Methods of forming a low-k dielectric layer and methods of fabricating a semiconductor device using the same

Patent metadata

Field	Value
Publication number	US-10134583-B2
Application number	US-201615349359-A
Country	US
Kind code	B2
Filing date	Nov 11, 2016
Priority date	Jan 19, 2016
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

A method of forming a dielectric layer includes forming a preliminary dielectric layer on a substrate using a silicon precursor and performing an energy treatment on the preliminary dielectric layer to form a dielectric layer. In the dielectric layer, a ratio of Si—CH 3 bonding unit to Si—O bonding unit ranges from 0.5 to 5.

First claim

What is claimed is:

1. A method of forming a dielectric layer, comprising:
forming a preliminary dielectric layer on a substrate using a silicon precursor containing a compound represented by the following Chemical Formula 1; and
performing an energy treatment on the preliminary dielectric layer to form the dielectric layer,

wherein, in the Chemical Formula 1,
n is 1 or 2,
at least two of R 1 , R 2 , R 3 , R 5 , and R 6 are —O—R 7 and others of R 1 , R 2 , R 3 , R 5 , and R 6 are each independently one of hydrogen, (C 1 -C 10 )alkyl, (C 3 -C 10 )alkenyl, (C 3 -C 10 )alkynyl, and (C 1 -C 10 )alkoxy,
R 7 is one of hydrogen, (C 1 -C 10 )alkyl, (C 3 -C 10 )alkenyl, and (C 3 -C 10 )alkynyl, and
R 4 is a porogen group including one of (C 3 -C 10 )alkenyl, (C 3 -C 10 )alkynyl, (C 3 -C 10 )aryl, (C 3 -C 10 )heteroaryl, (C 3 -C 10 )cycloalkyl, (C 3 -C 10 )cycloalkenyl, (C 3 -C 10 )cycloalkynyl, (C 3 -C 10 )heterocycloalkyl, (C 3 -C 10 )aryl(C 1 -C 10 )alkyl, (C 3 -C 10 )cycloalkyl(C 1 -C 10 )alkyl, and (C 3 -C 10 )heterocycloalkyl(C 1 -C 10 )alkyl,
wherein a ratio of a Si—CH 3 bonding unit to a Si—O bonding unit ranges from 0.5 to 5, and
wherein the (C 3 -C 10 )heteroaryl and the (C 3 -C 10 )heterocycloalkyl of the R 4 each independently include at least one heteroatom including one of —NR 8 —, —O—, and —S—, and R 8 is one of hydrogen and (C 1 -C 10 )alkyl.

2. The method of claim 1 , wherein at least two of R 1 , R 2 , R 3 , R 5 , and R 6 are (C 1 -C 5 )alkoxy, and others of R 1 , R 2 , R 3 , R 5 , and R 6 are (C 1 -C 5 )alkyl.

3. The method of claim 2 , wherein at least three of R 1 , R 2 , R 3 , R 5 , and R 6 are methoxy, and others of R 1 , R 2 , R 3 , R 5 , and R 6 are (C 1 -C 5 )alkyl.

4. The method of claim 1 , wherein the R 4 is one of 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, phenyl group, xylene group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopentenyl group, cyclopentadiene group, cyclohexadiene group, cycloheptadiene group, bicycloheptyl group, bicycloheptenyl group, cyclohexene oxide group, cyclopentene oxide group, terpinene group, limonene group, butadieneoxide, styrene, and fulvene.

5. The method of claim 1 , wherein a mean diameter of pores in the dielectric layer ranges from 0.5 nm to 5 nm.

6. The method of claim 1 , wherein a total volume of pores in the dielectric layer ranges from 8% to 35% of a total volume of the dielectric layer.

7. The method of claim 1 , wherein the dielectric layer has a Young's modulus of 6-15 GPa.

8. The method of claim 1 , wherein a ratio of Si—O cage structures to Si—O network structures in the dielectric layer ranges from 0.5 to 1.

9. A method of fabricating a semiconductor device, the method comprising:
forming a silicon insulating layer on a substrate using a silicon precursor, the silicon precursor including,
a molecule having a structure of Si—(CH 2 ) n —Si, wherein n is 1 or 2,
a porogen group configured to combine with at least one of the Si atoms in the molecule, the porogen group including one of (C 3 -C 10 )alkenyl, (C 3 -C 10 )alkynyl, (C 3 -C 10 )aryl, (C 3 -C 10 )heteroaryl (C 3 -C 10 )cycloalkyl, (C 3 -C 10 )cycloalkenyl, (C 3 -C 10 )cycloalkynyl, (C 3 -C 10 )heterocycloalkyl, (C 3 -C 10 )aryl(C 1 -C 10 )alkyl, (C 3 -C 10 )cycloalkyl(C 1 -C 10 )alkyl, and (C 3 -C 10 )heterocycloalkyl(C 1 -C 10 )alkyl, and
at least two (C 1 -C 5 )alkoxy groups configured to combine with the Si atoms in the molecule; and

forming at least one interconnection line in the silicon insulating layer
wherein the porogen group is a functional group directly bonded to the at least one of the Si atoms.

10. The method of claim 9 , wherein a ratio of Si—CH 3 bonding unit to Si—O bonding unit in the silicon insulating layer ranges from 0.5 to 5.

11. The method of claim 9 , wherein a ratio of Si—O cage structures to Si—O network structures in the silicon insulating layer ranges from 0.5 to 1.

12. The method of claim 9 , wherein the forming at least one interconnection line comprises:
patterning the silicon insulating layer to form at least one interconnection hole in the silicon insulating layer; and
forming a conductive layer to fill the at least one interconnection hole.

13. The method of claim 12 , wherein the forming at least one interconnection line further comprises forming a barrier layer to cover the at least one interconnection hole before the forming a conductive layer.

14. The method of claim 9 , wherein
the porogen group has a cyclic hydrocarbon structure, and
the porogen group is one of cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopentenyl group, cyclopentadiene group, cyclohexadiene group, cycloheptadiene group, bicycloheptyl group, bicycloheptenyl group, cyclohexene oxide group, cyclopentene oxide group, terpinene group, limonene group, butadieneoxide, styrene, and fulvene.

15. A method comprising:
forming a dielectric layer using a silicon precursor containing a compound represented by the following Chemical Formula 1:

wherein, in the Chemical Formula 1,
n is 1 or 2,
at least three of R 1 , R 2 , R 3 , R 5 , and R 6 are methoxy and the others are each independently one of hydrogen, (C 1 -C 10 )alkyl, (C 3 -C 10 )alkenyl, (C 3 -C 10 )alkynyl, and (C 1 -C 10 )alkoxy, and
R 4 is a porogen group directly bonded to the Si atom and including one of (C 3 -C 10 )alkenyl, (C 3 -C 10 )alkynyl, (C 3 -C 10 )aryl, (C 3 -C 10 )heteroaryl, (C 3 -C 10 )cycloalkenyl, (C 3 -C 10 )cycloalkynyl, (C 3 -C 10 )heterocycloalkyl, (C 3 -C 10 )aryl(C 1 -C 10 )alkyl, (C 3 -C 10 )cycloalkyl(C 1 -C 10 )alkyl, and (C 3 -C 10 )heterocycloalkyl(C 1 -C 10 )alkyl.

16. The method of claim 15 , wherein the forming a dielectric layer comprises:
forming a preliminary dielectric layer on the substrate using the silicon precursor; and
performing an energy treatment on the preliminary dielectric layer.

17. The method of claim 15 , wherein a total volume of pores in the dielectric layer ranges from 8% to 35% of a total volume of the dielectric layer.

18. The method of claim 15 , wherein a ratio of Si—O cage structures to Si—O network structures in the dielectric layer ranges from 0.5 to 1.

19. The method of claim 15 , wherein, in the Chemical Formula 1, Si—R4 is one of

20. The method of claim 15 , wherein the dielectric layer has a dielectric constant of 2.2-2.3.

Assignees

• Samsung Electronics Co Ltd
• Dnf Co Ltd

Inventors

• Hwang Sunhye
• Kim Myong Woon
• Cho Younjoung
• Lee Sang Ick
• Jeon Sang Yong
• Jung In Kyung
• Chung Wonwoong
• Choi Jungsik

Classifications

• H10P14/6922

  the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC · CPC title

• H10P14/6903

  containing silicon · CPC title

• H10P14/6684

  the compound comprising silicon and oxygen · CPC title

• H10P14/6538

  by exposure to UV light · CPC title

• H10P14/6516

  of treatments performed after formation of the materials · CPC title