Film deposition device, film deposition method, and method for manufacturing electronic device

Abstract

To provide a film deposition device capable of depositing a film on a film deposition object by sputtering using a rotary target made of an alloy of 2 or more components.SOLUTION: A film deposition device has: a cylindrical target made of an alloy of 2 or more components; and magnetic field generation means of creating a leakage magnetic field leaked from an outer periphery surface of the target while an angle around a rotation shaft parallel to a cylindrical center axial line is variably provided inside the target, and deposits an alloy thin film on a film deposition object arranged opposite to the target while rotating the target by sputtering. After a first alloy thin film is deposited on the film deposition object under a condition that the magnetic field generation means is set to a first angle, a second alloy thin film with a composition ratio different from that of the first alloy thin film is deposited on the first alloy thin film of the film deposition object under a condition that the magnetic field generation means is set to a second angle different from the first angle.SELECTED DRAWING: Figure 14

Description

[Technical field]

[0001] The present invention relates to a film formation apparatus and a film formation method for forming a film on a substrate by sputtering, and a method for manufacturing an electronic device. [Background technology]

[0002] As a deposition device for depositing a thin film of metal or metal oxide on a deposition target such as a substrate, there is a sputtering device that places a cylindrical target (hereinafter, referred to as a rotary target) facing a substrate and performs sputtering while rotating the rotary target. A sputtering device that uses a rotary target has the advantage that the surface of the target can be sputtered more uniformly than a planar sputtering device that uses a flat target. There is also a magnetron sputtering type sputtering device that arranges a magnet inside the rotary target and forms a magnetic field that leaks out of the rotary target, thereby increasing the plasma density near the surface of the rotary target (Patent Document 1).

[0003] An example of a thin film that can be formed by a sputtering device is a cathode metal film formed on an organic layer of an organic EL (electroluminescent) element. As a component of the cathode metal film, from the viewpoint of electron injection into the organic layer, alkali metals, alkaline earth metals, or alloys thereof having a low work function such as Mg are preferable, but from the viewpoint of oxidation resistance, metals having a high work function such as Au, Ag, and Al are preferable. In order to achieve both electron injection and oxidation resistance, there is a cathode metal film formed of an alloy mainly composed of Mg and Ag (Patent Document 2). In Patent Document 2, two targets, a flat target made of Mg and a flat target made of Ag, are placed in a chamber, and a voltage is applied to both targets simultaneously to perform sputtering, thereby forming a layer made of Mg-Ag alloy on the organic layer, and then a voltage is applied only to the Ag target to perform sputtering, thereby forming a layer made of Ag on the Mg-Ag alloy layer, thereby forming a cathode metal film made of a multilayer film with a difference in the composition ratio of Mg and Ag in the thickness direction.

[0004] Patent Document 3 describes a method for producing a rotary target made of an Mg-Ag alloy. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2020-200520 A [Patent Document 2] JP 2004-200047 A [Patent Document 3] JP 2013-204052 A Summary of the Invention [Problem to be solved by the invention]

[0006] The sputtering device in Patent Document 2 uses multiple independent flat targets made of each alloy component, and does not describe a sputtering device using a rotary target made of an alloy. Patent Document 3 describes a rotary target made of a two-component alloy, but does not describe a sputtering device using it.

[0007] An object of the present invention is to provide a film formation apparatus capable of forming a film on a film formation target by sputtering using a rotary target made of an alloy of two or more components. [Means for solving the problem]

[0008] The present invention includes a cylindrical target made of an alloy of two or more components, a magnetic field generating means provided inside the target such that an angle around a rotation axis parallel to the central axis of the cylindrical shape can be changed, the magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the target; having A film formation apparatus for forming an alloy thin film by sputtering on a film formation target disposed opposite the target while rotating the target, This film formation apparatus is characterized in that a first alloy thin film is formed on the object to be film-formed with the magnetic field generating means set at a first angle, and then a second alloy thin film having a composition ratio different from that of the first alloy thin film is formed on the first alloy thin film on the object to be film-formed with the magnetic field generating means set at a second angle different from the first angle.

[0009] The present invention relates to a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target such that an angle around a rotation axis parallel to a cylindrical central axis of the first target can be changed, the first magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target such that an angle around a rotation axis parallel to a cylindrical central axis of the second target can be changed, the second magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the second target; having A film formation apparatus for forming an alloy thin film by sputtering on a film formation target disposed opposite the first target while rotating the first target, and forming an alloy thin film by sputtering on the film formation target disposed opposite the second target while rotating the second target, a first alloy thin film is formed on the film-forming object while moving the film-forming object relative to the first target with the first magnetic field generating means set at a first angle; This is a film formation apparatus in which, with the second magnetic field generating means set to a second angle smaller than the first angle, the film formation object is moved relative to the second target while a second alloy thin film is formed on the first alloy thin film of the film formation object.

[0010] The present invention relates to a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target such that an angle around a rotation axis parallel to a cylindrical central axis of the first target can be changed, the first magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target such that an angle around a rotation axis parallel to a cylindrical central axis of the second target can be changed, the second magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the second target; having A film formation apparatus for forming an alloy thin film by sputtering on a film formation target disposed opposite the first target while rotating the first target, and forming an alloy thin film by sputtering on the film formation target disposed opposite the second target while rotating the second target, a first alloy thin film is formed on the object to be film-formed while moving the first target relative to the object to be film-formed with the first magnetic field generating means set at a first angle; and This is a film formation apparatus that forms a second alloy thin film on the first alloy thin film on the film formation object while moving the second target relative to the film formation object with the second magnetic field generating means set to a second angle smaller than the first angle.

[0011] The present invention includes a cylindrical target made of an alloy of two or more components, A rotating shaft parallel to the central axis of the cylindrical shape is provided inside the target such that the angle around the rotating shaft can be changed. a magnetic field generating means for generating a leakage magnetic field leaking from an outer peripheral surface of the target; A film forming method using a film forming apparatus having the following features: forming an alloy thin film by sputtering on a film-forming object disposed opposite the target while rotating the target; forming a first alloy thin film on the object while the magnetic field generating means is set at a first angle; forming a second alloy thin film having a composition ratio different from that of the first alloy thin film on the first alloy thin film of the film-forming target while the magnetic field generating means is set at a second angle different from the first angle; The film forming method is characterized by having the following features.

[0012] The present invention relates to a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target such that an angle around a rotation axis parallel to a cylindrical central axis of the first target can be changed, the first magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target such that an angle around a rotation axis parallel to a cylindrical central axis of the second target can be changed, the second magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the second target; A film forming method using a film forming apparatus having the following features: forming an alloy thin film by sputtering on a film-forming target disposed opposite the first target while rotating the first target; forming an alloy thin film by sputtering on the film-forming object disposed opposite the second target while rotating the second target; forming a first alloy thin film on the object to be film-formed while moving the object to be film-formed relative to the first target in a state in which the first magnetic field generating means is set at a first angle; forming a second alloy thin film on the first alloy thin film on the object to be film-formed while moving the object to be film-formed relative to the second target in a state in which the second magnetic field generating means is set to a second angle smaller than the first angle; The film forming method is characterized by having the following features.

[0013] The present invention relates to a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target such that an angle around a rotation axis parallel to a cylindrical central axis of the first target can be changed, the first magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target such that an angle around a rotation axis parallel to a cylindrical central axis of the second target can be changed, the second magnetic field generating means generating a leakage magnetic field leaking from an outer peripheral surface of the second target; A film forming method using a film forming apparatus having the following features: forming an alloy thin film by sputtering on a film-forming target disposed opposite the first target while rotating the first target; forming an alloy thin film by sputtering on the film-forming object disposed opposite the second target while rotating the second target; forming a first alloy thin film on the object to be film-formed while moving the first target relative to the object to be film-formed in a state in which the first magnetic field generating means is set at a first angle; forming a second alloy thin film on the first alloy thin film on the object to be film-formed while moving the second target relative to the object to be film-formed in a state in which the second magnetic field generating means is set to a second angle smaller than the first angle; The film forming method is characterized by having the following features. Effect of the Invention

[0014] According to the present invention, it is possible to provide a film formation apparatus capable of forming a film on a film formation target by sputtering using a rotary target made of an alloy of two or more components. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram showing the configuration of an organic EL element according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a diagram showing an in-line type film forming apparatus according to an embodiment. [Diagram 3] FIG. 2 is a diagram showing a cluster type film forming apparatus according to an embodiment. [Figure 4] FIG. 2 is a schematic diagram showing the configuration of a substrate transport type sputtering apparatus according to an embodiment. [Diagram 5] FIG. 2 is a schematic diagram showing the configuration of a substrate transport type sputtering apparatus according to an embodiment. [Figure 6]FIG. 2 is a schematic diagram showing the configuration of a magnet unit of the sputtering apparatus of the embodiment. [Figure 7] FIG. 4 is a diagram for explaining the angle of a magnet unit of the sputtering apparatus of the embodiment. [Figure 8] FIG. 2 is a schematic diagram showing the configuration of a rotating cathode unit moving type sputtering apparatus according to an embodiment. [Figure 9] FIG. 2 is a schematic diagram showing the configuration of a twin cathode type sputtering apparatus according to the embodiment. [Figure 10] FIG. 2 is a schematic diagram showing the configuration of a twin cathode type sputtering apparatus according to the embodiment. [Figure 11] FIG. 4 is a diagram showing the angle of a magnet unit of a twin cathode type sputtering apparatus according to an embodiment. [Figure 12] FIG. 4 is a diagram showing the angle of a magnet unit of a twin cathode type sputtering apparatus according to an embodiment. [Figure 13] 5A to 5C are diagrams showing the swinging operation of the magnet unit of the sputtering apparatus of the embodiment. [Figure 14] FIG. 4 is a diagram showing the relationship between the angle of the magnet unit of the sputtering device of the embodiment and the Mg composition ratio. [Figure 15] FIG. 4 is a diagram showing the difference in deposition amount depending on the alloy components in the sputtering apparatus of the embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The following is a detailed description of the embodiments of the present invention. However, the following embodiments merely exemplify preferred configurations of the present invention, and the scope of the present invention is not limited to these configurations. Furthermore, the hardware and software configurations, process flow, manufacturing conditions, dimensions, materials, shapes, etc. of the device in the following description are not intended to limit the scope of the present invention to these alone, unless otherwise specified. Although the embodiments describe multiple features, not all of these multiple features are essential to the invention, and multiple features may be combined in any manner. Furthermore, in the accompanying drawings, the same reference numbers are used for the same or similar configurations, and duplicated descriptions are omitted.

[0017] The film forming apparatus according to the present invention is used to deposit and form a thin film on a substrate (including a substrate on which a laminate is formed) in the manufacture of various electronic devices such as semiconductor devices, magnetic devices, and electronic components, and optical components. More specifically, the film forming apparatus according to the present invention is preferably used in the manufacture of electronic devices such as light-emitting elements, photoelectric conversion elements, and touch panels. In particular, it is particularly preferably applicable in the manufacture of organic light-emitting elements such as OLEDs (Organic Light Emitting Diodes), and organic photoelectric conversion elements such as organic thin-film solar cells. The electronic device in the present invention also includes a display device (e.g., an organic EL (Electro-Luminescence) display device) and a lighting device (e.g., an organic EL lighting device) equipped with a light-emitting element, and a sensor (e.g., an organic CMOS image sensor) equipped with a photoelectric conversion element. In addition, the present invention also includes a manufacturing method of an electronic device having a step of forming a thin film on a substrate using a film forming apparatus according to each of the following embodiments or a film forming apparatus obtained by modifying the film forming apparatus of each embodiment within the scope of the present invention.

[0018] 1 is a schematic diagram showing a typical layer structure of an organic EL element that can be manufactured using the film forming apparatus of the following embodiment. The OLED has an anode 61, an organic light-emitting layer 62, and a cathode 65 laminated on a substrate 6. The film forming apparatus according to the present invention is generally configured as follows. The film forming apparatus according to the present invention is suitably used when forming a cathode 65 on an organic light-emitting layer 62. The cathode 65 is an alloy thin film made of two-component metal materials. The first component of the alloy constituting the cathode 65 is an alkali metal, an alkaline earth metal, or an alloy thereof having a low work function such as Mg from the viewpoint of electron injection into the organic light-emitting layer 62, and the second component is a metal having a high work function such as Au, Ag, or Al from the viewpoint of oxidation resistance. In the following examples, the first component is Mg and the second component is Ag.

[0019] The cathode 65 is preferably configured as a multilayer film consisting of a first layer 63 and a second layer 64 formed on the first layer 63. This is because it is preferable to increase the Mg composition ratio on the side closer to the organic light-emitting layer 62 to increase the electron injection property, while it is preferable to increase the Ag composition ratio on the side closer to the external environment to increase the oxidation resistance. By forming the cathode 65 as a multilayer film having different composition ratios, it is possible to achieve both electron injection property and oxidation resistance. Thus, the first layer 63 and the second layer 64 are both Mg-Ag alloys, but the Mg composition ratio of the first layer 63 is made higher than that of the second layer 64, and the Ag composition ratio of the second layer 64 is made higher than that of the first layer 63. That is, the cathode 65 is configured as a multilayer film having different alloy composition ratios (having a gradient in the composition ratio) in the film thickness direction.

[0020] The alloy constituting the cathode 65 is not limited to this example, and may be another alloy mainly composed of a first component having excellent electron injection properties and a second component having excellent oxidation resistance. Examples of the first component include Li, Na, Mg, K, Ca, Cs, and Yb. Examples of the second component include Ag and Al.

[0021] The film forming apparatus of the present invention is not limited to the formation of a cathode for an OLED or a multilayer film having different alloy composition ratios in the thickness direction, but can be generally applied to the formation of a film made of an alloy of two or more components. In particular, the present invention is not limited to the formation of a cathode made of a multilayer film, but can also be applied to the formation of a cathode made of a single-layer alloy thin film. The film forming apparatus of the present invention is not limited to the formation of a film on an organic film, but can form a film on various surfaces as long as it is a combination of materials that can be formed by sputtering, such as metal materials and oxide materials.

[0022] The present invention is applicable to both an in-line type film forming apparatus as shown in FIG. 2 and a cluster type film forming apparatus as shown in FIG.

[0023] FIG. 2 is a schematic diagram showing a part of an in-line type film forming apparatus 100 in which a plurality of film forming chambers are connected. The film forming apparatus 100 has film forming chambers 101, 102, 103, and 104, and has an inspection chamber 105 at the rear of the film forming chamber 104. In each film forming chamber, an anode 61, an organic light emitting layer 62, a first layer 63 of a cathode 65, and a second layer 64 of a cathode 65 are formed. The substrate 6 on which the film is formed in the film forming chamber 104 is carried into the inspection chamber 105 at the rear. An inspection device (e.g., EPMA (electron probe microanalyzer)) capable of measuring the Mg composition ratio of the alloy thin film is installed in the inspection chamber 105, and composition analysis can be performed on the substrate 6 on which the Mg-Ag alloy thin film is formed in the film forming chamber 104. Note that both the first layer 63 and the second layer 64 constituting the cathode 65 may be formed in one film forming chamber.

[0024] 3 is a schematic diagram showing a part of a cluster-type film formation apparatus 111 in which a plurality of vacuum chambers are connected. In this film formation apparatus 111, a first cluster C1, a second cluster C2, and a third cluster C3 are connected in series. In addition to the film formation chambers 101 to 104, each cluster has a known chamber such as a mask stocker as appropriate, but the description thereof will be omitted here. An inspection chamber 105 is provided between the second cluster C2 and the third cluster C3. A composition analysis is performed in the inspection chamber 105 on the alloy thin film formed in the second cluster C2.

[0025] Each deposition chamber is equipped with a device for depositing a film by sputtering or vapor deposition. An example in which a heater device is provided will be described.

[0026] (Substrate transport type sputtering device) An example of a sputtering apparatus to which the present invention can be applied will be described with reference to Fig. 4. In the following description, the direction parallel to the transport direction S of the substrate 6 transported within the sputtering apparatus 1 is defined as the X direction, the direction parallel to the rotation axis of the cylindrical target 2 provided in the sputtering apparatus 1 is defined as the Y direction, and the vertical upward direction is defined as the Z direction. Fig. 4 is a diagram showing a schematic internal configuration of the sputtering apparatus 1 as viewed from the Y direction.

[0027] The sputtering apparatus 1 shown in Fig. 4 has a chamber 10 in which a substrate 6 and a target 2, which are objects to be deposited, are disposed. In the sputtering apparatus 1, the target 2 is disposed vertically below the substrate 6, and deposition is performed by depositing up with the deposition surface of the substrate 6 facing vertically downward. Note that the present invention is not limited to this, and may be configured such that the target 2 is disposed vertically above the substrate 6, and deposition is performed by depositing down with the deposition surface of the substrate 6 facing vertically upward. Alternatively, the substrate 6 may be set up vertically, and deposition may be performed with the deposition surface of the substrate 6 parallel to the vertical direction.

[0028] The rotating cathode unit 8 has the target 2, which is a cylindrical rotary target, and a magnet unit 3, which is disposed in the hollow inside the target 2 and serves as a magnetic field generating means for generating a magnetic field around the outer periphery of the target 2. A backing tube 2a is provided inside the target 2. The rotating cathode unit 8 is fixed to a chamber 10, and the target 2 is supported by the chamber 10 so as to be rotatable around the central axis of the cylinder. The target 2 rotates in the direction of arrow R by the driving force of a target drive device 11 being transmitted by a drive transmission means such as a gear. The arrow R is the clockwise direction in a cross section perpendicular to the Y direction shown in FIG. 4.

[0029] The target 2 is made of a film-forming material for forming a film on the substrate 6 by sputtering, and functions as a supply source of the film-forming material. Here, an example will be described in which a cathode 65 (upper electrode) made of an Mg-Ag alloy is formed by sputtering on the substrate 6 on which the OLED anode 61 and organic light-emitting layer 62 shown in Fig. 1 are already formed. Therefore, the material constituting the target 2 is a two-component alloy of Ag and Mg.

[0030] A layer formed of the film-forming material of the target 2 is formed on the outside of the backing tube 2a. The backing tube 2a is connected to a power source 13 and functions as a cathode to which a negative voltage is applied from the power source 13. The voltage may be applied directly to the target 2, in which case the backing tube 2a may not be provided. The power source 13 may be a DC power source, an AC power source, or a high-frequency power source depending on the material of the target 2. The chamber 10 is grounded. The target 2 is a cylindrical target, but the term "cylindrical" does not mean only a mathematically strict cylindrical target, but also includes a target whose generatrix is ​​not a straight line but a curved line, and a target whose cross section perpendicular to the central axis is not a mathematically strict "circle". In other words, the target 2 in the present invention may be a cylindrical target that can rotate around the central axis.

[0031] The magnet unit 3 forms a magnetic field on a part of the surface side of the target 2. The magnet unit 3 is provided inside the target 2 such that the angle around a central axis parallel to the central axis of the cylindrical shape of the target 2 can be changed. The magnet unit 3 is supported so as to be rotatable about the central axis. The magnet unit 3 rotates in a clockwise and counterclockwise direction in a cross section perpendicular to the Y direction shown in FIG. 4 as indicated by the arrow M, as the driving force of the magnet driving device 110 is transmitted by a drive transmission means such as a gear. The magnet unit 3 can be stationary at any angle. The rotation of the target 2 by the target driving device 11 and the rotation of the magnet unit 3 by the magnet driving device 110 are controlled independently.

[0032] The substrate 6 is carried in through one gate valve 17 provided on a side wall of the chamber 10. A film is formed on the substrate 6 by sputtering while the substrate 6 is transported horizontally (in the direction indicated by the arrow S) within the chamber 10 by the transport member 120. After a film is formed on the entire film-forming target surface of the substrate 6, the substrate 6 is carried out through a gate valve 18 provided on the other side wall of the chamber 10.

[0033] Gas introduction means 16 and exhaust means 15 are connected to chamber 10, and the pressure inside can be adjusted to a predetermined pressure. A sputtering gas (an inert gas such as argon or a reactive gas such as oxygen or nitrogen) is introduced into chamber 10 by gas introduction means 16 through an inlet 41 provided in chamber 10. Air is exhausted from the inside of chamber 10 through exhaust port 5 by exhaust means 15 such as a vacuum pump. In this way, the pressure inside chamber 10 is adjusted to a predetermined pressure.

[0034] The gas introduction means 16 has an inlet 41 and is composed of a supply source such as a gas cylinder (not shown), a piping system connecting the supply source and the inlet 41, and various vacuum valves, mass flow controllers, etc. provided in the piping system, and the supply amount can be adjusted by a flow control valve of the mass flow controller. The flow control valve has an electrically controllable configuration such as an electromagnetic valve. The inlet 41 is disposed on a vertical side wall of the chamber 10. The installation position of the inlet 41 is not limited to the side wall, and may be provided on the bottom wall or the ceiling wall. Also, the piping may extend into the chamber 10, and the inlet may open into the chamber 10. Also, a configuration in which a plurality of inlets 41 are provided and arranged along the rotation axis direction of the target 2 may be adopted.

[0035] The exhaust means 15 has a vacuum pump and a piping system connecting the vacuum pump and the exhaust port 5. The piping system is provided with an electrically controllable flow control valve such as a conductance valve, and the exhaust amount can be adjusted by the control valve. The exhaust port 5 is provided in the bottom wall of the chamber 10. The installation position of the exhaust port 5 is not limited to the bottom wall, and it may be provided in a vertical side wall or a ceiling wall. Also, the piping may extend into the chamber 10, and the exhaust port 5 may open into the chamber 10.

[0036] The control unit 14 controls the target driving device 11 to drive and rotate the target 2 in the direction of the arrow R while keeping the angle of the magnet unit 3 fixed, and controls the power supply 13 to apply a negative voltage to the target 2. When a voltage is applied to the target 2, the region where the magnetic field generated by the magnet unit 3 exists becomes the sputtering region A where plasma is concentrated and sputtered particles are generated. Since the magnet unit 3 is stationary with respect to the chamber 10 during the film formation process, the opposing angle between the sputtering region A and the film formation target surface of the substrate 6 is constant during the film formation process. The positive ionized inert gas ions in the plasma collide with the surface of the target 2, and the atoms and molecules of the material constituting the target 2 are ejected from the target 2. The particles of the film formation material ejected from the target 2 adhere to the film formation target surface of the substrate 6 and are deposited.

[0037] Here, the opposing angle between the sputtering region A and the film-forming surface of the substrate 6 is defined as, for example, the angle between a line segment that bisects the central angle of an arc corresponding to the sputtering region A on the cylindrical surface of the target 2 and a virtual plane including the film-forming surface of the substrate 6, within a virtual plane perpendicular to the rotation axis of the target 2.

[0038] As the substrate 6 is moved in the horizontal direction (indicated by the arrow S) by the transport member 120, the film formation target area of ​​the substrate 6 facing the sputtering area A moves in the horizontal direction. As a result, a film is formed on the film formation target surface of the substrate 6 sequentially from the downstream end to the upstream end in the transport direction S. As a result, the sputtering film is formed uniformly over the entire surface of the substrate 6. It can be done.

[0039] The area on the surface of the target 2 from which the sputtered particles are emitted moves in the circumferential direction as the target 2 rotates. Therefore, when focusing on a certain local area on the surface of the target 2, sputtering occurs intermittently at a period determined by the rotation speed of the target 2.

[0040] 5 is a diagram showing a schematic diagram of the internal configuration of the sputtering apparatus 1 as viewed from the X direction. The Y direction end of the target 2 is rotatably supported by a support block 210 and an end block 220. The support block 210 and the end block 220 are provided with a power transmission mechanism that transmits a driving force from a target driver 11, which is a rotation driver, to the target 2. The target driver 11 has a drive source such as a motor, and drives the target 2 to rotate via the power transmission mechanism.

[0041] FIG. 6 is a diagram showing a schematic configuration of the magnet unit 3 provided inside the target 2. The magnet unit 3 includes a central magnet 31 extending in a direction parallel to the rotation axis of the target 2, a peripheral magnet 32 ​​surrounding the central magnet 31 and having a polarity different from that of the central magnet 31, and a yoke plate 33. The peripheral magnet 32 ​​is composed of a pair of straight portions 32a and 32b extending in parallel to the central magnet 31, and turning portions 32c and 32d connecting both ends of the straight portions 32a and 32b. The magnetic field formed by the magnet unit 3 has magnetic field lines that loop back from the magnetic pole of the central magnet 31 toward the straight portions 32a and 32b of the peripheral magnet 32. As a result, a toroidal magnetic field tunnel extending in the direction of the rotation axis of the target 2 is formed near the surface of the target 2. This magnetic field captures electrons, concentrating plasma near the surface of the target 2, and increasing the efficiency of sputtering. The magnetic field of the magnet unit 3 generates high-density plasma, and the region where sputtered particles are generated intensively is defined as a sputtering region A.

[0042] The magnet unit 3 is fixed on a pedestal 34, and a rotation shaft 35 is fixed to the pedestal 34. The rotation shaft 35 extends parallel to the central axis of the cylindrical target 2, rotatably supports the pedestal 34 relative to the chamber 10, and rotates by the driving force of the magnet driving device 110. As a result, the magnet unit 3 is supported rotatably relative to the central axis, and the angle around the rotation shaft 35 parallel to the cylindrical central axis of the target 2 is set to be variable. The rotational movement of the magnet unit 3 is performed by the driving force of the magnet driving device 110. The magnet driving device 110 is configured to rotate the magnet unit 3 to an arbitrary angle and to stop it at that angle. As a result, it is possible to perform operations such as performing sputtering with the magnet unit 3 stationary during the film formation process, oscillating the magnet unit 3 during the film formation process as described later, and changing the angle of the magnet unit 3 to control the composition ratio when the film formation process is not being performed. In the sputtering apparatus 1, an example has been described in which the central axis of the rotation shaft 35 coincides with the central axis of the target 2, but the central axis of the rotation shaft 35 may be parallel to the central axis of the target 2. The driving force of the magnet driving device 110 is transmitted to the rotation shaft 35 via a power transmission mechanism (not shown). The magnet driving device 110 has a driving source such as a motor.

[0043] FIG. 7 shows the positional relationship between a substrate 6, a target 2, and a magnet unit 3 when a film is formed by sputtering up on a surface vertically below a substrate 6 placed above the target 2 using a cylindrical target 2.

[0044] Sputtering gas ions (e.g., Ar) generated by applying a negative voltage to the target 2 + When the target 2 is struck by the electrons, the atoms and molecules of the deposition material that constitutes the target 2 are released from the target 2 as sputtered particles. The location and direction in which these ejections (sputtered particles) are ejected from the surface of the target 2 can be set by the magnetic field formed in the vicinity of the surface of the target 2 by the magnet unit 3 .

[0045] In FIG. 7, the rotation center O of the target 2 and the rotation center of the rotation axis 35 of the magnet unit 3 coincide with each other. Sputtered particles are generated intensively in a sputtering region A defined by the positions of line segments D2 and D3 passing through the rotation center of the rotation axis 35 of the magnet unit 3 and the position between the central magnet 31 and the peripheral magnet 32. The sputtering region A may be a region determined based on the magnetic flux distribution of the magnetic field formed by the magnet unit 3. It may also be a region on the surface of the target 2 where the magnetic field strength has a certain value or more. It may also be determined based on the arrangement and structure of the magnets of the magnet unit 3, the position where sputtered particles are generated intensively, and phenomena generally, statistically, empirically, and experimentally observed as the direction in which substances emitted from the surface of the target 2 are emitted during sputtering.

[0046] The angle θ of the line segment D1 passing through the center of rotation of the rotation shaft 35 of the magnet unit 3 and the center of the sputtering region A is defined as the angle of the magnet unit 3. The angle θ of the magnet unit 3 is an angle based on the position where the line segment D1 is perpendicular to the film formation target surface of the substrate 6 (when the magnet unit 3 is located at the position shown by the dashed line in FIG. 7), and the clockwise direction in FIG. 7 is defined as positive.

[0047] (Moving cathode sputtering device) Another example of a sputtering apparatus to which the present invention can be applied will be described with reference to Fig. 8. Elements common to the above-mentioned substrate conveying type sputtering apparatus will be designated by common names and symbols, and detailed description thereof will be omitted.

[0048] The sputtering apparatus 1X shown in Fig. 8 is a sputtering apparatus in which a substrate 6 is fixed in a chamber 10 and a rotating cathode unit 8X is capable of reciprocating within the chamber 10. Fig. 8 is a diagram showing a schematic diagram of the internal configuration of the sputtering apparatus 1X as viewed from a direction parallel to the rotation axis of a cylindrical target 2 provided in the sputtering apparatus 1X (Y direction).

[0049] In the sputtering apparatus 1 of Fig. 4, the rotating cathode unit 8 does not move relative to the chamber 10, and the substrate 6 moves relative to the chamber 10, so that a film is formed on the film-formation target surface of the substrate 6, successively from the end on the downstream side in the transport direction of the substrate 6. In the sputtering apparatus 1X of Fig. 8, the rotating cathode unit 8X moves relative to the chamber 10, and the substrate 6 does not move relative to the chamber 10, so that a film is formed on the film-formation target surface of the substrate 6, successively from the end on the upstream side in the movement direction of the rotating cathode unit 8X.

[0050] The rotating cathode unit 8X has a moving stage 230, and a partition member 260 disposed around the target 2 is provided on the moving stage 230. The partition member 260 is open in the direction in which the substrate 6 is disposed (vertically upward).

[0051] The movable stage 230 is supported so as to be movable in the horizontal direction (indicated by the arrow T) along a pair of guide rails 250 via a conveying guide such as a linear bearing. The guide rails 250 are provided parallel to the X direction. The movable stage 230 is linearly driven in the X direction by the linear drive device 12. The linear drive device 12 may be any of various known linear motion mechanisms, such as a screw feed mechanism using a ball screw or the like that converts the rotational motion of a rotary motor into linear motion, or a linear motor. Therefore, the rotating cathode unit 8X moves in the X direction within the XY plane, and the target 2 moves in the X direction within the XY plane while rotating around a rotation axis parallel to the Y direction.

[0052] When the substrate 6 is carried into the chamber 10, it is held by the holder 6a vertically above the rotating cathode unit 8X. During the film formation process, the substrate 6 moves relative to the chamber 10. Without rotating, the rotating cathode unit 8X moves horizontally (in the direction indicated by the arrow T) while forming a film by sputtering. After the film is formed on the entire film-forming target surface of the substrate 6, the substrate 6 is unloaded from the chamber 10 through a gate valve 18 provided on the other side wall thereof.

[0053] When forming a film by sputtering in the sputtering apparatus 1X, the control unit 14 controls the target driving device 11 to rotate the target 2 in the direction of arrow R, and also controls the power supply 13 to apply a negative voltage to the target 2.

[0054] The rotating cathode unit 8X is moved in the direction of arrow T relative to the chamber 10 by the linear drive device 12, and therefore the sputtering region A moves in the direction of arrow T relative to the chamber 10. Furthermore, the magnet unit 3 does not rotate together with the target 2 during the film formation process, and therefore the opposing angle between the sputtering region A and the film formation target surface of the substrate 6 remains constant during the film formation process. During the film formation process, the substrate 6 is held by the holder 6a and does not move relative to the chamber 10.

[0055] As the rotating cathode unit 8X moves in the horizontal direction by the linear drive device 12, the sputtering region A of the target 2 moves along the film-forming surface of the substrate 6 relative to the chamber 10 together with the movement of the rotating cathode unit 8X. As a result, a film is formed on the film-forming surface of the substrate 6 sequentially from the upstream end to the downstream end in the moving direction T of the rotating cathode unit 8X as the rotating cathode unit 8X moves.

[0056] (Twin cathode type sputtering equipment) Another example of a sputtering apparatus to which the present invention can be applied will be described with reference to Figures 9 and 10. Elements common to the above single cathode type sputtering apparatuses 1 and 1X will be given common names and symbols and detailed descriptions thereof will be omitted.

[0057] Fig. 9 is a diagram showing a schematic internal configuration of the sputtering apparatus 1Y as viewed from a direction parallel to the rotation axis of a cylindrical second target 2R provided in the sputtering apparatus 1Y (Y direction). Fig. 10 is a diagram showing a schematic internal configuration of the sputtering apparatus 1Y as viewed from a direction parallel to the moving direction T of a rotating cathode unit 8Y moving in the sputtering apparatus 1Y (X direction).

[0058] In the sputtering apparatus 1Y of Figure 9, similar to the sputtering apparatus 1X of Figure 8, a rotating cathode unit 8Y moves relative to the chamber 10, while the substrate 6 does not move relative to the chamber 10, and a film is formed on the film formation target surface of the substrate 6 sequentially from the upstream end in the movement direction of the rotating cathode unit 8Y.

[0059] The rotating cathode unit 8 of the sputtering apparatus 1 in Figure 4 was composed of a cylindrical target 2 and a magnet unit 3, while the rotating cathode unit 8Y of the sputtering apparatus 1Y in Figure 9 is composed of a cylindrical first target 2L, a first magnet unit 3L which is a first magnetic field generating means provided inside the first target 2L with an angle around a rotation axis parallel to the central axis of the cylinder and which generates a leakage magnetic field leaking from the outer peripheral surface of the first target 2L, a cylindrical second target 2R, and a second magnet unit 3R which is a second magnetic field generating means provided inside the second target 2R with an angle around a rotation axis parallel to the central axis of the cylinder and which generates a leakage magnetic field leaking from the outer peripheral surface of the second target 2R. The configurations of the first target 2L and the first magnet unit 3L, and the configurations of the second target 2R and the second magnet unit 3R are similar to those of the target 2 and the magnet unit 3 of the sputtering apparatus 1 in Fig. 4, but the rotation directions of the first target 2L and the second target 2R by the target driving device 11Y are opposite to each other. The first target 2L rotates in the direction of arrow L, and the second target 2R rotates in the direction of arrow R opposite to the direction of arrow L. The first magnet unit 3L and the second magnet unit 3R rotate as shown by arrows ML and MR by the driving force of the magnet driving device 110Y.

[0060] The configuration in which the rotating cathode unit 8Y can move within the chamber 10 is the same as that of the sputtering apparatus 1X in FIG. 8. The rotating cathode unit 8Y has a moving stage 230, and a support block 210 and an end block 220 that rotatably support the first target 2L and the second target 2R. On the moving stage 230, the first target 2L and the second target 2R are arranged side by side in the moving direction T (parallel to the X direction) of the rotating cathode unit 8Y. The moving stage 230 is provided with a partition member 260 arranged to surround the first target 2L and the second target 2R. Note that in FIG. 10, the partition member 260 is omitted to avoid complication. The partition member 260 opens in the direction in which the substrate 6 is arranged (vertically upward).

[0061] When forming a film by sputtering in the sputtering apparatus 1Y, the control unit 14 controls the target driving device 11Y to rotate the first target 2L and the second target 2R in the directions of the arrows L and R, respectively, and controls the power supply 13 to apply a negative voltage to the first target 2L and the second target 2R. The manner of forming a film by sputtering is the same as that of the sputtering apparatus 1X in FIG.

[0062] FIG. 11 is a diagram showing the positional relationship of the first magnet unit 3L, the second magnet unit 3R, the first target 2L, the second target 2R, and the substrate 6 of the sputtering apparatus 1Y of FIG. 9. In FIG. 11, the rotation center O of the first target 2L and the rotation center of the rotation axis 35L of the first magnet unit 3L coincide with each other. Sputter particles are generated intensively in a sputtering region AL defined by the positions of the line segments D2L and D3L passing through the rotation center of the rotation axis 35L of the first magnet unit 3L and the position between the central magnet 31L and the peripheral magnet 32L. In addition, the rotation center O of the second target 2R and the rotation center of the rotation axis 35R of the second magnet unit 3R coincide with each other. Sputter particles are generated intensively in a sputtering region AR defined by the positions of the line segments D2R and D3R passing through the rotation center of the rotation axis 35R of the second magnet unit 3R and the position between the central magnet 31R and the peripheral magnet 32R.

[0063] The angle θL of the line segment D1L passing through the center of rotation of the rotation shaft 35L of the first magnet unit 3L and the center of the sputtering area AL is defined as the angle of the first magnet unit 3L. The angle θR of the line segment D1R passing through the center of rotation of the rotation shaft 35R of the second magnet unit 3R and the center of the sputtering area AR is defined as the angle of the second magnet unit 3R. The angles θL and θR of the first magnet unit 3L and the second magnet unit 3R are angles based on the position where the line segments D1L and D1R are perpendicular to the film formation target surface of the substrate 6 (when the first magnet unit 3L and the second magnet unit 3R are located at the position shown by the dashed line in FIG. 11), and the clockwise direction in FIG. 11 is defined as positive.

[0064] The first target 2L and the second target 2R are made of an Mg-Ag alloy of the same composition, and the angles θL and θR of the first magnet unit 3L and the second magnet unit 3R are equal. That is, the line segment D1L of the first magnet unit 3L and the line segment D1R of the second magnet unit 3R face in the same direction.

[0065] 12, the angles θL and θR of the first magnet unit 3L and the second magnet unit 3R may be set to have the same absolute value and opposite signs. In this case, the line segment D1L of the first magnet unit 3L and the line segment D1R of the second magnet unit 3R are oriented symmetrically with respect to the movement direction T (X direction) of the rotating cathode unit 8Y.

[0066] The outer diameter of the first target 2L and the second target 2R was 140 mm, and the distance between the centers of the first target 2L and the second target 2R was 300 mm.

[0067] The twin cathode sputtering apparatus 1Y in FIG. 9 is a rotating cathode unit moving type sputtering apparatus having two cathodes, but it is not limited to the sputtering apparatus 1 in FIG. The present invention is also applicable to a twin cathode type sputtering apparatus having two cathodes in a plate conveying type sputtering apparatus.

[0068] (Magnet unit swing type sputtering device) Another example of a sputtering apparatus to which the present invention can be applied will be described with reference to Fig. 13. Elements common to the above single cathode type sputtering apparatus 1 will be given common names and symbols and detailed description will be omitted.

[0069] 4, an example is shown in which the angle θ of the magnet unit 3 is adjusted before the start of film formation, and the magnet unit 3 is stationary at the adjusted angle θ during the film formation process. In contrast, the magnet unit 3 may be swung within a small angle range forward and backward from the adjusted angle θ during the film formation process.

[0070] FIG. 13 is a diagram showing the operation when the magnet unit 3 is swung. In FIG. 13, the magnet unit 3 shown by the solid line is at a position of angle θ determined before the start of film formation, as shown by the line segment D1. As shown by the dashed line, during the film formation process, the magnet unit 3 continues to move so as to swung between a first position shown by the line segment D11 and a second position shown by the line segment D12 within a range of angle δ centered on the position of angle θ. That is, during the film formation process, the line segment D1 of the magnet unit 3 swung in a range of θ-δ / 2 degrees to θ+δ / 2 degrees. This makes it possible to uniformize deposition unevenness caused by the shapes and arrangement of magnets such as the central magnet 31 and the peripheral magnets 32 that constitute the magnet unit 3.

[0071] As described later, since the angle θ of the magnet unit 3 affects the composition ratio of the alloy thin film to be formed, it is preferable that the angle δ of the oscillation range is small. For example, the oscillation range is set to within ±5 degrees around the initial angle θ. In this case, the magnet unit 3 oscillates in the range of θ-5 degrees to θ+5 degrees during the film formation process.

[0072] (Relationship between Mg composition ratio and angle of magnet unit) Next, control of the Mg composition ratio by adjusting the angle of the magnet unit, which is a feature of the present invention, will be described.

[0073] In this example, a cylindrical sputtering target made of an alloy material of Ag and Mg was used as the target 2. The composition ratio of Mg in the Mg-Ag alloy target was approximately 10 vol.%.

[0074] The manufacturing method of the target 2 will be described. After melting and alloying Ag with a purity of 99.9% or more and Mg with a purity of 99.9% or more, the molten metal was dropped from the bottom of a crucible and an inert gas such as argon was sprayed onto it to produce atomized Mg-Ag alloy powder. The particle size of the atomized powder was set to 1 μm or more and 1000 μm or less. The atomized powder was sprayed onto a backing tube 2a together with a high-velocity inert gas to produce a cylindrical target 2 made of Mg-Ag alloy. The backing tube 2a can be made of stainless steel (SUS304, SUS630, etc.), titanium, etc.

[0075] In this embodiment, an Mg-Ag alloy target is used, but an alloy or compound containing Cu, Al, Ti, Mo, Cr, Ag, Au, Ni, etc. may be used depending on the purpose. When used as a cathode for an OLED, examples of the first component include Li, Na, Mg, K, Ca, Cs, Yb, etc. Examples of the second component include Ag, Al, etc. The manufacturing method of the Mg-Ag alloy target is not limited to spraying of atomized powder, and it can be manufactured by any method such as casting, thermal spraying, sintering, etc.

[0076] The cylindrical target 2 made of the prepared Mg-Ag alloy was placed in a sputtering apparatus 1, and a film was formed on a substrate 6. A magnet unit 3 was disposed inside the target 2 (inside the backing tube 2a in the sputtering apparatus 1 of FIG. 4), and the orientation of the magnet unit 3 could be changed to any angle. Before starting film formation, the magnet unit 3 was adjusted to a predetermined angle θ, and sputtering film formation was performed while the target 2 was rotated at 10 rpm with the angle fixed.

[0077] The Ar gas pressure during sputtering deposition was 0.6 Pa, and the temperature of the substrate 6 was room temperature. The substrate 6 was transported above the target 2 in the direction indicated by the arrow S (see FIG. 7) at a predetermined speed to deposit the film.

[0078] The composition of the formed alloy thin film was analyzed by X-ray fluorescence. Here, the composition was analyzed by X-ray fluorescence, but other methods such as XRF (X-ray fluorescence), EDS (energy dispersive X-ray spectroscopy), EPMA (electron probe microanalyzer), XPS (X-ray photoelectron spectroscopy), SIMS (secondary ion mass spectrometry), GDMS (glow discharge mass spectrometry), and ICP (inductively coupled plasma mass spectrometry) can also be used to analyze the composition of the alloy thin film. Other methods such as transmission spectrum, reflection spectrum, emission spectrum, and spectroscopic ellipsometry can also be used.

[0079] Through intensive research, the inventors have found that when the angle θ of the magnet unit 3 in the backing tube 2a is changed to various angles to form a film, the Mg composition ratio of the formed alloy thin film changes depending on the angle θ. For example, when the angle θ of the magnet unit 3 is set to 0 degrees to form a film, the Mg composition ratio is 7.9 vol.%. On the other hand, when the angle θ of the magnet unit 3 is tilted to 20 degrees and 40 degrees to form a film, the Mg composition ratio is 8.4 vol.% and 9.4 vol.%, respectively. The results are shown in FIG. 14. In FIG. 14, the horizontal axis represents the angle θ of the magnet unit 3, and the vertical axis represents the Mg composition ratio of the formed alloy thin film. As shown in the results, the larger the angle θ of the magnet unit 3, the larger the Mg composition ratio of the obtained Mg-Ag alloy thin film. That is, the magnet unit 3 of this embodiment is configured so that the larger the angle from the reference position (θ=0 degrees) is, the larger the Mg composition ratio of the alloy thin film becomes. The fact that the Mg composition ratio of the Mg-Ag alloy thin film shows such a tendency is a new finding obtained by the present inventors through intensive research. Based on this finding, the present embodiment is characterized in that the Mg composition ratio of the Mg-Ag alloy thin film is controlled by adjusting the angle θ of the magnet unit 3.

[0080] The inventors verified the above-mentioned relationship between the angle θ of the magnet unit 3 and the Mg composition ratio of the Mg-Ag alloy thin film formed from the following viewpoints. The angle θ of the magnet unit 3 was set to 0 degrees, and the substrate 6 was placed stationary directly above the cylindrical target 2 to perform sputtering, and the deposition amount distribution of Ag and Mg on the substrate 6 was examined. The results are shown in FIG. 15. In FIG. 15, the horizontal axis represents the distance from the position where the deposition amount (film thickness) is the largest on the substrate 6 (hereinafter referred to as the maximum film thickness position). In this embodiment, the maximum film thickness position is the intersection position of the line segment D1 and the substrate 6 when θ=0 in FIG. 7, and is the position closest to the rotation center O of the target 2. The vertical axis represents the value normalized by the film thickness at the maximum film thickness position. As shown in FIG. 15, the film thickness of both Mg and Ag became smaller as it moved away from the maximum film thickness position. In addition, the change (decrease) in the film thickness of Mg depending on the distance from the maximum film thickness position was more gradual than that of Ag. That is, the deposition amount distribution of Mg has a mountain shape with a wider width and a lower peak compared to the deposition amount distribution of Ag. This shows that the composition ratio of Mg is relatively higher at the wide-angle side position (position farther away from the maximum film thickness position) than at the maximum film thickness position, which is consistent with the result that the Mg composition ratio increases when the angle θ of the magnet unit 3 is increased during the transport and deposition as described above.

[0081] In this way, in magnetron rotary sputtering using an Mg-Ag alloy target, In this case, the Mg composition ratio of the formed alloy thin film can be controlled by changing the angle θ of the magnet unit 3. Based on this finding, by controlling the sputtering apparatus 1 and the sputtering film formation process, it becomes possible to stably form an Mg-Ag alloy thin film having a desired Mg composition ratio.

[0082] Note that changing the angle θ of the magnet unit 3 changes not only the composition ratio but also the film thickness (film formation rate), but it is possible to obtain a desired film thickness by adjusting the voltage applied to the target 2 and the height of the magnet.

[0083] The above findings are not limited to Mg-Ag alloy targets, but can also be applied to magnetron rotary sputtering devices using alloy targets mainly composed of two kinds of materials that have different tendencies of film thickness change depending on the distance from the maximum film thickness position when magnetron rotary sputtering is performed, as shown in Fig. 15. That is, the target 2 is composed of an alloy of two or more components, and when a film is formed on a film-forming target using the target 2, the combination of two components is sufficient so that the deposition amount distribution of the first component has a mountain-like shape with a wider width and a lower peak than the deposition amount distribution of the second component. In addition, when the magnet unit 3 is configured so that the composition ratio of the first component of the alloy thin film increases as the angle from the reference position (the position of θ=0 degrees) increases, the control unit 14 increases the angle θ of the magnet unit 3 when the composition ratio of the first component is increased, and decreases the angle θ of the magnet unit 3 when the composition ratio of the first component is decreased, based on the composition ratio information of the alloy thin film.

[0084] In addition, when the magnet unit 3 is configured and the angle θ is defined such that the composition ratio of Mg (first component) increases as the absolute value of the angle from the reference position increases, as in this embodiment, the control unit 14 increases the absolute value of the angle θ of the magnet unit 3 when the composition ratio of Mg (first component) is to be increased, and decreases the absolute value of the angle θ of the magnet unit 3 when the composition ratio of Mg (first component) is to be decreased, based on the composition ratio information of the alloy thin film.

[0085] Depending on various conditions such as the shape, arrangement, and magnetic properties of each magnet constituting the magnet unit 3, the arrangement of the magnet unit 3 within the target 2, the components and composition ratio of the alloy constituting the target 2, the definition of the angle θ of the magnet unit 3, and the positional relationship between the target 2 and the substrate 6, it is considered that the relationship between the angle θ of the magnet unit 3 and the Mg composition ratio will not necessarily be the same as the relationship exemplified in Fig. 14. Even in such a case, according to the idea disclosed in the present invention, it is possible to control the Mg composition ratio with high precision by using the relationship between the angle θ of the magnet unit 3 and the Mg composition ratio in the actual sputtering apparatus 1 and adjusting the angle θ of the magnet unit 3 based on composition ratio information of the alloy thin film to be formed.

[0086] <Specific control examples> When forming a film by sputtering in the sputtering apparatus 1, the control unit 14 performs film formation multiple times by varying the angle setting of the magnet unit 3. Hereinafter, several examples of the film formation method characteristic of the present invention will be described.

[0087] <Example 1> (Substrate transport, round trip) In the first embodiment, the control of forming two alloy thin films having different composition ratios on a substrate 6 by a sputtering apparatus 1 will be described.

[0088] In Example 1, two film formations are performed by changing the angle θ of the magnet unit 3 while transporting the substrate 6 back and forth within the chamber 10. The substrate 6, on which layers up to the organic light-emitting layer 62 are laminated, is carried into the chamber 10. The first film formation is performed while transporting the substrate 6 in the S direction (first direction), and a first layer 63 of the cathode 65 as a first alloy thin film is formed on the organic light-emitting layer 62. At this time, the angle of the magnet unit 3 is set to a first angle θ1 based on the target Mg composition ratio of the first layer 63. The second film formation is performed while the substrate 6 is transported in the -S direction (the opposite direction to the S direction, the second direction), and a second layer 64 of the cathode 65 as a second alloy thin film is formed on the first layer 63 formed in the first film formation. At this time, the angle of the magnet unit 3 is set to a second angle θ2 different from the first angle θ1 based on the target Mg composition ratio of the second layer 64. As a result, in the sputtering device 1, two layers of alloy thin films having different Mg composition ratios constituting the cathode 65 are formed on the organic light-emitting layer 62 of the substrate 6. After the formation of the two-layer cathode 65 is completed, the substrate 6 is carried out from the chamber 10.

[0089] As described above, the first layer 63 has a large Mg composition ratio in the Mg-Ag alloy thin film from the viewpoint of electron injection. On the other hand, the second layer 64 has a small Mg composition ratio in the Mg-Ag alloy thin film from the viewpoint of oxidation resistance. As described in FIG. 6, FIG. 7, FIG. 14, etc., in magnetron sputtering using a rotary target made of Mg-Ag alloy by the sputtering device 1 of this embodiment, the larger the angle θ of the magnet unit 3, the larger the Mg composition ratio. Therefore, when forming a two-layer cathode 65 by the method of the first embodiment, the first angle θ1 of the magnet unit 3 during the first film formation is made larger than the second angle θ2 of the magnet unit 3 during the second film formation. As an example, by performing two film formations by reciprocating transportation, with the first angle θ1=40 degrees in the first film formation and the second angle θ2=0 degrees in the second film formation, it is possible to form an alloy multilayer film having different Mg composition ratios in the film thickness direction (there is a gradient in the Mg composition ratio in the film thickness direction).

[0090] Between the first and second film formations, the angle of the magnet unit 3 is changed from the first angle θ1 to the second angle θ2 by the magnet driving device 110. The magnet driving device 110 is composed of a servo motor or the like, for example, and the time required to change the angle of the magnet unit 3 is short, for example, about a few seconds, so changing the angle of the magnet unit 3 does not excessively increase the time required for film formation.

[0091] The method of forming a multilayer film by using one rotating cathode unit 8 fixed to the chamber 10 and setting the angle of the magnet unit 3 to a first angle and a second angle while transporting the substrate 6 back and forth in the chamber 10, as described in the first embodiment, can be applied to one film formation chamber or sputtering chamber of an in-line type film formation apparatus 100 as shown in FIG. 2. It can also be applied to one film formation chamber or sputtering chamber of a cluster type film formation apparatus 111 as shown in FIG. 3. In these cases, the first layer 63 and the second layer 64 of the cathode 65 can be formed in one film formation chamber (for example, the film formation chamber 104). When changing the angle θ of the magnet unit 3, the film formation time or the input power may be adjusted at the same time. By adjusting the film formation time or the input power, not only the Mg composition ratio but also the film thickness can be maintained constant while forming a thin film.

[0092] <Example 2> (Cathode movement, reciprocation) The method of forming a multilayer film similar to that of the first embodiment can also be applied to the sputtering apparatus 1X shown in FIG. 8. The control of forming two alloy thin films having different composition ratios on the substrate 6 by the sputtering apparatus 1X shown in FIG. 8 will be described. Specifically, the angle θ of the magnet unit 3 is changed while the rotating cathode unit 8X is transported back and forth in the chamber 10 to perform two film formations. The substrate 6 on which the organic light-emitting layer 62 is laminated is carried into the chamber 10. The first film formation is performed while the rotating cathode unit 8X is moved in the T direction (first direction), and the first layer 63 of the cathode 65 as the first alloy thin film is formed on the organic light-emitting layer 62. At this time, the angle of the magnet unit 3 is set to a first angle θ1 based on the target Mg composition ratio of the first layer 63. The second deposition is performed while moving the rotating cathode unit 8X in the -T direction (the opposite direction to the T direction, the second direction), and a second layer 64 of the cathode 65 as a second alloy thin film is deposited on the first layer 63 formed in the first deposition. At this time, the angle of the magnet unit 3 is set to a second angle θ2 different from the first angle θ1 based on the target Mg composition ratio of the second layer 64. As a result, in the sputtering device 1X, two layers of alloy thin films with different Mg composition ratios constituting the cathode 65 are deposited on the organic light-emitting layer 62 of the substrate 6. After the deposition of the two-layer cathode 65 is completed, the substrate 6 is placed in the chamber. It is carried out from bus 10.

[0093] The method of forming a multilayer film by setting the angle of the magnet unit 3 to a first angle and a second angle while reciprocating the rotating cathode unit 8X in the chamber 10 with respect to the substrate 6 fixed in the chamber 10, as described in the second embodiment, can be applied to one film formation chamber or sputtering chamber of an in-line type film formation apparatus 100 as shown in Fig. 2. It can also be applied to one film formation chamber or sputtering chamber of a cluster type film formation apparatus 111 as shown in Fig. 3. In these cases, the first layer 63 and the second layer 64 of the cathode 65 can be formed in one film formation chamber (for example, the film formation chamber 104).

[0094] <Example 3> (two cathodes, one-way substrate transport, in-line type) In the third embodiment, a control for forming two alloy thin films having different composition ratios on a substrate 6 using the in-line type film forming apparatus 100 shown in FIG. 2 will be described.

[0095] In Example 3, while transporting a substrate 6 in one direction, two layers of alloy thin films are continuously formed using two sputtering devices 1 with different settings of the angle θ of the magnet unit 3. Both the sputtering devices 1 provided in the film formation chamber 103 and the film formation chamber 104 have the configuration shown in Fig. 4, but the settings of the angle θ of the magnet unit 3 are different.

[0096] The substrate 6 on which the organic light-emitting layer 62 has been laminated is carried into the film-forming chamber 103. In the film-forming chamber 103, a first layer 63 (first alloy thin film) of the cathode 65 is formed on the organic light-emitting layer 62 while the substrate 6 is being transported in the S direction. At this time, the angle of the magnet unit 3 is set to a first angle θ1 based on the target Mg composition ratio of the first layer 63.

[0097] The substrate 6 on which the first layer 63 of the cathode 65 has been formed is carried into the film formation chamber 104. In the film formation chamber 104, the second layer 64 (second alloy thin film) of the cathode 65 is formed on the first layer 63 while the substrate 6 is being transported in the S direction. At this time, the angle of the magnet unit 3 is set to a second angle θ2 based on the target Mg composition ratio of the second layer 64.

[0098] As a result, in the film formation chambers 103 and 104, a two-layer alloy thin film constituting the cathode 65 is formed on the organic light-emitting layer 62 of the substrate 6. The substrate 6 on which the formation of the two-layer cathode 65 has been completed is carried out of the film formation chamber 104.

[0099] As in Example 1, the angle of the magnet unit 3 of the sputtering apparatus 1 in the film formation chamber 103 is set to be larger than the angle of the magnet unit 3 of the sputtering apparatus 1 in the film formation chamber 104 so that the first layer 63 has a large Mg composition ratio in the Mg-Ag alloy thin film from the viewpoint of electron injection property, and the second layer 64 has a small Mg composition ratio in the Mg-Ag alloy thin film from the viewpoint of oxidation resistance. As an example, by continuously forming films in two sputtering chambers with the first angle θ1=40 degrees in the first film formation and the second angle θ2=0 degrees in the second film formation, it is possible to form an alloy multilayer film having a different Mg composition ratio in the film thickness direction (the Mg composition ratio has a gradient in the film thickness direction).

[0100] <Modification 1> (two cathodes, one-way substrate transport, cluster type) The method of forming a multilayer film having different Mg composition ratios by successively performing film formation using two sputtering apparatuses having different angles θ of the magnet units 3, as described in Example 3, can be similarly performed using the film formation chambers 103 and 104 of a cluster-type film formation apparatus 111 as shown in FIG. 3.

[0101] <Modification 2> (two cathodes, one-way cathode movement, in-line type / cluster type) In Example 3, the sputtering apparatus 1 (which transports the substrate 6 and has the rotating cathode unit 8 fixed to the chamber 10) shown in FIG. 4 is provided in two film-forming chambers 103 and 104. However, it is also possible to form a multilayer film having different Mg composition ratios by continuously forming films in two film forming chambers 103 and 104 provided with a sputtering apparatus 1X (substrate 6 is fixed, and rotating cathode unit 8X is moved) shown in Fig. 8. This case can also be applied to the in-line type film forming apparatus 100 shown in Fig. 2 and the cluster type film forming apparatus 111 shown in Fig. 3.

[0102] As in Examples 1 to 3, by performing film formation multiple times while changing the angle θ of the magnet unit 3 of the rotating cathode unit 8, a multilayer film having different composition ratios (having a composition ratio gradient) in the film thickness direction can be formed by magnetron sputtering using a rotary target made of a two-component alloy material. According to this film formation method, since the target 2 can be made of an alloy such as Mg-Ag, it is possible to suppress instability of the sputtering process due to surface oxidation of the target compared to a case where the target is made of Mg alone. In addition, even if targets with the same composition ratio are used, the composition ratio of the formed alloy thin film can be changed by changing the angle of the magnet unit 3, so there is no need to prepare multiple targets with different composition ratios, which is advantageous in terms of cost.

[0103] In addition, in the magnetron rotary sputtering film formation using an alloy target of two or more components as described in Examples 1 to 3, the film formation method of adjusting the angle θ of the magnet unit 3 based on composition ratio information of the alloy thin film formed on the substrate 6, and the film formation method of forming a multilayer film having different composition ratios (having a composition ratio gradient) in the film thickness direction by magnetron sputtering using a rotary target made of an alloy material of two components by changing the angle θ of the magnet unit 3 of the rotating cathode unit 8 and performing film formation multiple times, can be applied to the in-line type film formation apparatus 100 shown in Figure 2, the cluster type film formation apparatus 111 shown in Figure 3, the substrate conveying type sputtering apparatus 1 shown in Figure 4, the rotating cathode unit moving type sputtering apparatus 1X shown in Figure 8, the twin cathode and rotating cathode unit moving type sputtering apparatus 1Y shown in Figure 9, the twin cathode and substrate conveying type sputtering apparatus not shown, and the magnet unit swinging type sputtering apparatus shown in Figure 13.

[0104] The above embodiment shows an example of the present invention, but the present invention is not limited to the configuration of the above embodiment, and may be appropriately modified within the scope of its technical concept. For example, the present invention is not limited to the configuration in which the substrate moves relative to the rotating cathode unit fixed in the chamber, or the configuration in which the rotating cathode unit moves relative to the substrate fixed in the chamber, but may be, for example, a configuration in which the substrate and the rotating cathode unit are fixed in the chamber, and the number of targets constituting the rotating cathode unit is increased so that the sputtering region as a whole covers the entire film formation target region, a configuration in which the substrate oscillates in a horizontal plane relative to the rotating cathode unit fixed in the chamber, or a configuration in which the rotating cathode unit oscillates in a horizontal plane relative to the substrate fixed in the chamber. Although a twin cathode type sputtering device having two targets is illustrated in FIG. 9, the number of targets may be three or more. [Explanation of symbols]

[0105] 1: Sputtering equipment 2: Target 3: Magnet unit 6: Substrate 35: Rotation axis 100: Film deposition equipment

Claims

1. a cylindrical target made of an alloy of two or more components; a magnetic field generating means provided inside the target, the magnetic field generating means being capable of varying the angle around a rotation axis parallel to the central axis of the cylindrical shape, and generating a leakage magnetic field leaking from the outer peripheral surface of the target; and A film formation apparatus for forming an alloy thin film by sputtering on a film formation target disposed opposite the target while rotating the target, the magnetic field generating means can be set to a first angle and a second angle different from the first angle, A film formation apparatus characterized in that when a first alloy thin film is formed on the film formation target, the magnetic field generating means is set to the first angle, and when a second alloy thin film having a composition ratio different from that of the first alloy thin film is formed on the first alloy thin film on the film formation target, the magnetic field generating means is set to the second angle.

2. When the first alloy thin film is formed on the film-forming object, the magnetic field generating means is set to the first angle, and the film-forming object is moved in a first direction relative to the target, 2. The film forming apparatus of claim 1, wherein when the second alloy thin film is formed on the first alloy thin film of the film forming object, the film forming object is moved in a second direction opposite to the first direction relative to the target while the magnetic field generating means is set to a second angle smaller than the first angle.

3. When the first alloy thin film is formed on the film-forming object, the magnetic field generating means is set to the first angle, and the target is moved in a first direction relative to the film-forming object; 2. The film forming apparatus of claim 1, wherein when the second alloy thin film is formed on the first alloy thin film of the film forming object, the magnetic field generating means is set to the second angle which is smaller than the first angle, and the target is moved in a second direction opposite to the first direction relative to the film forming object.

4. 4. The film deposition apparatus according to claim 1, wherein the first component of the alloy constituting the target is Mg and the second component is Ag.

5. The first component of the alloy constituting the target is Li, Na, Mg, K, Ca, Cs, 4. The film forming apparatus according to claim 1, wherein the first component is either Yb or Ag, and the second component is either Ag or Al.

6. A film forming apparatus according to any one of claims 1 to 3, wherein when a film is formed on the film forming object using the target, the deposition amount distribution of the first component of the alloy constituting the target has a mountain-like shape that is wider and has a lower peak than the deposition amount distribution of the second component.

7. the magnetic field generating means is configured so that the composition ratio of the first component in the alloy thin film increases as the angle from a reference position increases, The film deposition apparatus according to claim 4 , wherein the second angle is smaller than the first angle.

8. 4. The film deposition apparatus according to claim 1, wherein at least one of a voltage applied to the target and a film deposition time is adjusted according to an angle of the magnetic field generating means.

9. a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target, the first magnetic field generating means being capable of varying an angle around a rotation axis parallel to a cylindrical central axis of the first target, and generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target, the second magnetic field generating means being capable of varying an angle around a rotation axis parallel to the cylindrical central axis of the second target, and generating a leakage magnetic field leaking from an outer peripheral surface of the second target; and a film formation apparatus for forming an alloy thin film by sputtering on a film formation target disposed opposite the first target while rotating the first target, and for forming an alloy thin film by sputtering on the film formation target disposed opposite the second target while rotating the second target, the first magnetic field generating means can be set to a first angle, and the second magnetic field generating means can be set to a second angle smaller than the first angle; When forming a first alloy thin film on the film-forming target, the film-forming target is moved relative to the first target with the first magnetic field generating means set at a first angle; When a second alloy thin film is formed on the first alloy thin film of the film-forming object, the film-forming object is moved relative to the second target while the second magnetic field generating means is set to the second angle.

10. a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target, the first magnetic field generating means being capable of varying an angle around a rotation axis parallel to a cylindrical central axis of the first target, and generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target, the second magnetic field generating means being capable of varying an angle around a rotation axis parallel to the cylindrical central axis of the second target, and generating a leakage magnetic field leaking from an outer peripheral surface of the second target; and a film formation apparatus for forming an alloy thin film by sputtering on a film formation target disposed opposite the first target while rotating the first target, and for forming an alloy thin film by sputtering on the film formation target disposed opposite the second target while rotating the second target, the first magnetic field generating means can be set to a first angle, and the second magnetic field generating means can be set to a second angle smaller than the first angle; When forming a first alloy thin film on the film-forming target, the first target is moved relative to the film-forming target while the first magnetic field generating means is set at the first angle; When a second alloy thin film is formed on the first alloy thin film of the film-forming object, the film-forming apparatus moves the second target relative to the film-forming object while the second magnetic field generating means is set to the second angle.

11. 11. The film deposition apparatus according to claim 9, wherein the first component of the alloy constituting the first target and the second target is Mg, and the second component of the alloy is Ag.

12. 11. The film forming apparatus according to claim 9, wherein the first component of the alloy constituting the first target and the second target is one of Li, Na, Mg, K, Ca, Cs, and Yb, and the second component is Ag or Al.

13. The film forming apparatus according to claim 9 or 10, wherein when a film is formed on the film forming object using the first target and the second target, the deposition amount distribution of the first component of the alloy constituting the first target and the second target has a mountain-like shape that is wider and has a lower peak than the deposition amount distribution of the second component.

14. the first magnetic field generating means and the second magnetic field generating means are configured so that the composition ratio of the first component in the alloy thin film increases as the angle from a reference position increases, The film deposition apparatus according to claim 11 , wherein the second angle is smaller than the first angle.

15. 11. The film deposition apparatus according to claim 9, wherein at least one of a voltage applied to the first target and the second target and a film deposition time is adjusted according to angles of the first magnetic field generating means and the second magnetic field generating means.

16. 11. The film forming apparatus according to claim 1, wherein the film is formed continuously on a plurality of the film forming targets.

17. 11. The film forming apparatus according to claim 1, wherein the alloy thin film constitutes a cathode of an organic EL element.

18. The film forming apparatus according to any one of claims 1 to 3, 9 and 10, wherein the film forming apparatus is an in-line type film forming apparatus.

19. The film forming apparatus according to any one of claims 1 to 3, 9 and 10, wherein the film forming apparatus is a cluster type film forming apparatus.

20. a cylindrical target made of an alloy of two or more components; a magnetic field generating means provided inside the target, the magnetic field generating means being capable of varying the angle around a rotation axis parallel to the central axis of the cylindrical shape, and generating a leakage magnetic field leaking from the outer peripheral surface of the target; A film formation method using a film formation apparatus having the following: forming an alloy thin film by sputtering on a film-forming target disposed opposite the target while rotating the target; forming a first alloy thin film on the object to be film-formed while the magnetic field generating means is set at a first angle; forming a second alloy thin film having a composition ratio different from that of the first alloy thin film on the first alloy thin film of the film-forming target while the magnetic field generating means is set at a second angle different from the first angle; A film forming method comprising the steps of:

21. a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target, the first magnetic field generating means being capable of varying an angle around a rotation axis parallel to a cylindrical central axis of the first target, and generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target, the second magnetic field generating means being capable of varying an angle around a rotation axis parallel to the cylindrical central axis of the second target, and generating a leakage magnetic field leaking from an outer peripheral surface of the second target; A film formation method using a film formation apparatus having the following: forming an alloy thin film by sputtering on a film-forming target disposed opposite the first target while rotating the first target; forming an alloy thin film by sputtering on the film-forming target disposed opposite the second target while rotating the second target; forming a first alloy thin film on the film-forming object while moving the film-forming object relative to the first target with the first magnetic field generating means set at a first angle; a step of depositing a second alloy thin film on the first alloy thin film on the film-deposition target while moving the film-deposition target relative to the second target, with the second magnetic field generating means set to a second angle smaller than the first angle; A film forming method comprising the steps of:

22. a cylindrical first target made of an alloy of two or more components; a first magnetic field generating means provided inside the first target, the first magnetic field generating means being capable of varying an angle around a rotation axis parallel to a cylindrical central axis of the first target, and generating a leakage magnetic field leaking from an outer peripheral surface of the first target; a cylindrical second target made of an alloy having the same composition as the first target; a second magnetic field generating means provided inside the second target, the second magnetic field generating means being capable of varying an angle around a rotation axis parallel to the cylindrical central axis of the second target, and generating a leakage magnetic field leaking from an outer peripheral surface of the second target; A film formation method using a film formation apparatus having the following: forming an alloy thin film by sputtering on a film-forming target disposed opposite the first target while rotating the first target; forming an alloy thin film by sputtering on the film-forming target disposed opposite the second target while rotating the second target; forming a first alloy thin film on the film-forming target while moving the first target relative to the film-forming target with the first magnetic field generating means set at a first angle; a step of depositing a second alloy thin film on the first alloy thin film on the film-deposition target while moving the second target relative to the film-deposition target, with the second magnetic field generating means set to a second angle smaller than the first angle; A film forming method comprising the steps of:

23. A method for manufacturing an electronic device, comprising manufacturing an electronic device using the film forming method according to any one of claims 20 to 22.

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