Aminosilanes for Shallow Trench Isolation Films

• US 20100009546A1
• Filed: 06/26/2009
• Published: 01/14/2010
• Est. Priority Date: 07/11/2008
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Lee, Chia-Chien, Han, Bing, Xiao, Manchao, Weigel, Scott Jeffrey, Cheng, Hansong, O'Neill, Mark Leonard
• Granted Patent: US 7,999,355 B2
• Time in Patent Office: Days
• US Class Current: 438/781
• CPC Class Codes: C23C 18/122 Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
• CPC Class Codes: C23C 18/1245 Inorganic substrates other than metallic
• CPC Class Codes: C23C 18/143 Radiation by light, e.g. photolysis or pyrolysis
• CPC Class Codes: C23C 18/145 Radiation by charged particles, e.g. electron beams or ion irradiation
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/3121 Layers comprising organo-silicon compounds
• CPC Class Codes: H01L 21/316 composed of oxides or glassy oxides or oxide based glass

Abstract

The present invention is a process for spin-on deposition of a silicon dioxide-containing film under oxidative conditions for gap-filling in high aspect ratio features for shallow trench isolation used in memory and logic circuit-containing semiconductor substrates, such as silicon wafers having one or more integrated circuit structures contained thereon, comprising the steps of:

• • providing a semiconductor substrate having high aspect ratio features;
  • contacting the semiconductor substrate with a liquid formulation comprising a low molecular weight aminosilane;
  • forming a film by spreading the liquid formulation over the semiconductor substrate;
  • heating the film at elevated temperatures under oxidative conditions.
    Compositions for this process are also set forth.

Claims

1. A process for spin-on deposition of a silicon dioxide-containing film for gap-fillable features used in a memory or logic circuit-containing semiconductor substrate, comprising the steps of:

providing a semiconductor substrate having gap-fillable features to be filled with an insulator;

contacting the semiconductor substrate with a liquid formulation comprising an aminosilane;

forming a film by spreading the liquid formulation over the semiconductor substrate and filling the features;

heating the film to form a silicon dioxide-containing film.

2. The process of claim 1 wherein the aminosilane is represented by the formula:

R_(4-x)Si(NR′

R″

)_x

where x=1-4;

R can be independently the same or varied amongst halogens, alkoxy, acetoxy, hydrogen, monovalent organic groups;

R′ and

R″

can be independently the same or varied between hydrogen and monovalent organic groups.

3. The process of claim 1 wherein the aminosilane is selected from the group consisting of isopropylaminosilane, diisopropylaminosilane, bis(isopropylamino)silane, tris(isopropylamino)silane, tetrakis(isopropylamino)silane, tertiarybutylaminosilane, bis(tertiarybutylamino)silane, tris(tertiarybutylamino)silane, tetrakis(tertiarybutylamino)silane, diethylaminosilane, bis(diethylamino)silane, tris(diethylamino)silane, tetrakis(diethylamino)silane, ethylmethylaminosilane, bis(ethylmethylamino)silane, tris(ethylmethylamino)silane, tetrakis(ethylmethylamino)silane, dimethylaminosilane, bis(dimethylamino)silane, tris(dimethylamino)silane, tetrakis(dimethylamino)silane, phenylmethylaminosilane, bis(phenylmethylamino)silane, tris(phenylmethylamino)silane, tetrakis(phenylmethylamino)silane, acetoxyethyltris(dimethylamino)silane, hexamethylcyclotrisilazane, tetraisocyanatosilane and mixtures thereof.

4. The process of claim 1 wherein the liquid formulation contains a solvent.

5. The process of claim 4 wherein the solvent is selected from the group consisting of glycol ethers, alcohols, glycol ether acetates, esters, amines, amides, ketones and mixtures thereof.

6. The process of claim 1 wherein the film is annealed at a temperature in the range of 500°

to 1500°

C.

7. The process of claim 6 wherein prior to annealing, the film is cured at a soft-bake temperature in the range of 50°

to 500°

C.

8. The process of claim 1 wherein the aminosilane comprises a mixture of a first aminosilane and a source of silicon or silica or a second aminosilane different from the first aminosilane or combinations of all three.

9. The process of claim 8 wherein the mixture comprises an aminosilane selected from a first group consisting of bis(tertiarybutylamino)silane and di-isopropylaminosilane and a chemical of a second group selected from the group consisting of di-isopropylaminosilane, triethoxysilane, tetraacetoxysilane, tetraethylorthosilicate, tetramethoxysilane, tetrapropoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methylacetoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltriacetoxysilane, hexaethoxydisilane, hexamethoxydisilane and mixtures thereof;

where when the aminosilane of the first group is di-isopropylaminosilane, the chemical of the second group is not di-isopropylaminosilane.

10. The process of claim 1 wherein the spreading the liquid formulation over the semiconductor substrate is performed by spinning the semiconductor substrate as the liquid formulation contacts the semiconductor substrate.

11. A process for spin-on deposition of a silicon dioxide-containing film to gap-fill high aspect ratio features in shallow trench isolation structures used for front end of the line used in a memory or logic circuit-containing semiconductor wafer, comprising the steps of:

providing a semiconductor wafer having high aspect ratio features;

dispensing a liquid formulation onto the semiconductor wafer, wherein the formulation comprises an aminosilane selected from the group consisting of bis(tertiarybutylamino)silane and di-isopropylaminosilane and a solvent selected from the group consisting of glycol ethers, alcohols, glycol ether acetates, esters, amines, amides, ketones and mixtures thereof;

forming a film on the semiconductor wafer by spinning the semiconductor wafer to spread the liquid formulation over the semiconductor wafer and filling the high aspect ratio feature with the film;

curing the film at soft-bake temperatures in the range of 50to 500°

C.;

annealing the film at a temperature in the range of 500°

to 1500°

C. under oxidative conditions.

12. The process of claim 11 wherein the liquid formulation comprises an aminosilane selected from a first group consisting of bis(tertiarybutylamino)silane and di-isopropylaminosilane and a chemical of a second group selected from the group consisting of di-isopropylaminosilane, triethoxysilane, tetraacetoxysilane, tetraethylorthosilicate, tetramethoxysilane, tetrapropoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methylacetoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltriacetoxysilane, hexaethoxydisilane, hexamethoxydisilane and mixtures thereof;

wherein when the aminosilane of the first group is di-isopropylaminosilane, the chemical of the second group is not di-isopropylaminosilane.

13. The process of claim 11 wherein the solvent is selected from the group consisting of ethanol, isopropanol, propanol, pentanol and mixtures thereof.

14. The process of claim 11 wherein the film formation is catalyzed.

15. The process of claim 14 wherein the film formation is catalyzed with a catalyst selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid, maleic acid, oxalic acid and mixtures thereof.

16. The process of claim 11 wherein the deposited silicon dioxide-containing film is further cured using UV energy.

17. A spin on composition useful for gap filling silicon dioxide depositions comprising a monomeric aminosilane and a solvent for the aminosilane.

18. The composition of claim 17 where the aminosilane is represented by the formula:

R_(4-x)Si(NR′

R″

)_x

where x=1-4;

R can be independently the same or varied amongst halogens, alkoxy, acetoxy, hydrogen, and monovalent organic groups;

R′ and

R″

can be independently the same or varied between hydrogen and monovalent organic groups.

19. The composition of claim 17 wherein the aminosilane is selected from the group consisting of isopropylaminosilane, diisopropylaminosilane, bis(isopropylamino)silane, tris(isopropylamino)silane, tetrakis(isopropylamino)silane, tertiarybutylaminosilane bis(tertiarybutylamino)silane, tris(tertiarybutylamino)silane, tetrakis(tertiarybutylamino)silane, diethylaminosilane, bis(diethylamino)silane, tris(diethylamino)silane, tetrakis(diethylamino)silane, ethylmethylaminosilane, bis(ethylmethylamino)silane, tris(ethylmethylamino)silane, tetrakis(ethylmethylamino)silane, dimethylaminosilane, bis(dimethylamino)silane, tris(dimethylamino)silane, tetrakis(dimethylamino)silane, phenylmethylaminosilane, bis(phenylmethylamino)silane, tris(phenylmethylamino)silane, tetrakis(phenylmethylamino)silane, acetoxyethyltris(dimethylamino)silane, and mixtures thereof.

20. The composition of claim 17 wherein the solvent is selected from the group consisting of glycol ethers, alcohols, glycol ether acetates, esters, amines, amides, ketones and mixtures thereof.

21. The composition of claim 17 wherein an aminosilane selected from a first group consisting of bis(tertiarybutylamino)silane and di-isopropylaminosilane and a chemical of a second group selected from the group consisting of di-isopropylaminosilane, triethoxysilane, tetraacetoxysilane, tetraethylorthosilicate, tetramethoxysilane, tetrapropoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methylacetoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltriacetoxysilane, hexaethoxydisilane, hexamethoxydisilane and mixtures thereof;

wherein when the aminosilane of the first group is di-isopropylaminosilane, the chemical of the second group is not di-isopropylaminosilane.

22. The composition of claim 17 including a catalyst selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid, maleic acid, oxalic acid and mixtures thereof.

23. A spin on composition useful for gap filling silicon dioxide depositions, comprising;

an aminosilane selected from the group consisting of isopropylaminosilane, diisopropylaminosilane, bis(isopropylamino)silane, tris(isopropylamino)silane, tetrakis(isopropylamino)silane, tertiarybutylaminosilane bis(tertiarybutylamino)silane, tris(tertiarybutylamino)silane, tetrakis(tertiarybutylamino)silane, diethylaminosilane, bis(diethylamino)silane, tris(diethylamino)silane, tetrakis(diethylamino)silane, ethylmethylaminosilane, bis(ethylmethylamino)silane, tris(ethylmethylamino)silane, tetrakis(ethylmethylamino)silane, dimethylaminosilane, bis(dimethylamino)silane, tris(dimethylamino)silane, tetrakis(dimethylamino)silane, phenylmethylaminosilane, bis(phenylmethylamino)silane, tris(phenylmethylamino)silane, tetrakis(phenylmethylamino)silane, acetoxyethyltris(dimethylamino)silane, and mixtures thereof;

a solvent selected from the group consisting of glycol ethers, alcohols, glycol ether acetates, esters, amines, amides, ketones and mixtures thereof; and

,

catalyst selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid, maleic acid, oxalic acid and mixtures thereof.

24. A spin on composition useful for gap filling silicon dioxide depositions, comprising:

an aminosilane selected from a first group consisting of bis(tertiarybutylamino)silane and di-isopropylaminosilane and a chemical of a second group selected from the group consisting of di-isopropylaminosilane, triethoxysilane, tetraacetoxysilane, tetraethylorthosilicate, tetramethoxysilane, tetrapropoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methylacetoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltriacetoxysilane, hexaethoxydisilane, hexamethoxydisilane and mixtures thereof;

where when the aminosilane of the first group is di-isopropylaminosilane, the chemical of the second group is not di-isopropylaminosilane;

a solvent selected from the group consisting of glycol ethers, alcohols, glycol ether acetates, esters, amines, amides, ketones and mixtures thereof; and

,

catalyst selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid, maleic acid, oxalic acid and mixtures thereof.

25. A spin on composition useful for gap filling silicon dioxide depositions, comprising:

an aminosilane selected from the group consisting of bis(tertiarybutylamino)silane and di-isopropylaminosilane;

a solvent selected from the group consisting of glycol ethers, alcohols, glycol ether acetates, esters, amines, amides, ketones and mixtures thereof; and

,

catalyst selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid, maleic acid, oxalic acid and mixtures thereof.