Magnetron sputtering apparatus and substrate processing method

Abstract

This invention provides a magnetron sputtering apparatus and a substrate processing method that can suppress the generation of film defects and foreign matter with a simple mechanism when generating plasma for CVD using a magnetron sputtering apparatus. [Solution] The magnetron sputtering apparatus comprises a vacuum chamber 2 into which a material gas is introduced, a substrate holding section 3 for holding a substrate B, a base unit 4, a power supply connected to the base unit 4, and a CVD processing attachment 7. The base unit 4 has a magnetic circuit 42 for generating a magnetic field. The CVD processing attachment 7 has a plate-shaped member 70 attached to the base unit 4, an electrode 71 provided on the plate-shaped member 70, a case section 72 that houses the plate-shaped member 70 and the electrode 71 in an internal space into which a reaction gas is introduced, and a cover section 73 attached to the open end of the case section 72, covering the opening of the case section 72 and separating the space inside the vacuum chamber 2 from the internal space inside the case section 72.

Description

Technical Field

[0001] The present invention relates to a magnetron sputtering apparatus and a substrate processing method, and particularly to a magnetron sputtering apparatus for sputtering a target to form a film on a substrate, and a substrate processing method using a CVD processing attachment for generating CVD processing plasma to perform CVD processing.

Background Art

[0002] In recent years, in order to achieve carbon neutrality, interest in semiconductors has been increasing as a means of energy saving in digital devices. Support and subsidies for semiconductor manufacturing are also becoming active as national policies. With these circumstances, the number of companies and organizations trying to newly enter the semiconductor business is increasing. Also, educational institutions are showing increasing interest in curricula and practical training related to semiconductor fabrication.

[0003] When newly introducing a sputtering apparatus to enter the semiconductor business, there are cases where it is difficult to secure a sufficient area for the sputtering apparatus and its peripheral equipment. Also, the introduction of a sputtering apparatus requires various infrastructure facilities. Generally, when trying to form a SiO2 film as an insulating film using RF magnetron sputtering, the film formation rate is very slow, and there is a risk of reduced productivity. Therefore, in order to increase productivity, it was necessary to increase the number of cathodes or increase the input power. Also, although it was conceivable to separately introduce a plasma CVD apparatus, which is said to have a relatively high film formation rate, there was a risk of requiring a high equipment introduction cost.

[0004] For example, Patent Document 1 discloses a film forming apparatus that performs film formation by sputtering and film formation by plasma CVD (chemical vapor deposition) on a substrate within one chamber. In this film forming apparatus, the electrode serving as a target for sputtering is shared as a discharge electrode for plasma CVD, reducing the scale of the film forming apparatus. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 3773320 [Overview of the project] [Problems that the invention aims to solve]

[0006] As described in Patent Document 1, when a target serving as a sputtering cathode is used as a discharge electrode, and a plasma is generated by introducing a material gas (i.e., precursor) and a reaction gas for CVD processing into a chamber, a simple plasma CVD film deposition is possible. However, in this method, reaction products of the precursor accumulate on the surface of the target used as the discharge electrode, and the deposits may peel off, potentially generating fine particles. Such fine peeled fragments can adhere to the substrate and cause defects or foreign matter in the film, which may limit the use of plasma CVD processing with a target as a discharge electrode to only a few applications.

[0007] The present invention has been made in view of the above problems, and the object of the present invention is to provide a magnetron sputtering apparatus and a substrate processing method that can suppress the generation of film defects and foreign matter with a simple mechanism when generating plasma for CVD in a magnetron sputtering apparatus. [Means for solving the problem]

[0008] The aforementioned problem is solved by the magnetron sputtering apparatus of the present invention, which is a magnetron sputtering apparatus for sputtering a target and depositing a film on a substrate, comprising: a vacuum chamber; a substrate holding part provided in the vacuum chamber and holding the substrate; a base unit provided in the vacuum chamber and positioned opposite the substrate holding part at a distance from it; a power supply connected to the base unit; and a CVD processing attachment detachably attached to the base unit for generating CVD processing plasma and performing CVD processing, wherein a material gas is introduced into the space within the vacuum chamber, and the base unit generates a magnetic field The CVD processing attachment has a magnetic circuit for generating a magnetic field, and the CVD processing attachment is made of a magnetic material and is positioned opposite the magnetic circuit and attached to the base unit from which the target has been removed. The attachment has an electrode provided on the surface of the plate-shaped member opposite to the surface facing the magnetic circuit. The attachment has a case portion that is detachably attached to the base unit and houses the plate-shaped member and the electrode in an internal space into which a reaction gas is introduced. The attachment has a cover portion that is attached to the opening end of the case portion, covers the opening of the case portion, and separates the space in the vacuum chamber from the internal space of the case portion.

[0009] In this way, by supplying the reaction gas to the inside of the cover and the material gas to the vacuum chamber, a pressure difference is created in the internal space of the CVD processing attachment, allowing for film deposition by plasma CVD without contaminating the discharge electrode with reaction products. Furthermore, since the power supply, gas, cooling water, and power supply control system, which are expensive and require space, can be shared between the plasma generation mechanism for CVD processing and the plasma generation mechanism for sputtering, plasma for CVD processing can be generated easily and at low cost. Therefore, when generating plasma for CVD using a magnetron sputtering apparatus, the generation of film defects and foreign matter can be suppressed with a simple mechanism.

[0010] In this case, the electrode may have a hollow cathode. With the above configuration, by generating plasma in a narrow cylindrical (hollow) cathode, a higher density plasma can be generated inside the hollow cathode compared to glow discharge using a parallel plate cathode. Furthermore, having multiple hollow cathodes allows for distribution of the load on the electrodes.

[0011] In this case, it is preferable to place a magnet inside the hollow cathode. According to the above configuration, by providing a magnet, the plasma discharge can be sustained and stabilized over a wide pressure range.

[0012] In this case, the CVD processing attachment has a reaction gas inlet for introducing the reaction gas into the internal space of the case portion, and the reaction gas inlet is preferably formed in the case portion. With the above configuration, since an inlet is formed in the case, the reaction gas can be directly introduced into the CVD treatment attachment, making it possible to increase the pressure in the internal space of the case with a simple configuration.

[0013] In this case, the power supply is preferably a high-frequency power supply, and the reaction gas is preferably oxygen gas. According to the above configuration, by using oxygen gas as the reaction gas introduced when using a high-frequency power supply, sputtering of the electrodes can be suppressed.

[0014] In this case, the power supply is an AC power supply or a bipolar pulse power supply, and the CVD processing attachment has a plurality of electrodes, and a voltage is applied to the plurality of electrodes by the power supply. With the above configuration, by using an AC power supply or a bipolar pulse power supply as the power source, it is possible to easily supply a large amount of power compared to an RF power supply.

[0015] The aforementioned problem is solved by the substrate processing method of the present invention, which uses a CVD processing attachment that is detachably attached to the base unit of a magnetron sputtering apparatus for sputtering a target to form a film on a substrate, and generates a CVD processing plasma to perform CVD processing, comprising: an attachment attachment step of attaching the CVD processing attachment to the base unit from which the target has been removed; a gas introduction step of introducing a reaction gas into the interior of the CVD processing attachment; and a CVD film formation step of generating a CVD processing plasma using the base unit to which the CVD processing attachment is attached to perform CVD processing, wherein in the attachment attachment step, a plate-shaped magnetic material is used. The problem is solved by arranging the member opposite to the magnetic circuit of the base unit that generates a magnetic field, arranging the electrode on the surface of the plate-shaped member opposite to the surface facing the magnetic circuit, attaching a case to the base unit so as to house the plate-shaped member and the electrode in an internal space, attaching a cover to the open end of the case to cover the opening of the case and partition the space inside the vacuum chamber from the internal space of the case, introducing a material gas into the vacuum chamber and introducing the reaction gas into the internal space of the case in the gas introduction step, and supplying power from a power supply connected to the base unit to generate plasma for CVD processing using the electrode in the CVD film formation step.

[0016] In this way, by supplying the reaction gas to the inside of the cover and the material gas to the vacuum chamber, a pressure difference is created in the internal space of the CVD processing attachment, allowing for film deposition by plasma CVD without contaminating the discharge electrode with reaction products. Furthermore, since the power supply, gas, cooling water, and power supply control system, which are expensive and require space, can be shared between the plasma generation mechanism for CVD processing and the plasma generation mechanism for sputtering, plasma for CVD processing can be generated easily and at low cost. Therefore, when generating plasma for CVD using a magnetron sputtering apparatus, the generation of film defects and foreign matter can be suppressed with a simple mechanism.

Advantages of the Invention

[0017] According to the magnetron sputtering apparatus and the substrate processing method of the present invention, when generating plasma for CVD in the magnetron sputtering apparatus, generation of film defects and foreign matters can be suppressed with a simple mechanism.

Brief Description of the Drawings

[0018] [Figure 1] It is a schematic diagram of a magnetron sputtering apparatus in a sputtering form. [Figure 2] It is a schematic diagram of a magnetron sputtering apparatus in a CVD form. [Figure 3] It is a cross-sectional view taken along line III-III of FIG. 2. [Figure 4] It is a perspective view of the first unit. [Figure 5] It is a perspective view of the second unit. [Figure 6] It is a diagram showing a state where a target is removed from a base unit and an attachment for CVD processing is attached. [Figure 7] It is a cross-sectional view taken along line VII-VII of FIG. 5. [Figure 8] It is a process diagram of the substrate processing method. [Figure 9] It is a schematic diagram of a magnetron sputtering apparatus in a CVD form in the second embodiment. [Figure 10] It is a perspective view of the first unit of the second embodiment. [Figure 11] It is a perspective view of the second unit of the second embodiment. [Figure 12] It is a diagram showing a state where a target is removed from a base unit of the second embodiment and an attachment for CVD processing is attached. [Figure 13] It is the foreign matter evaluation result of the substrate surface in Example 2. [Figure 14] It is the foreign matter evaluation result of the substrate surface in the comparative example. [Figure 15] It is a diagram showing the relationship between the oxygen introduction amount and the film formation rate. [Figure 16] This diagram shows the relationship between oxygen intake and hardness. [Modes for carrying out the invention]

[0019] <First Embodiment> Hereinafter, a magnetron sputtering apparatus and substrate processing method according to one embodiment of the present invention (hereinafter referred to as "this embodiment") will be described with reference to Figures 1 to 8.

[0020] <Magnetron sputtering apparatus> The magnetron sputtering apparatus 1 of this embodiment is an apparatus that sputters a target T and deposits a film on a substrate B. The magnetron sputtering apparatus 1 generates a high-density sputtering plasma by forming a magnetic field using magnetic force, and improves sputtering efficiency by making it easier for ions in the gas to collide with the surface of the target T. The magnetron sputtering apparatus 1 is configured to be switchable between a sputtering mode (Figure 1) in which sputtering plasma is generated during film deposition on substrate B and film deposition is performed, and a CVD mode (Figure 2) in which CVD plasma is generated during film deposition on substrate B and CVD is performed.

[0021] As shown in Figure 1, the magnetron sputtering apparatus 1 comprises a vacuum chamber 2, a substrate holding section 3 for holding a substrate B, a base unit 4 positioned opposite and spaced apart from the substrate holding section 3, a power supply 5 connected to the base unit 4, and a sputtering attachment 6 for generating sputtering plasma and performing film deposition on the substrate B. Furthermore, as shown in Figures 2 and 3, the magnetron sputtering apparatus 1 also comprises a CVD processing attachment 7 for generating CVD plasma and performing CVD processing on the substrate B.

[0022] Here, substrate B is the object to be coated with a film, which is attached to the substrate holder 3, and can be made of materials such as stainless steel, glass, or resin. The shape of substrate B may be a plate, a sheet, a three-dimensional shape (3D shape), or a long film.

[0023] The magnetron sputtering apparatus 1 is configured to be switchable between a first unit SU in the sputtering configuration shown in Figure 4 and a second unit CU in the CVD configuration shown in Figure 5. In other words, as shown in Figure 6, the first unit SU consists of a base unit 4 and a sputtering attachment 6, and the second unit CU consists of a base unit 4 and a CVD processing attachment 7.

[0024] As shown in Figure 1, the sputtering magnetron sputtering apparatus 1 has a sputtering attachment 6 mounted on a base unit 4. When gas is introduced into the vacuum chamber 2 and power is supplied from the power supply 5, sputtering plasma is generated to sputter the target T and deposit a film on the substrate B. As shown in Figure 2, the CVD-type magnetron sputtering apparatus 1 has a CVD processing attachment 7 mounted on a base unit 4. When a material gas is introduced into the vacuum chamber 2, a reaction gas is introduced into the CVD processing attachment 7, and power is supplied from the power supply 5, a CVD plasma is generated, allowing the substrate B to undergo CVD processing.

[0025] CVD (Chemical Vapor Deposition) is a method of depositing a thin film onto the surface of substrate B by introducing a thin-film source gas into a vacuum chamber 2 to generate plasma. CVD can create oxide films and nitride films on substrate B. Furthermore, a hybrid film deposition process combining CVD treatment and sputtering may be performed as a surface treatment for substrate B. In the hybrid film deposition process, an oxide film or nitride film is generated on the surface of substrate B by CVD treatment, and then a further film is deposited on the surface of the oxide film or nitride film by sputtering.

[0026] In addition to CVD, other film deposition processes such as ALD may be performed. Furthermore, in addition to film deposition processes, surface modification processes such as cleaning, hydrophilization, oxidation, organic matter removal, etching, ashing, and desmearing may be performed.

[0027] Specifically, one surface treatment for substrate B is bombardment, which involves cleaning the substrate B by ionizing argon gas. Bombardment is a process that uses argon gas to generate plasma, cleaning the surface of substrate B and imparting functional groups to the surface. Bombardment can improve the wettability and adhesion of the substrate B surface. Another surface treatment for substrate B is organic plasma ashing (ashing treatment), which involves ashing using plasma-activated oxygen gas. Organic plasma ashing is a process that removes organic matter as a gas by reacting plasma-activated oxygen with organic matter. Another surface treatment for substrate B involves creating a glassy carbon film and then etching the surface of the glassy carbon film with plasma-generated oxygen gas. Thus, the magnetron sputtering apparatus 1 can also perform surface modification treatment and further film deposition treatment after film deposition on substrate B.

[0028] In this invention, by changing the attachments mounted on the base unit 4, the equipment and facilities necessary for each process can be shared. Therefore, multiple surface treatments, such as surface modification and film formation, can be performed easily and at low cost.

[0029] <Vacuum Chamber> As shown in Figures 1 to 3, the vacuum chamber 2 is a hollow rectangular parallelepiped container whose interior can be depressurized by a vacuum pump. The vacuum chamber 2 houses the substrate holder 3, the base unit 4, and the like. The vacuum chamber 2 is made of a metal with high corrosion resistance and heat resistance, such as stainless steel. Note that the shape of the vacuum chamber 2 is not limited to this; it may also be cylindrical.

[0030] A substrate holder 3 is positioned in the center of the vacuum chamber 2, and a base unit 4 is positioned on the side. The sides of the vacuum chamber 2 are also provided with a vacuum exhaust port 20 for connecting to a vacuum pump, an Ar gas inlet 21 for introducing argon gas into the vacuum chamber 2, a reaction gas inlet 22 for introducing reaction gas into the vacuum chamber 2, and a material gas inlet 23 for introducing material gas into the vacuum chamber 2. Note that the relative positions of these components are not limited to these and can be set as appropriate. In the sputtering configuration shown in Figure 1, argon gas is introduced into the space inside the vacuum chamber 2 from the Ar gas inlet 21, and the reaction gas is introduced into the space inside the vacuum chamber 2 from the reaction gas inlet 22. In the CVD configuration shown in Figure 2, the material gas is introduced into the space inside the vacuum chamber 2 from the material gas inlet 23, and the reaction gas is introduced into the interior of the CVD processing attachment 7 from the reaction gas inlet 22.

[0031] A pressure control controller is provided at the vacuum exhaust port 20, and the pressure inside the vacuum chamber 2 is automatically controlled. The Ar gas inlet 21 introduces argon gas for sputtering into the vacuum chamber 2. The type of sputtering gas introduced through the Ar gas inlet 21 is not limited to argon; other types of gas may also be used. The Ar gas supply source G1, which supplies the argon gas, is equipped with an on / off valve V1 and a flow rate control controller (not shown), and the type and flow rate of the sputtering gas are appropriately selected according to the surface treatment of the substrate B.

[0032] The reaction gas inlet 22 introduces the reaction gas into the vacuum chamber 2 or the CVD processing attachment 7. The reaction gas introduced from the reaction gas inlet 22 is, for example, oxygen gas. The gas supply source G2 for the reaction gas is equipped with an on / off valve V2 and a flow control controller (not shown), and the type and flow rate of the reaction gas are appropriately selected according to the surface treatment of the substrate B.

[0033] The material gas inlet 23 introduces the material gas into the vacuum chamber 2. A material gas supply system G3 is located outside the vacuum chamber 2. The material gas supply system G3 comprises a liquid raw material tank G3a and a vaporizer G3b that vaporizes the raw material in the liquid raw material tank G3a. The vaporizer G3b vaporizes the raw material in the liquid raw material tank G3a and supplies it to the vacuum chamber 2 as material gas. The vaporizer G3b is equipped with an on / off valve V3 and a flow control controller (not shown), and the type and flow rate of the material gas are appropriately selected according to the CVD treatment of the substrate B.

[0034] Furthermore, using argon gas as the sputtering gas allows for efficient sputtering. However, the sputtering gas is not limited to argon; nitrogen gas, oxygen gas, carbon dioxide gas, hydrogen gas, water vapor, methane gas, or mixtures thereof may also be used. Furthermore, using oxygen gas as the gas for CVD processing can suppress sputtering of the cathode when a high-frequency power supply is used. However, the gas for CVD processing is not limited to oxygen gas; argon gas, nitrogen gas, or a mixed gas may also be used.

[0035] <Substrate holding part> As shown in Figures 1 to 3, the substrate holder 3 is provided inside the vacuum chamber 2 and holds the substrate B. Specifically, the substrate holder 3 has, for example, a drum shape and is provided in the center of the vacuum chamber 2 and rotates horizontally. Multiple substrates B can be attached to the substrate holder 3. As the substrate holder 3 rotates, multiple substrates B are uniformly surface-treated. The configuration of the substrate holder 3 is not limited to this; it may have a dome shape that opens downwards, be installed on the ceiling of the vacuum chamber 2, and rotate and move up and down. Furthermore, the substrate holder 3 may be used to attach a single substrate B, and may not rotate or move up and down.

[0036] <Base Unit> As shown in Figures 1 to 3, the base unit 4 has a rectangular shape and is installed inside the vacuum chamber 2. The base unit 4 is positioned opposite the substrate holder 3 at a distance from it and is connected to the power supply 5. More specifically, the base unit 4 is installed on the side of the vacuum chamber 2 and is positioned opposite the substrate holder 3, which is located in the center of the vacuum chamber 2, at a predetermined distance from it. Figure 3 is a cross-sectional view taken along line III-III in Figure 2, and is a schematic diagram of the magnetron sputtering apparatus 1 as seen from above. Figure 3 shows the base unit 4 with the CVD processing attachment 7 attached. The number of base units 4 may be one or two or more.

[0037] As shown in Figure 3, the base unit 4 includes an anode base 40 provided on the side of the vacuum chamber 2, a cathode base 41 housed in the anode base 40, a magnetic circuit 42 for generating a magnetic field, and a cooling passage 43 for cooling the magnetic circuit 42 and the backing plate.

[0038] The anode base 40 has a rectangular shape and houses the cathode base 41 and magnetic circuit 42 inside. In the sputtering configuration, as shown in Figure 4, the target shield Ts is attached to the outer surface of the anode base 40. In the CVD processing configuration, as shown in Figure 5, the case portion 72, which will be described later, is attached to the outer surface of the anode base 40. Furthermore, the cathode base 41 is attached to the back side of the anode base 40 via an insulating insulator 75, as shown in Figure 3.

[0039] As shown in Figures 6 and 7, the cathode base 41 has a rectangular shape and is provided with a housing portion 41a for housing the magnetic circuit 42. A power supply 5 is connected to the cathode base 41, and a voltage is applied to the cathode of the sputtering attachment 6 (sputtering backing plate P, described later) or the cathode of the CVD processing attachment 7 (electrode 71, described later).

[0040] In the sputtering method, with the target T attached to the cathode base 41, a voltage is applied to the cathode base 41, causing the sputtering gas to be ionized. When the ions collide with the target T, particles from the target T are ejected and adhere to the surface of the substrate B, thus forming a film on the substrate B. In the CVD process, with the plate-shaped member 70 and electrode 71 attached to the cathode base 41, a voltage is applied to the cathode base 41, causing the reaction gas to be ionized and a film to be formed on the substrate B.

[0041] The magnetic circuit 42 is constructed by providing permanent magnets on a yoke. The yoke of the magnetic circuit 42 is a rectangular member made of magnetic stainless steel such as SUS430 or SUS410. The permanent magnet consists of a rectangular central magnet placed in the center of the yoke and rectangular annular outer magnets arranged around the central magnet. The shapes of the yoke, central magnet, and outer magnets may be circular. In a sputtering configuration where the sputtering attachment 6 is attached to the base unit 4, the magnetic circuit 42 generates a magnetic field on the surface of the target T. By generating a magnetic field on the surface of the target T using the magnetic circuit 42, the sputtering efficiency can be improved.

[0042] The cooling passage 43 is a flow path through which cooling water passes, and it cools the magnetic circuit 42 and the backing plate. The cooling water passing through the cooling passage 43 cools the permanent magnets of the magnetic circuit 42, the sputtering backing plate P and target T, and the CVD processing backing plate 74 and electrode 71. The cooling passage 43 has multiple cooling pipes 43a. Since the plate-shaped member 70 and the electrode 71 can be cooled by the cold water flowing from the cooling pipes 43a, the cooling efficiency of the plate-shaped member 70 and the electrode 71 can be improved.

[0043] <Power supply> Power supply 5 is a high-frequency (RF) power supply and is connected to base unit 4. By applying a voltage to target T using power supply 5, the sputtering gas can be converted into plasma. Also, by applying a voltage to electrode 71 using power supply 5, the reaction gas for CVD processing can be converted into plasma. Power supply 5 outputs high-frequency power. High-frequency power is power at frequencies such as 13.56MHz and 27.12MHz, and can output, for example, 30W to 5000W.

[0044] Power supply 5 is shared by the first unit SU, which uses a sputtering method, and the second unit CU, which uses a CVD (Chemical Vapor Deposition) method. By sharing power supply 5, CVD processing can be performed without installing a new power supply unit for CVD processing. Furthermore, by using a high-frequency power supply 5, sputtering of the cathode can be suppressed. Note that power supply 5 is not limited to a high-frequency power supply, but may also be a DC cathode power supply.

[0045] <Sputtering attachment> As shown in Figures 1 and 3, the sputtering attachment 6 is detachably attached to the base unit 4 and generates sputtering plasma during film deposition on the substrate B to perform the film deposition process. The sputtering attachment 6 includes a rectangular target T, a sputtering backing plate P for cooling the target T, and rectangular target shields Ts.

[0046] As shown in Figures 1, 4, and 6, the target T is a rectangular plate member. For example, the material of the target T can be an inorganic substance such as metals, oxides, carbides, and sulfides, or a composite inorganic compound thereof, or an organic compound such as fluororesin, or a composite compound of inorganic and organic substances, and can be appropriately selected according to the application of film formation. The rectangular target T is generally about 500mm x 500mm to 1500mm x 1500mm in size and 5mm to 20mm in thickness. The target T may also be a circular plate-like member.

[0047] The target T is mounted to the cathode base 41 via a sputtering backing plate P. The target shield Ts have a rectangular shape and are attached to the surface of the base unit 4 (more specifically, the anode base 40) so as to surround the target T. The target shield Ts are made of, for example, stainless steel, titanium, molybdenum, etc. By providing target shields Ts, it is possible to suppress the exposure of components other than the target T (for example, the mounting portion of the sputtering backing plate P) to the plasma and prevent sputtering. More specifically, it is possible to prevent plasma irradiation of parts other than the sputtering backing plate P and target T, thereby suppressing the wrapping (i.e., adhesion) of sputtered material. Furthermore, the target shields Ts can be used as the anode.

[0048] The sputtering backing plate P is a cooling plate used to suppress the temperature rise of the target T, and is a metal plate made of a material such as copper, molybdenum, or aluminum. The sputtering backing plate P is positioned in contact with the cooling passage 43 and is cooled by cooling water. By cooling the sputtering backing plate P, it is possible to suppress the target T from becoming too hot due to the plasma generated in the vacuum chamber 2. Furthermore, the sputtering backing plate P becomes the cathode of the first unit SU in the sputtering configuration.

[0049] The sputtering backing plate P is soldered to the back of the target T. The target T and the sputtering backing plate P may be integrated or constructed as separate components. As shown in Fig. 6, the sputtering backing plate P is arranged to face the outer surface of the cooling channel 43 (i.e., arranged on the surface side of the magnetic circuit 42) and is attached to the surface side of the cathode base 41. Mounting holes (not shown) are formed at the peripheral edge of the sputtering backing plate P, and the sputtering backing plate P is fixed to the mounting hole 41b of the cathode base 41 with screws through the mounting holes.

[0050] <CVD Processing Attachment> As shown in Figs. 5 to 7, the CVD processing attachment 7 is detachably attached to the base unit 4 and generates CVD plasma to perform CVD processing on the substrate B. The CVD processing attachment 7 includes a plate-like member 70 arranged to face the magnetic circuit 42, an electrode 71 provided on a surface of the plate-like member 70 opposite to the surface facing the magnetic circuit 42, a rectangular tube-shaped case portion 72 that houses the plate-like member 70 and the electrode 71 inside, a cover portion 73 attached to the open end portion 72a of the case portion 72, a CVD backing plate 74 for cooling the plate-like member 70, an insulator 75 arranged between the anode base 40 and the cathode base 41, a magnet 76 arranged inside the electrode 71, and an inlet 77 for introducing a reaction gas inside the case portion 72 and the cover portion 73. As shown in Fig. 3, the inlet � is formed in the case portion 72.

[0051] As shown in Fig. 7, the plate-like member 70 is made of a magnetic material, is arranged to face the magnetic circuit 42, and is attached to the base unit 4 from which the target T has been removed. Specifically, the plate-like member 70 is a shunt plate and is formed of a material such as iron, nickel, cobalt, etc. Since the plate-like member 70 can block the vertical magnetic field generated by the magnetic circuit 42, even when the CVD processing attachment 7 is attached to the base unit 4, the CVD processing of the substrate B can be performed without being affected by the magnetic field. Also, by blocking the magnetic force generated from the magnetic circuit 42 with the plate-like member 70, sputtering of the electrode 71 formed on the plate-like member 70 can be suppressed.

[0052] The back surface 70a of the plate-shaped member 70 (the surface facing the magnetic circuit 42) is positioned opposite the magnetic circuit 42. More specifically, as shown in Figure 7, a CVD processing backing plate 74 is provided on the side of the magnetic circuit 42, and the plate-shaped member 70 is provided on the surface side of the CVD processing backing plate 74. A mounting portion 70c for attaching the electrode 71 is formed on the surface 70b of the plate-shaped member 70 (the surface opposite to the back surface 70a) at a position corresponding to the electrode 71. The mounting portion 70c is formed in a convex shape toward the side (i.e., toward the substrate B side). By fitting the base end of the cylindrical electrode 71 into the mounting portion 70c, the electrode 71 can be firmly attached to the plate-shaped member 70. The mounting portion 70c may also be a groove into which the base end of the electrode 71 can be inserted.

[0053] The electrode 71 has multiple hollow cathodes 71a. More specifically, the base end of each hollow cathode 71a is fitted into each mounting portion 70c of the plate-shaped member 70, thereby attaching the multiple hollow cathodes 71a to the surface 70b of the plate-shaped member 70. Electrode 71 (hollow cathode 71a) becomes the cathode of the second unit CU in the CVD processing configuration.

[0054] The hollow cathode 71a is a thin, cylindrical (hollow) type cathode. Preferably, the hollow cathode 71a has a diameter of φ20mm to φ40mm and a length of 10mm to 80mm (aspect ratio 1:0.5 to 1:2). However, the above range is not limited to any size within which hollow discharge occurs. Generally, hollow discharge occurs when the product of the gas pressure and the aperture size is within a predetermined range.

[0055] By generating plasma for CVD processing using the hollow cathode 71a as the cathode, a higher density plasma can be generated inside the hollow cathode 71a compared to glow discharge using parallel plate electrodes. Furthermore, having multiple hollow cathodes 71a allows for distribution of the load on electrode 71. The diameter and length of each hollow cathode 71a may be the same or different. In this embodiment, a total of nine hollow cathodes 71a are provided in a single row in the vertical direction at the center of the plate-shaped member 70, but the number and arrangement of the hollow cathodes 71a are not limited to this. Furthermore, the shape of the hollow cathode is not limited to a cylindrical shape, but may be partition-like or rectangular tube-like with intervals and lengths that allow hollow discharge to occur.

[0056] The case portion 72 is detachably attached to the anode base 40 of the base unit 4 and houses the plate-shaped member 70 and the electrode 71 inside. An inlet 77 for introducing reaction gas is provided on the side of the case portion 72. The case portion 72 is a hollow container with a rectangular tube shape and an opening. An open end 72a is formed on the substrate B side of the case portion 72. A flange 72b that bends outward is formed on the base unit 4 side of the case portion 72. A case mounting hole 72c is formed in the flange 72b, and the case portion 72 is fixed to the anode base 40 with screws via the case mounting hole 72c. Note that the case portion 72 is not limited to a rectangular tube shape, but may also be cylindrical.

[0057] The case mounting holes 72c are through holes formed in the flange 72b. The case mounting holes 72c may also be formed as elongated holes. Even in devices with different mounting hole positions, the case portion 72 can be suitably attached to the anode base 40.

[0058] The cover portion 73 is a rectangular plate member that serves as the anode for the electrode 71. By using the cover portion 73 as the anode for the electrode 71, the anode is positioned closer to the plasma generation electrode compared to the case where the inner wall of the vacuum chamber 2 is used as the anode, thus enabling the generation of a high-density plasma. The cover portion 73 is attached to the open end 72a of the case portion 72 and covers the opening of the case portion 72. In other words, as shown in Figure 3, the cover portion 73 is a component that separates the space inside the vacuum chamber 2 from the internal space of the case portion 72.

[0059] The cover portion 73 has through holes 73a formed therein, which allow the plasma generated by the electrode 71 to pass through. As shown in Figures 5 and 7, the through holes 73a are elongated holes extending in the vertical direction and are formed at positions corresponding to the electrode 71. By making the through-hole 73a an elongated hole, the plasma can be narrowed. By narrowing the emitted plasma, when the reaction gas is introduced into the case section 72, a pressure difference is more easily generated between the inside of the case section 72 and the inside of the vacuum chamber 2. Note that the size and shape of the through-hole 73a are not limited to this. For example, the through-hole 73a may be a plurality of small holes corresponding to the shape and position of each electrode 71.

[0060] In this way, the cover portion 73 can separate the space inside the vacuum chamber 2 from the internal space inside the case portion 72, thereby increasing the pressure inside the case portion 72 and decreasing the pressure inside the vacuum chamber 2. Therefore, when introducing the thin-film material gas into the vacuum chamber 2 during CVD processing, it is possible to suppress the inflow of the material gas into the internal space of the case portion 72, which would cause the electrode 71 to be contaminated by the deposition of the gas.

[0061] A cover mounting hole 73b is formed in the peripheral edge of the cover portion 73. The cover portion 73 is fixed to the open end 72a of the case portion 72 with screws via the cover mounting hole 73b. The anode for electrode 71 is not limited to the cover portion 73; it may also be the inner wall of the vacuum chamber 2 or the case portion 72.

[0062] The CVD backing plate 74 is a cooling plate for suppressing the temperature rise of the plate-shaped member 70, and is a metal plate made of a material such as copper, molybdenum, or aluminum. The CVD backing plate 74 is positioned in contact with the cooling passage 43 and is cooled by cooling water. By cooling the CVD backing plate 74, it is possible to suppress the plate-shaped member 70 from becoming hot due to the plasma generated in the vacuum chamber 2.

[0063] A plate-shaped member 70 is attached to the surface of the CVD processing backing plate 74 by screws. That is, the plate-shaped member 70 is attached to the base unit 4 via the CVD processing backing plate 74. The CVD processing backing plate 74 may be integrated with the plate-shaped member 70 by soldering it to the back surface 70a of the plate-shaped member 70, or it may be formed as a separate part. As shown in Figure 7, the CVD backing plate 74 is positioned facing the surface of the magnetic circuit 42 and is placed on the surface of the cathode base 41. Holes (not shown) are formed in the peripheral edge of the CVD backing plate 74, and the CVD backing plate 74 is fixed to the mounting holes 41b of the cathode base 41 with screws through these holes.

[0064] In this embodiment, the first unit SU in the sputtering configuration and the second unit CU in the CVD processing configuration are each equipped with a backing plate. However, the configuration is not limited to this, and the first unit SU and the second unit CU may be configured to share a backing plate. When the backing plate is shared, the target T and the sputtering backing plate P are configured as separate components, and the plate-shaped member 70 and the CVD processing backing plate 74 are configured as separate components.

[0065] The insulator 75 is made of an insulator such as ceramic, and electrically insulates the anode base 40 and the cathode base 41 from each other. The insulator 75 may be provided to fill the space around the electrode 71. In this case, plasma generation at the outer periphery of the electrode 71 is suppressed. Therefore, energy can be concentrated inside the hollow cathode 71a.

[0066] The magnet 76 is positioned inside the electrode 71. Specifically, the magnet 76 is housed inside the hollow cathode 71a. A positioning member 76a is provided around the magnet 76. The positioning member 76a is a member that holds a magnet 76 at the center of the base end of the hollow cathode 71a. The positioning member 76a is, for example, a donut-shaped, non-magnetic, heat-resistant metal member. By placing the magnet 76 in the center of the hollow cathode 71a, the density of the generated plasma can be increased. Also, since the gas pressure in sputtering is usually around 0.1 Pa to 1 Pa, similar pressure conditions are required when generating plasma for CVD processing. Therefore, by placing the magnet 76, the plasma density can be increased and the plasma discharge in this pressure range can be stabilized.

[0067] As shown in Figure 3, the inlet 77 is a piping joint for introducing reaction gas into the internal space of the case portion 72 (i.e., the space enclosed by the case portion 72 and the cover portion 73). A pipe extending from the reaction gas inlet 22 is connected to the inlet 77. In this way, by introducing the reaction gas into the internal space of the case section 72 from the inlet 77, the pressure inside the case section 72 can be increased, and the pressure inside the vacuum chamber 2 can be decreased. Therefore, when introducing the thin-film material gas into the vacuum chamber 2 during CVD processing, it is possible to suppress the inflow of the material gas into the inside of the case section 72, which would cause the electrode 71 to be contaminated by film formation. Furthermore, since the inlet 77 is formed in the case section 72, the reaction gas can be directly introduced into the inside of the CVD processing attachment 7, making it possible to increase the internal pressure of the case section 72 and the cover section 73 with a simple configuration.

[0068] In this way, by supplying the reaction gas to the internal space of the case portion 72 and the material gas to the space inside the vacuum chamber 2, a pressure difference is created in the internal space of the CVD processing attachment 7, allowing a film to be formed on the substrate B by CVD processing without contaminating the discharging electrode 71 with reaction products.

[0069] <Substrate Processing Method> As shown in Figure 8, the magnetron sputtering apparatus 1 of this embodiment processes the surface of substrate B by the following substrate processing method. This substrate processing method involves processing the surface of a substrate B using a CVD processing attachment 7, which is detachably attached to the base unit 4 of a magnetron sputtering apparatus 1 that sputters a target T to deposit a film on the substrate B, and generates a CVD processing plasma to perform CVD processing. Specifically, the substrate processing method includes an attachment attachment step (step S1) in which the CVD processing attachment 7 is attached to the base unit 4, a substrate preparation step (step S2) in which the substrate B to be deposited on is prepared, a gas introduction step (step S3) in which a reaction gas is introduced into the interior of the CVD processing attachment 7, and a CVD film deposition step (step S4) in which a CVD processing plasma is generated by the base unit 4 to which the CVD processing attachment 7 is attached and CVD processing is performed.

[0070] In the attachment installation process (step S1), the operator attaches the CVD processing attachment 7 to the base unit 4 from which the target T has been removed. Specifically, the operator positions a plate-shaped member 70 made of magnetic material opposite the magnetic circuit 42 of the base unit 4 that generates a magnetic field inside the vacuum chamber 2. More specifically, the worker positions the CVD backing plate 74, which is attached to the back surface 70a of the plate-shaped member 70, facing the surface of the magnetic circuit 42, and places it on the surface of the cathode base 41, securing it with screws. The worker also attaches the cover portion 73 to the opening end 72a of the case portion 72 so as to cover the opening of the case portion 72. Then, the case portion 72 is attached to the anode base 40 of the base unit 4, housing the plate-shaped member 70 and the electrode 71 inside the case portion 72. At this point, the cover portion 73 separates the space inside the vacuum chamber 2 from the internal space inside the case portion 72. In this way, the operator attaches the CVD processing attachment 7 to the base unit 4 and switches the magnetron sputtering apparatus 1 from the first unit SU in sputtering mode to the second unit CU in CVD processing mode.

[0071] In the substrate preparation step (step S2), the worker attaches the substrate B to be deposited on to the substrate holding unit 3. The worker attaches the substrate B to the substrate holding unit 3 so that it is separated from and facing the base unit 4.

[0072] In the gas introduction process (step S3), the operator introduces the material gas into the vacuum chamber 2 and the reaction gas into the CVD processing attachment 7. More specifically, the operator uses a vacuum pump to exhaust the air from the vacuum chamber 2 through the vacuum exhaust port 20. Then, the operator introduces the material gas into the vacuum chamber 2 through the material gas inlet 23, and introduces the reaction gas into the case section 72 and the cover section 73 through the reaction gas inlet 22.

[0073] In the CVD film deposition process (step S4), the operator supplies power from the power supply 5 connected to the cathode base 41 of the base unit 4, generates CVD plasma using the electrode 71, and performs the CVD process. More specifically, material gas is introduced into the vacuum chamber 2, and reaction gas is introduced into the CVD processing attachment 7. Power is then supplied from the power supply 5 connected to the cathode base 41. At this time, CVD processing plasma is generated by an electrode 71 provided on the surface 70b of the plate-shaped member 70 (the surface opposite to the surface facing the magnetic circuit 42) to deposit a film on the substrate B. Specifically, the operator applies a voltage to the electrode 71 via the cathode base 41 using the power supply 5, thereby turning the material gas and reaction gas into plasma. Then, by generating CVD processing plasma in the vacuum chamber 2, a film is deposited on the surface of the substrate B.

[0074] In this way, when a reaction gas is introduced into the CVD processing attachment 7, a pressure difference is created between the inside of the case portion 72 and the inside of the vacuum chamber 2. Because the pressure inside the CVD processing attachment 7 is higher and the pressure inside the vacuum chamber 2 is lower, when introducing the thin-film material gas into the vacuum chamber 2 during CVD processing, it is possible to suppress the flow of the material gas into the inside of the case portion 72 and the deposition of a film on the electrode 71, thereby preventing contamination. Therefore, by supplying the reaction gas into the cover portion 73 and creating a pressure difference with the material gas supplied into the vacuum chamber 2, a film can be formed on the substrate B by CVD processing without contaminating the discharging electrode 71 with reaction products.

[0075] Furthermore, sputtering may be performed using the first unit SU before CVD processing, or after CVD processing, the process may be switched from the second unit CU to the first unit SU for sputtering. In the sputtering process, a sputtering plasma is generated using a sputtering backing plate P, and the target T is sputtered to perform film deposition on the substrate B. In addition to sputtering and CVD, surface modification and other film deposition processes may also be performed, and the number of times each process is performed and the content of each step may be changed. For example, a surface modification process may be performed before or after the CVD film deposition process, and the film deposition process may be performed multiple times.

[0076] Furthermore, if multiple base units 4 are provided in a single vacuum chamber 2, CVD processing and sputtering processing may be performed simultaneously or consecutively. In this case, the surface treatment of the substrate B is performed by generating CVD processing plasma or sputtering plasma while the vacuum chamber 2 is under reduced pressure.

[0077] <Second Embodiment> Next, the first unit SU and the second unit CU of the dual-type magnetron sputtering apparatus 101 of the second embodiment will be described with reference to Figures 9 to 12. As shown in Figure 9, the base unit 104 has an anode base 140, a cathode base 141, two magnetic circuits 142, and a cooling passage 143. The sputtering attachment 106 has two targets T, as shown in Figure 10. The CVD processing attachment 107 has multiple electrodes 171, a case portion 172, and a cover portion 173, as shown in Figure 12. The case portion 172 is used for both the sputtering attachment 106 and the CVD processing attachment 107.

[0078] As shown in Figure 9, the base unit 104 includes an anode base 140, a cathode base 141 housed in the anode base 140, and two magnetic circuits 142 that generate a magnetic field. Multiple cooling pipes 143a are provided in the magnetic circuits 142.

[0079] As shown in Figure 12, the sputtering attachment 106 includes two rectangular plate-shaped targets T, two sputtering backing plates P for cooling each target T, and rectangular plate-shaped target shields Ts. The target shields Ts have openings Ts1 formed therein to expose the targets T. The target shields Ts are also attached to the case portion 172 as shown in Figure 10.

[0080] As shown in Figures 9 and 12, the CVD processing attachment 107 includes two plate-shaped members 170 positioned opposite each magnetic circuit 142, electrodes 171 provided on the surface 170b of each plate-shaped member 170, a rectangular tubular case portion 172 that houses each plate-shaped member 170 and each electrode 171, a cover portion 173 attached to the case portion 172, and two CVD processing backing plates 174. Figure 12 shows the case portion 172 attached to the base unit 104.

[0081] The plate-shaped member 170 is made of a magnetic material, is positioned opposite the magnetic circuit 142, and is attached to the cathode base 141 from which the target T has been removed. Each of the two electrodes 171 has nine hollow cathodes 171a. In other words, the CVD processing attachment 107 has 18 hollow cathodes 171a. The case section 172 is detachably attached to the anode base 140 of the base unit 104 and houses the plate-shaped member 170 and the electrode 171 inside. The case section 172 is provided with an inlet 177. In this way, by introducing the reaction gas into the internal space of the case section 172 from the inlet 177, the pressure in the internal space of the case section 172 can be increased and the pressure in the space inside the vacuum chamber 2 can be decreased. The cover portion 173 is a rectangular plate-shaped member and has a cover body portion 173a attached to the case portion 172, two protrusions 173b protruding from the cover body portion 173a toward the substrate holding portion 3, and through holes 173c formed on the front end surfaces of the protrusions 173b. The protrusions 173b have a box-like shape with space inside and house the electrodes 171. The through holes 173c allow the plasma generated by the electrodes 171 to pass through.

[0082] As shown in Figure 9, the power supply 105 of the dual-type magnetron sputtering apparatus 101 is either an AC power supply or a bipolar pulse power supply. The power supply 105 is connected to the cathode base 141 of the base unit 104. By applying voltage to the two targets T by the power supply 105, the sputtering gas can be turned into plasma. In addition, by applying voltage to multiple electrodes 171 (specifically, a total of 18 hollow cathodes 171a in 9 x 2 rows) by the power supply 105, the reaction gas for CVD processing can be turned into plasma. Since the power of the AC power supply is 40 kHz or similar, it can easily supply high power compared to an RF power supply.

[0083] Thus, by using an AC power supply or a bipolar pulse power supply as the power supply 105, a large amount of power can be supplied more easily compared to an RF power supply. Furthermore, since AC discharge is performed between the pair of electrodes 171, the electrodes 171 can function alternately as anode and cathode. At this time, since it is in a floating state with respect to the vacuum chamber 2, the loss of anode function due to contamination inside the vacuum chamber 2 (i.e., anode loss due to insulating material deposition) can be suppressed, and stable discharge can be sustained for a long period of time.

[0084] In this embodiment, a sputtering apparatus equipped with a CVD treatment attachment according to the present invention, and a surface treatment method using the CVD treatment attachment were mainly described. However, the embodiments described above are merely examples to facilitate understanding of the present invention and do not limit it. The present invention can be modified and improved without departing from its spirit, and of course, equivalents thereof are included. [Examples]

[0085] The following describes embodiments of the present invention. In Examples 1 to 10, a CVD-type magnetron sputtering apparatus equipped with a CVD processing attachment was used to generate CVD plasma and perform CVD processing on the substrate. As a comparative example, a conventional magnetron sputtering apparatus was used without a CVD processing attachment to generate CVD plasma and perform CVD processing on the substrate.

[0086] <Example 1> First, a CVD (Chemical Vapor Deposition) attachment was mounted to a 5-inch x 20-inch planar magnetron cathode with a matching device capable of applying a high frequency of 13.56 MHz, using a carousel-type magnetron sputtering apparatus with an inner diameter of φ1000 mm. When mounting the CVD attachment, the target and target shield of the magnetron sputtering apparatus were removed, and then the backing plate, electrodes, case, cover, etc. of the CVD attachment were each attached to the base unit. The sputtering system used included a rotary pump + mechanical booster pump for the rough exhaust system, a turbomolecular pump for the high-vacuum exhaust system, and a Meissner coil for moisture trapping inside the vacuum chamber. During the plasma CVD process, the Meissner trap was stopped because the precursor was trapped.

[0087] HMDSO (hexamethyldisiloxane) was used as the precursor for CVD. The HMDSO precursor was filled into a stainless steel tank and vaporized directly using a vaporizer while controlling the flow rate with a liquid mass flow controller, and then introduced into the vacuum chamber. Oxygen gas was used as the reaction gas, and its flow rate was controlled by a mass flow controller before it was introduced into the apparatus.

[0088] After opening the sputtering apparatus to the atmosphere, a 100 x 100 x 1.1 mm soda-lime glass substrate for film evaluation and a Si wafer for refractive index measurement were placed in the rotating drum, which serves as the substrate holder, and the apparatus was evacuated to a vacuum. Without substrate heating (RT), ionization vacuum gauge measured 8 × 10 -4 After evacuating to a vacuum of Pa, the precursor was set to 0.4 g / min and the oxygen gas to 0 sccm and introduced into the vacuum chamber. A 1000 W output from the high-frequency power supply was applied to the CVD processing attachment to generate plasma, and film deposition was performed for 18 minutes and 36 seconds. The pressure at this time was measured using a diaphragm vacuum gauge and was 0.37 Pa.

[0089] After stopping the output of the high-frequency power supply applied to the target, the introduction of the precursor was stopped and the vacuum chamber was opened to the atmosphere. When the substrate was removed from the rotating drum and its appearance was checked, a transparent film had been deposited on the substrate. Reaction products were observed to adhere to the surface of the CVD treatment attachment and the discharge electrode surface inside, but no detachment of the adhered substances was observed.

[0090] The film thickness of the film deposited on the substrate was measured at 497 nm using a Bruker DektakXT palpation profiler. Visible spectral characteristics were measured at 550 nm using a Hitachi High-Tech Science U4100 spectrophotometer, yielding a spectral transmittance of 89.5%, a spectral reflectance of 8.7%, and a spectral absorptance of 1.8%. Furthermore, the refractive index of the film deposited on the Si wafer at 550 nm was measured at 1.525 using a JASCO M-220 spectroscopic ellipsometer. The film composition was measured using a JEOL JPS-900MC XPS scanner, and the composition ratio was O: 19.8%, C: 48.8%, and Si: 31.4%. Furthermore, the film hardness was measured using an Elionix ENT-2100 nanoindenter and was found to be 2.7 GPa.

[0091] <Example 2> After opening the sputtering apparatus to the atmosphere in the same manner as in Example 1, a 100 × 100 × 1.1 mm soda-lime glass substrate for film evaluation and a Si wafer for refractive index measurement were placed on the rotating drum and the apparatus was evacuated to a vacuum. Without substrate heating (RT), ionization vacuum gauge measured 8 × 10 -4 After evacuating to a vacuum of Pa, a precursor was introduced into the vacuum chamber with a setting of 0.4 g / min and an oxygen gas level of 100 sccm. A 1000 W output from a high-frequency power supply was applied to the CVD processing attachment to generate plasma, and film deposition was performed for 25 minutes. The pressure at this time was measured using a diaphragm vacuum gauge and was 0.75 Pa.

[0092] After stopping the output of the high-frequency power supply applied to the target, the precursor and oxygen gas introduction were stopped, and the vacuum chamber was opened to the atmosphere. When the substrate was removed from the rotating drum and its appearance was checked, a transparent film had been deposited on the substrate. As shown in Figure 13, no reaction products were observed adhering to the surface of the CVD processing attachment or the discharge electrode surface inside it. At this time, the particle count was 482. The particle count was measured using a particle counter (WM3) and was calculated by subtracting the total values ​​of S, M, and L before film formation from the total values ​​of S, M, and L after film formation.

[0093] The film thickness of the film deposited on the substrate was measured at 500 nm using a Bruker DektakXT palpation profiler. The deposition rate was slower compared to the case without oxygen introduction. Furthermore, the visible spectral characteristics were measured using a Hitachi High-Tech Science U4100 spectrophotometer, showing a spectral transmittance of 91%, spectral reflectance of 7.5%, and spectral absorptance of 1.5% at a wavelength of 550 nm. In addition, the refractive index of the film deposited on the Si wafer at a wavelength of 550 nm was measured at 1.47 using a JASCO M-220 spectroscopic ellipsometer. The film composition was measured using a JEOL JPS-900MC XPS and was found to be O: 41.1%, C: 23.3%, and Si: 35.6%. Furthermore, the film hardness was measured using an Elionix ENT-2100 nanoindenter and was found to be 2.3 GPa.

[0094] <Examples 3-10> CVD treatment was performed in the same manner as in Examples 1 and 2. The conditions for each example are as follows. (Example 3) RT / HMDSO 0.4g / min / O2200sccm (Example 4) RT / HMDSO 0.2g / min / O2100sccm (Example 5) RT / HMDSO 0.2g / min / O2200sccm (Example 6) 230℃ / HMDSO4 0.4g / min / O20sccm (Example 7) 230℃ / HMDSO4 0.4g / min / O2 100sccm (Example 8) 230℃ / HMDSO4 0.4g / min / O2200sccm (Example 9) 230℃ / HMDSO4 0.2g / min / O2 100sccm (Example 10) 230℃ / HMDSO4 0.2g / min / O2200sccm

[0095] <Comparative Example> As a comparative example, a carousel-type magnetron sputtering apparatus with an inner diameter of φ1000 mm was used, similar to Example 1. In the comparative example, CVD plasma was generated without using a CVD processing attachment, and the substrate was subjected to CVD processing. The sputtering cathode was a 5-inch x 20-inch planar magnetron cathode with a matching device capable of applying a high frequency of 13.56 MHz, to which an SiO2 target was mounted.

[0096] After opening the sputtering apparatus to the atmosphere in the same manner as in Example 1, a 100 × 100 × 1.1 mm soda-lime glass substrate for film evaluation and a Si wafer for refractive index measurement were placed on the rotating drum and the apparatus was evacuated to a vacuum. Without substrate heating (RT), ionization vacuum gauge measured 8 × 10 -4 After evacuating to a vacuum of Pa, a precursor was introduced into the vacuum chamber with a setting of 0.4 g / min and an oxygen gas level of 100 sccm. A 1000 W output from a high-frequency power supply was applied to the SiO2 target to generate plasma, and film deposition was carried out for 23 minutes. The pressure at this time was measured using a diaphragm vacuum gauge and was 0.72 Pa.

[0097] After stopping the power applied to the target, the precursor and oxygen gas introduction were stopped, and the vacuum chamber was opened to the atmosphere. When the substrate was removed from the rotating drum and its appearance was checked, a transparent film had been deposited on the substrate. The surface of the SiO2 target was discolored brown, and partial delamination was observed, with the delamination fragments accumulating at the bottom of the vacuum chamber. As shown in Figure 12, the particle count was 19,311. The particle count was measured using a particle counter (WM3) and was calculated by subtracting the total S, M, and L values ​​before film formation from the total S, M, and L values ​​after film formation. Furthermore, after repeated film deposition, the amount of particles directly beneath the plasma source was higher compared to Example 2.

[0098] The film thickness of the film deposited on the substrate was measured at 515 nm using a Bruker DektakXT palpation profiler. The visible spectral characteristics were measured using a Hitachi High-Tech Science U4100 spectrophotometer, showing a spectral transmittance of 91.5%, spectral reflectance of 7.3%, and spectral absorptance of 1.2% at a wavelength of 550 nm. Furthermore, the refractive index of the film deposited on the Si wafer at 550 nm was measured at 1.46 using a JASCO M-220 spectroscopic ellipsometer. The film composition was measured using a JEOL JPS-900MC XPS, and the composition ratio was O: 39.7%, C: 25.4%, and Si: 34.9%. Furthermore, the film hardness was measured using an Elionix ENT-2100 nanoindenter and was found to be 2.4 GPa.

[0099] The experimental results for Examples 1 to 10 and the comparative examples are shown in Table 1.

[0100] [Table 1] *1 Soda-lime glass, 1.1mm thick, measured at a wavelength of 550nm using a Hitachi High-Tech Science U4100 spectrophotometer. *2 On a Si wafer, measured with a JASCO M-220 spectroscopic ellipsometer at a wavelength of 550 nm. *3 Elionix ENT-2100 nanoindenter, load 1mN *4 Discharge by SiO2 target

[0101] Figure 13 shows the relationship between oxygen introduction rate and film deposition rate. Figure 14 shows the relationship between oxygen introduction rate and hardness. Examples 1-10 revealed that as the amount of oxygen introduced increased, the carbon concentration in the membrane decreased and the membrane hardened. Furthermore, for the same amount of oxygen introduced, a lower amount of HMDSO resulted in a lower carbon concentration in the membrane, indicating more advanced oxidation and thus a harder membrane. A similar trend was observed with increasing temperature, with higher temperatures leading to more advanced oxidation and a harder membrane.

[0102] From these results, it became clear that when generating CVD plasma in a magnetron sputtering apparatus using a CVD processing attachment, the amount of particles is reduced, and the generation of film defects and foreign matter can be suppressed. [Explanation of Symbols]

[0103] 1.101 Magnetron sputtering apparatus 2. Vacuum Chamber 3 Board holding part 4. 104 Base Unit 5, 105 Power supply 6. 106 Sputtering Attachment 7. 107 CVD Processing Attachment 20 Vacuum exhaust port 21 Ar gas inlet 22 Reaction gas inlet 23 Material gas inlet 40, 140 anode base 41, 141 Cathode Base 41a Storage area 41b Mounting hole 42, 142 Magnetic Circuits 43, 143 Cooling path 43a, 143a Cooling pipes 70, 170 Plate-shaped members 70a Reverse side 70b, 170b surface 70c mounting part 71, 171 electrode 71a, 171a Hollow cathode 72, 172 Case section 72a Open end 72b Flange 72c case mounting holes 73, 173 Cover part 73a, 173c Passing hole 73b Cover mounting holes 173a Cover body 173b Protrusion 74, 174 CVD backing plate 75 Insulator 76 Magnets 76a Positioning member 77, 177 Inlet TU First Unit CU Second Unit P Sputtering Backing Plate T Target Ts Target Shield Ts1 opening B substrate G1 Argas Source G2 gas supply source G3 Material Gas Supply System G3a Liquid Raw Material Tank G3b vaporizer V1, V2, V3 On / Off Valves

Claims

1. A magnetron sputtering apparatus that deposits a film onto a substrate by sputtering a target, Vacuum chamber and A substrate holding section is provided within the vacuum chamber and holds the substrate, A base unit provided within the vacuum chamber and positioned opposite the substrate holding portion at a distance from it, The power supply connected to the base unit, The base unit is detachably attached to a CVD processing attachment for generating CVD processing plasma and performing CVD processing, A material gas is introduced into the space within the vacuum chamber. The base unit has a magnetic circuit that generates a magnetic field, The aforementioned CVD processing attachment is A plate-shaped member made of a magnetic material, positioned opposite the magnetic circuit, and attached to the base unit from which the target has been removed, An electrode provided on the plate-shaped member on the side opposite to the surface facing the magnetic circuit, A case portion is detachably attached to the base unit, housing the plate-shaped member and the electrode in an internal space, and into which a reaction gas is introduced. A magnetron sputtering apparatus characterized by having a cover portion attached to the open end of the case portion, covering the opening of the case portion, and separating the space in the vacuum chamber from the internal space of the case portion.

2. The magnetron sputtering apparatus according to claim 1, characterized in that the electrode has a hollow cathode.

3. The magnetron sputtering apparatus according to claim 2, characterized in that a magnet is placed inside the hollow cathode.

4. The CVD processing attachment has a reaction gas inlet for introducing the reaction gas into the internal space of the case portion, The magnetron sputtering apparatus according to claim 1 or 2, characterized in that the reaction gas inlet is formed in the case portion.

5. The power supply is a high-frequency power supply, The magnetron sputtering apparatus according to claim 1 or 2, characterized in that the reaction gas is oxygen gas.

6. The aforementioned power supply is an AC power supply or a bipolar pulse power supply. The CVD processing attachment has a plurality of electrodes, The magnetron sputtering apparatus according to claim 1 or 2, characterized in that a voltage is applied to the plurality of electrodes by the power supply.

7. A substrate processing method using a CVD processing attachment that is detachably attached to the base unit of a magnetron sputtering apparatus for sputtering a target and depositing a film on a substrate, and for generating CVD processing plasma and performing CVD processing, The attachment mounting step involves attaching the CVD processing attachment to the base unit from which the target has been removed, A gas introduction step of introducing a reaction gas into the CVD processing attachment, The process includes a CVD film deposition step in which a CVD processing plasma is generated by the base unit to which the CVD processing attachment is attached, and a CVD processing step is performed. In the aforementioned attachment mounting process, A plate-shaped member made of a magnetic material is placed opposite the magnetic circuit of the base unit that generates a magnetic field. The electrodes are positioned on the surface of the plate-shaped member opposite to the surface facing the magnetic circuit. The case portion is attached to the base unit so as to house the plate-shaped member and the electrode in the internal space. A cover portion is attached to the open end of the case portion, covering the opening of the case portion and separating the space inside the vacuum chamber from the internal space of the case portion. In the gas introduction step, the material gas is introduced into the vacuum chamber, and the reaction gas is introduced into the internal space of the case. A substrate processing method characterized in that, in the CVD film deposition step, power is supplied from a power supply connected to the base unit to generate CVD processing plasma using the electrodes and perform CVD processing.

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