# US 7,410,915 B2 · Method of forming carbon polymer film using plasma CVD > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,410,915 B2 - Document ID: US7410915B2 - Status: Granted - Kind: B2 - Application number: 11/387,527 - Filed: 2006-03-23 - Published: 2007-09-27 - Granted: 2008-08-12 - Earliest claimed: 2006-03-23 - Assignees: ASM Japan K.K.; Samsung Electronic Co., Ltd. - Inventors: Yoshinori Morisada; Kamal Kishore Goundar; Masashi Yamaguchi; Nobuo Matsuki; Kyu Tae Na; Eun Kyung Baek - Web page: https://patentgrep.com/patent/US7410915B2 ## CPC - H10P 50/73: {using masks for insulating materials} - H10P 14/683: {carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC} - H10P 50/71: {using masks for conductive or resistive materials} - B05D 1/62: {Plasma-deposition of organic layers (plasma deposition in general C23C14/00, C23C16/00)} - H10P 14/6336: {in the presence of a plasma [PECVD]} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) ## Abstract A method of forming 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 (CαHβXγ, 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. which is not substituted by a vinyl group or an acetylene group; introducing the vaporized gas and CO2 gas or H2 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, thereby reducing extinction coefficient (k) at 193 nm and increasing mechanical hardness. ## Claims ### Claim 1 A method of forming a hydrocarbon-containing polymer film on a semiconductor substrate by a capacitively-coupled plasma CVD apparatus, which comprises: vaporizing a hydrocarbon-containing liquid monomer (CαHβXγ, 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. which is not substituted by a vinyl group or an acetylene group; introducing said vaporized gas and CO2 gas or H2 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 and controlling an extinction coefficient at 193 nm and a mechanical hardness of the forming hydrocarbon-containing polymer film at 0.38 or less and 0.5 GPa or higher, respectively, as a function of a flow rate of the CO2 gas or H2 gas. ### Claim 2 (depends on 1) The method according to claim 1, wherein the flow rate of the CO2 gas or H2 gas is greater than a flow rate of the vaporized gas. ### Claim 3 (depends on 2) The method according to claim 2, wherein the CO2 gas is used at a flow rate of 800 sccm or more. ### Claim 4 (depends on 1) The method according to claim 1, wherein the CO2 gas is used at a flow rate of 350 sccm or more. ### Claim 5 (depends on 1) The method according to claim 1, wherein the H2 gas is used at a flow rate of 200 sccm or more. ### Claim 6 (depends on 5) The method according to claim 5, wherein the H2 gas is used at a flow rate of 300 sccm or more. ### Claim 7 (depends on 1) The method according to claim 1, wherein the extinction coefficient and the mechanical hardness of the forming hydrocarbon-containing polymer film are controlled at 0.35 or less and 0.8 GPa or higher, respectively, as a function of the flow of the CO2 gas or H2 gas. ### Claim 8 (depends on 1) The method according to claim 1, wherein the extinction coefficient and the mechanical hardness of the forming hydrocarbon-containing polymer film are controlled further as a function of a temperature of the substrate. ### Claim 9 (depends on 8) The method according to claim 8, wherein the temperature is controlled at 400° C. or higher. ### Claim 10 (depends on 1) The method according to claim 1, wherein said liquid monomer is a cyclic hydrocarbon. ### Claim 11 (depends on 10) The method according to claim 10, wherein said cyclic hydrocarbon is a substituted or non-substituted benzene. ### Claim 12 (depends on 11) The method according to claim 11, wherein said substituted or non-substituted benzene is C6H6-nRn (wherein n is 0, 1, 2, or 3); R is independently —CH3 or —C2H5. ### Claim 13 (depends on 12) The method according to claim 12, wherein said substituted benzene is any one of 1,3,5-trimethylbenzene, o-xylene, m-xylene or p-xylene. ### Claim 14 (depends on 1) The method according to claim 1, wherein said liquid monomer is a linear hydrocarbon. ### Claim 15 (depends on 1) The method according to claim 1, wherein said liquid monomer is a hydrocarbon wherein γ is equal to zero. ### Claim 16 (depends on 1) The method according to claim 1, wherein only said liquid monomer is used as a reaction gas. ### Claim 17 (depends on 1) The method according to claim 1, wherein said liquid monomer is introduced into a heater disposed upstream of said reaction chamber and vaporized. ### Claim 18 (depends on 17) The method according to claim 17, wherein said 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 80° C. or lower or at a temperature which is at least approximately 50° C. lower than that of vaporization by heat. ### Claim 19 (depends on 17) The method according to claim 17, wherein said liquid monomer is flow-controlled by a valve, which is disposed upstream of said heater and kept at approximately 80° C. or lower or at a temperature which is at least approximately 50° C. lower than that of vaporization by heat, and its introduction into said heater is blocked except when a film is being formed. ### Claim 20 (depends on 1) The method according to claim 1, further comprising introducing an inert gas into the reaction chamber prior to the plasma polymerization. ### Claim 21 (depends on 1) The method according to claim 1, 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. ### Claim 22 (depends on 1) The method according to claim 1, wherein as an additive gas, a dry gas containing N, O and F is further introduced into the reaction chamber. ### Claim 23 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: placing a semiconductor device substrate in a CVD reaction chamber; vaporizing a hydrocarbon-containing liquid monomer (CαHβXγ, 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 and CO2 gas or H2 gas into the CVD reaction chamber inside which the substrate is placed; and forming a hard mask comprising a hydrocarbon-containing polymer film on said substrate by plasma polymerization of said gas and controlling an extinction coefficient at 193 nm and a mechanical hardness of the forming hydrocarbon-containing polymer film at 0.38 or less and 0.5 GPa or higher, respectively, as a function of a flow rate of the CO2 gas or H2 gas. ### Claim 24 (depends on 23) The method according to claim 23, wherein the flow rate of the CO2 gas or H2 gas is greater than a flow rate of the vaporized gas. ### Claim 25 (depends on 23) The method according to claim 23, wherein the CO2 gas is used at a flow rate of 350 sccm or more. ### Claim 26 (depends on 25) The method according to claim 25, wherein the CO2 gas is used at a flow rate of 800 sccm or more. ### Claim 27 (depends on 25) The method according to claim 25, wherein the extinction coefficient and the mechanical hardness of the forming hydrocarbon-containing polymer film are controlled further as a function of a temperature of the substrate. ### Claim 28 (depends on 27) The method according to claim 27, wherein the temperature is controlled at 400° C. or higher. ### Claim 29 (depends on 23) The method according to claim 23, wherein the H2 gas is used at a flow rate of 200 sccm or more. ### Claim 30 (depends on 29) The method according to claim 29, wherein the H2 gas is used at a flow rate of 300 sccm or more. ### Claim 31 (depends on 23) The method according to claim 23, wherein the extinction coefficient and the mechanical hardness of the forming hydrocarbon-containing polymer film are controlled at 0.35 or less and 0.8 GPa or higher, respectively, as a function of the flow of the CO2 gas or H2 gas. ### Claim 32 (depends on 23) The method according to claim 23, wherein said liquid monomer is a cyclic hydrocarbon. ### Claim 33 (depends on 32) The method according to claim 32, wherein said cyclic hydrocarbon is a substituted or non-substituted benzene. ### Claim 34 (depends on 23) The method according to claim 23, wherein said liquid monomer is a linear hydrocarbon. ### Claim 35 (depends on 23) The method according to claim 23, wherein said liquid monomer is a hydrocarbon wherein γ is equal to zero. ### Claim 36 (depends on 23) The method according to claim 23, wherein only said liquid monomer is used as a reaction gas. ### Claim 37 (depends on 23) The method according to claim 23, wherein said liquid monomer is introduced into a heater disposed upstream of the reaction chamber and vaporized. ### Claim 38 (depends on 37) The method according to claim 37, wherein said 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 80° C. or lower or at a temperature which is at least approximately 50° C. lower than that of vaporization by heat. ### Claim 39 (depends on 37) The method according to claim 37, wherein said liquid monomer is flow-controlled by a valve, which is disposed upstream of said heater and kept at approximately at 80° C. or lower or at a temperature which is at least approximately 50° C. lower than that of vaporization by heat, and its introduction into said heater is blocked except when a film is being formed. ### Claim 40 (depends on 23) The method according to claim 23, further comprising introducing an inert gas into the reaction chamber prior to the plasma polymerization.