FLOWABLE SILICON-CARBON-NITROGEN LAYERS FOR SEMICONDUCTOR PROCESSING

• US 20130217240A1
• Filed: 08/21/2012
• Published: 08/22/2013
• Est. Priority Date: 09/09/2011
• Status: Abandoned Application

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Mallick, Abhijit Basu, Ingle, Nitin K., Wang, Linlin, Underwood, Brian S.
• Application Number:
  US13/590,611
• Publication Number:
  US 20130217240A1
• Time in Patent Office: Days
• US Class Current: 438/778
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: H01L 21/02167 the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/31111 by chemical means

Abstract

Methods are described for forming a dielectric layer on a semiconductor substrate. The methods may include providing a silicon-containing precursor and an energized nitrogen-containing precursor to a chemical vapor deposition chamber. The silicon-containing precursor and the energized nitrogen-containing precursor may be reacted in the chemical vapor deposition chamber to deposit a flowable silicon-carbon-nitrogen material on the substrate. The methods may further include treating the flowable silicon-carbon-nitrogen material to form the dielectric layer on the semiconductor substrate.

Claims

1. A method of forming a dielectric layer on a semiconductor substrate, the method comprising:

providing a silicon-containing precursor and an energized nitrogen-containing precursor to a chemical vapor deposition chamber;

reacting the silicon-containing precursor and the energized nitrogen-containing precursor in the chemical vapor deposition chamber to deposit a flowable silicon-carbon-nitrogen material on the substrate; and

treating the flowable silicon-carbon-nitrogen material to form the dielectric layer on the semiconductor substrate.

2. The method of claim 1, wherein the silicon-containing precursor comprises 1,3,5-trisilapentane, 1,4,7-trisilaheptane, disilacyclobutane, trisilacyclohexane, 3-methylsilane, silacyclopentene, silacyclobutene, or trimethylsilylacetylene.

3. The method of claim 1, wherein the silicon-containing precursor comprises:

(i) SiR₄, Si₂R₆, Si₃R₈, Si₄R₁₀, or Si₅R₁₂, wherein each R group is independently hydrogen (—

H) or a saturated or unsaturated alkyl group;

(ii) a silylalkane or silylalkene having the formula R₃Si—

[CH₂]_n—

SiR₃, wherein n may be an integer from 1 to 10, and each of the R groups are independently a hydrogen (—

H), or a saturated or unsaturated alkyl group;

(iii) a silylalkane or silylalkene having the formula R₃Si—

[CH₂]_x—

SiR₂—

[CR₂]_y—

SiR₃, wherein x and y are independently an integer from 1 to 10, and each of the R groups are independently a hydrogen (—

H), or a saturated or unsaturated alkyl group;

(iv) a silacycloalkane or silacycloalkene selected from the group consisting of silacyclopropanes, silacyclobutanes, silacyclopentanes, silacyclohexanes, silacycloheptanes, silacyclooctanes, silacyclononanes, silacyclopropenes, silacyclobutenes, silacyclopentenes, silacyclohexenes, silacycloheptenes, silacyclooctenes, and silacyclononenes;

(v) H_4-x-yCX_y(SiR₃)_x, where x is 1, 2, 3, or 4, y is 0, 1, 2 or 3, each X is independently a hydrogen or halogen (e.g., F, Cl, Br), and each R is independently a hydrogen (—

H) or an alkyl group;

(vi) (SiR₃)_xC(SiR₃)_x, where x is 1 or 2, and each R is independently a hydrogen (—

H) or an alkyl group;

or

(vii) R—

[(CR′

₂)_x—

(SiR″

₂)_y—

(CR′

₂)_z]_n—

R wherein each R, R′

, and R″

are independently a hydrogen, an alkyl group, an unsaturated alkyl group, a silane group, or

—

[(CH₂)_x1—

(SiH₂)_y1—

(CH₂)_z1]_n1—

R′

″

wherein x1, y1 and z1 are independently a number from 0 to 10, and n1 is a number from 0 to 10,

and wherein x, y and z are independently a number from 0 to 10, and n is a number from 0 to 10.

4. The method of claim 1, wherein the silicon-containing precursor comprises a silicon-and-nitrogen containing precursor selected from the group consisting of:

(i) R_4-xSi(NR₂)_x, where x may be 1, 2, 3, or 4, and each R is independently a hydrogen (—

H) or an alkyl group;

(ii) R_4-yN(SiR₃)_y, where y may be 1, 2, or 3, and each R is independently a hydrogen (—

H) or an alkyl group;

or

(iii) an substituted or unsubstituted ring structure comprising at least one Si atom and at least one nitrogen atom in the ring.

5. The method of claim 1, wherein the silicon-containing precursor comprises one of 1,3,5-trisilapentane or 1,4,7-trisilaheptane.

6. The method of claim 1, wherein the energized nitrogen-containing precursor comprises energized ammonia or an energized fragment of ammonia.

7. The method of claim 1, wherein the energized ammonia is produced in a remote plasma system fluidly coupled to the chemical vapor deposition chamber.

8. The method of claim 1, wherein the flowable silicon-carbon-nitrogen material comprises Si—

H bonds.

9. The method of claim 8, wherein the treating of the flowable silicon-carbon-nitrogen material reduces the number of Si—

H bonds in the material.

10. The method of claim 1, wherein the treating of the flowable silicon-carbon-nitrogen material comprises exposing the material to a plasma.

11. The method of claim 10, wherein the plasma for treating the flowable silicon-carbon-nitrogen material is located in the chemical vapor deposition chamber.

12. The method of claim 10, wherein the plasma is an inductively-coupled plasma or a capacitively-coupled plasma.

13. A method of treating a flowable silicon-carbon-nitrogen layer to reduce a wet etch rate ratio (WERR) of the layer, the method comprising:

forming the flowable silicon-carbon-nitrogen layer on a substrate by chemical vapor deposition of a silicon-containing precursor and an activated nitrogen precursor;

exposing the flowable silicon-carbon-nitrogen layer to plasma, wherein the plasma exposure reduces the number of Si—

H bonds and increases the number of Si—

C bonds in the layer, and wherein the plasma exposure reduces the WERR of the layer.

14. The method of claim 13, wherein the flowable silicon-containing precursor comprises 1,3,5-trisilapentane, 1,4,7-trisilaheptane, disilacyclobutane, trisilacyclohexane, 3-methylsilane, silacyclopentene, silacyclobutene, or trimethylsilylacetylene.

15. The method of claim 13, wherein the flowable silicon-containing precursor comprises:

(i) SiR₄, Si₂R₆, Si₃R₈, Si₄R₁₀, or Si₅R₁₂, wherein each R group is independently hydrogen (—

H) or a saturated or unsaturated alkyl group;

(ii) a silylalkane or silylalkene having the formula R₃Si—

[CH₂]_n—

SiR₃, wherein n may be an integer from 1 to 10, and each of the R groups are independently a hydrogen (—

H), or a saturated or unsaturated alkyl group;

(iii) a silylalkane or silylalkene having the formula R₃Si—

[CR₂]_x—

SiR₂—

[CR₂]_y—

SiR₃, wherein x and y are independently an integer from 1 to 10, and each of the R groups are independently a hydrogen (—

H), or a saturated or unsaturated alkyl group;

(iv) a silacycloalkane or silacycloalkene selected from the group consisting of silacyclopropanes, silacyclobutanes, silacyclopentanes, silacyclohexanes, silacycloheptanes, silacyclooctanes, silacyclononanes, silacyclopropenes, silacyclobutenes, silacyclopentenes, silacyclohexenes, silacycloheptenes, silacyclooctenes, and silacyclononenes;

(v) H_4-x-yCX_y(SiR₃)_x, where x is 1, 2, 3, or 4, y is 0, 1, 2 or 3, each X is independently a hydrogen or halogen (e.g., F, Cl, Br), and each R is independently a hydrogen (—

H) or an alkyl group;

(vi) (SiR₃)_xC═

C(SiR₃)_x, where x is 1 or 2, and each R is independently a hydrogen (—

H) or an alkyl group;

or

(vii) R—

[(CR′

₂)_x—

(SiR″

₂)_y—

(CR′

₂)_z]_n—

R, wherein each R, R′

, and R″

are independently a hydrogen, an alkyl group, an unsaturated alkyl group, a silane group, or

—

[(CH₂)_x1—

(SiH₂)_y1—

(CH₂)_z1]_n1—

R′

″

wherein x1, y1 and z1 are independently a number from 0 to 10, and n1 is a number from 0 to 10,

and wherein x, y and z are independently a number from 0 to 10, and n is a number from 0 to 10.

16. The method of claim 13, wherein the flowable silicon-containing precursor comprises a silicon-and-nitrogen containing precursor selected from the group consisting of:

(i) R_4-xSi(NR₂)_x, where x may be 1, 2, 3, or 4, and each R is independently a hydrogen (—

H) or an alkyl group;

(ii) R_4-yN(SiR₃)_y, where y may be 1, 2, or 3, and each R is independently a hydrogen (—

H) or an alkyl group;

or

(iii) an substituted or unsubstituted ring structure comprising at least one Si atom and at least one nitrogen atom in the ring.

17. The method of claim 13, wherein the activated nitrogen precursor comprises ammonia or an ammonia fragment that has been exposed to a plasma.

18. The method of claim 13, wherein the plasma exposure reduces the number of C—

H bonds and increases the number of Si—

Si bonds, Si—

N bonds, and C—

N bonds in the silicon-carbon-nitrogen layer.

19. The method of claim 13, wherein the plasma is an inductively-coupled plasma or a capacitively-coupled plasma.

20. The method of claim 13, wherein the plasma exposure decreases the WERR of the silicon-carbon-nitrogen layer in both dilute hydrofluoric acid and hot phosphoric acid.