult control of mask layer silicon dioxide and high cost of a dry etching processing process in the existing wet etching of gallium oxide, and provides a novel method for etching patterned gallium oxide by a full wet method.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
a method for wet etching patterned gallium oxide is characterized by comprising the following steps:
s1, preparing a gallium oxide layer on the substrate;
s2, preparing a photoresist mask pattern layer on the surface of the gallium oxide layer by a photoetching method;
s3, preparing an aluminum metal layer on the surface of the photoresist mask pattern layer to obtain a sample;
s4, stripping the photoresist mask pattern layer of the sample and the metal aluminum above the photoresist mask pattern layer, and forming a patterned metal aluminum mask layer on the gallium oxide layer;
s5, preparing a silicon dioxide mask layer on the surface of the gallium oxide layer covered with the metal aluminum mask layer;
s6, performing wet etching to remove the metal aluminum mask layer below the silicon dioxide layer to obtain a patterned silicon dioxide mask layer;
s7, under the protection of the silicon dioxide mask layer, performing wet etching on the gallium oxide layer;
and S8, performing wet etching to remove the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
Further, in step S1, the substrate is a sapphire substrate, a single crystal silicon substrate, a silicon carbide substrate, or a diamond substrate;
the gallium oxide layer is prepared by any one of metal organic chemical vapor deposition, molecular beam epitaxy, pulsed laser deposition, magnetron sputtering, atomic layer deposition, sol-gel method, halide vapor epitaxy and atomized chemical vapor deposition, and the thickness of the gallium oxide layer is 20 nm-2 μm.
Further, in step S2, the photolithography method specifically includes: coating AZ5214 reverse photoresist or other photoresist suitable for metal stripping on the gallium oxide layer, and forming the photoresist mask pattern layer by exposure and development, wherein the minimum size and the interval of the patterns of the photoresist mask pattern layer are larger than 2 μm.
Further, in step S3, the aluminum metal layer is formed by electron beam evaporation or thermal evaporation, and a metal aluminum film with a thickness of 50-1000 nm is formed on the surface of the photoresist mask pattern layer.
Further, in step S4, the step of peeling off the photoresist mask pattern layer of the sample and the metal aluminum thereon is to soak the sample one prepared in step S3 in acetone at 60 ℃ until the photoresist mask pattern layer and the metal aluminum thereon are completely peeled off.
Further, in step S5, the silicon dioxide layer is prepared by any one of chemical vapor deposition, physical vapor deposition and atomic layer deposition, and the thickness of the silicon dioxide mask layer is smaller than that of the aluminum metal layer.
Further, in step S6, the wet etching is to etch away all the aluminum metal at 50-80 ℃ by using 85% concentrated phosphoric acid or a special aluminum etching solution, and during the etching of the aluminum metal, the silicon dioxide attached above the aluminum metal is also peeled off; the special aluminum etching liquid is a mixed liquid of phosphoric acid, acetic acid, nitric acid and water.
Further, in step S7, the wet etching is performed by using 85% concentrated phosphoric acid as an etching solution, and the etching temperature is 135-155 ℃; or concentrated sulfuric acid is used as etching liquid, and the etching temperature is 150-190 ℃.
Further, in step S8, the wet etching is performed by using a diluted hydrofluoric acid solution, a mixture of ammonia and hydrofluoric acid, or a mixture of ammonium fluoride and hydrofluoric acid as an etching solution, and the etching temperature ranges from 20 ℃ to 35 ℃.
Further, in step S1, the substrate is a sapphire substrate, the thickness of the gallium oxide layer is 100nm, and the gallium oxide layer is prepared by an atomic layer deposition method;
in step S2, the photoresist used is AZ5214 inverse photoresist, and the minimum size and the pitch of the pattern of the photoresist mask pattern layer are 3 μm;
in the step S3, the aluminum metal layer is formed by electron beam evaporation to form a metal aluminum film with a thickness of 100nm on the surface of the photoresist mask pattern layer;
in step S5, the silicon dioxide mask layer is prepared by a physical vapor deposition method, and the thickness of the silicon dioxide mask layer is 50 nm;
in step S6, the etching liquid adopted by the wet etching is aluminum etching liquid, and the etching temperature is 60 ℃;
in step S7, the etching solution adopted by the wet etching is a hot phosphoric acid solution with the concentration of 85%, and the etching temperature is 140 ℃;
in step S8, the etching solution used in the wet etching is a diluted hydrofluoric acid solution, and the etching temperature is 30 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the invention, the metal aluminum and the silicon dioxide attached to the surface of the metal aluminum are stripped by only adopting a wet etching process of the metal aluminum in the patterning process of the silicon dioxide mask layer to obtain the patterned silicon dioxide mask layer, and compared with the process of adopting a dry etching process to etch the silicon dioxide mask layer in the wet etching process of the patterned gallium oxide, the wet etching process of the silicon dioxide is not adopted, so that the etching rate is high, the control is difficult, and the dry etching process is not adopted, so that the cost is saved to a great extent;
2. the patterned gallium oxide mask layer is obtained by etching the metal aluminum, and the target pattern cannot be deformed due to the etching of the metal aluminum, so that the method is low in cost and can obtain the target pattern to a greater extent.
Drawings
FIG. 1 is a flowchart of a wet etching process for patterning gallium oxide according to an embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating a structure of a patterned gallium oxide layer by wet etching according to an embodiment of the invention; wherein the content of the first and second substances,
(a) a schematic diagram of preparing a gallium oxide layer on a sapphire substrate;
(b) the schematic diagram of preparing a photoresist mask pattern layer on a gallium oxide layer is shown;
(c) the schematic diagram of preparing the aluminum metal layer by adopting an evaporation method;
(d) a schematic diagram of a patterned aluminum metal layer formed by a lift-off process;
(e) a schematic diagram of a silicon dioxide mask layer formed on a gallium oxide layer covered with a patterned aluminum metal layer;
(f) forming a schematic diagram of a graphical silicon dioxide mask layer after wet etching of metal aluminum;
(g) the schematic diagram of the gallium oxide layer is etched by a wet method under the patterned silicon dioxide mask layer;
(i) and etching the silicon dioxide mask layer by a wet method to obtain a schematic diagram of the graphical gallium oxide layer.
The reference numbers are as follows:
101-substrate, 102-gallium oxide layer, 103-photoresist mask pattern layer, 104-aluminum metal layer and 105-silicon dioxide mask layer.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Example one
As shown in fig. 1-2, the method for wet etching patterned gallium oxide provided by the present invention comprises the following steps:
step 1: depositing a gallium oxide layer 102 on a substrate 101 by using an atomic layer deposition method, wherein the thickness of the gallium oxide layer 102 is 100nm, and the substrate (101) is a sapphire substrate in this embodiment, as shown in fig. 2 (a);
step 2: preparing a photoresist mask pattern layer 103 with a pattern on a gallium oxide layer 102 by using a conventional photoetching technology, specifically, coating AZ5214 reverse photoresist on the gallium oxide layer 102, and forming the photoresist mask pattern layer 103 by exposure and development, wherein the minimum size and the interval of the pattern of the photoresist mask pattern layer 103 are 3 microns, as shown in fig. 2 (b);
and step 3: forming an aluminum metal layer 104 of 100nm on the photoresist mask pattern layer 103 by electron beam evaporation to obtain a sample one, as shown in fig. 2 (c);
and 4, step 4: soaking the first sample in the step 3 in acetone at 60 ℃, and stripping the photoresist mask pattern layer 103 of the first sample and the metal aluminum attached above the photoresist mask pattern layer to form a patterned aluminum metal layer, as shown in fig. 2 (d);
and 5: depositing a silicon dioxide mask layer 105 with a thickness of 50nm on the surface covered with the patterned aluminum metal layer by a physical vapor deposition method, as shown in fig. 2 (e);
and 6: performing wet etching by using an aluminum etching solution (a mixed solution of phosphoric acid, nitric acid, acetic acid and water) at the temperature of 60 ℃, and removing the metal aluminum mask layer below the silicon dioxide layer to obtain a patterned silicon dioxide mask layer, as shown in fig. 2 (f);
and 7: under the protection of the patterned silicon dioxide mask layer, wet etching is carried out at 140 ℃ by adopting hot phosphoric acid solution with the concentration of 85%, and the gallium oxide layer which is not covered with the silicon dioxide mask layer is etched, as shown in fig. 2 (g);
and 8: wet etching is performed at 30 ℃ by using a dilute hydrofluoric acid solution to etch away the silicon dioxide mask layer, so as to obtain a patterned gallium oxide layer, as shown in fig. 2 (i).
Example two
The invention provides a method for etching graphical gallium oxide by a wet method, which comprises the following steps:
step 1: depositing a gallium oxide layer 102 on the sapphire substrate by utilizing an atomic layer deposition method, wherein the thickness of the gallium oxide layer 102 is 500 nm;
step 2: preparing a photoresist mask pattern layer 103 with a pattern on a gallium oxide layer 102 by utilizing a conventional photoetching technology, specifically, coating AZ5214 reverse photoresist on the gallium oxide layer 102, and forming the photoresist mask pattern layer 103 through exposure and development, wherein the minimum size of the pattern of the photoresist mask pattern layer 103 is 4 microns, and the minimum distance is 10 microns;
and step 3: forming a 400nm aluminum metal layer 104 on the photoresist mask pattern layer 103 through electron beam evaporation to obtain a second sample;
and 4, step 4: soaking the second sample in the step 3 in acetone at 60 ℃, and stripping off the photoresist mask pattern layer 103 of the second sample and the metal aluminum attached above the photoresist mask pattern layer to form a patterned aluminum metal layer;
and 5: depositing a silicon dioxide mask layer 105 with the thickness of 200nm on the surface of the aluminum metal layer covered with the graph by a physical vapor deposition method;
step 6: wet etching is carried out at the temperature of 50 ℃ by adopting aluminum etching liquid (mixed liquid of phosphoric acid, nitric acid, acetic acid and water), and a metal aluminum mask layer below the silicon dioxide layer is removed to obtain a patterned silicon dioxide mask layer;
and 7: under the protection of a patterned silicon dioxide mask layer, adopting a hot phosphoric acid solution with the concentration of 85 percent to carry out wet etching at the temperature of 135 ℃, and etching the gallium oxide layer which is not covered by the silicon dioxide mask layer;
and 8: and (3) carrying out wet etching by adopting a diluent of hydrofluoric acid at the temperature of 20 ℃, and etching the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
EXAMPLE III
The invention provides a method for etching graphical gallium oxide by a wet method, which comprises the following steps:
step 1: depositing a gallium oxide layer 102 on the sapphire substrate by utilizing an atomic layer deposition method, wherein the thickness of the gallium oxide layer 102 is 2 microns;
step 2: preparing a photoresist mask pattern layer 103 with a pattern on a gallium oxide layer 102 by utilizing a conventional photoetching technology, specifically, coating AZ5214 reverse photoresist on the gallium oxide layer 102, and forming the photoresist mask pattern layer 103 through exposure and development, wherein the minimum size of the pattern of the photoresist mask pattern layer 103 is 5 microns, and the minimum distance is 10 microns;
and 3, step 3: forming an 800nm aluminum metal layer 104 on the photoresist mask pattern layer 103 through electron beam evaporation to obtain a third sample;
and 4, step 4: soaking the sample III in the step 3 in acetone at 60 ℃, and stripping off the photoresist mask pattern layer 103 of the sample III and the metal aluminum attached above the photoresist mask pattern layer to form a patterned aluminum metal layer;
and 5: depositing a silicon dioxide mask layer 105 with the thickness of 500nm on the surface of the aluminum metal layer covered with the graph by a physical vapor deposition method;
step 6: performing wet etching by using an aluminum etching solution (a mixed solution of phosphoric acid, nitric acid, acetic acid and water) at the temperature of 80 ℃, and removing a metal aluminum mask layer below the silicon dioxide layer to obtain a patterned silicon dioxide mask layer;
and 7: under the protection of a patterned silicon dioxide mask layer, adopting hot phosphoric acid solution with the concentration of 85% to perform wet etching at the temperature of 145 ℃, and etching the gallium oxide layer which is not covered by the silicon dioxide mask layer;
and 8: and (3) carrying out wet etching by adopting a hydrofluoric acid diluent at the temperature of 25 ℃, and etching the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
Example four
The invention provides a method for etching graphical gallium oxide by a wet method, which comprises the following steps:
step 1: depositing a gallium oxide layer 102 on the sapphire substrate by utilizing an atomic layer deposition method, wherein the thickness of the gallium oxide layer 102 is 1 micrometer;
step 2: preparing a photoresist mask pattern layer 103 with patterns on a gallium oxide layer 102 by utilizing a conventional photoetching technology, specifically, coating AZ5214 reverse photoresist on the gallium oxide layer 102, and forming the photoresist mask pattern layer 103 through exposure and development, wherein the minimum size and the interval of the patterns of the photoresist mask pattern layer 103 are 6 microns;
and step 3: forming a 600nm aluminum metal layer 104 on the photoresist mask pattern layer 103 through electron beam evaporation to obtain a sample four;
and 4, step 4: soaking the sample four in the step 3 in acetone at 60 ℃, and stripping the photoresist mask pattern layer 103 of the sample four and the metal aluminum attached above the photoresist mask pattern layer to form a patterned aluminum metal layer;
and 5: depositing a silicon dioxide mask layer 105 with the thickness of 300nm on the surface of the aluminum metal layer covered with the graphics by a physical vapor deposition method;
step 6: wet etching is carried out at the temperature of 70 ℃ by adopting aluminum etching liquid (mixed liquid of phosphoric acid, nitric acid, acetic acid and water), and a metal aluminum mask layer below the silicon dioxide layer is removed to obtain a patterned silicon dioxide mask layer;
and 7: under the protection of a patterned silicon dioxide mask layer, adopting a hot phosphoric acid solution with the concentration of 85 percent to carry out wet etching at the temperature of 155 ℃, and etching the gallium oxide layer which is not covered by the silicon dioxide mask layer;
and 8: and (3) carrying out wet etching by adopting a hydrofluoric acid diluent at the temperature of 35 ℃, and etching the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
EXAMPLE five
The invention provides a method for etching graphical gallium oxide by a wet method, which comprises the following steps:
step 1: depositing a gallium oxide layer 102 on a monocrystalline silicon substrate by utilizing an atomic layer deposition method, wherein the thickness of the gallium oxide layer 102 is 1 mu m;
step 2: preparing a photoresist mask pattern layer 103 with patterns on a gallium oxide layer 102 by utilizing a conventional photoetching technology, specifically, coating AZ5214 reverse photoresist on the gallium oxide layer 102, and forming the photoresist mask pattern layer 103 through exposure and development, wherein the minimum size and the interval of the patterns of the photoresist mask pattern layer 103 are 6 microns;
and step 3: forming a 300nm aluminum metal layer 104 on the photoresist mask pattern layer 103 in a thermal evaporation mode to obtain a sample five;
and 4, step 4: soaking the sample five in the step 3 in acetone at 60 ℃, and stripping off the photoresist mask pattern layer 103 of the sample five and the metal aluminum attached above the photoresist mask pattern layer to form a patterned aluminum metal layer;
and 5: depositing a silicon dioxide mask layer 105 with the thickness of 150nm on the surface of the aluminum metal layer covered with the graphics by a chemical vapor deposition method;
step 6: wet etching is carried out at the temperature of 70 ℃ by adopting 85% concentrated phosphoric acid, and the metal aluminum mask layer below the silicon dioxide layer is removed to obtain a patterned silicon dioxide mask layer;
and 7: under the protection of the patterned silicon dioxide mask layer, adopting concentrated sulfuric acid solution as etching liquid, and carrying out wet etching at the temperature of 170 ℃ to etch the gallium oxide layer which is not covered with the silicon dioxide mask layer;
and 8: and carrying out wet etching by adopting a mixed solution of ammonia water and hydrofluoric acid at the temperature of 35 ℃, and etching the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
EXAMPLE six
The invention provides a method for etching graphical gallium oxide by a wet method, which comprises the following steps:
step 1: depositing a gallium oxide layer 102 on a monocrystalline silicon substrate by utilizing an atomic layer deposition method, wherein the thickness of the gallium oxide layer 102 is 100 nm;
step 2: preparing a photoresist mask pattern layer 103 with a pattern on a gallium oxide layer 102 by utilizing a conventional photoetching technology, specifically, coating AZ5214 reverse photoresist on the gallium oxide layer 102, and forming the photoresist mask pattern layer 103 through exposure and development, wherein the minimum size of the pattern of the photoresist mask pattern layer 103 is 2 microns, and the minimum distance is 3 microns;
and step 3: forming a 100nm aluminum metal layer 104 on the photoresist mask pattern layer 103 in a thermal evaporation manner to obtain a sixth sample;
and 4, step 4: soaking the sample six in the step 3 in acetone at 60 ℃, and stripping off the photoresist mask pattern layer 103 of the sample six and the metal aluminum attached above the photoresist mask pattern layer to form a patterned aluminum metal layer;
and 5: depositing a silicon dioxide mask layer 105 with the thickness of 50nm on the surface of the aluminum metal layer covered with the graphics by a chemical vapor deposition method;
step 6: wet etching is carried out at the temperature of 50 ℃ by adopting 85% concentrated phosphoric acid, and the metal aluminum mask layer below the silicon dioxide layer is removed to obtain a patterned silicon dioxide mask layer;
and 7: under the protection of the patterned silicon dioxide mask layer, adopting concentrated sulfuric acid solution as etching liquid, and carrying out wet etching at the temperature of 150 ℃ to etch the gallium oxide layer which is not covered with the silicon dioxide mask layer;
and 8: and carrying out wet etching by adopting a mixed solution of ammonia water and hydrofluoric acid at the temperature of 20 ℃, and etching the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
EXAMPLE seven
The invention provides a method for etching graphical gallium oxide by a wet method, which comprises the following steps:
step 1: depositing a gallium oxide layer 102 on a monocrystalline silicon substrate by utilizing an atomic layer deposition method, wherein the thickness of the gallium oxide layer 102 is 100 nm;
step 2: preparing a photoresist mask pattern layer 103 with patterns on the gallium oxide layer 102 by using a conventional photoetching technology, specifically, coating AZ5214 reverse photoresist on the gallium oxide layer 102, and forming the photoresist mask pattern layer 103 by exposure and development, wherein the minimum size and the interval of the patterns of the photoresist mask pattern layer 103 are 3 microns;
and step 3: forming a 100nm aluminum metal layer 104 on the photoresist mask pattern layer 103 in a thermal evaporation manner to obtain a sample seven;
and 4, step 4: soaking the sample seven in the step 3 in acetone at 60 ℃, and stripping off the photoresist mask pattern layer 103 of the sample seven and the metal aluminum attached above the photoresist mask pattern layer to form a patterned aluminum metal layer;
and 5: depositing a silicon dioxide mask layer 105 with the thickness of 50nm on the surface of the aluminum metal layer covered with the graphics by a chemical vapor deposition method;
step 6: wet etching is carried out at the temperature of 50 ℃ by adopting 85% concentrated phosphoric acid, and the metal aluminum mask layer below the silicon dioxide layer is removed to obtain a patterned silicon dioxide mask layer;
and 7: under the protection of the patterned silicon dioxide mask layer, adopting concentrated sulfuric acid solution as etching liquid, and carrying out wet etching at the temperature of 190 ℃ to etch the gallium oxide layer which is not covered with the silicon dioxide mask layer;
and 8: and carrying out wet etching by adopting a mixed solution of ammonia water and hydrofluoric acid at the temperature of 28 ℃, and etching the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
The seven embodiments can successfully prepare the patterned gallium oxide layer meeting the requirements.
In other embodiments of the present invention, in step 1, besides the single crystal silicon substrate and the sapphire substrate, a silicon carbide substrate or a diamond substrate may be used, and besides the atomic layer deposition method, any one of metal organic chemical vapor deposition, molecular beam epitaxy, pulsed laser deposition, magnetron sputtering, a sol-gel method, halide vapor epitaxy, or atomized chemical vapor deposition may be used to prepare the gallium oxide layer 102; in step S5, in addition to the physical vapor deposition and the chemical vapor deposition methods, the silicon dioxide mask layer 105 may be prepared by an atomic layer deposition method; in step S8, wet etching may be performed by using a mixture of ammonium fluoride and hydrofluoric acid as an etching solution, in addition to using a mixture of diluted hydrofluoric acid, ammonia water, and hydrofluoric acid as an etching solution.
In the invention, metal organic chemical vapor deposition is abbreviated as MOCVD, molecular beam epitaxy is abbreviated as MBE, pulsed laser deposition is abbreviated as PLD, magnetron sputtering is abbreviated as PVD, atomic layer deposition is abbreviated as ALD, sol-gel method, halide vapor phase epitaxy is abbreviated as HVPE, atomized chemical vapor deposition is abbreviated as Mist-CVD, and physical vapor deposition is abbreviated as PVD.
In the invention, the metal aluminum and the silicon dioxide attached to the surface of the metal aluminum are stripped by only adopting a wet etching process of the metal aluminum in the patterning process of the silicon dioxide mask layer to obtain the patterned silicon dioxide mask layer.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for wet etching patterned gallium oxide is characterized by comprising the following steps:
s1, preparing a gallium oxide layer (102) on the substrate (101);
s2, preparing a photoresist mask pattern layer (103) on the surface of the gallium oxide layer (102) by a photoetching method;
s3, preparing an aluminum metal layer (104) on the surface of the photoresist mask pattern layer (103) to obtain a sample;
s4, stripping the photoresist mask pattern layer (103) of the sample and the metal aluminum above the photoresist mask pattern layer, and forming a patterned metal aluminum mask layer on the gallium oxide layer (102);
s5, preparing a silicon dioxide mask layer (105) on the surface of the gallium oxide layer (102) covered with the metal aluminum mask layer;
s6, performing wet etching to remove the metal aluminum mask layer below the silicon dioxide mask layer (105) to obtain a patterned silicon dioxide mask layer;
s7, under the protection of the silicon dioxide mask layer, performing wet etching on the gallium oxide layer (102);
and S8, performing wet etching to remove the silicon dioxide mask layer to obtain the patterned gallium oxide layer.
2. The method for wet etching patterned gallium oxide according to claim 1, wherein:
in step S1, the substrate (101) is a sapphire substrate, a single crystal silicon substrate, a silicon carbide substrate, or a diamond substrate;
the gallium oxide layer (102) is prepared by any one of metal organic chemical vapor deposition, molecular beam epitaxy, pulsed laser deposition, magnetron sputtering, atomic layer deposition, sol-gel method, halide vapor phase epitaxy and atomized chemical vapor deposition, and the thickness of the gallium oxide layer (102) is 20 nm-2 mu m.
3. The method for wet etching patterned gallium oxide according to claim 2, wherein:
in step S2, the photolithography method specifically includes: coating AZ5214 reverse photoresist or other photoresist suitable for metal stripping on the gallium oxide layer (102), and forming the photoresist mask pattern layer (103) by exposure and development, wherein the minimum pattern size and the spacing of the photoresist mask pattern layer (103) are larger than 2 μm.
4. The method for wet etching patterned gallium oxide according to claim 3, wherein:
in step S3, the aluminum metal layer (104) is formed by electron beam evaporation or thermal evaporation to form a metal aluminum film with a thickness of 50-1000 nm on the surface of the photoresist mask pattern layer (103).
5. The method for wet etching patterned gallium oxide according to any one of claims 1-4, wherein:
in step S4, the step of peeling the photoresist mask pattern layer (103) of the sample and the metal aluminum thereon is to soak the sample prepared in step S3 in acetone at 60 ℃ until the photoresist mask pattern layer (103) and the metal aluminum thereon are completely peeled.
6. The method for wet etching patterned gallium oxide according to claim 5, wherein:
in step S5, the silicon dioxide mask layer (105) is prepared by any one of chemical vapor deposition, physical vapor deposition and atomic layer deposition, and the thickness of the silicon dioxide mask layer (105) is smaller than that of the aluminum metal layer (104).
7. The method for wet etching patterned gallium oxide according to claim 6, wherein:
in the step S6, the wet etching is to etch away all the metallic aluminum at 50-80 ℃ by using 85% concentrated phosphoric acid or special aluminum etching liquid; the special aluminum etching liquid is a mixed liquid of phosphoric acid, acetic acid, nitric acid and water.
8. The method for wet etching patterned gallium oxide according to claim 7, wherein:
in the step S7, the wet etching adopts 85% concentrated phosphoric acid as etching liquid, and the etching temperature range is 135-155 ℃; or concentrated sulfuric acid is used as etching liquid, and the etching temperature is 150-190 ℃.
9. The method for wet etching patterned gallium oxide according to claim 8, wherein:
in step S8, the wet etching is performed by using a hydrofluoric acid diluent, a mixture of ammonia and hydrofluoric acid, or a mixture of ammonium fluoride and hydrofluoric acid as an etching solution, and the etching temperature ranges from 20 ℃ to 35 ℃.
10. The method for wet etching patterned gallium oxide according to claim 9, wherein:
in step S1, the substrate (101) is a sapphire substrate, the thickness of the gallium oxide layer (102) is 100nm, and the gallium oxide layer (102) is prepared by an atomic layer deposition method;
in step S2, the photoresist used is AZ5214 inverse photoresist, and the minimum size and the pitch of the pattern of the photoresist mask pattern layer (103) are 3 μm;
in the step S3, the aluminum metal layer (104) is formed by forming a metal aluminum film with a thickness of 100nm on the surface of the photoresist mask pattern layer (103) in an electron beam evaporation manner;
in step S5, the silicon dioxide layer (105) is prepared by a physical vapor deposition method, and the thickness of the silicon dioxide mask layer (105) is 50 nm;
in step S6, the wet etching adopts aluminum etching liquid as etching liquid, and the etching temperature is 60 ℃;
in step S7, the etching solution adopted by the wet etching is a hot phosphoric acid solution with the concentration of 85%, and the etching temperature is 140 ℃;
in step S8, the etching solution used in the wet etching is a diluted hydrofluoric acid solution, and the etching temperature is 30 ℃.
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