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CN-121986149-A - Etching composition and method for manufacturing semiconductor device using the same

CN121986149ACN 121986149 ACN121986149 ACN 121986149ACN-121986149-A

Abstract

The present invention relates to an etching composition and a method for manufacturing a semiconductor device using the same, the etching composition including an inorganic acid and a silanol-based compound, and the content of the silanol-based compound in the etching composition and the viscosity of the etching composition satisfying formula 1, whereby a sufficient etching selectivity ratio with respect to a nitride film of an oxide film can be ensured while suppressing abnormal growth in a high-temperature wet etching process, and bubbles are not generated immediately after manufacturing, so that deterioration in etching process efficiency or damage to etching equipment is not caused, and excellent workability due to low viscosity is provided.

Inventors

  • LI ZHENXU
  • Lin Tingxun
  • SONG BINGXUE
  • LI CHENGYU

Assignees

  • 秀博瑞殷株式公社

Dates

Publication Date
20260505
Application Date
20241008
Priority Date
20231012

Claims (20)

  1. 1. An etching composition, wherein, Comprising: an inorganic acid is used for preparing the inorganic acid, Silanol-based compound, and The balance of solvent; The silanol-based compound content based on the total weight of the etching composition and the viscosity of the etching composition satisfy the following formula 1: [ 1] V≤0.184*C+48.1 In the above formula 1, C is the content (wt%) of the silanol-based compound based on the total weight of the etching composition, and V is the viscosity (cP) of the etching composition.
  2. 2. The etching composition of claim 1, wherein, The silanol-based compound is contained in an amount of 0.1% by weight or more and 50% by weight or less.
  3. 3. The etching composition of claim 1, wherein, Further satisfying the following formula 2: [ 2] 0.184*C+44.3≤V≤0.184*C+48.1。
  4. 4. The etching composition of claim 1, wherein, The etching composition has an APHA value of 35 or less.
  5. 5. The etching composition of claim 1, wherein, The silanol-based compound is a silanol-based compound represented by the following chemical formula 1 or a condensate thereof: [ chemical formula 1] In the chemical formula 1 described above, a compound having the formula, R 1 is selected from the group consisting of aminoalkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, acetoxy group and haloalkylacetoxy group having 1 to 20 carbon atoms, R 2 and R 3 are hydroxy groups.
  6. 6. The etching composition of claim 1, wherein, The silanol group compound is 3-aminopropyl silanetriol or condensate thereof.
  7. 7. The etching composition of claim 1, wherein, The silanol-based compound has a CAS number of 68400-07-7.
  8. 8. The etching composition of claim 1, wherein, The inorganic acid is contained in an amount of 50 to 85 parts by weight based on 100 parts by weight of the entire etching composition.
  9. 9. The etching composition of claim 1, wherein, The inorganic acid includes one or more selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrochloric acid, and perchloric acid.
  10. 10. The etching composition of claim 1, wherein, The etching composition further comprises an ammonium-based composition.
  11. 11. The etching composition of claim 10, wherein, The ammonium composition includes one or more selected from the group consisting of ammonium chloride, ammonium phosphate, ammonium acetate, ammonium sulfate, ammonium formate, and metal amine complex salts.
  12. 12. The etching composition of claim 1, wherein, The etching composition is used for etching a silicon nitride film.
  13. 13. The etching composition of claim 1, wherein, The etching composition has a silicon nitride film/silicon oxide film etching selectivity of 30 or more.
  14. 14. The etching composition of claim 1, wherein, The absolute value of the rate of change in the etching rate of the nitride film is 20% or less during the etching process from 100ppm to 2000ppm in the silicon ion concentration.
  15. 15. The etching composition of claim 1, wherein, The height of bubbles forming the immediate surface of the etching composition is 0.5cm or less.
  16. 16. The etching composition of claim 1, wherein, The etching composition has an etching rate of 40 to 80 a/min for the silicon nitride film at an etching process temperature of 165 ℃.
  17. 17. The etching composition of claim 1, wherein, The etching composition has an etching rate of 1 angstrom/min or less for a silicon oxide film at an etching process temperature of 165 ℃.
  18. 18. A method of manufacturing a semiconductor device, wherein, The method comprises the following steps: Forming a structure by stacking an insulating film and a sacrificial film on a substrate, and An etching process using the etching composition according to claim 1 is performed to remove the sacrificial film to form a spatial region.
  19. 19. The method for manufacturing a semiconductor device according to claim 18, wherein, The sacrificial film includes silicon nitride, and the insulating film includes silicon oxide.
  20. 20. The method for manufacturing a semiconductor device according to claim 18, wherein, In the etching process, the sacrificial film has a higher etching rate than the insulating film.

Description

Etching composition and method for manufacturing semiconductor device using the same Cross-reference to related applications The present application claims priority based on korean patent application No. 10-2023-0135525 at 12 of 10 months of 2023, korean patent application No. 10-2024-0096376 at 22 of 7 months of 2024 and korean patent application No. 10-20240096377 at 22 of 7 months of 2024, and the entire contents disclosed in the korean patent application are incorporated herein as part of the present specification. Technical Field The present invention relates to an etching composition and a method for manufacturing a semiconductor device using the same, and more particularly, to an etching composition for etching a nitride film with a high selectivity and a method for manufacturing a semiconductor device using the same. Background In recent years, with the multifunction of information communication apparatuses, there is a demand for a large capacity and high integration of semiconductor devices including memory devices. As the size of memory cells is reduced due to high integration, operation circuits and wiring structures included in the memory device for operation and electrical connection of the memory device are also complicated. In a manufacturing process of a highly miniaturized (down scaling) semiconductor device, oxide films and nitride films as representative insulating films may be used individually or alternately stacked, respectively, and a selective etching process of the nitride film formed of patterns of various shapes may be required in order to construct a complicated and miniaturized structure, for example, a three-dimensional structure of an electronic device. In particular, there is a need for an etching composition that is capable of ensuring a sufficient etching selectivity of a nitride film relative to an oxide film without causing problems such as the occurrence of unnecessary particles in the etching process of the nitride film or the undesired growth of byproducts on the oxide film surface. In a semiconductor (integrated circuit) device, an oxide film such as a silicon oxide film (SiO 2) and a nitride film such as a silicon nitride film (SiN x) are used as typical insulating films, and each of the films is formed by alternately stacking one or more layers. Such oxide films and nitride films are also used as hard masks for forming conductive patterns such as metal wirings. In the wet etching process for removing the nitride film, an etching composition in which phosphoric acid (phosphorus acid) and deionized water (deionized water) are mixed is generally used. At this time, the deionized water is added for the purpose of preventing a decrease in etching rate and a change in etching selectivity to the oxide film, but when the nitride film is removed by a wet etching process, a defect is generated due to a slight change in the amount of deionized water, and there is a limit in etching the nitride film to a desired level due to a decrease in the etching selectivity of the nitride film to the oxide film. Accordingly, in order to improve the effect of an etching composition composed of only phosphoric acid and deionized water, in particular, in order to improve the selectivity of a nitride film/oxide film etched based on the etching composition, an improved technique for further including an additive substance in the etching composition for use has been developed. However, even in this modified technique, the additive is used at a low content of about less than 3% by weight based on the total weight of the etching liquid. This is because, when the additive is used in an amount of about 3 wt% or more, on the contrary, a sufficient etching rate of the nitride film cannot be ensured due to the reason that the additive used in excess itself acts as an impurity or the like, or the etching selectivity to the oxide film cannot be satisfied, and there is another problem that the effect of improving the use of the additive cannot be sufficiently obtained due to the very small amount of the additive used. In addition, the etching process may be performed at a high temperature exceeding 150 ℃, and in this case, there is a problem that the etching performance cannot be sufficiently ensured or abnormal growth is caused when the temperature exceeds a predetermined range due to the additive for the etching selectivity. Therefore, there has been a need for an etching composition which can be used without any problem even under high-temperature wet etching process conditions, can sufficiently achieve an improvement effect by using an additive, and has an excellent selectivity of a basic nitride film to an oxide film. Disclosure of Invention Problems to be solved by the invention The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an etching composition which can suppress abnormal growth even in a wet etching process at a hig