CN111925796B - High-selectivity silicon nitride etching solution, preparation method and application thereof - Google Patents
High-selectivity silicon nitride etching solution, preparation method and application thereof Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 158
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 81
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 66
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940126062 Compound A Drugs 0.000 claims abstract description 27
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000004065 semiconductor Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001035 drying 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
- 239000010408 film Substances 0.000 description 89
- 239000000243 solution Substances 0.000 description 58
- 239000000377 silicon dioxide Substances 0.000 description 19
- 235000012431 wafers Nutrition 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- Weting (AREA)
Abstract
The inventionDiscloses a silicon nitride etching solution with high selectivity ratio, a preparation method and application thereof. The invention provides an etching solution which comprises the following components in parts by weight: 0.5-10 parts of compound A, 76.5-84.6 parts of phosphoric acid and 13.5-14.9 parts of water. The etching solution of the present invention has a proper etching rate selection ratio for the silicon oxide film and the silicon nitride film, can selectively remove the silicon nitride film, can prolong the service life of the etching solution, and can adapt to the increase of the number of the laminated structure layers.
Description
Technical Field
The invention relates to a silicon nitride etching solution with high selectivity ratio, a preparation method and application thereof.
Background
Such as a silicon oxide film and a silicon nitride film are representative insulator films, and the silicon oxide film or the silicon nitride film may be used alone or in the form of a laminate (laminate) in which one or more thin films are alternately stacked in a semiconductor manufacturing process. In addition, the oxide film or the nitride film is also used as a hard mask for forming a conductive pattern such as a metal wiring.
In the wet etching process for removing the nitride film, an aqueous phosphoric acid solution is generally used. There are many problems with the aqueous phosphoric acid solution alone, such as: the etching rate selection ratio of silicon oxide and silicon nitride is improper, and more particles and precipitates exist in the solution in a short time in the process, so that the service life of liquid medicine is short, the increase of the layer number of the laminated structure cannot be adapted, and the like. In order to solve these problems, it is considered to add an additive to the phosphoric acid aqueous solution to improve the etching capability of the phosphoric acid aqueous solution.
Disclosure of Invention
The technical problem to be solved by the invention is that the etching rate selection ratio of the existing etching solution to the silicon oxide film and the silicon nitride film is not proper. The invention provides a silicon nitride film etching solution with a high selectivity ratio, and a preparation method and application thereof. The etching solution can selectively remove the silicon nitride film, prolongs the service life of the etching solution, and can adapt to the increase of the number of layers of the laminated structure.
The present invention mainly solves the above-mentioned problems by the following technical means.
The invention provides an etching solution which comprises the following components in parts by weight: 0.5-10 parts of compound A, 76.5-84.6 parts of phosphoric acid and 13.5-14.9 parts of water;
in a preferred embodiment of the present invention, the etching solution comprises the following components in parts by weight: 0.5-10 parts of compound A, 76.5-84.6 parts of phosphoric acid and 13.5-14.9 parts of water.
In a preferred embodiment of the present invention, the weight part of the compound a is 0.5 to 10 parts, for example, 0.5 part, 1.0 part, 4.5 parts, 9.5 parts or 10 parts, preferably 1 to 9.5 parts, and more preferably 4.5 parts.
In a preferred embodiment of the invention, the weight fraction of the phosphoric acid is 76.4 to 84.6 parts; such as 76.4 parts, 76.9 parts, 81.2 parts, 84.2 parts, or 84.6; preferably 76.9 to 81.2 parts; more preferably 81.2 parts.
In a preferred embodiment of the present invention, the weight fraction of water is 13.5-14.9 parts, such as 13.5 parts, 13.6 parts, 14.3 parts, 14.8 parts or 14.9 parts, preferably 13.6-14.8 parts, and more preferably 14.3 parts.
In a preferred embodiment of the present invention, the etching solution comprises the following components by mass: 0.5% -10% of compound A, 76.5% -84.6% of phosphoric acid and 13.5% -14.9% of water.
In a preferred embodiment of the present invention, the mass percentage of the compound a is 1.0% to 9.5%; preferably 4.5% to 9.5%, more preferably 4.5%.
In a preferred embodiment of the invention, the mass percentage of the phosphoric acid is 76.5% -84.2%; preferably 76.9% -81.2%; more preferably 81.2%.
In a preferred embodiment of the invention, the mass percent of the water is 14% -14.8%; preferably 14.3% -14.8%; more preferably 14.3%.
In a preferred embodiment of the present invention, the water is selected from one or more of deionized water, distilled water, pure water and ultrapure water.
In a preferred embodiment of the present invention, the etching solution comprises the following components by mass: 1% -9.5% of compound A, 76.9% -84.2% of phosphoric acid and 13.6% -14.9% of water.
In a preferred embodiment of the present invention, the mass ratio of compound a to phosphoric acid is 1: 7.65-1: 169; preferably 1: 8-1: 77; more preferably 1: 8-1: 18; it is also preferably 1: 18.
in a preferred embodiment of the present invention, the etching solution comprises the following components by mass: 0.5% of compound a, 84.6% of phosphoric acid and 14.9% of water.
In a preferred embodiment of the present invention, the etching solution comprises the following components by mass: 4.5% of Compound A, 81.2% of phosphoric acid and 14.3% of water.
In a preferred embodiment of the present invention, the etching solution comprises the following components by mass: 1% compound a, 84.2% phosphoric acid and 14.8% water.
In a preferred embodiment of the present invention, the etching solution comprises the following components by mass: 9.5% of compound a, 76.9% of phosphoric acid and 13.6% of water.
In a preferred embodiment of the present invention, the etching solution comprises the following components by mass: 10% of compound a, 76.5% of phosphoric acid and 13.5% of water.
In a preferred embodiment of the present invention, the etching solution is used for etching a silicon nitride film.
In a preferred embodiment of the present invention, when the etching solution is an etching solution for etching a silicon nitride film, the etching is performed in the presence of a silicon oxide film. The silicon nitride film may be a silicon nitride film formed on a patterned silicon semiconductor wafer. The thickness of the silicon nitride film can be
The silicon oxide film may beA silicon oxide film formed on the patterned silicon semiconductor wafer; the thickness of the silicon oxide film is
The silicon oxide film and the silicon nitride film are of a laminated structure of the silicon oxide film and the silicon nitride film, and the number of layers of the laminated structure can be 10-200.
The invention also provides a preparation method of the etching solution, which comprises the following steps of mixing the components of the etching solution. The compound A is preferably added into the phosphoric acid aqueous solution in the mixing mode of the components, and the mixture is uniformly stirred.
The raw materials in the etching solution can also be stored in a packaged form of a plurality of independent components.
The invention also provides application of the etching solution in etching silicon nitride films and/or silicon oxide films. The silicon nitride film may be a silicon nitride film formed on a silicon semiconductor wafer. The silicon nitride film may be a silicon nitride film formed on a patterned silicon semiconductor wafer. The thickness of the silicon nitride film can be
The silicon oxide film may be a silicon oxide film formed on a silicon semiconductor wafer. The silicon oxide film may be a silicon oxide film formed on a patterned silicon semiconductor wafer. The thickness of the silicon oxide film may be
In one embodiment, when the etching is in the presence of a silicon oxide film and a silicon nitride film, the silicon oxide film and the silicon nitride film are a stacked structure of a silicon oxide film and a silicon nitride film. When the etching is in the presence of a silicon oxide film and a silicon nitride film, the etching selectively etches the silicon oxide film. In the laminated structure, the thickness of the silicon oxide film may be set to
The thickness of the silicon nitride film can be
In the laminated structure, the number of layers of the laminated structure can be 10-200, such as 32, 64, 128 or 192.
In one embodiment, the application comprises the steps of: and soaking the silicon wafer with the silicon oxide film and/or the silicon nitride film in the etching solution, taking out the wafer, cleaning and drying.
The temperature of the soaking may be a temperature conventional in the art, preferably 100-180 ℃, more preferably 150-165 ℃, and most preferably 157-161 ℃.
The soaking time may be a time conventional in the art, preferably 1-30min, more preferably 5-20min, most preferably 8-15min (e.g., 10 min).
The invention also provides the application of the compound A as an etching solution additive;
the mass percentage of the compound A in the etching solution can be 0.01-10%, such as 1.0-9.5%; also for example 4.5% -9.5%, more for example 4.5%.
In the application, the etching solution can be an etching solution for etching a silicon nitride film, and the etching can be performed in the presence of a silicon oxide film. The silicon nitride film and the silicon oxide film may be defined as described above.
In the present invention, "room temperature" means 20 to 40 ℃ unless otherwise specified.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The phosphoric acid used in the invention is a concentrated phosphoric acid aqueous solution with the mass percentage of 85%. In the case of other concentrations of concentrated phosphoric acid, the amount of concentrated phosphoric acid converted to that concentration can be calculated by equivalent amounts.
The concentration of each component in the etching solution is mass percent, namely the mass of each component accounts for the total mass of the etching solution.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the etching solution of the invention has proper etching rate selection ratio of the silicon oxide film and the silicon nitride film when etching, can selectively remove the silicon nitride film, prolongs the service life of the etching solution and can adapt to the increase of the number of laminated structures.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
1. Preparation of etching solution
Structure of compound a:
structure of compound B:
the preparation of compound a and compound B is referred to patent CN 108884116A;
respectively adding a compound A or a compound B into a phosphoric acid raw material at room temperature to obtain etching solutions in examples 1-5 and comparative example 1; the etching solution in comparative example 2 was a phosphoric acid raw material.
The raw materials of the phosphoric acid used in the invention are all concentrated phosphoric acid with the mass percentage of 85 percent. In the case of other concentrations of concentrated phosphoric acid, the amount of concentrated phosphoric acid converted to that concentration can be calculated by equivalent amounts.
The concentration of the additive (compound A or compound B) in the invention is mass percent, i.e. the mass of the additive accounts for the total mass of the etching solution.
Examples 1 to 5, comparative examples 1 to 2
TABLE 1 percentage of compound A or compound B in the etching solution to the total mass of the etching solution
| The amount of Compound A or Compound B added | |
| Example 1 | 4.5% Compound A |
| Example 2 | 1.0% of Compound A |
| Example 3 | 9.5% Compound A |
| Example 4 | 0.5% of Compound A |
| Example 5 | 10% of Compound A |
| Comparative example 1 | 4.5% Compound B |
| Comparative example 2 | ━ |
。
2. Etching experiment
Method for detecting etching rate
Etching an object: oxidation by oxygenA silicon film and a silicon nitride film; wherein the two films are deposited on the patterned silicon semiconductor wafer to a thickness of
And forming a deposit on the patterned silicon semiconductor wafer to a thickness of
The silicon nitride film of (1).
Etching temperature: 159 ℃ plus or minus 2 ℃.
Etching container: a quartz tank.
Etching time: the silicon oxide film and the silicon nitride film were etched for 720 seconds and 6000 seconds, respectively.
The speed measurement method comprises the following steps: the film thicknesses of the silicon oxide film and the silicon carbide film were measured before and after etching using a film thickness measuring apparatus (NANO VIEW, SEMG-1000), and the etching rate was calculated by dividing the difference between the initial thickness and the thickness after etching by the etching time (minutes). The selectivity ratio represents the ratio of the silicon carbide film etching rate (SiNE/R) to the oxide film etching rate (SiO E/R).
Initial silica concentration: 0ppm of
② method for detecting service life
In both of silicon oxide film etching and silicon nitride film etching, the etching metabolite contains silicon dioxide, and the concentration of silicon dioxide dissolved in the etching solution gradually increases as the etching time increases. Thus, an etching solution in which the concentration of silicon dioxide was gradually increased (0ppm/80ppm/120ppm/300ppm/500ppm) was prepared as an initial etching solution, and the etching rates and the selectivity of silicon oxide and silicon nitride films were measured, respectively.
After dissolving silicon dioxide with different concentrations in the etching solutions of examples 1 to 5 and comparative examples 1 and 2, etching experiments were performed, and the etching rates of the silicon oxide film and the silicon nitride film were respectively measured and selected as follows:
application examples 1 to 7
The etching rates and selectivity of the silicon oxide film and the silicon nitride film etched using the etching solutions of examples 1 to 5 and comparative examples 1 and 2 at an initial silicon dioxide concentration of 0ppm are shown in Table 2:
TABLE 2 etch rates and selectivity ratios for silicon oxide and silicon nitride films at an initial silicon dioxide concentration of 0ppm
Application examples 8 to 14
The etching rates and selectivity of the silicon oxide film and the silicon nitride film etched using the etching solutions of examples 1 to 5 and comparative examples 1 and 2 at an initial silicon dioxide concentration of 80ppm are detailed in Table 3:
TABLE 3 etch rates and selectivity for silicon oxide and silicon nitride films at an initial silicon dioxide concentration of 80ppm
Application examples 15 to 21
The etching rates and selectivity ratios of the silicon oxide film and the silicon nitride film etched using the etching solutions of examples 1 to 5 and comparative examples 1 and 2 at an initial silicon dioxide concentration of 120ppm are detailed in Table 4:
TABLE 4 etch rates and selectivity ratios for silicon oxide and silicon nitride films at an initial silicon dioxide concentration of 120ppm
Application examples 22 to 28
The etching rates and selectivity ratios of the silicon oxide film and the silicon nitride film etched using the etching solutions of examples 1 to 5 and comparative examples 1 and 2 at an initial silicon dioxide concentration of 300ppm are detailed in Table 5:
TABLE 5 etch rates and selectivity for silicon oxide and silicon nitride films at an initial silicon dioxide concentration of 300ppm
Application examples 29 to 35
The etching rates and selectivity of the silicon oxide film and the silicon nitride film etched using the etching solutions of examples 1 to 5 and comparative examples 1 and 2 at an initial silicon dioxide concentration of 500ppm are shown in Table 6:
TABLE 6 etch rates and selectivity for silicon oxide and silicon nitride films at an initial silicon dioxide concentration of 500ppm
Note: within the error range of the experimental system of the present invention, the selection ratio interval is preferably 500-900. The over-etching phenomenon is gradually aggravated when the height is lower, and the back-wetting phenomenon is gradually aggravated when the height is higher.
As is clear from the results of the experiments conducted in the above application examples 1-35, the etching solutions in examples 1-3 have good selectivity when the selectivity of the initial silicon dioxide is 0ppm, 0ppm, 120ppm, 300ppm or 500ppm, respectively, and is within 500-1000. Example 4 the selectivity of the etching process was 329-443 at 0ppm, 0ppm, 120ppm, 300ppm or 500ppm of the initial silicon dioxide, respectively, and the selectivity was slightly over-etched, which was superior to that of comparative example 2. Example 5 the selectivity in etching was 900-987 at 0ppm, 0ppm, 120ppm, 300ppm or 500ppm of the initial silica, respectively, with slight wet-back phenomenon, which was significantly weaker than that of comparative example 1. The etchant of comparative example 1 has a severe phenomenon of sticking back, and the addition of compound B to phosphoric acid causes the etchant to have a severe phenomenon of sticking back. In comparative example 2, there was a severe over-etching phenomenon due to no addition of the additive. In summary, the over-etching phenomenon of the etching solution can be reduced by adding the compound A into the phosphoric acid, and the etching solution can reach a better selection ratio by adding the compound A with the mass fraction of 1.0-9.5%.
(iii) etching of laminated structures with different layers
Etching an object: silicon wafer having a cross-laminated structure of
And a silicon oxide layer of
The silicon nitride layers of (2) are cross-laminated. The number of layers of the laminated structure is respectively as follows: 32 layers/64 layers/128 layers/192 layers.
Etching conditions: the initial concentration of silicon dioxide in the etching solution was 0ppm
The detection method comprises the following steps: after etching the wafer at 159 ℃. + -. 2 ℃ for 10min, the wafer was taken out, washed, dried and the etching of the layered structure in the wafer was observed by TEM section.
Evaluation criteria: the A level is the etching completion of the silicon nitride layer and the silicon oxide layer is not damaged; the B level is the silicon nitride layer which is etched but damaged; the C level is that the silicon nitride layer is not etched.
Application examples 36 to 42
The etching experiments were carried out using the etching solutions of examples 1 to 5 and comparative examples 1 and 2, and the etching results are shown in Table 7:
TABLE 7 etching results of silicon wafers having a cross-laminated structure
From the results of practical examples 36 to 42, it was found that the etching of the 32-, 64-and 128-layer silicon wafers was completed by the etching solutions of practical examples 1 to 3 and the silicon oxide layers were not damaged. The etching solution in example 4 was subjected to the above-described etching experiment to etch the silicon nitride layer of the silicon wafer of 32, 64 and 128 layers but damage the silicon oxide layer. The etching solutions in example 5 and comparative example 1 were subjected to the above-described etching experiment to finish etching of the silicon nitride layer. The etching solution in comparative example 2 was subjected to the above-described etching experiment to completely etch the silicon nitride layers of the 32-layer and 64-layer silicon wafers but to damage the silicon oxide layers and to leave the silicon nitride layers of the 128-layer silicon wafers unetched.
Claims (15)
1. An etching solution comprises the following components in parts by weight: 1-9.5 parts of compound A, 76.5-84.6 parts of phosphoric acid and 13.5-14.9 parts of water;
2. the etching solution according to claim 1, wherein the etching solution is an etching solution for etching a silicon nitride film;
and/or the mass ratio of the compound A to the phosphoric acid is 1: 8-1: 77.
3. the etching solution of claim 2, wherein the mass ratio of the compound a to the phosphoric acid is 1: 8-1: 18.
4. the etching solution according to claim 3, wherein the mass ratio of the compound A to the phosphoric acid is 1: 18.
5. the etching solution of claim 2, wherein the compound a is present in an amount of 1.0 part, 4.5 parts, or 9.5 parts by weight;
and/or the weight fraction of phosphoric acid is 76.5 parts, 76.9 parts, 81.2 parts, 84.2 parts or 84.6;
and/or the weight fraction of the water is 13.5 parts, 13.6 parts, 14.3 parts, 14.8 parts or 14.9 parts;
and/or, when the etching solution is used for etching a silicon nitride film, the etching is carried out in the presence of a silicon oxide film;
and/or, when the etching solution is an etching solution for etching a silicon nitride film, the silicon nitride film is a silicon nitride film formed on a patterned silicon semiconductor wafer;
and/or, when the etching solution is used for etchingWhen etching the silicon nitride film, the thickness of the silicon nitride film is
6. The etching solution of claim 5, wherein the compound A is present in an amount of 4.5 parts by weight;
and/or the weight fraction of the phosphoric acid is 76.9 to 81.2;
and/or the weight fraction of the water is 13.6-14.8 parts.
7. The etching solution according to claim 6, wherein the weight fraction of phosphoric acid is 81.2 parts;
and/or the weight fraction of the water is 14.3 parts.
8. The etching solution according to any one of claims 1, 2 or 5, wherein the water is selected from one or more of deionized water, distilled water, pure water and ultrapure water;
and/or the mass percent of the compound A is 4.5-9.5%;
and/or the mass percent of the phosphoric acid is 76.5-84.2%;
and/or the mass percent of the water is 14-14.8%;
and/or, when the etching solution is an etching solution for etching a silicon nitride film, the etching is performed in the presence of a silicon oxide film, the silicon oxide film being a silicon oxide film formed on a patterned silicon semiconductor wafer;
and/or, when the etching solution is used for etching silicon nitride film and the etching is carried out in the presence of silicon oxide film, the thickness of the silicon oxide film is
And/or when the etching solution is used for etching the silicon nitride film and the etching is carried out in the presence of the silicon oxide film, the silicon oxide film and the silicon nitride film are of a laminated structure of the silicon oxide film and the silicon nitride film, and the number of layers of the laminated structure is 10-200.
9. The etching solution according to claim 8, wherein the mass percent of the compound A is 4.5%;
and/or the mass percent of the phosphoric acid is 76.9-81.2%;
and/or the mass percent of the water is 14.3-14.8%.
10. The etching solution according to claim 9, wherein the phosphoric acid is 81.2% by mass;
and/or the mass percentage of the water is 14.3 percent.
11. The etching solution according to claim 1, wherein the etching solution comprises the following components in percentage by mass according to any one of scheme 1, scheme 2 or scheme 3;
scheme 1, 4.5% compound a, 81.2% phosphoric acid and 14.3% water;
scheme 2, 1% compound a, 84.2% phosphoric acid and 14.8% water;
scheme 3, 9.5% compound a, 76.9% phosphoric acid and 13.6% water.
12. Use of an etching solution according to any one of claims 1 to 11 for etching silicon nitride films and/or silicon oxide films.
13. The use according to claim 12, characterized in that said use comprises the following steps: soaking the silicon wafer with the silicon oxide film and/or the silicon nitride film in the etching solution, taking out the wafer, cleaning and drying;
and/or, the silicon nitride film is formed on a silicon semiconductor wafer;
and/or, the silicon oxide film is formed on a silicon semiconductor wafer;
and/or, when the etching is in the presence of a silicon oxide film and a silicon nitride film, the etching selectively etches the silicon oxide film;
and/or, when the etching is performed in the presence of a silicon oxide film and a silicon nitride film, the silicon oxide film and the silicon nitride film have a laminated structure of the silicon oxide film and the silicon nitride film.
14. The use of claim 13 wherein said silicon nitride film has a thickness of
And/or, the silicon nitride film is a silicon nitride film formed on a patterned silicon semiconductor wafer;
and/or, the silicon oxide film is formed on a patterned silicon semiconductor wafer;
and/or the thickness of the silicon oxide film is
And/or the number of layers of the laminated structure is 10-200;
and/or the soaking temperature is 100-180 ℃;
and/or, the soaking time is 1-30 min.
15. The application of a compound A as an etching solution additive;
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| CN202010817215.8A CN111925796B (en) | 2020-08-14 | 2020-08-14 | High-selectivity silicon nitride etching solution, preparation method and application thereof |
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| CN105573052A (en) * | 2014-10-30 | 2016-05-11 | 拉姆科技有限公司 | Etchant compositions for nitride layers and methods of manufacturing semiconductor devices using the same |
| CN110437837A (en) * | 2018-05-03 | 2019-11-12 | 三星Sdi株式会社 | Etch combination for silicon nitride and the method that is etched using it |
| CN110551503A (en) * | 2018-05-31 | 2019-12-10 | Ltcam株式会社 | Composition for wet etching silicon nitride |
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| CN105573052A (en) * | 2014-10-30 | 2016-05-11 | 拉姆科技有限公司 | Etchant compositions for nitride layers and methods of manufacturing semiconductor devices using the same |
| CN105384778A (en) * | 2015-10-26 | 2016-03-09 | 苏州科技学院 | Preparation method of alkyl - dimethoxy (phosphorus heterocycle) silane compound as fire retardant |
| KR102071598B1 (en) * | 2018-02-09 | 2020-01-30 | 에스케이하이닉스 주식회사 | High selectivity Etchant composition for Nitride etching |
| CN110437837A (en) * | 2018-05-03 | 2019-11-12 | 三星Sdi株式会社 | Etch combination for silicon nitride and the method that is etched using it |
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