Method for forming a dopant-containing film

Abstract

In a film forming method for forming a film of a metal compound containing a metal dopant on a substrate (S) in order to control the dopant concentration or its distribution in the film, the method includes a first step (P1) of sputter depositing the metal compound on the substrate in a metal mode with a flow rate of a reaction gas less than a predetermined value, and a second step (P2) of sputter depositing the metal dopant on the substrate in a reaction mode with the flow rate of the reaction gas equal to or greater than the predetermined value, the steps being carried out simultaneously. After the film formation in the second step is completed and, simultaneously therewith or after a lapse of a predetermined time, the film formation in the first step is completed, the method includes a fourth step (P4) of continuing the supply of the reaction gas to the substrate for a predetermined time.

Claims

1. A method for forming a film of a metal compound containing a metal dopant on a substrate, comprising the steps of: a first step of sputtering the metal compound on the substrate in a metal mode with a flow rate of a reactive gas less than a predetermined value; a second step of sputtering the metal dopant on the substrate in a reactive mode in which the flow rate of the reactive gas is equal to or greater than the predetermined value; a third step of sputtering the metal compound on the substrate in the metal mode after the first step and the second step are performed in parallel; a fourth step of reacting the film formed on the substrate after the third step.

2. The film of the metal compound containing the metal dopant is The metal compound is the main component of the film-forming material, The metal dopant as a dopant for the main film-forming material is contained in an amount of more than 0 atomic % and 5 atomic % or less; In the first step and the third step, the metal compound as the main film-forming material is sputter-formed in the metal mode; 2. The film forming method according to claim 1, wherein in the second step, the metal dopant as the dopant is sputtered in the reactive mode.

3. a deposition chamber into which a substrate to be deposited is placed; a pressure reducer for reducing the pressure in the film formation chamber to a predetermined pressure; a discharge gas introducing device for introducing a discharge gas into the film forming chamber; a first sputtering electrode on which a first target serving as a main film forming material is mounted and which is provided so as to face the substrate; a first chimney that covers a first space in front of the first target and the first sputtering electrode by a first shutter in an openable and closable manner; a second sputtering electrode on which a second target serving as a dopant for the main film forming material is mounted and which is provided so as to face the substrate; a second chimney that covers a second space in front of the second target and the second sputtering electrode by a second shutter in an openable and closable manner; a discharge gas introducing device that introduces a discharge gas into the first space and the film formation chamber; a reactive gas introducing device that introduces a reactive gas into the film forming chamber through the second space; a DC power source for supplying power to the first sputtering electrode and the second sputtering electrode; an electrode voltage controller for controlling a rectangular wave applied from the DC power supply to each of the first sputtering electrode and the second sputtering electrode; a shutter opening / closing controller for controlling opening / closing of the first shutter and the second shutter; a gas introduction controller for controlling each of the discharge gas introducer and the reactive gas introducer; A reactive sputtering apparatus including an overall controller that controls the electrode voltage controller, the shutter opening / closing controller, and the gas introduction controller, A film forming method for forming a film on a substrate, the film containing the main film forming material as a main component and the dopant, comprising: a first process of introducing a discharge gas into the film formation chamber and the reactive gas into the second space, applying a pulse voltage from the DC power supply to each of the first sputtering electrode and the second sputtering electrode, closing the second shutter and opening the first shutter, and forming an ultra-thin film of the first target on the substrate; a second step of opening the second shutter under the conditions of the first step to simultaneously form an ultra-thin film of the first target and an ultra-thin film of the second target on the substrate; a third step of closing the second shutter under the conditions of the second step and forming an ultra-thin film of the first target on the substrate; a fourth step of closing the first shutter after the third step and reacting the film formed on the substrate under conditions of the third step.

4. a deposition chamber into which a substrate to be deposited is placed; a pressure reducer for reducing the pressure in the film formation chamber to a predetermined pressure; a discharge gas introducing device for introducing a discharge gas into the film forming chamber; a first sputtering electrode on which a first target serving as a main film forming material is mounted and which is provided so as to face the substrate; a first chimney that covers a first space in front of the first target and the first sputtering electrode by a first shutter in an openable and closable manner; a second sputtering electrode on which a second target serving as a dopant for the main film forming material is mounted and which is provided so as to face the substrate; a second chimney that covers a second space in front of the second target and the second sputtering electrode by a second shutter in an openable and closable manner; a discharge gas introducing device that introduces a discharge gas into the first space and the film formation chamber; a reactive gas introducing device that introduces a reactive gas into the film forming chamber through the second space; a DC power source for supplying power to the first sputtering electrode and the second sputtering electrode; an electrode voltage controller for controlling a rectangular wave applied from the DC power supply to each of the first sputtering electrode and the second sputtering electrode; a shutter opening / closing controller for controlling opening / closing of the first shutter and the second shutter; a gas introduction controller for controlling each of the discharge gas introducer and the reactive gas introducer; a general controller that controls the electrode voltage controller, the shutter opening / closing controller, and the gas introduction controller in a general manner, A film forming method for forming a film on a substrate, the film containing the main film forming material as a main component and the dopant, comprising: a first process of introducing a discharge gas into the film formation chamber and the reactive gas into the second space, applying a pulse voltage from the DC power source to the first sputtering electrode, stopping the application of the DC voltage to the second sputtering electrode, opening the first shutter and the second shutter, and forming an ultra-thin film of the first target on the substrate; a second step of applying a pulse voltage to the second sputtering electrode under the conditions of the first step to simultaneously form an ultra-thin film of the first target and an ultra-thin film of the second target on the substrate; a third step of stopping the application of a DC voltage to the second sputtering electrode under the conditions of the second step and forming an ultra-thin film of the first target on the substrate; a fourth step of closing the first shutter after the third step and reacting the film formed on the substrate under conditions of the third step.

5. a deposition chamber into which a substrate to be deposited is placed; a pressure reducer for reducing the pressure in the film formation chamber to a predetermined pressure; a discharge gas introducing device for introducing a discharge gas into the film forming chamber; a first sputtering electrode on which a first target serving as a main film forming material is mounted and which is provided so as to face the substrate; a first chimney that covers a first space in front of the first target and the first sputtering electrode by a first shutter in an openable and closable manner; a second sputtering electrode on which a second target serving as a dopant for the main film forming material is mounted and which is provided so as to face the substrate; a second chimney that covers a second space in front of the second target and the second sputtering electrode by a second shutter in an openable and closable manner; a discharge gas introducing device that introduces a discharge gas into the first space and the film formation chamber; a reactive gas introducing device that introduces a reactive gas into the film forming chamber through the second space; a DC power source for supplying power to the first sputtering electrode and the second sputtering electrode; an electrode voltage controller for controlling a rectangular wave applied from the DC power supply to each of the first sputtering electrode and the second sputtering electrode; a shutter opening / closing controller for controlling opening / closing of the first shutter and the second shutter; a gas introduction controller for controlling each of the discharge gas introducer and the reactive gas introducer; A reactive sputtering apparatus including an overall controller that controls the electrode voltage controller, the shutter opening / closing controller, and the gas introduction controller, A film forming method for forming a film on a substrate, the film containing the main film forming material as a main component and the dopant, comprising: a first process of introducing a discharge gas into the film formation chamber and the reactive gas into the second space, applying a pulse voltage from the DC power source to the first sputtering electrode, stopping the application of the DC voltage to the second sputtering electrode, opening the first shutter and the second shutter, and forming an ultra-thin film of the first target on the substrate; a second step of applying a pulse voltage to the second sputtering electrode under the conditions of the first step to simultaneously form an ultra-thin film of the first target and an ultra-thin film of the second target on the substrate; a third step of stopping the application of a DC voltage to the second sputtering electrode under the conditions of the second step and forming an ultra-thin film of the first target on the substrate; and a fourth step of, after the third step, stopping application of a pulse voltage to the first sputtering electrode under the conditions of the third step, and reacting the film formed on the substrate.

6. The electrode voltage controller includes: a first pulse wave conversion switch connected between the DC power supply and the first sputtering electrode, for converting a DC voltage applied to the first sputtering electrode into a pulse wave voltage; a second pulse wave conversion switch connected between the DC power supply and the second sputtering electrode and configured to convert a DC voltage applied to the second sputtering electrode into a pulse wave voltage; The general controller includes: The film formation method according to any one of claims 3 to 5, further comprising a programmable oscillator that controls the first pulse wave conversion switch, the second pulse wave conversion switch, the shutter opening / closing controller, and the gas introduction controller in accordance with a programmed pulse control signal pattern, the programmable pulse control signal pattern corresponding to a first sputtering target power to be supplied to the first sputtering electrode, a second sputtering target power to be supplied to the second sputtering electrode, target opening / closing timings of the first shutter and the second shutter, and target introduction timings of the discharge gas and the reactive gas to be introduced into the film formation chamber.

7. 6. The film forming method according to claim 3, wherein the first step, the second step, the third step, and the fourth step are repeated until a predetermined film thickness is reached.

8. 6. The film forming method according to claim 3, wherein the film mainly composed of the main film forming material contains the dopant in an amount of more than 0 atomic % and not more than 5 atomic %.