Silicone polymer insulation film on semiconductor substrate and method for forming the film

• US 6,455,445 B2
• Filed: 03/28/2001
• Issued: 09/24/2002
• Est. Priority Date: 02/05/1998
• Status: Expired due to Term

• Current Assignee: ASM Japan K.K. (ASM International NV)
• Original Assignee: ASM Japan K.K. (ASM International NV)
• Inventors: Matsuki, Nobuo
• Primary Examiner(s): Sherry, Michael
• Assistant Examiner(s): KILDAY, LISA A
• Application Number:
  US09/820,075
• Publication Number:
  US 20010021590A1
• Time in Patent Office: 545 Days
• Field of Search: 427/589, 437/235, 438/758, 438/788, 438/789, 438/790
• US Class Current: 438/789
• CPC Class Codes: B05D 1/62 Plasma-deposition of organic layers plasma deposition in general C23C14/00, C23C16/00
• CPC Class Codes: C08G 77/00 Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: H01L 21/02126 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 Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/3121 Layers comprising organo-silicon compounds
• CPC Class Codes: H01L 21/3122 layers comprising polysiloxane compounds
• CPC Class Codes: H01L 23/296 Organo-silicon compounds
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: H01L 2924/12044 OLED
• CPC Class Codes: Y10S 257/914 Polysilicon containing oxygen, nitrogen, or carbon, e.g. sipos

Abstract

A siloxan polymer insulation film has a dielectric constant of 3.3 or lower and has —SiR₂O— repeating structural units. The siloxan polymer has dielectric constant, high thermal stability and high humidity-resistance on a semiconductor substrate. The siloxan polymer is formed by directly vaporizing a silicon-containing hydrocarbon compound expressed by the general formula Si_αO_βC_xH_y (α, β, x, and y are integers) and then introducing the vaporized compound to the reaction chamber of the plasma CVD apparatus. The residence time of the source gas is lengthened by reducing the total flow of the reaction gas, in such a way as to form a siloxan polymer film having a micropore porous structure with low dielectric constant.

Claims

1. A method for forming a siloxan polymer insulation film on a semiconductor substrate by plasma treatment, comprising the steps of:

vaporizing a silicon-containing hydrocarbon compound to produce a material gas for silicone polymer, said silicon-containing hydrocarbon having the formula Si_α

O<sub>α

−

1</sub>R<sub>2α

−

β

+2</sub>(OC_nH_2n+1)_β

wherein α

is an integer of 1-3, β

is 0, 1, or 2, n is an integer of 1-3, and R is C_1-6 hydrocarbon attached to Si;

introducing the material gas into a reaction chamber for plasma CVD processing wherein a semiconductor substrate is placed;

introducing an additive gas comprising an inert gas and optionally an oxidizing gas, said oxidizing gas being used in an amount less than the material gas; and

forming a siloxan polymer film having —

SiR₂O—

repeating structural units on the semiconductor substrate by activating plasma polymerization reaction in the reaction chamber where a reaction gas composed of the material gas and the additive gas is present, while controlling the flow of the reaction gas to lengthen a residence time, Rt, of the reaction gas in the reaction chamber, wherein 100 msec≦

Rt,

2. The method according to claim 1, wherein the residence time is determined by correlating the dielectric constant with the residence time.

3. The method according to claim 1, wherein the additive gas comprises at least either argon (Ar) or Helium (He).

4. The method according to claim 1, wherein the flow of the reaction gas is controlled to render the relative dielectric constant of the silicone polymer film lower than 3.30.

5. The method according to claim 1, wherein the flow of the reaction gas is controlled to render the dielectric constant of the silicone polymer film no more than 3.1.

6. The method according to claim 1, wherein Rt is no less than 165 msec.

7. The method according to claim 1, wherein the additive gas is exclusively an inert gas.

8. A method for forming a siloxan polymer insulation film on a semiconductor substrate by plasma treatment, comprising the steps of:

vaporizing a silicon-containing hydrocarbon compound to produce a material gas for silicone polymer, said silicon-containing hydrocarbon having the formula Si_α

O<sub>α

−

1</sub>R<sub>2α

−

β

+2</sub>(OC_nH_2n+1)_β

wherein α

is an integer of 1-3, β

is 0 or 1, n is an integer of 1-3, and R is C_1-6 hydrocarbon attached to Si;

introducing the material gas into a reaction chamber for plasma CVD processing wherein a semiconductor substrate is placed;

introducing an additive gas comprising an inert gas and an oxidizing gas, said oxidizing gas being used in an amount less than the material gas; and

forming a siloxan polymer film having —

SiR₂O—

repeating structural units on the semiconductor substrate by activating plasma polymerization reaction in the reaction chamber where a reaction gas composed of the material gas and the additive gas is present, while controlling the flow of the reaction gas to lengthen a residence time, Rt, of the reaction gas in the reaction chamber, wherein 100 msec≦

Rt,

9. A method for forming a siloxan polymer insulation film on a semiconductor substrate by plasma treatment, comprising the steps of:

vaporizing a silicon-containing hydrocarbon compound to produce a material gas for silicone polymer, said silicon-containing hydrocarbon having the general formula Si_α

O_β

C_xH_y wherein α

,β

,x, and y are integers;

introducing the material gas into a reaction chamber for plasma CVB processing wherein a semiconductor substrate is placed;

introducing an additive gas; and

forming a siloxan polymer film having −

SiR₂O−

repeatin structural units on the semiconductor substrate by activating plasma polymerization in the reaction chamber where a reaction gas composed of the material gas and the additive gas is present, while controlling the flow of the reaction gas to lenghthen a residence time, Rt, of the reaction gas in the reaction chamber, wherein 100 msec≦

Rt,

10. The method according to claim 9, wherein the alkoxy present in the silicon-containing hydrocarbon compound has 1 to 3 carbon atoms.

11. The method according to claim 9, wherein the hydrocarbon present in the silicon-containing hydrocarbon compound has 1 to 6 carbon atoms.

12. The method according to claim 9, wherein the silicon-containing hydrocarbon compound has 1 to 3 silison atoms.

13. The method according to claim 9, wherein the silicon-containing hydrocarbon compound has formula Si_α

O<sub>α

-1</sub>R<sub>2α

β

+2</sub>(OC_nH_2n+1)_β

wherein α

is an integer of 1-3, β

is 0, 1,or 2, n is an integer of 1-3, and R is C_1-6 hydrocarbon attached Si.

14. The method according to claim 9, wherein the additive gas comprises at least either argon (Ar) or Helium (He).

15. The method according to claim 9, wherein the additive gas comprises either an oxidizing agent or a reducing agent.

16. The method according to claim 14, wherein the additive gas further comprises either an oxidizing agent or a reducing agent.

17. The method according to claim 9, wherein the silicon-containing hydrocarbon compound is selected from the group consisting of:

wherein R1 and R2 are independently CH₃, C₂H₃, C₂H₅, C₃H₇ or C₆H₅, and m and n are any integer,

wherein R1, R2 and R3 are independently CH₃, C₂H₃, C₂H₅, C₃H₇ or C₆H₅, and n is any integer,

wherein R1, R2, R3 and R4 are independently CH₃, C₂H₃, C₂H₅, C₃H₇ or C₆H₅, and m and n are any integer,

wherein R1, R2, R3, R4, R5 and R6 are independently CH₃, C₂H₃, C₂H₅, C₃H₇ or C₆H₅, ir the additive gases are argon (Ar), Helium (He) and either nitrogen oxide (N₂O)or oxygen (O₂), and

wherein R1, R2, R3 and R4 are independently CH₃, C₂H₃, C₂H₅, C₃H₇ or C₆H₅, if the additive gases are argon (Ar), Helium (He) and either nitrogen oxide (N₂O) or oxygen (O₂).

18. The method according to claim 9, wherein the flow of the reaction gas is controlled to render the relative dielectic constant of the silicone polymer film lower than 3.30.