Supercritical fluid(SCF) silylation process

• US 6,673,521 B2
• Filed: 12/12/2000
• Issued: 01/06/2004
• Est. Priority Date: 12/12/2000
• Status: Expired due to Term

• Current Assignee: Google LLC (Alphabet Inc.)
• Original Assignee: International Business Machines Corporation
• Inventors: Medeiros, David R., Moreau, Wayne M., McCullough, Kenneth J., Simons, John P., Taft, Charles J.
• Primary Examiner(s): Duda, Kathleen
• Application Number:
  US09/735,404
• Publication Number:
  US 20030036023A1
• Time in Patent Office: 1,120 Days
• Field of Search: 430/311, 430/313, 430/329, 430/331, 430/315, 134/1, 134/1.3
• US Class Current: 430/315
• CPC Class Codes: G03F 7/265 Selective reaction with inorganic or organometallic reagents after image-wise exposure, e.g. silylation
• CPC Class Codes: G03F 7/40 Treatment after imagewise removal, e.g. baking

Abstract

A process of silylation of object surfaces using a mixture of a silylation agent in admixture with an inert liquified gas, such as carbon dioxide.

Claims

1. A method of silylation of workpiece surface, film, or fabric, comprising contacting the workpiece surface, film, or fabric, with a silylation agent and a supercritical liquid fluid.

2. The method defined in claim 1 wherein said supercritical liquid fluid is CO₂.

3. The method defined in claim 1 wherein said silylation agent is an organosilicon compound selected from compounds having the following molecular formulas:

SiR_yX<sub>4−

y</sub> and (R_w X<sub>3−

w</sub> Si)₂ Z,

wherein;

y=1 to 4;

w=1 to 3;

R=alkyl, aryl, H, alkoxy, arylalkyl, fluoro, fluoroalkyl and where applicable, R has from 1 to 10 carbon atoms;

X=halide; and

Z=oxygen or amino or imino or alkylimino or alkanoylimino.

4. The method defined in claim 1 wherein said silylation agent comprises reactive aminosilanes, R_nSiX, where R is aryl, alkyl alkoxy, fluoroaklyl, fluoraryl, fluoroalkoxy, and X is a halogen, amino, epoxy, isocyanate, OH, or acid group.

5. The method defined in claim 1 wherein said workpiece surface comprises silicon, germanium, or silicon dioxide.

6. The method defined in claim 1 comprising a film which comprises a photoresist containing reactive sites selected from the group consisting of phenol groups, acid groups, or epoxy groups.

7. The method defined in claim 1 comprising a fabric made from a textile comprising fibers with reactive sites selected from the group of alcohol(—

OH), phenolic, amino, —

COOH or epoxy groups.

8. The method defined in claim 1 comprising a workpiece made from lignin materials which have reactive sites capable of silylation.

9. The method defined in claim 1 comprising a bulk organic synthesis of silylation carried out in supercritical liquid fluid as solvent for the reaction media.

10. The method defined in claim 9 wherein said workpiece surface comprises, silicon germanium, aluminum, tin, titanium, zinc or silicon dioxide.

11. The method defined in claim 9 wherein said workpiece is a film which comprises a photoresist containing reactive sites selected from the group consisting of phenol groups, acid groups, or epoxy groups.

12. The method defined in claim 1 wherein said workpiece is selected from the group consisting of a semiconductor surface, a film, and a fabric;

said silylation agent is an organosilicon compound selected from compounds having the following molecular formulas;

SiR_yX<sub>4−

y</sub> and (R_w X<sub>3−

w</sub> Si)₂ Z,

wherein;

y=1 to 4;

w=1 to 3;

R=alkyl, aryl, H, alkoxy, arylalkyl, fluoro, fluoroalkyl and where applicable, R has from 1 to 10 carbon atoms;

X=halide; and

Z=oxygen or amino or imino or alkylimino or alkanoylimino;

and said fluid is CO₂.

13. The method defined in claim 12 wherein said workpiece is made from lignin materials having sites capable of silylation.

14. The method defined in claim 1 wherein said workpiece is selected from the group consisting of a semiconductor surface, a film, and a fabric;

said silylation agent comprises reactive aminosilanes, R_nSiX, where R is aryl, alkyl alkoxy, fluoroalkyl, fluoraryl, fluoroalkoxy, and X is a halogen, amino, epoxy, isocyanate, —

OH, or acid group and n is 1-4,

and said fluid is CO₂;

said reaction being carried at a pressure of between about 1069 psi and 10,000 and at a temperature of about 31°

C.

15. The method defined in claim 14 wherein said CO₂ fluid contains up to 10% by weight of a cosolvent selected from the group consisting of cyclohexanone, N-methyl pyrrolidone, THF, ethane and acetonitrile.

16. The method defined in claim 1 wherein said workpiece is a silicon wafer;

and said silylation agent is selected from the group consisting of tetra alkyl orthosilicates, Si(OR)₄, and poly(alkyl)siloxanes, tetraethyl orthosilicate, also known as tetraethoxysilane, poly(phenylmethyl)siloxane, dimethyl silicone, diethyl silicone, phenylmethyl silicone, methylhydrogen silicone, ethylhydrogen silicone, phenylhydrogen silicone, methylethyl silicone, phenylethyl silicone, diphenyl silicone, methyltrifluoropropyl silicone, ethyltrifluoropropyl silicone, polydimethyl silicone, tetrachlorophenylethyl silicone, tetrachlorophenylmethyl silicone, tetrachlorophenylhydrogen silicone, tetrachlorophenylphenyl silicone, methylvinyl silicone and ethylvinyl silicone cyclic silicones include hexamethyl cyclo-trisiloxane, octamethyl cyclo-tetrasiloxane, hexaphenyl cyclotrisiloxane and octaphenyl cyclotetrasiloxane and mixtures thereof;

said reaction being carried at a pressure of between about 1069 psi and 10,000 and at a temperature of about 31°

C.

17. The method defined in claim 1 wherein said workpiece is a fabric made from a textile comprising fibers with reactive sites selected from the group of alcohol(—

OH), phenolic, amino, —

COOH or epoxy groups;

said silylation agent is an organosilicon compound selected from compounds having the following molecular formulas;

SiR_yX<sub>4−

y</sub> and (R_w X<sub>3−

w</sub> Si)₂ Z,

wherein;

y=1 to 4;

w=1 to 3;

R=alkyl, aryl, H, alkoxy, arylalkyl, fluoro, fluoroalkyl and where applicable, R has from 1 to 10 carbon atoms;

X=halide; and

Z=oxygen or amino or imino or alkylimino or alkanoylimino;

and said fluid is CO₂;

said reaction being carried at a pressure of between about 1069 psi and 10,000 and at a temperature greater than 31°

C.

18. The method defined in claim 1 wherein said workpiece is a resist having a reactive moiety located substantially on the surface thereof;

said silylation agent is hexamethyl disilazane (HMDS);

said fluid is CO₂;

and the reaction being carried at a pressure of between about 1069 psi and 10,000 and at a temperature greater than 31°

C.

19. A method for silylation of a chemical compounds, comprising contacting a mixture of a silylation agent selected from the group consisting of HMDS, Me₃SiCl with Et3N, THF, or Li₂S CH₃CN;

(Me₃Si)₂NH and Me₃SiCl, Pyridine;

Me₃SiNEt₂;

CH₃C(OSiMe₃)═

NSiMe₃;

Me₃SiCH₂CO₂Et;

Me₃SiNHSO₂OSiMe₃ with CH₂Cl₂;

Me₃SiNHCO₂SiMe₃;

Me═

C(OMe)OSiMe₃;

Me₃SiCH₂CH═

CH;

(Me₃ SiO)₂ SO₂;

N,O-Bis(trimethylsilyl)trifluoroacetamide;

N,N′

-Bistrimethylsilylurea;

Me₃SiSEt;

Isopropenyloxytrimethylsilane;

Methyl 3-trimethylsiloxy-2-butenoate;

N-methyl-N-trimethylsilylacetamide;

trimethylsilyl cyanide;

Me₃SiOC(O)NMe₃;

trimethylsilylimidazole;

trimethylsilyl trichloroacetate;

3-Trimethylysilyloxazolidinone; and

trimethylysilyl trifluoromethanesulfonate, and a supercritical liquid fluid.