Film deposition apparatus, thin film formation method and fabrication method of device

Abstract

To provide a film deposition apparatus capable of depositing a uniform crystal film at an excellent film deposition efficiency while controlling an orientation direction of a film deposited on a surface of a substrate.SOLUTION: A film deposition apparatus has a raw material supply part 17 for supplying a raw material to a surface of a substrate 12, and a plasma generation part 19 for generating an inductive coupling plasma of a gas supplied from the gas supply part 18. The plasma generation part 19 has an IPC electrode 3a arranged in a first side in an X-axis direction crossing a Z-axis direction from the raw material supply part 17 when seen from the Z-axis direction, and an ICP electrode 3b arranged in an opposite side of the first side in the X-axis direction from the raw material supply part 17 when seen from the Z-axis direction. The ICP electrodes 3a-3b are arranged such that a first distance between a substrate holder 11 and the ICP electrode 3a in the Z-axis direction is larger than a second distance between the substrate holder 11 and the ICP electrode 3b in the Z-axis direction.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a film forming apparatus for forming a thin film, a thin film forming method, and an element manufacturing method. [Background technology]

[0002] Piezoelectric thin films made of lead zirconate titanate (Pb(Zr,Ti)O3) (hereinafter referred to as PZT), which has excellent piezoelectric and ferroelectric properties, are being investigated, and piezoelectric thin films are being applied to memory elements such as non-volatile memory (FeRAM), as well as MEMS (Micro Electro Mechanical Systems) technology such as inkjet heads and acceleration sensors.

[0003] In recent years, it has been studied to form a (200)-oriented Pt film on a (100)-oriented Si substrate via a (200)-oriented ZrO2 film or the like, thereby forming a piezoelectric film with good piezoelectric properties on the Pt film (Patent Document 1). However, even with reactive evaporation equipment, the orientation direction and film quality of the piezoelectric film are still not satisfactory, and the yield is poor, hindering mass production. For these reasons, improvements in film formation equipment such as reactive evaporation equipment have been desired. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-154015 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a film deposition apparatus that can deposit a uniform crystalline film while controlling the orientation direction of the film deposited on the surface of a substrate, and that has excellent film deposition efficiency. [Means for solving the problem]

[0006] As a result of extensive investigation, the present inventors have found that the above-mentioned problems can be solved by the following configuration. [1] A film forming apparatus for forming a film on a surface of a substrate by supplying a raw material to the surface of the substrate, a chamber that can be evacuated; a substrate holder that holds a substrate within the chamber; a raw material supply unit that is disposed in the chamber at a distance from the substrate holding unit in a first direction and that supplies a raw material to a surface of the substrate held by the substrate holding unit in the chamber; a gas supply unit that supplies a gas into the chamber; a plasma generating unit provided between the substrate holding unit and the raw material supply unit, the plasma generating unit generating an inductively coupled plasma of the gas supplied by the gas supply unit; and The plasma generating unit is a first electrode disposed on a first side in a second direction intersecting with the first direction relative to the raw material supply unit when viewed from the first direction; a second electrode disposed on a side opposite to the first side in the second direction relative to the raw material supply unit when viewed from the first direction; Including, A film forming apparatus, wherein the first electrode and the second electrode are arranged so that a first distance between the substrate holding part and the first electrode in the first direction is greater than a second distance between the substrate holding part and the second electrode in the first direction. [2] The raw material supply unit a first crucible that is disposed on the first side in the second direction relative to a center of the raw material supply unit when viewed from the first direction, and is filled with a first evaporation material; a second crucible that is disposed on a side opposite to the first side in the second direction relative to a center of the raw material supply unit when viewed from the first direction, and is filled with a second evaporation material; Including, the raw material supply unit evaporates the first evaporation material or the second evaporation material, and supplies the raw material made of the evaporated first evaporation material or the second evaporation material to a surface of a substrate held by the substrate holding unit; the first electrode is disposed on the first side in the second direction relative to the first crucible when viewed from the first direction; The film forming apparatus according to [1], wherein the second electrode is positioned on the opposite side of the second crucible from the first side in the second direction when viewed from the first direction. [3] When viewed from the first direction, a central portion of each of the first crucible and the second crucible is disposed on a second side in a third direction intersecting both the first direction and the second direction relative to a central portion of the raw material supply unit; the raw material supply unit includes a third crucible filled with a third evaporation material, When viewed from the first direction, a central portion of the third crucible is disposed on a side opposite to the second side in the third direction with respect to a central portion of the raw material supply part; the plasma generation unit includes a third electrode that is disposed on a side opposite to the second side in the third direction with respect to the raw material supply unit when viewed from the first direction, the first electrode is disposed on the first side in the second direction relative to the third electrode when viewed from the third direction; the second electrode is disposed on a side opposite to the first side in the second direction relative to the third electrode when viewed from the third direction; The film formation apparatus described in [2], wherein the first electrode, the second electrode, and the third electrode are arranged so that the first distance between the substrate holding part and the first electrode in the first direction is greater than the third distance between the substrate holding part and the third electrode in the first direction, and the third distance between the substrate holding part and the third electrode in the first direction is greater than the second distance between the substrate holding part and the second electrode in the first direction. [4] A film forming apparatus described in any one of [1] to [3], wherein each of the first electrode and the second electrode has a concave curved shape or a parabolic shape curved along the outer periphery of the substrate held by the substrate holding part when viewed from the first direction. [5] The plasma generating unit includes a fourth electrode provided between the substrate holding unit and the first and second electrodes, and configured to generate inductively coupled plasma of the gas supplied by the gas supply unit by applying a high-frequency voltage thereto; the fourth electrode has a ring shape when viewed from the first direction, and is disposed so as to surround the substrate held by the substrate holder; The fourth electrode is a first portion that is disposed on the first side in the second direction relative to a center portion of the fourth electrode when viewed from the first direction; a second portion disposed on a side opposite to the first side in the second direction relative to a central portion of the fourth electrode when viewed from the first direction; Including, The film forming apparatus according to any one of [1] to [3], wherein the fourth electrode is positioned so that a third distance between the substrate holding portion and the first portion in the first direction is greater than a fourth distance between the substrate holding portion and the second portion in the first direction. [6] The film forming apparatus according to any one of [1] to [3], wherein each of the first electrode and the second electrode generates the inductively coupled plasma by applying DC and / or AC excitation current through an RF cut filter. [7] A film forming apparatus for forming a film on a surface of a substrate by supplying a raw material to the surface of the substrate, a chamber that can be evacuated; a substrate holder that holds a substrate within the chamber; a raw material supply unit that is disposed in the chamber at a distance from the substrate holding unit in a first direction and that supplies a raw material to a surface of the substrate held by the substrate holding unit in the chamber; a gas supply unit that supplies a gas into the chamber; a plasma generating unit provided between the substrate holding unit and the raw material supply unit, the plasma generating unit generating an inductively coupled plasma of the gas supplied by the gas supply unit; and the plasma generation unit is provided between the substrate holding unit and the raw material supply unit, and includes a first electrode that generates inductively coupled plasma of the gas supplied by the gas supply unit by applying a high-frequency voltage thereto; the first electrode has a ring shape when viewed from the first direction, and is disposed so as to surround the substrate held by the substrate holder; The first electrode is a first portion disposed on a first side in a second direction intersecting with the first direction relative to a center portion of the first electrode when viewed from the first direction; a second portion disposed on a side opposite to the first side in the second direction relative to a central portion of the first electrode when viewed from the first direction; Including, A film forming apparatus, wherein the first electrode is positioned so that a first distance between the substrate holding part and the first portion in the first direction is greater than a second distance between the substrate holding part and the second portion in the first direction. [8] The film forming apparatus according to any one of [1] to [3] or [7], further comprising an ion acceleration unit provided between the substrate holding unit and the raw material supply unit, for accelerating the inductively coupled plasma generated by the plasma generation unit. [9] The film formation apparatus according to [8], wherein a fourth direction in which the ion acceleration unit accelerates the inductively coupled plasma is inclined with respect to the first direction.

[10] A substrate heating unit that heats the substrate; a control unit for controlling the operation of the substrate heating unit; and The film forming apparatus described in any one of [1] to [3] or [7], wherein the control unit controls the operation of the substrate heating unit so as to alternately turn the substrate heating unit on and off when forming a film on the surface of the substrate held by the substrate holding unit.

[11] A method for forming a thin film using a film formation apparatus, wherein the film formation apparatus is the film formation apparatus according to any one of [1] to

[10] .

[12] A method for producing an element including a thin film, the method comprising forming the thin film by the method for forming a thin film according to

[11] . [Effects of the Invention]

[0007] The film deposition apparatus of the present invention has the advantage that it is possible to deposit a uniform crystalline film while controlling the orientation direction of the film deposited on the surface of the substrate, and that it has excellent film deposition efficiency. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a diagram schematically illustrating an example of a preferred mode of a film forming apparatus according to an embodiment. [Figure 2] 1 is a diagram schematically illustrating an example of an ICP electrode that can be suitably used in a film forming apparatus according to an embodiment. [Figure 3] FIG. 2 is a diagram schematically illustrating another example of an ICP electrode that can be suitably used in the film forming apparatus according to the embodiment. [Figure 4] FIG. 2 is a diagram schematically illustrating another example of an ICP electrode that can be suitably used in the film forming apparatus according to the embodiment. [Figure 5] FIG. 2 is a diagram schematically illustrating another example of an ICP electrode that can be suitably used in the film forming apparatus according to the embodiment. [Figure 6] 1 is a plan view schematically showing an example of a preferred mode of a plasma generating unit in a film forming apparatus according to an embodiment; [Figure 7] 1 is a side view schematically showing an example of a preferred mode of a plasma generating unit in a film forming apparatus according to an embodiment. [Figure 8] FIG. 10 is a plan view schematically showing another example of a preferred mode of the plasma generating section in the film forming apparatus according to the embodiment. [Figure 9] FIG. 10 is a side view schematically showing another example of a preferred mode of the plasma generating unit in the film forming apparatus according to the embodiment. [Figure 10]FIG. 10 is a plan view schematically showing another example of a preferred mode of the plasma generating section in the film forming apparatus according to the embodiment. [Figure 11] 1 is a graph showing a schematic diagram of the relationship between the number of ICP electrodes and the tilt angle of the film. [Figure 12] FIG. 10 is a diagram schematically illustrating another example of a preferred mode of the film forming apparatus according to the embodiment. [Figure 13] FIG. 10 is a diagram schematically illustrating another example of a preferred mode of the film forming apparatus according to the embodiment. [Figure 14] 1 is a diagram schematically illustrating an example of a preferred mode of a sputtering apparatus according to an embodiment. [Figure 15] FIG. 1 is a diagram showing the results of XRD measurements in Examples. [Figure 16] FIG. 10 is a diagram showing the measurement results of the tilt angle in the examples. [Figure 17] 1A and 1B are diagrams schematically illustrating a preferred example of a MEMS transducer. [Figure 18] 1 is a schematic diagram illustrating an example cross-sectional view of a portion of a wafer including a piezoelectric actuator suitable for application to a fluid ejection device. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0009] The film forming apparatus of the present invention will be described below with reference to the drawings, but the present invention is not limited to these specific examples.

[0010] (Embodiment) First, we will describe a film formation apparatus according to an embodiment of the present invention, a thin film formation method using the film formation apparatus, and an element fabrication method for fabricating an element including a thin film. The film formation apparatus of this embodiment is a film formation apparatus that forms a film on the surface of a substrate by supplying raw materials to the surface of the substrate. An example of a preferred embodiment of the film formation apparatus of this embodiment is shown in FIG. 1. The film formation apparatus of FIG. 1 includes crucibles CR1-CR2, metal sources 1a-1b filled in the crucibles CR1-CR2, earths 2a-2h, ICP electrodes 3a-3b, cut filters 4a-4b, DC power supplies 5a-5c, RF power supplies 6a-6c, lamps 7a-7b, an Ar source 8, a reactive gas source 9, a power supply 10, a substrate holder 11, a substrate 12, an ICP ring 13, a cut filter 14, a vacuum chamber 15, and a rotation shaft 16.

[0011] ICP electrodes 3a and 3b in FIG. 1 have a generally concave curved or parabolic shape that curves toward the center of substrate 12. In other words, when viewed from the Z-axis direction (first direction), each of ICP electrodes 3a and 3b has a generally concave curved or parabolic shape that curves along the outer periphery of substrate 12 held by substrate holder 11. Suitable examples of ICP electrodes (ICP generators) 3a and 3b having a generally concave curved or parabolic shape include the generally concave curved ICP electrode shown in FIG. 2 and the parabolic ICP electrodes shown in FIGS. 3 to 5. In FIGS. 2 to 5, ICP electrodes 3a and 3b are represented by ICP electrode 3. As shown in FIG. 1, the ICP electrodes are installed so that the openings of the generally concave curved or parabolic ICP electrodes that curve toward the center of substrate 12 are inclined with respect to the deposition surface of the substrate.

[0012] As shown in FIG. 1, substrate 12 is mounted on substrate holder 11. Next, power supply 10 and a rotation mechanism (not shown) are used to rotate rotation shaft 16, thereby rotating substrate 12. Substrate 12 is heated by lamps 7a and 7b, and a vacuum chamber 15 is evacuated using a vacuum pump (not shown) to create a vacuum or reduced pressure. Thereafter, Ar gas is introduced into vacuum chamber 15 from Ar source 8, and argon plasma is formed on substrate 12 using DC power supplies 5a and 5b, RF power supplies 6a and 6b, ICP electrodes 3a and 3b, cut filters 4a and 4b, and earths 2a and 2h, thereby cleaning the surface of substrate 12.

[0013] Ar gas is introduced into the vacuum chamber 15, and a reactive gas is introduced using the reactive gas source 9. At this time, by alternately turning on and off the lamps 7a to 7b, which are lamp heaters, a better quality crystal growth film can be formed.

[0014] Next, the film forming apparatus of this embodiment will be described in more detail. The film forming apparatus of this embodiment has a vacuum chamber 15 as a chamber, a substrate holder 11 as a substrate holding unit, a raw material supply unit 17, a gas supply unit 18, and a plasma generation unit 19. The vacuum chamber 15 can be evacuated. The substrate holder 11 holds a substrate 12 within the vacuum chamber 15.

[0015] The raw material supply unit 17 is disposed in the vacuum chamber 15 at an interval from the substrate holder 11 in, for example, the vertical Z-axis direction (first direction), and supplies raw material to the surface of the substrate 12 held by the substrate holder 11 in the vacuum chamber 15, and includes crucibles CR1-CR2 and metal sources 1a-1b as evaporation materials. Although not shown, when the film forming apparatus is an electron beam evaporation apparatus, the raw material supply unit 17 may include an electron gun for generating an electron beam to be incident on the evaporation material, and a magnetic field generation unit for generating a magnetic field for making the electron beam incident on the evaporation material.

[0016] Gas supply unit 18 supplies gas into vacuum chamber 15 and includes an Ar source 8 and a reactive gas source 9. Plasma generation unit 19 is provided between substrate holder 11 and raw material supply unit 17 and generates inductively coupled plasma of the gas supplied by gas supply unit 18, and includes ICP electrodes 3a-3b, cut filters 4a-4b, DC power supplies 5a-5b, and RF power supplies 6a-6b.

[0017] 6 and 7 are a plan view and a side view schematically showing one example of a preferred mode of the plasma generating section in the film forming apparatus according to the embodiment.

[0018] In the film forming apparatus of this embodiment, plasma generation unit 19 includes ICP electrode (first electrode) 3a and ICP electrode (second electrode) 3b. When viewed from the Z-axis direction (first direction), ICP electrode 3a is disposed on a first side in the X-axis direction (second direction), which is a direction intersecting the Z-axis direction (first direction), relative to raw material supply unit 17. When viewed from the first direction, ICP electrode 3b is disposed on the opposite side from the first side in the X-axis direction (second direction) relative to raw material supply unit 17.

[0019] ICP electrode 3a and ICP electrode 3b are arranged so that a first distance between substrate holder 11 and ICP electrode 3a in the Z-axis direction (first direction) is greater than a second distance between substrate holder 11 and ICP electrode 3b in the Z-axis direction (first direction). In other words, the height position of ICP electrode 3a or ICP electrode 3b can be changed so that a plane connecting ICP electrode 3a and ICP electrode 3b is inclined with respect to a plane (horizontal plane) perpendicular to the Z-axis direction (first direction) (the same applies when the number of ICP electrodes is three or more). Although not shown in the drawings, the height position of ICP electrode 3a or ICP electrode 3b can be changed by attaching ICP electrode 3a or ICP electrode 3b to a support column aligned along the Z-axis direction (first direction) at any position in the Z-axis direction (first direction) (the same applies when the number of ICP electrodes is three or more).

[0020] As a result, the plane passing through ICP electrodes 3a and 3b is inclined relative to the horizontal plane, i.e., the plane perpendicular to the Z-axis direction, so that the disk-shaped region RG1 where the inductively coupled plasma density is high, formed between ICP electrodes 3a and 3b, is inclined relative to the horizontal plane. Therefore, for example, the orientation direction of the film formed on the surface of the substrate can be inclined relative to the orientation direction of the film formed on the surface of the substrate when the plane passing through ICP electrodes 3a and 3b is not inclined relative to the horizontal plane. As a result, it is possible to obtain a uniform crystalline film with high yield in a short time while controlling the orientation direction of the film formed on the surface of the substrate.

[0021] Preferably, the raw material supply unit 17 includes a crucible CR1 and a crucible CR2. When viewed from the Z-axis direction (first direction), the crucible CR1 is disposed on a first side in the X-axis direction (second direction) from the center of the raw material supply unit 17, and is filled with a metal source 1a as a first evaporation material. When viewed from the Z-axis direction (first direction), the crucible CR2 is disposed on the opposite side to the first side in the X-axis direction (second direction) from the center of the raw material supply unit 17, and is filled with a metal source 1b as a second evaporation material. The raw material supply unit 17 evaporates the metal source 1a or the metal source 1b, and supplies the evaporated raw material composed of the metal source 1a or the metal source 1b to the surface of the substrate 12 held by the substrate holder 11.

[0022] When viewed from the Z-axis direction (first direction), ICP electrode 3a is disposed on a first side in the X-axis direction (second direction) relative to crucible CR1, and ICP electrode 3b is disposed on the opposite side of the first side in the X-axis direction (second direction) relative to crucible CR2 when viewed from the Z-axis direction (first direction). By disposing them in this manner, ICP electrode 3a and ICP electrode 3b can be reliably disposed on both sides of raw material supply unit 17 when viewed from the Z-axis direction (first direction).

[0023] 8 and 9 are a plan view and a side view, respectively, showing another preferred example of the plasma generating unit in the film forming apparatus according to the embodiment. In the example shown in Fig. 8 and Fig. 9, the raw material supply unit 17 includes three crucibles, and the plasma generating unit 19 includes three ICP electrodes.

[0024] Preferably, when viewed from the Z-axis direction (first direction), the central portion of each of the crucibles CR1 and CR2 is disposed closer to the second side in the Y-axis direction (third direction) that intersects with both the Z-axis direction (first direction) and the X-axis direction (second direction) than the central portion of the raw material supply unit 17. The raw material supply unit 17 includes a crucible CR3 filled with a metal source 1c as a third evaporation material. When viewed from the Z-axis direction (first direction), the central portion of the crucible CR3 is disposed closer to the second side in the Y-axis direction (third direction) than the central portion of the raw material supply unit 17.

[0025] Plasma generation unit 19 includes ICP electrode 3c in addition to ICP electrode 3a and ICP electrode 3b. When viewed from the Z-axis direction (first direction), ICP electrode 3c is located on the opposite side of the second side in the Y-axis direction (third direction) from raw material supply unit 17. When viewed from the Y-axis direction (third direction), ICP electrode 3a is located on the first side in the X-axis direction (second direction) from ICP electrode 3c. When viewed from the Y-axis direction (third direction), ICP electrode 3b is located on the opposite side of the first side in the X-axis direction (second direction) from ICP electrode 3c.

[0026] ICP electrode 3a, ICP electrode 3b, and ICP electrode 3c are arranged so that a first distance between substrate holder (substrate holding portion) 11 and ICP electrode 3a in the Z-axis direction (first direction) is greater than a third distance between substrate holder 11 and ICP electrode 3c in the Z-axis direction (first direction), and so that the third distance between substrate holder 11 and ICP electrode 3c in the Z-axis direction (first direction) is greater than a second distance between substrate holder 11 and ICP electrode 3b in the Z-axis direction (first direction).

[0027] As a result, the plane passing through ICP electrodes 3a, 3b, and 3c is inclined relative to the horizontal plane, i.e., the plane perpendicular to the Z-axis direction, so that a disk-shaped region RG1 where the density of the inductively coupled plasma formed between ICP electrodes 3a, 3b, and 3c is high is inclined relative to the horizontal plane. Therefore, for example, the orientation direction of a film formed on the surface of a substrate can be inclined relative to the orientation direction of a film formed on the surface of a substrate when the plane passing through ICP electrodes 3a, 3b, and 3c is not inclined relative to the horizontal plane.

[0028] In this specification, "arranging ICP electrode 3a closer to the first side in the X-axis direction (second direction) than ICP electrode 3c" means that the center of ICP electrode 3a in the X-axis direction (second direction) is closer to the first side in the X-axis direction (second direction) than the center of ICP electrode 3c in the X-axis direction (second direction). Also, "arranging ICP electrode 3b on the opposite side from the first side in the X-axis direction (second direction) than ICP electrode 3c" means that the center of ICP electrode 3b in the X-axis direction (second direction) is closer to the first side in the X-axis direction (second direction) than the center of ICP electrode 3c in the X-axis direction (second direction).

[0029] Fig. 10 is a plan view schematically illustrating another example of a preferred configuration of the plasma generation unit in the film formation apparatus of the embodiment. In the example shown in Fig. 10, the raw material supply unit 17 includes four crucibles CR1 to CR4, and the plasma generation unit includes four ICP electrodes 3a to 3d. Crucible CR4 is filled with a metal source 1d as a fourth evaporation material. Fig. 11 is a graph schematically illustrating the relationship between the number of ICP electrodes and the tilt angle of the film. The horizontal axis of Fig. 11 represents the number of ICP electrodes when the angle at which the plane passing through the multiple ICP electrodes is tilted relative to the horizontal plane is constant.

[0030] As shown in Fig. 10, when raw material supply unit 17 includes four crucibles CR1 to CR4, the same can be done as when raw material supply unit 17 includes three crucibles CR1 to CR3 as shown in Fig. 8. Also, as shown in Fig. 11, the greater the number of ICP electrodes, the greater the angle at which the orientation direction of the film formed on the surface of the substrate can be tilted relative to the orientation direction of the film formed on the surface of the substrate when the plane passing through the multiple ICP electrodes is not tilted relative to the horizontal plane.

[0031] Preferably, as shown in FIG. 1, the plasma generating unit 19 is provided between the substrate holder 11 and the ICP electrodes 3a and 3b, and includes an ICP ring (fourth electrode) 13 that generates inductively coupled plasma of the gas supplied by the gas supply unit 18 by applying a high-frequency voltage.

[0032] ICP ring 13 has a ring shape when viewed from the Z-axis direction (first direction), and is arranged to surround substrate 12 held by substrate holder 11. ICP ring 13 includes a first portion that is arranged on a first side in the X-axis direction (second direction) from a central portion of ICP ring 13 when viewed from the Z-axis direction (first direction), and a second portion that is arranged on the opposite side to the first side in the X-axis direction (second direction) from the central portion of ICP ring 13 when viewed from the Z-axis direction (first direction).

[0033] ICP ring 13 is positioned so that a third distance between substrate holder 11 and a first portion of ICP ring 13 in the Z-axis direction (first direction) is greater than a fourth distance between substrate holder 11 and a second portion of ICP ring 13 in the Z-axis direction (first direction). In other words, the height position of each portion of ICP ring 13 can be changed so that a plane including ICP ring 13 is inclined with respect to a horizontal plane, i.e., a plane perpendicular to the Z-axis direction. Although not shown in the drawings, the height position of each portion of ICP ring 13 can be changed by attaching the first or second portion of ICP ring 13 to a support column along the Z-axis direction (first direction) at any position in the Z-axis direction (first direction).

[0034] Since the plasma generating unit 19 includes an ICP ring 13 provided between the substrate holder 11 and the ICP electrodes 3a and 3b, even when the lifetime of the ions or radicals contained in the generated plasma is shorter than that of oxygen plasma, for example, when forming a film made of a metal nitride by supplying nitrogen plasma to the surface of the substrate 12, a plasma with sufficient plasma density can be generated near the surface of the substrate 12.

[0035] Furthermore, by positioning the ICP ring 13 so that a third distance between the substrate holder 11 and a first portion of the ICP ring 13 in the Z-axis direction (first direction) is greater than a fourth distance between the substrate holder 11 and a second portion of the ICP ring 13 in the Z-axis direction (first direction), a disk-shaped region of high density inductively coupled plasma formed within the ICP ring 13 is tilted with respect to the horizontal plane. Therefore, for example, the orientation direction of a film deposited on the surface of a substrate can be tilted with respect to the orientation direction of a film deposited on the surface of a substrate when the plane including the ICP ring 13 is not tilted with respect to the horizontal plane. As a result, a uniform crystalline film can be obtained with high yield in a short time while controlling the orientation direction of the film deposited on the surface of the substrate.

[0036] Each of ICP electrodes 3a and 3b generates inductively coupled plasma by applying DC and / or AC excitation current through cut filters 4a and 4b as RF cut filters. Also, ICP ring 13 generates inductively coupled plasma by applying DC and / or AC excitation current through cut filter 14 as RF cut filter. This ensures the generation of inductively coupled plasma.

[0037] Preferably, the film forming apparatus includes an ion acceleration unit 20. The ion acceleration unit 20 is provided between the substrate holder 11 and the raw material supply unit 17, and accelerates the inductively coupled plasma generated by the plasma generation unit 19. This allows a uniform crystalline film to be obtained with high yield in a short time.

[0038] More preferably, the fourth direction, which is the direction in which the ion acceleration unit 20 accelerates the inductively coupled plasma, is inclined with respect to the Z-axis direction (first direction). This makes it possible to obtain a uniform crystalline film with high yield in a short time while controlling the orientation direction of the film formed on the surface of the substrate.

[0039] Preferably, the film forming apparatus includes lamps 7a-7b as substrate heating units and a control unit CP. The lamps 7a-7b heat the substrate 12. The control unit CP controls the operation of the lamps 7a-7b, and alternately turns the lamps 7a-7b on and off when forming a film on the surface of the substrate 12 held by the substrate holder 11. In this case, for example, by alternately performing deposition and crystallization of the raw material on the surface of the substrate 12, a higher quality film can be formed as the film deposited on the surface of the substrate 12.

[0040] Another example of a preferred embodiment of the film formation apparatus of this embodiment is shown in FIG. 12. The film formation apparatus shown in FIG. 12 differs from that shown in FIG. 1 in that, instead of the ICP ring 13 and cut filter 14 shown in FIG. 1, ICP electrodes 3e-3f, cut filters 4c-4d, DC power supply 5d, RF power supply 6d, and earths 2i-2j are provided between the substrate holder 11 and the ICP electrodes 3a-3b and near the substrate 12. Similar to the ICP electrodes 3a-3b, the ICP electrodes 3e-3f are positioned such that the first distance between the substrate holder 11 and the ICP electrode 3e in the Z-axis direction (first direction) is greater than the second distance between the substrate holder 11 and the ICP electrode 3f in the Z-axis direction (first direction). This configuration improves crystal growth on the substrate, making it easier to achieve uniform crystal film formation while controlling the orientation of the film formed on the surface of the substrate.

[0041] Another example of a suitable mode of the film formation apparatus of this embodiment is shown in Fig. 13. The film formation apparatus shown in Fig. 13 differs from the example shown in Fig. 1 in that it includes an ICP ring 13a and a cut filter 14a provided between substrate holder 11 and raw material supply unit 17 and in the vicinity of raw material supply unit 17, instead of ICP electrodes 3a and 3b, cut filters 4a and 4b, DC power supply 5b, RF power supply 6b, and earths 2e and 2f shown in Fig. 1.

[0042] 13 , plasma generation unit 19 is provided between substrate holder 11 and raw material supply unit 17, and includes ICP ring 13a that generates inductively coupled plasma of gas supplied to gas supply unit 18 by applying a high-frequency voltage. ICP ring 13a has a ring shape when viewed from the Z-axis direction (first direction) and is disposed so as to surround substrate 12 held by substrate holder 11. ICP ring 13a includes a first portion that is disposed on a first side in the X-axis direction (second direction) that intersects with the Z-axis direction (first direction) from a center of ICP ring 13a when viewed from the Z-axis direction (first direction), and a second portion that is disposed on the opposite side from the first side in the X-axis direction (second direction) from the center of ICP ring 13a when viewed from the Z-axis direction (first direction).

[0043] ICP ring 13a is positioned so that a first distance between substrate holder 11 and a first portion of ICP ring 13a in the Z-axis direction (first direction) is greater than a second distance between substrate holder 11 and a second portion of ICP ring 13a in the Z-axis direction (first direction). In other words, the height positions of each portion of ICP ring 13a can be changed so that a plane including ICP ring 13a is inclined with respect to a horizontal plane, i.e., a plane perpendicular to the Z-axis direction. Although not shown, the height positions of each portion of ICP ring 13a can be changed by, for example, attaching the first or second portion of ICP ring 13a to a support column aligned along the Z-axis direction (first direction) at any position in the Z-axis direction (first direction).

[0044] By positioning the ICP ring 13a so that a first distance between the substrate holder 11 and a first portion of the ICP ring 13a in the Z-axis direction (first direction) is greater than a second distance between the substrate holder 11 and a second portion of the ICP ring 13a in the Z-axis direction (first direction), a disk-shaped region of high density inductively coupled plasma formed within the ICP ring 13a is tilted with respect to the horizontal plane. Therefore, for example, the orientation of a film deposited on the surface of a substrate can be tilted with respect to the orientation of a film deposited on the surface of a substrate when the plane including the ICP ring 13a is not tilted with respect to the horizontal plane. As a result, a uniform crystalline film can be obtained with high yield in a short time while controlling the orientation of the film deposited on the surface of the substrate.

[0045] The film forming apparatus shown in FIG. 13 may include both the ICP rings 13 and 13a, or may include only one of the ICP rings 13 and 13a.

[0046] FIG. 14 shows a preferred embodiment of the sputtering apparatus of this embodiment. The sputtering apparatus shown in FIG. 14 includes at least earths 2a-2d, ICP electrodes 3a-3b, cut filters 4a-4b, DC power supplies 5a-5b, RF power supplies 6a-6b, lamps 7a-7b, a reactive gas source 9, a substrate 12, a vacuum chamber 15, a rotating shaft 16, a target holder 211, a target 220, a substrate support 221, and a heater 227. The side of the substrate support 221 is tapered, forming a tapered portion 221a. This configuration not only facilitates maintenance, but also ensures that installation space for the lamps 7a-7b is secured in a position suitable for film formation. In combination with the ICP electrodes 3a-3b, the quality of film formation can be improved.

[0047] The metal is not particularly limited as long as it is a metal that undergoes martensitic transformation by heat treatment or processing, and may be a known metal. The metal is usually contained in the metal film as a main component of the metal film. Examples of the metal that undergoes martensitic transformation include Fe-Cr-Ni, Fe, Fe-Ni, Fe-Ni-Co, Fe-Si, Fe-Cr, Fe-Mn, Fe-Mn-C, Fe-Mn-Ni, Fe-Mn-Cr, Fe-C, Fe-N, Fe-Ni-C, Fe-Cr-C, Fe-Cu-C, Fe-Si-C, Fe-Cr-Ni-C, Co, Co-Ni, Co-Fe, Mn-Cu, In-Tl, In-Tl-Li, Na, Zr, Tl, Hf, Ti, Ti-Al, Ti-Cu, Ti-Cr, Ti-Fe, Ti-Mn, Ti-Mo, Ti-V, Ti-Zr , Ti-Al-V, Zr-U, Cu-Al-Ni, Cu-Al, Ag-Cd, Au-Cd, Au-Cd-Cu, Li, Li-Mg, Cu-Zn, U, U-Cr, Hg, etc.

[0048] In this embodiment, the metal preferably contains Fe, Cr, or Ni, more preferably contains Fe and Cr, and is more preferably stainless steel. Within these preferred ranges, the bending strength can be improved. The term "main component" refers to any metal whose atomic ratio in the metal film is 0.5 or greater. In this embodiment, the atomic ratio of the metal to all metal elements in the metal film is preferably 0.7 or greater, and more preferably 0.8 or greater.

[0049] In this embodiment, the metal film is preferably oriented in the (100) direction. The "oriented in the (100) direction" means that the crystal orientation angle detected by X-ray diffraction is oriented in the (100) direction, and more specifically, the peak ratio in the (100) direction to the total peaks of the metal film detected by X-ray diffraction is 50% or more, and preferably the peak ratio is 90% or more.

[0050] In this embodiment, the thickness of the metal film is preferably 100 μm or less, and more preferably 1 μm to 10 μm. This preferred range makes it a better intermediate film for crystal growth in a functional film.

[0051] The metal film can be easily obtained by forming a metal compound film containing Hf and / or Zr by crystal growth as a first layer in the (100) direction on a crystalline substrate such as a Si substrate, and then forming the same metal film by crystal growth as a second layer. This is a new finding made by the present inventors. The metal compound film is preferably an oxide or nitride containing Hf and / or Zr, and more preferably a nitride containing Hf and / or Zr.

[0052] The crystal substrate (hereinafter also simply referred to as "substrate") is not particularly limited as long as the substrate material, etc., does not impede the object of the present invention, and may be a known crystal substrate. It may be an organic compound or an inorganic compound. In this embodiment, it is preferable that the crystal substrate contains an inorganic compound. In this embodiment, it is preferable that the substrate has crystals on part or all of its surface, more preferably a crystal substrate having crystals on all or part of the main surface on the crystal growth side, and most preferably a crystal substrate having crystals on the entire main surface on the crystal growth side.

[0053] The crystal is not particularly limited as long as it does not impede the object of the present invention, and the crystal structure is also not particularly limited. However, it is preferably a cubic, tetragonal, trigonal, hexagonal, orthorhombic, or monoclinic crystal, and more preferably a crystal oriented in (100) or (200). The crystal substrate may have an off-axis angle, for example, an off-axis angle of 0.2° to 12.0°. Here, the "off-axis angle" refers to the angle between the substrate surface and the crystal growth plane. The shape of the substrate is not particularly limited as long as it is plate-shaped and serves as a support for the epitaxial film. It may be an insulating substrate or a semiconductor substrate. In this embodiment, the substrate is preferably a Si substrate, more preferably a crystalline Si substrate, and most preferably a crystalline Si substrate oriented in (100).

[0054] Examples of the substrate material include a Si substrate, one or more metals belonging to Groups 3 to 15 of the periodic table, or oxides of these metals. The shape of the substrate is not particularly limited, and may be substantially circular (e.g., circle, ellipse, etc.) or polygonal (e.g., triangle, square, rectangle, pentagon, hexagon, heptagon, octagon, nonagon, etc.), and various shapes can be suitably used. In addition, in this embodiment, a large-area substrate can be used, and by using such a large-area substrate, the area of ​​the epitaxial film can be increased.

[0055] In this embodiment, the crystal substrate preferably has a flat surface, but it is also preferable that the crystal substrate have an uneven surface on part or all of its surface, as this can improve the quality of the crystal growth of the epitaxial film. The crystal substrate having an uneven surface may have an uneven portion consisting of concave or convex portions formed on part or all of its surface, and the uneven portion is not particularly limited as long as it consists of convex or concave portions. It may be an uneven portion consisting of convex portions, an uneven portion consisting of concave portions, or an uneven portion consisting of convex and concave portions. Furthermore, the uneven portion may be formed of regular convex or concave portions, or irregular convex or concave portions.

[0056] In this embodiment, the unevenness is preferably formed periodically, and more preferably periodically and regularly patterned. The shape of the unevenness is not particularly limited and may be, for example, striped, dotted, meshed, or random. In this embodiment, a dotted or striped shape is preferred, and a dotted shape is more preferred. Furthermore, when the unevenness is patterned periodically and regularly, the pattern shape of the unevenness is preferably a polygonal shape such as a triangle, a quadrangle (e.g., a square, a rectangle, or a trapezoid), a pentagon, or a hexagon, a circle, or an ellipse. When the unevenness is formed in a dotted shape, the lattice shape of the dots is preferably a lattice shape such as a square lattice, an oblique lattice, a triangular lattice, or a hexagonal lattice, and more preferably a triangular lattice.

[0057] The cross-sectional shape of the concave or convex portions of the uneven portion is not particularly limited, but examples thereof include a U-shape, an inverted U-shape, a wave shape, or a polygonal shape such as a triangle, a quadrangle (for example, a square, a rectangle, or a trapezoid), a pentagon, or a hexagon.The thickness of the crystal substrate is not particularly limited, but is preferably 50 to 2000 μm, and more preferably 100 to 1000 μm.

[0058] The piezoelectric layer is not particularly limited as long as it is a piezoelectric layer made of a piezoelectric material. The piezoelectric material may also be a known piezoelectric material, but in this embodiment, it is preferable that the piezoelectric material contains Pb and Ti. The semiconductor layer is not particularly limited as long as it is a semiconductor layer made of a semiconductor. The semiconductor may be a known semiconductor, but in this embodiment, it is preferable that the semiconductor contains Si, SiC, GaN, or Ga2O3. In this specification, the terms "film" and "layer" may be interchangeable depending on the case or situation.

[0059] In this embodiment, the piezoelectric layer or the semiconductor layer is preferably stacked on the second layer via a third layer and a fourth layer. The third layer is preferably made of a metal different from the metal, and the fourth layer is preferably made of a conductive metal oxide. Examples of the metal in the third layer include gold, silver, platinum, palladium, silver-palladium, copper, nickel, and alloys thereof. In this embodiment, the third layer preferably contains a metal belonging to Group 10 or 11 of the periodic table, and more preferably contains platinum.

[0060] The conductive metal oxide is not particularly limited as long as it does not impede the object of the present invention, and may be a known conductive metal oxide. In this embodiment, however, it preferably contains Sr and / or Ru, and is more preferably an SRO film containing Sr and Ru.

[0061] The first, second, third, and fourth layers can be deposited by known deposition techniques. In this embodiment, the deposition technique is preferably vapor deposition (including MBE) or sputtering. The thickness of each layer is not particularly limited, but is preferably 10 nm to 100 μm, and more preferably 50 nm to 30 μm.

[0062] The metal film or laminate structure obtained as described above can be suitably used in elements such as piezoelectric elements or semiconductor elements using known means. That is, the method for producing an element according to the present embodiment is a method for producing an element including the thin film according to the present embodiment, characterized in that the thin film is formed by the thin film forming method according to the present embodiment described above. Furthermore, the element can be suitably used in electronic devices according to conventional methods. For example, various electronic devices can be constructed by connecting the laminate structure as a piezoelectric element to a power source and an electric / electronic circuit, and mounting or packaging the layer on a circuit board.

[0063] In this embodiment, the electronic device is preferably a piezoelectric device, and can be used as a piezoelectric device in electronic devices such as inkjet printer heads, microactuators, gyroscopes, and motion sensors. Furthermore, for example, by connecting an amplifier and a rectifier circuit and packaging the device, the device can be used in various sensors such as magnetic sensors. It can also be applied to constant-voltage-driven memory, and, for example, by connecting a storage element and a rectifier power management circuit, the device becomes an energy conversion device (energy harvester) that generates power from external magnetic fields or vibrations. The energy conversion device is incorporated into power supply systems and wearable devices (earphones / hearable devices, smart watches, smart glasses, smart contact lenses, cochlear implants, cardiac pacemakers, etc.).

[0064] In this embodiment, the laminated structure is preferably used in, for example, smart glasses, AR headsets, MEMS mirrors for LiDAR systems, piezoelectric MEMS ultrasonic transducers (PMUTs) for advanced medical applications, and piezo heads for commercial and industrial 3D printers.

[0065] The electronic device is suitably used in electronic devices in the usual manner, and can be applied to various electronic devices in addition to the above-mentioned electronic devices, and more specific examples of suitable electronic devices include liquid ejection heads, liquid ejection apparatuses, vibration wave motors, optical devices, vibration devices, imaging devices, piezoelectric acoustic components, and audio playback devices, audio recording devices, mobile phones, and various information terminals that have such piezoelectric acoustic components.

[0066] Furthermore, the electronic device is also applied to a system in the usual manner, and examples of such a system include a sensor system. [Example]

[0067] Example 1 The crystal growth surface of a Si substrate (100) was treated by RIE, and in the presence of oxygen, a metal vapor deposition source was thermally reacted with oxygen in the film deposition apparatus shown in Figure 1 to form a HfZrO single crystal on the Si substrate. The deposition conditions for this film formation were as follows. Although not shown, the output and the orientation of the substrate relative to the vapor deposition source were adjusted appropriately based on the angle between the ICP electrode and the substrate, such as by slightly tilting the substrate relative to the vapor deposition source, to form the film. Vapor deposition source: Hf, Zr Voltage: 3.5~4.75V Pressure: 3×10 -2 ~6×10 -2 Pa Substrate temperature: 450~700℃

[0068] Next, a SUS304 single crystal film was formed in the same manner as above, except that Fe, Cr, and Ni were used as the metals of the evaporation source.

[0069] Next, a platinum (Pt) metal film was formed as a conductive film on the single crystal film of the crystalline metal oxide by sputtering under the following conditions. Equipment: ULVAC sputtering equipment QAM-4 Pressure: 1.20×10 -1 Pa Target: Pt Power: 100W(DC) Thickness: 100nm Substrate temperature: 450~600℃

[0070] Next, an SRO film was formed on the conductive film by sputtering under the following conditions. Equipment: ULVAC sputtering equipment QAM-4 Power: 150W(RF) Gas: Ar Pressure: 1.8Pa Substrate temperature: 600℃ Thickness: 20nm

[0071] Next, a PbTiO3 film was deposited on the SRO film as a piezoelectric film. The resulting laminated structure had good adhesion and crystallinity. Furthermore, the crystal substrate of the laminated structure, the crystalline metal oxide single crystal film, and the conductive film were analyzed using an X-ray diffractometer. Figure 15 shows the XRD measurement results. A SUS304 single crystal film with good crystallinity was formed, and the crystallinity of the PbTiO3 film and other films was also good. Furthermore, when the inclination angle of the single crystal film was measured using an X-ray diffractometer, it was found that the (002) plane of the HfZrO single crystal was inclined at an angle of 8.5° relative to the deposition surface, as shown in Figure 15.

[0072] In addition, in the film formation apparatus of FIG. 1, film formation was performed while changing the height difference (antenna shift amount) between both ends of the ICP electrode in the X-axis direction (horizontal direction), that is, while changing the inclination angle (0.1° to 89°) from the horizontal plane of the plane passing through the ICP electrode. <200> The tilt angle was measured. The measurement results of the tilt angle are shown in Figure 16. As is clear from Figure 16, <200> It was found that the tilt angle of the ICP electrode has a positive correlation with the difference in height (antenna shift) between both ends in the X-axis direction (horizontal direction) of the ICP electrode. This indicates that the orientation direction of the crystalline film can be easily tilted by adjusting the tilt angle from the horizontal plane of the plane passing through the ICP electrode using the film deposition apparatus shown in Figure 1. Furthermore, the crystallinity of the obtained film was evaluated using an X-ray diffraction apparatus, including the difference from when it was not tilted. The results showed that by depositing the film with the plane passing through the ICP electrode tilted from the horizontal plane, the crystallinity was improved, and not only the crystallinity but also the performance of the functional film could be significantly improved.

[0073] (Test example) Although not shown in the figure, as a test example, a cantilever beam of a microelement was fabricated using a FIB FB2100 (Hitachi High-Technologies Corporation) and its fracture strength characteristics were evaluated using a nanoindenter NanoTest Xtreme (Micro Materials Corporation). The fracture strength of Si was found to be approximately 1 GPa, a fairly constant value. Considering that the bending strength of bulk Si single crystal material is approximately 300 MPa (according to a paper), this indicates that micromaterials have great strength. Furthermore, in the case of a SUS304 single crystal thin film, the fracture strength was approximately 5 GPa, approximately five times the bending strength of single crystal Si. This indicates that using a SUS304 single crystal thin film for the beam (the moving part, equivalent to the active layer of an SOI substrate) of a MEMS device can be expected to significantly improve not only the displacement of the MEMS device but also its lifespan characteristics.

[0074] (Application example) Examples of applications of the resulting laminated structure will be described in more detail below with reference to the drawings, but the present invention is not limited to these examples. In the present invention, unless otherwise specified, piezoelectric devices and the like can be manufactured from the laminated structure using known means.

[0075] 17 shows an example of an acoustic MEMS transducer constituting a MEMS microphone in which the laminated structure of this embodiment is preferably used. The MEMS transducer can constitute an acoustic emission device (for example, a speaker).

[0076] The MEMS microphone configured with the acoustic MEMS transducer of Fig. 17 is a cantilever-type MEMS microphone, and includes a Si substrate 21 having two cantilever beams 28A and 28B and a cavity 30. Each of the cantilever beams 28A and 28B is fixed at its respective end to the Si substrate 21, and a gap 29 is provided between the cantilever beams 28A and 28B. The cantilever beams 28A and 28B are formed, for example, by a layered structure including PZT films 26a and 26b as multiple piezoelectric films, and are alternated with multiple electrode layers, namely Pt films 24a, 24b, and 24c and SRO films 25a, 25b, 25c, and 25d.

[0077] The Pt film 24a is provided on a SUS film 23, which is provided on a HfZrN film 22. Compared with the use of SiO2, SiN, or the like, the use of the HfZrN film 22 provides superior adhesion to the Si substrate and crystallinity, and the crystallinity can be further improved up to the multiple layers thereon, resulting in superior piezoelectric properties and durability.

[0078] 18 shows an example of application of the laminated structure of this embodiment to a printing application, particularly to a fluid ejection device that can be used in the form of an inkjet printhead. Specifically, it shows a cross-sectional view of a portion of a wafer equipped with a piezoelectric actuator including Pt films 34a, 34b and SRO films 35a, 35b as electrode layers and a PZT film 36 as a piezoelectric film. In addition to the piezoelectric actuator, the wafer of FIG. 18 also includes a chamber 41 for containing a fluid. Chamber 41 is configured to take in fluid from a tank (not shown) via a flow path 40.

[0079] 18 includes a Si substrate 31, on which an HfZrN film 32 and a SUS film 33 are laminated, facing a chamber 41. In FIG. 18, the use of the HfZrN film 32 provides better adhesion and crystallinity with the Si substrate than when SiO2, SiN, or the like is used, and further improves the crystallinity of the multiple layers thereupon, resulting in better piezoelectric properties and durability. The HfZrN film 32 has, for example, a quadrangular shape in a top view (not shown), but the shape may be any of a square, a rectangle, a rectangle with rounded corners, a parallelogram, and the like.

[0080] On the SUS film 33, a Pt film 34a, an SRO film 35a, a PZT film 36 as a piezoelectric film, an SRO film 35b, and a Pt film 34b are laminated in this order to form a piezoelectric actuator. The piezoelectric actuator further includes an insulating film 37 extending over the Pt film 34a and the SRO film 35a as electrode films, the PZT film 36 as a piezoelectric film, and the Pt film 34b and the SRO film 35b as electrode films. The insulating film 37 includes a dielectric material used for electrical insulation, and this dielectric material may be a known dielectric material, such as a SiO2 layer, a SiN layer, or an Al2O3 layer. The thickness of the insulating layer containing the insulating film as a constituent material is not particularly limited, but is preferably between about 10 nm and about 10 μm.

[0081] The conductive paths 39 are provided on the insulating layer (insulating film) 37 and are in contact with the Pt film 34a and the SRO film 35a as electrodes, and the Pt film 34b and the SRO film 35b as electrodes, respectively, allowing selective access during use. The conductive paths may be made of a known conductive material, and a suitable example of such a conductive material is aluminum (Al).

[0082] The passivation layer 42 is provided on the insulating film 37, the Pt film 34b and the SRO film 35b serving as electrodes, and the conductive path 39. The passivation layer 42 may be made of any dielectric material used for passivating the piezoelectric actuator, and the dielectric material is not particularly limited and may be any known dielectric material. Suitable examples of the dielectric material include SiN and SiON (silicon oxynitrate). The thickness of the passivation layer is not particularly limited, but is preferably between about 0.1 μm and about 3 μm. A conductive pad 38 is also provided along the piezoelectric actuator and is electrically connected to the conductive path 39. The passivation layer 42 functions as a barrier layer to protect the piezoelectric element from humidity and the like. [Explanation of symbols]

[0083] 1a~1d Metal source 2a~2j Earth 3, 3a~3f ICP electrode 4a~4d Cut Filter 5a~5d DC power supply 6a~6d RF power supply 7a~7b Lamps 8 Ar source 9. Reactive Gas Source 10 Power supply 11 PCB holder 12 PCB 13, 13a ICP ring 14, 14a cut filter 15 Vacuum chamber 16 Rotation Axis 17 Raw material supply department 18 Gas supply section 19 Plasma generating unit 20 Ion acceleration section 21, 31 Si substrate 22, 32 HfZrN film 23 SUS membrane 24a~24c, 34a, 34b Pt film 25a~25d, 35a, 35b SRO membrane 26a, 26b, 36 PZT membrane 28A, 28B Cantilever beam 29 Gap 30 cavities 33 SUS membrane 37 Insulating film 38 Conductive Pad 39 Conductive Path 40 Flow path 41 Chamber 42 Passivation Layer 211 Target Holder 220 Target 221 Substrate support 221a Tapered section 227 Heater CR1~CR4 crucible CP control section RG1 area

Claims

1. A film forming apparatus for forming a film on a surface of a substrate by supplying a raw material to the surface of the substrate, a chamber that can be evacuated; a substrate holder that holds a substrate within the chamber; a raw material supply unit that is disposed in the chamber at a distance from the substrate holding unit in a first direction and that supplies a raw material to a surface of the substrate held by the substrate holding unit in the chamber; a gas supply unit that supplies a gas into the chamber; a plasma generating unit provided between the substrate holding unit and the raw material supply unit, the plasma generating unit generating an inductively coupled plasma of the gas supplied by the gas supply unit; and The plasma generating unit is a first electrode disposed on a first side in a second direction intersecting with the first direction relative to the raw material supply unit when viewed from the first direction; a second electrode disposed on a side opposite to the first side in the second direction with respect to the raw material supply unit when viewed from the first direction; Including, A film forming apparatus, wherein the first electrode and the second electrode are arranged so that a first distance between the substrate holding part and the first electrode in the first direction is greater than a second distance between the substrate holding part and the second electrode in the first direction.

2. The raw material supply unit a first crucible that is disposed on the first side in the second direction relative to a center of the raw material supply unit when viewed from the first direction, and is filled with a first evaporation material; a second crucible that is disposed on a side opposite to the first side in the second direction with respect to a center of the raw material supply unit when viewed from the first direction, and is filled with a second evaporation material; Including, the raw material supply unit evaporates the first evaporation material or the second evaporation material, and supplies the raw material made of the evaporated first evaporation material or the second evaporation material to a surface of a substrate held by the substrate holding unit; the first electrode is disposed on the first side in the second direction relative to the first crucible when viewed from the first direction, The film forming apparatus according to claim 1 , wherein the second electrode is disposed on a side opposite to the first side in the second direction relative to the second crucible when viewed from the first direction.

3. When viewed from the first direction, a central portion of each of the first crucible and the second crucible is disposed on a second side in a third direction intersecting both the first direction and the second direction relative to a central portion of the raw material supply unit, the raw material supply unit includes a third crucible filled with a third evaporation material, When viewed from the first direction, a central portion of the third crucible is disposed on a side opposite to the second side in the third direction with respect to a central portion of the raw material supply part, the plasma generation unit includes a third electrode that is disposed on a side opposite to the second side in the third direction with respect to the raw material supply unit when viewed from the first direction, the first electrode is disposed on the first side in the second direction relative to the third electrode when viewed from the third direction; the second electrode is disposed on a side opposite to the first side in the second direction relative to the third electrode when viewed from the third direction, 3. The film formation apparatus of claim 2, wherein the first electrode, the second electrode, and the third electrode are arranged such that the first distance between the substrate holding part and the first electrode in the first direction is greater than the third distance between the substrate holding part and the third electrode in the first direction, and the third distance between the substrate holding part and the third electrode in the first direction is greater than the second distance between the substrate holding part and the second electrode in the first direction.

4. The film forming apparatus of any one of claims 1 to 3, wherein each of the first electrode and the second electrode has a concave curved shape or a parabolic shape curved along the outer periphery of the substrate held by the substrate holding portion when viewed from the first direction.

5. the plasma generation unit includes a fourth electrode that is provided between the substrate holder and the first and second electrodes, and that generates inductively coupled plasma of the gas supplied by the gas supply unit by applying a high-frequency voltage to the fourth electrode; the fourth electrode has a ring shape when viewed from the first direction, and is disposed so as to surround the substrate held by the substrate holder; The fourth electrode is a first portion disposed on the first side in the second direction relative to a central portion of the fourth electrode when viewed from the first direction; a second portion disposed on a side opposite to the first side in the second direction relative to a central portion of the fourth electrode when viewed from the first direction; Including, The film forming apparatus of any one of claims 1 to 3, wherein the fourth electrode is positioned so that a third distance between the substrate holding portion and the first portion in the first direction is greater than a fourth distance between the substrate holding portion and the second portion in the first direction.

6. 4. The film forming apparatus according to claim 1, wherein the inductively coupled plasma is generated by applying a DC and / or AC excitation current to each of the first electrode and the second electrode through an RF cut filter.

7. A film forming apparatus for forming a film on a surface of a substrate by supplying a raw material to the surface of the substrate, a chamber that can be evacuated; a substrate holder that holds a substrate within the chamber; a raw material supply unit that is disposed in the chamber at a distance from the substrate holding unit in a first direction and that supplies a raw material to a surface of the substrate held by the substrate holding unit in the chamber; a gas supply unit that supplies a gas into the chamber; a plasma generating unit provided between the substrate holding unit and the raw material supply unit, the plasma generating unit generating an inductively coupled plasma of the gas supplied by the gas supply unit; and the plasma generating unit is provided between the substrate holding unit and the raw material supply unit, and includes a first electrode that generates inductively coupled plasma of the gas supplied by the gas supply unit by applying a high-frequency voltage thereto; the first electrode has a ring shape when viewed from the first direction, and is disposed so as to surround the substrate held by the substrate holder; The first electrode is a first portion disposed on a first side in a second direction intersecting with the first direction relative to a center portion of the first electrode when viewed from the first direction; a second portion disposed on a side opposite to the first side in the second direction relative to a central portion of the first electrode when viewed from the first direction; Including, A film forming apparatus, wherein the first electrode is positioned so that a first distance between the substrate holding portion and the first portion in the first direction is greater than a second distance between the substrate holding portion and the second portion in the first direction.

8. 8. The film forming apparatus according to claim 1, further comprising an ion acceleration unit provided between the substrate holding unit and the raw material supply unit, for accelerating the inductively coupled plasma generated by the plasma generation unit.

9. 9. The film deposition apparatus according to claim 8, wherein a fourth direction in which the ion acceleration unit accelerates the inductively coupled plasma is inclined with respect to the first direction.

10. a substrate heating unit that heats the substrate; a control unit for controlling the operation of the substrate heating unit; and The film forming apparatus of any one of claims 1 to 3 or claim 7, wherein the control unit controls the operation of the substrate heating unit so as to alternately turn the substrate heating unit on and off when forming a film on the surface of the substrate held by the substrate holding unit.

11. A method for forming a thin film by using a film formation apparatus, wherein the film formation apparatus is the film formation apparatus according to any one of claims 1 to 3 or claim 7.

12. A method for producing an element including a thin film, the method comprising forming the thin film by the method for forming a thin film according to claim 11.

Images