MONOALKYL TIN COMPOUNDS WITH LOW POLYALKYL CONTAMINATION, THEIR COMPOSITIONS AND METHODS

• US 20190315782A1
• Filed: 04/11/2018
• Published: 10/17/2019
• Est. Priority Date: 04/11/2018
• Status: Active Grant

• Current Assignee: Inpria Corporation (JSR Corporation)
• Original Assignee: Inpria Corporation (JSR Corporation)
• Inventors: Edson, Joseph B., Lamkin, Thomas J., Earley, William, Wambach, Truman
• Granted Patent: US 10,787,466 B2
• Time in Patent Office: Days
• CPC Class Codes: C07F 7/2224 Compounds having one or more tin-oxygen linkages
• CPC Class Codes: C07F 7/2284 Compounds with one or more Sn-N linkages

Abstract

A pure composition comprises a monoalkyltin trialkoxide compound represented by the chemical formula RSn(OR′)₃ or a monoalkyl tin triamide compound represented by the chemical formula RSn(NR′₂)₃ and no more than 4 mole % dialkyltin compounds relative to the total tin amount, where R is a hydrocarbyl group with 1-31 carbon atoms, and wherein R′ is a hydrocarbyl group with 1-10 carbon atoms. Methods are described for the formation of the pure compositions. A solid composition comprises a monoalkyl triamido tin compound represented by the chemical formula RSn—(NR′COR″)₃, where R is a hydrocarbyl group with 1-31 carbon atoms, and where R′ and R″ are independently a hydrocarbyl group with 1-10 carbon atoms. The compositions are suitable for the formation of resist compositions suitable for EUV patterning in which the compositions have a high EUV absorption.

Claims

1. A method to form a monoalkyltin triamide compound, the method comprising,

reacting an alkylating agent selected from the group consisting of RMgX, R₂Zn, RZnNR′

₂, or a combination thereof, with Sn(NR′

₂)₄ in a solution comprising an organic solvent,

wherein R is a hydrocarbyl group with 1-31 carbon atoms,

wherein X is a halogen, and

wherein R′

is a hydrocarbyl group with 1-10 carbon atoms.

2. The method of claim 1 wherein the solution has a concentration between about 0.01 M and about 5 M in tin.

3. The method of claim 1 wherein the organic solvent comprises an alkane, an aromatic hydrocarbon, an ether, or mixtures thereof.

4. The method of claim 1 wherein the solution has a concentration of alkylating agent from about ±

25% relative to a stoichiometric reaction of the tin reagent and the alkylating agent.

5. The method of claim 1 wherein the reaction is performed under an inert atmosphere with gradual addition of the alkylating agent with shading from ambient lighting.

6. The method of claim 1 wherein the alkylating agent is added gradually over a time period of 10 minutes to 90 minutes.

7. The method of claim 1 wherein the reaction is performed over a period of 15 minutes to 24 hours at a temperature from −

100°

C. to 100°

C.

8. The method of claim 1 wherein the solution further comprises from 0.25 to 4 mole equivalents of neutral coordinating base relative to tin.

9. A method to selectively form a monoalkyltin trialkoxide compound with low dialkyl tin contamination, the method comprising,

reacting RSn(NR′

₂)₃ with an alcohol represented by the formula HOR″

in an organic solvent to form RSnOR″

₃, wherein the RSn(NR′

₂)₃ reactant has no more than about 4 mole % dialkyl tin contaminants and is the product of the method of claim 1, wherein R is a hydrocarbyl group with 1-31 carbon atoms, and wherein R′ and

R″

are independently a hydrocarbyl group with 1-10 carbon atoms.

10. The method of claim 9 wherein the reaction is performed with a tetradentate chelating agent in an amount from about 0.5 mole % to about 15 mole % relative to the tin molar quantity.

11. A method for forming monoalkyl triamido tin, the method comprising,

reacting a monoalkyltin triamide compound represented by the chemical formula RSn(NR′

₂)₃ with an amide (R″

CONHR′

″

) in an organic solvent, wherein R is a hydrocarbyl group with 1-31 carbon atoms, and wherein R′

, R″ and

R′

″

are independently a hydrocarbyl with 1-8 carbon atoms; and

collecting a solid product represented by the formula RSn(NR′

″

COR″

)₃.

12. The method of claim 11 wherein the monoalkyl tin triamide is at an initial concentration from about 0.1M to about 8M and wherein the solvent is an alkane, an aromatic hydrocarbon, or an ether.

13. The method of claim 11 wherein the amide is added gradually over a period of at least about 2 minutes.

14. The method of claim 11 wherein the solid product is crystalline and has no more than about 1 mole percent relative to tin of contaminants of dialkyltin compounds.

15. A method for forming a monoalkyl tin trialkoxide, the method comprising,

reacting a monoalkyl triamido tin compound (RSn(NR′

″

COR″

)₃) with an alkali alkoxide compound (QOR′

, where Q is an alkali metal atom) in an organic solvent to form a product compound represented by the chemical formula RSn(OR′

)₃, wherein R is a hydrocarbyl group with 1-31 carbon atoms and wherein R′

, R″ and

R′

″

are independently a hydrocarbyl group with 1-10 carbons.

16. The method of claim 16 wherein the alkoxide donating compound is provided in at least a stoichiometric amount.

17. The method of claim 16 wherein the solvent is an alkane, an aromatic hydrocarbon, or an ether.