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KR-20260068061-A - Method for the preparation and purification of organotin compounds, method for inhibiting the formation of dialkyl tin compounds, and method for the selective removal of tetrakis(dialkylamino)tin compounds

KR20260068061AKR 20260068061 AKR20260068061 AKR 20260068061AKR-20260068061-A

Abstract

An aspect of the present disclosure relates to a method for producing a high-purity organotin compound that may include the use of specific additives or reaction conditions. Additionally, a method for purifying an organotin compound and suppressing the formation of impurities within the organotin compound is described.

Inventors

  • 양, 리
  • 응우옌, 타오
  • 이시이, 코키
  • 히오키, 유타
  • 마쓰자카, 코키

Assignees

  • 젤리스트 인코퍼레이티드
  • 미쯔비시 케미컬 주식회사

Dates

Publication Date
20260513
Application Date
20240905
Priority Date
20231201

Claims (20)

  1. A method for synthesizing a monoalkyl tin triamide compound having the formula (1) by reacting a monoalkyl tin trihalide compound having the formula (5) with a metal amide compound having the formula (6) or (7), wherein the reaction is carried out in the presence of a tin tetrahalide having the formula (4): R 1 Sn(NR 1 ' 2 ) 3 (1) SnX 4 (4) R 1 SnX 3 (5) M 1 NR 1 ' 2 (6) M 2 (NR 1 ' 2 ) 2 (7) Here, R1 is an alkyl group having about 1 to 30 carbon atoms that can be substituted with at least one halogen, oxygen, or nitrogen atom; R1 ' is an alkyl group having about 1 to 10 carbon atoms; M1 is a monovalent metal, M2 is a divalent metal, and each X is independently F, Cl, Br, or I.
  2. A method for synthesizing a monoalkyl tin triamide compound having the chemical formula (1), R 1 Sn(NR 1' 2 ) 3 (1) Here, R1 and R1 ' are each independently a primary alkyl group having about 1 to about 10 carbon atoms or a secondary alkyl group having about 3 to about 10 carbon atoms, and the method is: (a) a step of preparing a metal dialkylamide solution; (b) a step of preparing a mixture comprising a tin tetrahalide compound having chemical formula (4) and a monoalkyl tin trihalide compound having chemical formula (5); and (c) A method comprising the step of adding the above mixture to a metal dialkylamide solution. SnX 4 (4) R 1 SnX 3 (5) Here, each X is independently F, Cl, Br, or I.
  3. A method for synthesizing a monoalkyl tin triamide compound having chemical formula (1) and containing a dialkyl tin diamide compound having chemical formula (2) in an undetectable amount, R 1 Sn(NR 1' 2 ) 3 (1) R 1 2 Sn(NR 1' 2 ) 2 (2) Here, R1 and R1 ' are each independently a primary alkyl group having about 1 to about 10 carbon atoms or a secondary alkyl group having about 3 to about 10 carbon atoms, and the method is: (a) a step of lithiating a dialkylamine in a solution containing a first solvent to produce a lithium dialkylamide with a concentration of up to about 10 wt% in the solution; (b) a step of preparing a premixed solution comprising tetrachlorotin and an alkyltrichlorotin compound R₁SnCl₃ in a second solvent, wherein the amount of tetrachlorotin in the premixed solution is about 0.1 to about 5 mol% relative to the amount of the alkyltrichlorotin compound; (c) a step of preparing a reaction mixture by adding a premixed solution to lithium dimethylamide at about -10°C to about 10°C, wherein the amount of lithium dimethylamide in the reaction mixture is at least about 3.09 equivalents relative to the amount of alkyl trichlorotin compound; (d) a step of removing the LiCl salt product by filtration; and (e) a method comprising the step of removing the first solvent and the second solvent under vacuum to produce a product containing a monoalkyl tin triamide having the formula (1) and a dialkyl tin diamide compound having the formula (2) in an undetectable amount.
  4. A method for synthesizing a monoalkyl tin triamide compound having a chemical formula (1) and containing a dialkyl tin diamide compound having a chemical formula (2) in an undetectable amount, R 1 Sn(NR 1' 2 ) 3 (1) R 1 2 Sn(NR 1' 2 ) 2 (2) Here, R1 and R1 ' are each independently a primary alkyl group having about 1 to about 10 carbon atoms or a secondary alkyl group having about 3 to about 10 carbon atoms, and the method is: (a) a step of lithiating a dialkylamine in a solution containing a first solvent to produce lithium dimethylamide with a concentration of up to about 10 wt% in the solution; (b) a step of adding a tetrachlorotin solution in a second solvent to lithium dialkylamide at about -15°C to about 0°C to prepare a reaction mixture containing about 0.3% to about 2 mol% of tetrakis(dialkylamino)tin relative to the amount of lithium dialkylamide; (c) a step of adding a solution of alkyl trichlorotin compound R₁SnCl₃ in a third solvent to a reaction mixture at about -15°C to about 10°C, wherein the amount of lithium dimethylamide in the reaction mixture is at least about 3.09 equivalents relative to the amount of alkyl trichlorotin compound, and the amount of tetrachlorotin in the reaction mixture is about 0.1 mol% to about 5 mol% relative to the amount of alkyl trichlorotin compound; (d) a step of removing the LiCl salt product by filtration; and (e) a method comprising the step of removing the first solvent, the second solvent, and the third solvent under vacuum to produce a product containing a monoalkyl tin triamide compound having the formula (1) and a dialkyl tin diamide compound having the formula (2) in an undetectable amount.
  5. A method for synthesizing a monoalkyl tin triamide compound having a chemical formula (1) and containing a dialkyl tin diamide compound having a chemical formula (2) in an undetectable amount, R 1 Sn(NR 1' 2 ) 3 (1) R 1 2 Sn(NR 1' 2 ) 2 (2) Here, R1 and R1 ' are each independently a primary alkyl group having about 1 to about 10 carbon atoms or a secondary alkyl group having about 3 to about 10 carbon atoms, and the method is: (a) a step of lithiating a dialkylamine in a solution containing a first solvent to produce lithium dimethylamide with a concentration of up to about 10 wt% in the solution; (b) a step of preparing a reaction mixture by adding a tetrakis(dialkylamino)tin solution in a second solvent to lithium dimethylamide at about -15°C to about 0°C, wherein the amount of tetrakis(dialkylamino)tin in the reaction mixture is about 0.3 mol% to about 2 mol% relative to the amount of lithium dialkylamide; (c) a step of adding a solution of the alkyl trichlorotin compound R₁SnCl₃ in a third solvent to the reaction mixture at about -15°C to about 0°C, wherein the amount of lithium dimethylamide in the reaction mixture is at least about 3.09 equivalents relative to the amount of the alkyl trichlorotin compound; (d) a step of removing the LiCl salt product by filtration; and (e) a method comprising the step of removing the first solvent, the second solvent, and the third solvent under vacuum to produce a product containing a monoalkyl tin triamide compound having the formula (1) and an undetectable amount of the dialkyl tin diamide compound having the formula (2).
  6. In paragraph 3, R1 is an isopropyl group, and the compound having chemical formula (1) has chemical formula (3) method: (3).
  7. In paragraph 4, R1 is an isopropyl group, and the compound having chemical formula (1) has chemical formula (3) method: (3).
  8. In claim 5, R1 is an isopropyl group, and the compound having chemical formula (1) has chemical formula (3) method: (3).
  9. In claim 1 or 2, R1 is an isopropyl group, and the compound having formula (1) has formula (3) method: (3).
  10. A method according to claim 6, wherein a compound having chemical formula (1) contains an undetectable amount of a substance having a chemical shift in the 119 Sn NMR spectrum at around -84 ppm.
  11. A method according to claim 7, wherein a compound having chemical formula (1) contains an undetectable amount of a substance having a chemical shift in the 119 Sn NMR spectrum at around -84 ppm.
  12. A method according to claim 8 or 9, wherein a compound having chemical formula (1) contains an undetectable amount of a substance having a chemical shift in the 119 Sn NMR spectrum at around -84 ppm.
  13. A method for preparing a tin composition (P1) comprising a monoalkyl tin compound having the chemical formula (A1) and having a purity of at least about 80 mol%, the method comprising the steps of contacting a raw tin compound having the chemical formula (B1) with a reactant (M1) in an organic solvent and mixing the raw tin compound having the chemical formula (B1) and the reactant (M1) in an organic solvent at a contact temperature T1 for a mixing time t, wherein the mixing is performed at a contact temperature T1 for at least half of the time t, and the contact temperature T1 is within the range of about 10°C to about 70°C. (a) At least 50% by weight of a raw tin compound having the chemical formula (B1) is mixed with the reactant (M1) at a contact temperature T1, or (b) A method in which at least 50% by weight of the reactant (M1) is mixed with a raw tin compound having the formula (B1) at a contact temperature T1: R 2 SnX 2 3 (A1) R 2 SnY 2 3 (B1) Here , R₂ is an organic group having about 1 to 30 carbon atoms that can be substituted with at least one halogen, oxygen, or nitrogen atom, and each X₂ is independently selected from the group consisting of OR₂ ', NR₂'₂ , and C≡CR₂ ' , where each R₂ ' is independently an organic group having about 1 to 10 carbon atoms that can be substituted with at least one halogen, and where there is more than one R₂ ' in the molecule, they may be identical or different and may be bonded together to form a ring structure, and each Y₂ is independently selected from the group consisting of a halogen atom, OR', and NR'₂ , and (M1) is a compound having the chemical formula MX2 , MX22 , or MX23 , where M represents a metal atom of Group 1, Group 2, Group 12, or Group 13.
  14. A method for preparing a tin composition (P1) comprising a monoalkyl tin compound having the formula (A1) and having a purity of at least about 80 mol%, wherein the method comprises the steps of contacting a raw tin compound having the formula (B1) with a reactant (M1) in an organic solvent and mixing the raw tin compound having the formula (B1) and the reactant (M1) in an organic solvent at a contact temperature T1 for a mixing time t, wherein the mixing is performed at a contact temperature T1 for at least half of the time t, and the lower limit of T1 is a temperature at which the production ratio (A1 ) /( A2 ) of the monoalkyl tin compound having the formula ( A1 ) from the reaction intermediate R2SnX22Y2 versus the dialkyl tin compound having the formula ( A2 ) from the disproportionation of R2SnX22Y2 is 600 or greater, and the upper limit of T1 is less than the lowest value among the decomposition temperatures of (B1), (A1), and (M1). (a) At least 50% by weight of a raw tin compound having the chemical formula (B1) is mixed with the reactant (M1) at a contact temperature T1, or (b) A method in which at least 50% by weight of the reactant (M1) is mixed with a raw tin compound having the formula (B1) at a contact temperature T1: R 2 SnX 2 3 (A1) R 2 SnY 2 3 (B1) Here , R₂ is an organic group having about 1 to 30 carbon atoms that can be substituted with at least one halogen, oxygen, or nitrogen atom, and each X₂ is independently selected from the group consisting of OR₂ ', NR₂'₂ , and C≡CR₂ ' , where each R₂ ' is independently an organic group having about 1 to 10 carbon atoms that can be substituted with at least one halogen, and where there is more than one R₂ ' in the molecule, they may be identical or different and may be bonded together to form a ring structure, and each Y² is independently selected from the group consisting of a halogen atom, OR', and NR'₂ , and (M1) is a compound having the chemical formula MX2 , MX22 , or MX23 , where M represents a metal atom of Group 1, Group 2, Group 12, or Group 13.
  15. A method according to claim 13 or 14 in which the temperature fluctuation range when the raw material tin compound (B1) and the reactant (M1) come into contact is 10°C or less.
  16. A method according to claim 13 or 14, wherein the temperature range of T1 is about 22°C to about 30°C.
  17. In claim 13 or 14, the method is carried out using a reactor having a jacket that can be heated and cooled, and the temperature difference between the contact temperature (T1) and the jacket temperature is maintained within about 10°C.
  18. A method for preparing a tin composition (P11) comprising a monoalkyl tin compound having the chemical formula (A11), the method comprising the steps of contacting a raw tin compound having the chemical formula (B11) with a reactant (M11) in an organic solvent and mixing the raw tin compound having the chemical formula (B11) and the reactant (M11) in an organic solvent at a contact temperature T1 for a mixing time t, wherein the mixing is performed at a contact temperature T1 for at least half of the time t, and the contact temperature T1 is within the range of about 10°C to about 70°C. (a) At least 50% by weight of a raw tin compound having the chemical formula (B11) is mixed with the reactant (M11) at a contact temperature T1, or (b) A method in which at least 50% by weight of the reactant (M11) is mixed with a raw tin compound having the formula (B11) at a contact temperature T1: R 2''' Sn(OR 2' ') 3 (A11) R 2''' Sn(NR 2' ) 3 (B11) Herein, each R 2''' is a secondary or tertiary organic group having about 3 to 30 carbon atoms that can be independently substituted with at least one halogen atom, oxygen atom, or nitrogen atom; each R 2 ' is an organic group having about 1 to 10 carbon atoms that can be independently identical or different and can be substituted with at least one halogen atom; each R 2 '' is an organic group having about 2 to 10 carbon atoms that can be independently identical or different and can be substituted with at least one halogen atom, wherein if there is more than one R 2 '' in the molecule, the structures may be different from each other and may be bonded together to form a ring structure; (M11) is a compound having the chemical formula HOR 2 ''.
  19. A method according to claim 18 in which the temperature fluctuation range when the raw material tin compound (B11) and the reactant (M11) come into contact is 10°C or less.
  20. In claim 18, the method wherein the temperature range of T1 is approximately 22°C to approximately 30°C.

Description

Method for the preparation and purification of organotin compounds, method for inhibiting the formation of dialkyl tin compounds, and method for the selective removal of tetrakis(dialkylamino)tin compounds Cross-reference regarding related applications The present application claims priority to U.S. Provisional Application No. 63/663,442 filed June 24, 2024; U.S. Provisional Application No. 63/537,260 filed September 8, 2023; and Japanese Patent Application No. 2023-204285 filed December 1, 2023, the disclosures of which are incorporated herein by reference in their entirety. In recent years, against the backdrop of the paradigm shift toward an advanced information society, there is a demand to handle larger amounts of information at faster speeds and with higher accuracy. Technologies related to integrated circuits and semiconductor devices are advancing rapidly every day. Advancements in semiconductor design require the formation of fine features on semiconductor substrates. Individual features can be approximately 22 nanometers (nm) or smaller, and in some cases, less than 10 nm. One challenge in the fabrication of devices having such fine features is the ability to reliably and reproducibly form photolithography masks with sufficient resolution. Achieving feature sizes smaller than the wavelength of light requires the use of complex high-resolution techniques, such as multiple patterning. Therefore, the development of photolithography techniques using light with much shorter wavelengths, such as extreme ultraviolet (EUV) with wavelengths of 10 nm to 15 nm (e.g., 13.5 nm), is critical. Conventional organic chemical amplification resists (CARs) have low adsorption coefficients, particularly in the EUV range. Consequently, the diffusion of photoactive chemical species may be obscured, and line edge roughness may occur. Therefore, CARs have potential drawbacks when used in EUV lithography. Thus, there is a need for improved EUV photoresist materials that possess characteristics such as thinner thickness, better absorbance, and excellent etch resistance. As semiconductor manufacturing continues to advance, feature sizes continue to shrink, driving the need for new processing methods. Certain organotin compounds have been shown to be useful for the deposition of tin oxide hydroxide coatings in applications such as extreme ultraviolet (EUV) lithography techniques. For example, alkyl tin compounds provide radiation-sensitive Sn-C bonds that can be used to pattern structures via lithography. Materials used in microelectronic manufacturing are required to be extremely pure, with strict limits established for organic contamination (e.g., reaction by-products), metal contamination, and particle contamination. Since chemicals come into contact with semiconductor substrates and organometallic impurities within compounds such as diisopropylbis(dimethylamino)tin and (iPr) ₂Sn ( NMe₂ ) ₂ can affect the properties of the resulting films, purity requirements are generally stringent, and particularly so for lithography applications. While precise purity targets are determined by various factors including performance metrics, a typical minimum purity target is 3N + . Residual metals present in the chemicals can be deposited on the semiconductor substrate and degrade the electrical performance of the manufactured devices. Typical specifications for metals are less than 10 ppb for individual metals and not exceeding ~100 ppb for total metals. Recently, materials with liquid chemical vapor deposition (CVD), such as organotin, have begun to be used as resist materials, particularly for EUV applications. To achieve high-quality film formation, extremely high-purity resist materials are required. For this reason, a tin compound having a single organic group (hereinafter sometimes referred to as a "monoalkyltin compound") was synthesized (JP-A2020-122959). However, purification of such compounds is typically required. For example, before using a monoalkyl tin compound as a resist material, water, residual solvent used in synthesis, and metal-based impurities are removed by distillation (JP-A2020-122959). It is known that organotin compounds can be involved in side reactions, such as disproportionation reactions, to produce by-products during synthesis or purification. In particular, monoalkyltin compounds are prone to producing decomposition products. Specifically, since dialkyltin compounds produced as by-products in the reaction process have similar boiling points and are difficult to remove by distillation, the amount of such impurities must be reduced by adjusting the reaction conditions and post-treatment conditions. A method for obtaining high-purity monoalkyltin compounds is disclosed in U.S. Patent Application No. 2022/0242888, wherein high-purity monoalkyltin compounds can be obtained by a reaction at low temperatures combined with the use of excessive reaction reagents. As mentioned above, the processing and performance