Method of forming a carbon polymer film using plasma CVD

• US 20070218705A1
• Filed: 09/20/2006
• Published: 09/20/2007
• Est. Priority Date: 08/09/2004
• Status: Active Grant

• Current Assignee: ASM Japan K.K. (ASM International NV)
• Original Assignee: ASM Japan K.K. (ASM International NV)
• Inventors: Matsuki, Nobuo, Morisada, Yoshinori, Umemoto, Seijiro, Lee, Jea
• Granted Patent: US 7,470,633 B2
• Time in Patent Office: Days
• US Class Current: 438/780
• CPC Class Codes: B05D 1/62 Plasma-deposition of organic layers plasma deposition in general C23C14/00, C23C16/00
• CPC Class Codes: G03F 7/167 from the gas phase, by plasma deposition G03F7/2035 takes precedence
• CPC Class Codes: H01L 21/02118 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC polymers per se C08G, photoresist per se G03F
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0332 characterised by their composition, e.g. multilayer masks, materials
• CPC Class Codes: H01L 21/3127 Layers comprising fluoro (hydro)carbon compounds, e.g. polytetrafluoroethylene
• CPC Class Codes: H01L 21/3146 Carbon layers, e.g. diamond-like layers

Abstract

A method forms a hydrocarbon-containing polymer film on a semiconductor substrate by a capacitively-coupled plasma CVD apparatus. The method includes the steps of: vaporizing a hydrocarbon-containing liquid monomer (C_αH_βX_γ, wherein α and β are natural numbers of 5 or more; γ is an integer including zero; X is O, N or F) having a boiling point of about 20° C. to about 350° C.; introducing the vaporized gas into a CVD reaction chamber inside which a substrate is placed; and forming a hydrocarbon-containing polymer film on the substrate by plasma polymerization of the gas.

Claims

1. A method of forming a hydrocarbon-containing polymer film on a semiconductor substrate by a capacitively-coupled plasma CVD apparatus, which comprises the steps of:

vaporizing a hydrocarbon-containing liquid monomer (C_α

H_β

X_γ

, wherein α and

β

are natural numbers of 5 or more;

γ

is an integer including zero;

X is O, N or F) having a boiling point of about 20°

C. to about 350°

C.;

introducing said vaporized gas into a CVD reaction chamber inside which a substrate is placed; and

forming a hydrocarbon-containing polymer film on said substrate by plasma polymerization of said gas.

2. The method according to claim 1, wherein said liquid monomer has no benzene structure.

3. The method according to claim 2, wherein said non-benzene liquid monomer is non-cyclic.

4. The method according to claim 2, wherein said non-benzene liquid monomer is a hydrocarbon wherein γ

is equal to zero.

5. The method according to claim 2, wherein said non-benzene liquid monomer is an unsaturated hydrocarbon.

6. The method according to claim 5, wherein said unsaturated hydrocarbon is selected from the group consisting of isoprene(2-methyl-1,3-butadiene), 2,3-methyl-1,3-butadiene, 3-methyl-1,2-butadiene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1,4-methyl-1,3-butadiene, and 1,2-methyl-1,3-butadiene.

7. The method according to claim 2, wherein said non-benzene liquid monomer is a saturated hydrocarbon.

8. The method according to claim 3, wherein said non-cyclic liquid monomer is one or more hydrocarbons selected from the group consisting of C_nH_2n+2 (n is an integer of 5 or greater) and C_nH_2(n−

m)+2 (n is an integer of 5 or greater, m is an integer of 1 or greater but smaller than n).

9. The method according to claim 2, wherein only said non-benzene liquid monomer is used as a reaction gas.

10. The method according to claim 2, wherein said non-benzene liquid monomer is introduced into a heater disposed upstream of said reaction chamber and vaporized.

11. The method according to claim 10, wherein said non-benzene liquid monomer is flow-controlled upstream of said heater by a valve, and its introduction into said heater is blocked, except when a film is being formed, by a shutoff valve disposed between said flow control valve and said heater and kept approximately at 50°

C. or lower.

12. The method according to claim 2, further comprising introducing an inert gas into the reaction chamber prior to the plasma polymerization.

13. The method according to claim 2, wherein as an additive gas, an organic gas CnHm (wherein n is an integer of 4 or less including zero;

m is any natural number) is further introduced into the reaction chamber.

14. The method according to claim 2, wherein as an additive gas, a dry gas containing N, O, and/or F is further introduced into the reaction chamber.

15. The method according to claim 2, wherein the forming polymer film has a density of 1.2 g/cm³ to 2.2 g/cm³.

16. The method according to claim 2, wherein the forming polymer film is a hard mask.