WO2023157553A1 - Dispositif de dépôt chimique en phase vapeur par plasma et procédé de fabrication de film - Google Patents

Dispositif de dépôt chimique en phase vapeur par plasma et procédé de fabrication de film Download PDF

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Publication number
WO2023157553A1
WO2023157553A1 PCT/JP2023/001507 JP2023001507W WO2023157553A1 WO 2023157553 A1 WO2023157553 A1 WO 2023157553A1 JP 2023001507 W JP2023001507 W JP 2023001507W WO 2023157553 A1 WO2023157553 A1 WO 2023157553A1
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WO
WIPO (PCT)
Prior art keywords
pair
magnetic field
film
field generating
gas supply
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Application number
PCT/JP2023/001507
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English (en)
Japanese (ja)
Inventor
壮登 高澤
智之 妹尾
順平 小笹
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2023157553A1 publication Critical patent/WO2023157553A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a plasma CVD apparatus and a film manufacturing method.
  • a method using a plasma CVD apparatus is known as a method for forming a film on a substrate.
  • a plasma CVD apparatus including a pair of film-forming rolls, a pair of magnetic field generating members, and a gas supply section has been proposed (see, for example, Patent Document 1 below).
  • a pair of film-forming rolls are arranged to face each other while being separated from each other.
  • a pair of deposition rolls are connected to a power supply.
  • a pair of magnetic field generating members are arranged inside each of the pair of film forming rolls. Also, the pair of magnetic field generating members generates a magnetic field between the pair of film forming rolls.
  • Plasma is generated by the application of power to the deposition roll. Plasma is confined between the pair of film forming rolls by the magnetic field generated by the magnetic field generating member and converges on the opposing surfaces of the pair of film forming rolls.
  • a long base material is stretched over a pair of film forming rolls, and supplied from a gas supply unit while running on the opposite surfaces of the pair of film forming rolls.
  • a component derived from the raw material gas is deposited on the surface of the substrate.
  • Patent Literature 1 There is a demand to change the physical properties of the film according to the application and purpose.
  • the plasma CVD apparatus described in Patent Literature 1 has a problem that it cannot sufficiently satisfy the above-described requirements.
  • the present invention provides a plasma CVD apparatus and film manufacturing method that can change the physical properties of the film.
  • a pair of film-forming rolls arranged to face each other at a distance and arranged inside each of the pair of film-forming rolls generate a magnetic field between the pair of film-forming rolls.
  • a pair of magnetic field generating members for adjusting the positions of the pair of magnetic field generating members
  • a pair of position adjusting members for adjusting the positions of the pair of magnetic field generating members
  • a gas supply section for supplying a film forming gas between the pair of film forming rolls.
  • a pair of the position adjusting members are defined by a distance between the center of one of the magnetic field generating members and the gas supply section and a distance between the center of the other magnetic field generating member and the gas supply section.
  • a plasma CVD apparatus configured to adjust the positions of the pair of magnetic field generating members so that
  • This plasma CVD apparatus includes a pair of position adjusting members for adjusting the positions of the pair of magnetic field generating members.
  • the pair of position adjustment members are arranged such that the distance between the center of one magnetic field generating member and the gas supply section is the same as the distance between the center of the other magnetic field generation member and the gas supply section. Adjust the positions of the pair of magnetic field generating members. Therefore, the physical properties of the film can be changed.
  • a pair of film-forming rolls arranged to face each other at a distance and arranged inside each of the pair of film-forming rolls to generate a magnetic field between the pair of film-forming rolls and a gas supply section for supplying a film-forming gas between the pair of film-forming rolls, wherein the center of the magnetic field-generating member is aligned with the axis of the pair of film-forming rolls.
  • It includes a plasma CVD apparatus arranged on the side of the gas supply unit with respect to the connecting line segment.
  • the center of the magnetic field generating member is arranged on the gas supply section side with respect to the line connecting the axes of the pair of film forming rolls. Therefore, the physical properties of the film can be changed.
  • a pair of film-forming rolls arranged to face each other at a distance and arranged inside each of the pair of film-forming rolls generate a magnetic field between the pair of film-forming rolls.
  • a gas supply section for supplying a film-forming gas between the pair of film-forming rolls, wherein the center of the magnetic field-generating member is aligned with the axis of the pair of film-forming rolls.
  • a plasma CVD device is provided on the opposite side of the connecting line from the gas supply unit.
  • the center of the magnetic field generating member is arranged on the opposite side of the gas supply section with respect to the line connecting the axes of the pair of film forming rolls. Therefore, the physical properties of the film can be changed.
  • an angle between the second line segment connecting the center of the magnetic field generating member and the axis of the film forming roll and the line segment is 1 degree or more and 45 degrees or less.
  • the angle formed by the second line segment and the line segment is 1 degree or more, it is possible to successfully adjust the physical properties of the film. Since the angle formed by the second line segment and the line segment is 45 degrees or less, it is possible to suppress a decrease in film formation rate.
  • the present invention (5) further comprises a pair of position adjusting members for adjusting the positions of the pair of magnetic field generating members respectively, wherein the pair of position adjusting members are arranged between the center of one of the magnetic field generating members and the gas.
  • the positions of the pair of magnetic field generating members are adjusted so that the distance between the gas supply unit and the distance between the center of the other magnetic field generating member and the gas supply unit are the same.
  • the plasma CVD apparatus according to any one of (2) to (4) is included.
  • the present invention (6) is the plasma CVD apparatus according to (1) or (5), wherein the position adjusting member is configured to rotate the magnetic field generating member around the axis of the film forming roll. including.
  • the position adjustment member rotates the magnetic field generation member about the axis of the film forming roll, so the position adjustment of the magnetic field generation member is easy.
  • the present invention (7) is a method for producing a film, using the plasma CVD apparatus according to any one of (1) to (6) to form a film on the surface of a substrate and adjust physical properties of the film. including.
  • the physical properties of the film can be changed.
  • FIG. 1 is a schematic diagram of a plasma CVD apparatus according to one embodiment of the present invention
  • FIG. 2 is a cross-sectional view taken along a plurality of holes of the positioning member in FIG. 1
  • 3A and 3B are manufacturing process diagrams for forming a film on a substrate.
  • FIG. 3A is a step of preparing a base material.
  • FIG. 3B is a step of forming a membrane on a substrate. It is a mode of adjusting the plasma CVD apparatus of FIG. 1 by the first method. This is a mode of adjusting the plasma CVD apparatus of FIG. 1 by the second method.
  • 6A and 6B show the position adjusting member in the plasma CVD apparatus of the first modified example, which is the position adjusting member before fine adjustment.
  • FIG. 1 is a schematic diagram of a plasma CVD apparatus according to one embodiment of the present invention
  • FIG. FIG. 2 is a cross-sectional view taken along a plurality of holes of the positioning member in FIG. 1
  • FIG. 6A is a schematic diagram.
  • FIG. 6B is a cross-sectional view of the positioning member.
  • 7A and 7B show the position adjustment member in the plasma CVD apparatus of the first modified example after fine adjustment.
  • FIG. 7A is a schematic diagram.
  • FIG. 7B is a cross-sectional view of the positioning member.
  • FIG. 11 is a cross-sectional view of a position adjusting member of a second modified example; It is the schematic of the plasma CVD apparatus of a 3rd modification. It is the schematic of the plasma CVD apparatus of a 4th modification.
  • FIG. 1 Plasma CVD Apparatus
  • FIG. 1 One embodiment of the plasma CVD apparatus of the present invention will be described with reference to FIGS. 1 to 5.
  • FIG. 1 is a diagrammatic representation of the plasma CVD apparatus of the present invention.
  • the plasma CVD apparatus 1 includes a pair of film forming rolls 2A and 2B, a pair of magnetic field generating members 3A and 3B, a pair of position adjusting members 4A and 4B, and a gas supply unit 5. And prepare.
  • the plasma CVD apparatus 1 further includes a guide roll 6, an exhaust section (not shown), and a casing (not shown).
  • a pair of film-forming rolls 2A and 2B are arranged to face each other while being separated from each other in the first direction.
  • the first direction corresponds to the horizontal direction on the paper surface of FIG.
  • Each of the pair of film forming rolls 2A and 2B extends in the second direction.
  • the second direction is orthogonal to the first direction.
  • the second direction corresponds to the depth direction on the paper surface of FIG.
  • the axis 21A of the film forming roll 2A and the axis 21B of the film forming roll 2B extend in the second direction and are parallel to each other.
  • a line segment L connecting the axes 21A and 21B extends along the first direction.
  • Each of the pair of film forming rolls 2A and 2B has a cylindrical shape.
  • a pair of film forming rolls 2A and 2B are connected to a power source (not shown).
  • a pair of magnetic field generating members 3A and 3B are arranged inside each of the pair of film forming rolls 2A and 2B.
  • a pair of magnetic field generating members 3A and 3B generate a magnetic field between a pair of film forming rolls 2A and 2B.
  • the pair of magnetic field generating members 3A, 3B are configured to be movable (slidable) along the circumferential direction of the pair of film forming rolls 2A, 2B by the operation of a pair of position adjusting members 4A, 4B which will be described later. there is Each of the pair of magnetic field generating members 3A and 3B extends in the second direction.
  • the magnetic field generating member 3A includes a yoke 31A and a plurality of magnets 32A.
  • the yoke 31A is a plate curved along the circumferential direction of the film forming roll 2A.
  • the center of curvature of the yoke 31A is located on the axis 21A of the film forming roll 2A.
  • the yoke 31A has a first surface 311A and a second surface 312A. 311 A of 1st surfaces face this internal peripheral surface in the vicinity of the internal peripheral surface of 2 A of film-forming rolls.
  • the second surface 312A faces the shaft 21A of the film forming roll 2A.
  • the material of the yoke 31A has magnetic permeability.
  • a plurality of magnets 32A are arranged on the first surface 311A of the yoke 31A.
  • the plurality of magnets 32A are arranged at equal intervals in the circumferential direction.
  • two magnets 321A, 322A arranged at one end and the other end in the circumferential direction are respectively located at one end and the other end of the yoke 31A in the circumferential direction.
  • a center 30A of the magnetic field generating member 3A is located in a central portion between the two magnets 321A and 322A in the circumferential direction.
  • the center 30A is located at the center of gravity of the magnet 32A located at the center in the circumferential direction. If the number of magnets 32A is an even number, the center 30A is located between two magnets 32A located on both sides of the central portion in the circumferential direction.
  • the magnetic field generating member 3B has the same configuration as the magnetic field generating member 3A described above. In this embodiment, the magnetic field generating member 3B is arranged symmetrically with respect to the plane S passing through the midpoint C of the line segment L. As shown in FIG.
  • the plane S is parallel to the axes 21A and 21B.
  • the magnetic field generating member 3B includes a yoke 31B and a plurality of magnets 32B.
  • the center 30B of the magnetic field generating member 3B is located in the center between the two magnets 321B and 322B in the circumferential direction.
  • a pair of position adjustment members 4A, 4B A pair of position adjusting members 4A and 4B adjust the positions of the pair of magnetic field generating members 3A and 3B, respectively. Each of the pair of position adjustment members 4A and 4B is connected to each of the pair of magnetic field generation members 3A and 3B. The configuration and operation of the pair of position adjusting members 4A, 4B will be described later.
  • the gas supply unit 5 supplies a film forming gas between the pair of film forming rolls 2A and 2B. A film forming gas will be described later.
  • the gas supply unit 5 is arranged on one side of the shafts 21A and 21B in the first direction when projected in the first direction.
  • the gas supply unit 5 is a port connected to a gas supply source (not shown).
  • the gas supply part 5 extends in the second direction.
  • the gas supply units may be aligned and spaced apart from each other in the second direction.
  • the gas supply unit 5 ejects gas toward one side in the third direction.
  • the third direction is orthogonal to the first direction and the second direction.
  • the third direction is the gas ejection direction (supply direction).
  • the guide roll 6 is arranged on one side of the pair of film forming rolls 2A and 2B in the first direction.
  • the guide roll 6 is arranged such that the elongated base material 101 is in contact with the facing surfaces 2AS and 2BS of the pair of film forming rolls 2A and 2B.
  • one pair of guide rolls 6 is provided.
  • Each of the pair of guide rolls 6 is arranged outside the pair of film forming rolls 2A and 2B in the second direction.
  • a guide roll 6 is parallel to the pair of film forming rolls 2A and 2B.
  • the guide roll 6 extends in the second direction.
  • the exhaust unit (not shown) is connected to a vacuum pump (not shown).
  • the exhaust section evacuates a chamber in a casing (not shown).
  • the casing (not shown) includes a pair of film-forming rolls 2A and 2B, a pair of magnetic field generating members 3A and 3B, a pair of position adjusting members 4A and 4B, a gas supply section 5, and a guide roll. 6 and an exhaust section (not shown).
  • a pair of film-forming rolls 2A and 2B and a guide roll 6 are rotatably supported by the casing.
  • the casing includes a pair of magnetic field generating members 3A and 3B and a pair of position adjusting members 4A and 4B so that the positions of the pair of magnetic field generating members 3A and 3B can be adjusted by the operation of the pair of position adjusting members 4A and 4B. Adjustment members 4A and 4B are supported.
  • the casing is provided with a gas supply section 5 and an exhaust section.
  • the casing defines a chamber in its interior.
  • Pair of Position Adjustment Members 4A and 4B The positions of the pair of magnetic field generating members 3A and 3B are adjusted so that the distance between 30B and the gas supply unit 5 is the same.
  • Each of the pair of position adjusting members 4A and 4B is arranged at the end of the plasma CVD apparatus 1 in the second direction.
  • the position adjusting member 4A includes a fixed plate 41A, a movable plate 42A, a connecting portion (not shown), and a bolt 43A.
  • the fixed plate 41A is arranged near the end of the film forming roll 2A in the second direction.
  • the fixed plate 41A is fixed to a casing (not shown) so as not to move relative to the shaft 21A of the film forming roll 2A.
  • the fixed plate 41A extends in the first direction and the third direction.
  • the fixed plate 41A has a flat plate shape.
  • the fixing plate 41A has a plurality of holes 411A.
  • the plurality of holes 411A are aligned at predetermined intervals along a rotational trajectory about the shaft 21A.
  • Each of the plurality of holes 411A extends in the second direction.
  • the hole 411A is a round hole.
  • the interval IA between the centers of two holes 411A adjacent in the circumferential direction is defined by the line segment connecting one hole 411A and the shaft 21A and the hole 411A adjacent to the one hole 411A and the shaft 21A.
  • the angle ⁇ formed by the connecting line segments is, for example, 3 degrees or more, preferably 5 degrees or more, more preferably 7 degrees or more, and is, for example, 30 degrees or less, preferably 20 degrees or less, more preferably It is set to be 15 degrees or less.
  • a female thread is cut on the inner peripheral surface of the hole 411A.
  • the movable plate 42A is arranged on one side of the fixed plate 41A in the second direction.
  • the movable plate 42A extends in the first direction and the third direction.
  • the movable plate 42A has a flat plate shape.
  • 42 A of movable plates are provided with 421 A of holes.
  • Hole 421A extends in the second direction.
  • the hole 421A is a round hole.
  • hole 421A has the same diameter as hole 411A.
  • the inner peripheral surface of the hole 421A is internally threaded.
  • a connecting portion (not shown) is connected to the movable plate 42A and the yoke 31A.
  • the connecting portion prevents the movable plate 42A and the yoke 31A from moving relative to each other.
  • the connecting portion can rotate the yoke 31A by rotating the movable plate 42A about the shaft 21A. That is, the yoke 31A is interlocked with the movement of the movable plate 42A by the connecting portion.
  • the bolt 43A extends in the second direction. Specifically, the bolt 43A has a rod portion 431A and a head 432A. The rod portion 431A extends in the second direction. The rod portion 431A is inserted through one hole 411A in the fixed plate 41A and the hole 421A in the movable plate 42A and screwed therewith. The movable plate 42A is fixed to the fixed plate 41A by screwing the bolts 43A into the holes 411A and 421A.
  • the bolt 43A is inserted through the central hole 411A among the plurality of holes 411A, so that the center 30A of the magnetic field generating member 3A is positioned on the line segment L.
  • the position adjusting member 4B has the same configuration as the position adjusting member 4A described above.
  • the position adjusting member 4B is arranged plane-symmetrically with respect to the plane S described above.
  • the position adjusting member 4B includes a fixed plate 41B, a movable plate 42B, a connecting portion (not shown), and bolts 43B.
  • the fixed plate 41B has a plurality of holes 411B.
  • the spacing IB between the centers of two holes 411B adjacent in the circumferential direction is the same as the spacing IB described above.
  • An angle ⁇ formed by a line segment connecting one hole 411B and the shaft 21B and a line segment connecting the hole 411B adjacent to the one hole 411B and the shaft 21B is the same as the angle ⁇ described above.
  • the bolt 43B is inserted through the central hole 411B of the plurality of holes 411B, so that the center 30B of the magnetic field generating member 3B is positioned on the line segment L. As shown in FIG. Specifically, the hole 411B through which the bolt 43B for the shaft 21B is inserted is symmetrical with respect to the plane S with respect to the hole 411A through which the bolt 43A for the shaft 21A is inserted.
  • a base material 101 is prepared as shown in FIG. 3A.
  • the base material 101 is long.
  • the type of base material 101 is not limited.
  • Examples of the base material 101 include resin films, metal foils, and paper.
  • Examples of resin films include polyester films, polyolefin films, and polyimide films. Polyester films include, for example, polyethylene terephthalate films.
  • Polyolefin films include polyethylene films, polypropylene films, and cycloolefin films (COP).
  • metal foil include copper foil.
  • a resin film is preferred, and a polyolefin film is more preferred.
  • the surface 101S of the base material 101 may be subjected to public treatment.
  • the thickness of the base material 101 is, for example, 10 ⁇ m or more and 1000 ⁇ m or less.
  • the base material 101 is wound around a pair of film forming rolls 2A and 2B and a guide roll 6. Subsequently, the base material 101 is run with respect to the pair of film forming rolls 2A and 2B and the guide roll 6. As shown in FIG.
  • the running speed is, for example, 0.1 m/min or more and 100 m/min or less.
  • the chamber is evacuated from the exhaust unit by driving a vacuum pump (not shown). Electric power is applied to the pair of film forming rolls 2A and 2B. Electric power is 0.1 kW or more and 10 kW or less, for example. Plasma is then generated between the pair of film-forming rolls 2A and 2B. At the same time, gas is supplied to the chamber from a gas supply source (not shown) through the gas supply section 5 .
  • the gas is not limited as long as it can be supplied to the plasma CVD apparatus 1 .
  • Gases include, for example, raw material gases and reaction gases.
  • Source gases include Si-containing gas, C-containing gas, and Ti-containing gas.
  • Si-containing gas include aminosilane.
  • Aminosilanes include, for example, trisilylamine (TSA).
  • C-containing gases include, for example, methane, ethane, ethylene, and acetylene.
  • Ti-containing gas include titanium tetrachloride.
  • reactive gases examples include oxygen and nitrogen.
  • the gas is described, for example, in JP-A-2008-196001.
  • the flow rate of gas is not limited.
  • the gas flow rate is, for example, 10 ml/m or more and 10,000 ml/m or less.
  • the unit [ml/m] is synonymous with [sccm].
  • Plasma is generated between a pair of film-forming rolls 2A and 2B and confined therebetween.
  • the plasma converges on the facing surfaces 2AS and 2BS of the film forming rolls 2A and 2B based on the magnetic forces generated by the magnetic field generating members 3A and 3B.
  • the gas is decomposed by the plasma.
  • the film 102 is formed on the surface 101S of the substrate 101 .
  • the membrane 102 differs depending on the type of gas.
  • the film 102 When the raw material gas contains a Si-containing gas, the film 102 contains Si as a main component. Examples of the film 102 described above include silicon oxynitride. When the raw material gas contains a C-containing gas, the film 102 contains C as a main component. When the raw material gas contains a Ti-containing gas, the film 102 contains Ti as a main component.
  • a laminate sheet 103 is manufactured in which the substrate 101 and the film 102 are provided in order on one side in the thickness direction.
  • the thickness of the film 102 is, for example, 1 nm or more, preferably 10 nm or more, and is, for example, 1,000 ⁇ m or less, preferably 100 ⁇ m or less, more preferably 10 ⁇ m or less.
  • adjusting the film 102 does not mean adjusting the physical properties of the film 102 already formed on the surface 101S of the substrate 101 .
  • the adjustment of the film 102 means evaluating the physical properties of the film 102 that has already been formed, and then adjusting the plasma CVD apparatus 1 to separately form the film 102 having physical properties different from those of the film 102 described above. do.
  • the method includes a first method and a second method.
  • the center 30A of the magnetic field generating member 3A is aligned with the line segment L in the third direction. place it on the side.
  • the center 30B of the magnetic field generating member 3B is arranged on the gas supply section 5 side with respect to the line segment L in the third direction.
  • the gas supply unit 5 side with respect to the line segment L is the upstream side with respect to the line segment L in the gas supply direction.
  • the bolt 43A is pulled out (removed) from the holes 411A and 421A. This releases the fixation of the movable plate 42A to the fixed plate 41A. Subsequently, as indicated by the arrow in FIG. 4, the movable plate 42A is moved (rotated) in the circumferential direction to move the center 30A toward the gas supply unit 5 with respect to the line segment L in the third direction ( rotate). After that, the bolt 43A is inserted through another hole 411A in the fixed plate 41A and the hole 421A in the movable plate 42A and screwed into them. The other holes 411A are positioned away from the gas supply section 5 with respect to the holes 411A in the central portion. As a result, the movable plate 42A is again fixed to the fixed plate 41A.
  • the bolt 43B is pulled out from the hole 411B and the hole 421B. This releases the fixation of the movable plate 42B to the fixed plate 41B. Subsequently, as shown in FIG. 4, the movable plate 42B is moved (rotated) in the circumferential direction, and the center 30B is moved (rotated) toward the gas supply unit 5 with respect to the line segment L in the third direction. ). After that, the bolt 43B is inserted through another hole 411B in the fixed plate 41B and the hole 421A in the movable plate 42B and screwed into them. As a result, the movable plate 42B is fixed again to the fixed plate 41B.
  • the amount of movement of the center 30A and the amount of movement of the center 30B are the same. Then, the distance between the center 30A of the magnetic field generating member 3A and the gas supply section 5 and the distance between the center 30B of the magnetic field generating member 3B and the gas supply section 5 are the same.
  • the angle X1 between the second line segment L1 connecting the center 30A of the magnetic field generating member 3A and the axis 21A of the film forming roll 2A and the line segment L is, for example, 1 degree or more, preferably , 5 degrees or more and, for example, 45 degrees or less, preferably 35 degrees or less. If the angle X1 is equal to or greater than the lower limit described above, the physical properties of the film 102 can be successfully adjusted. If the angle X1 is equal to or less than the upper limit described above, it is possible to suppress a decrease in film formation rate.
  • the angle X1 is, for example, a multiple of ⁇ regarding the hole 411A of the fixing plate 41A.
  • the angle Y1 between the third line segment (an example of the second line segment) L2 connecting the center 30B of the magnetic field generating member 3B and the axis 21B of the film forming roll 2B and the line segment L described above is It is the same as the angle X1 described above.
  • the angle Y1 is, for example, 1 degree or more, preferably 5 degrees or more, and is, for example, 45 degrees or less, preferably 35 degrees or less. If the angle Y1 is equal to or greater than the lower limit described above, the physical properties of the film 102 can be successfully adjusted. If the angle Y1 is equal to or less than the upper limit described above, it is possible to suppress a decrease in film formation rate.
  • the angle Y1 is, for example, a multiple of ⁇ described above for the hole 411B of the fixing plate 41B.
  • the film 102 made of silicon oxynitride is produced using the plasma CVD apparatus 1 after adjusting the arrangement of the pair of magnetic field generating members 3A and 3B. has superior water vapor barrier properties and high light transmittance to the film 102 made of silicon oxynitride manufactured using the plasma CVD apparatus 1 before adjustment.
  • the film 102 with adjusted water vapor barrier properties and light transmittance is manufactured.
  • the center 30A of the magnetic field generating member 3A is placed in the third direction with respect to the line segment L by the gas supply section 5. placed on the opposite side of the At the same time, the center 30B of the magnetic field generating member 3B is arranged on the side opposite to the gas supply section 5 with respect to the line segment L in the third direction.
  • the side opposite to the gas supply section 5 with respect to the line segment L is the downstream side with respect to the line segment L in the gas supply direction.
  • the bolt 43A in FIGS. 1 and 2 is pulled out (removed) from the hole 411A and the hole 421A. This releases the fixation of the movable plate 42A to the fixed plate 41A. Subsequently, as indicated by the arrow in FIG. 5, the movable plate 42A is moved (rotated) in the circumferential direction so that the center 30A is moved to the side opposite to the gas supply section 5 with respect to the line segment L in the third direction. Move (rotate). After that, the bolt 43A is inserted through another hole 411A in the fixed plate 41A and the hole 421A in the movable plate 42A and screwed into them. The other hole 411A is located in the direction of approaching the gas supply section 5 with respect to the hole 411A in the central portion. As a result, the movable plate 42A is again fixed to the fixed plate 41A.
  • the bolt 43B in FIGS. 1 and 2 is pulled out from the holes 411B and 421B. This releases the fixation of the movable plate 42B to the fixed plate 41B. Subsequently, as indicated by the arrow in FIG. 5, the movable plate 42B is moved (rotated) in the circumferential direction so that the center 30B is moved to the side opposite to the gas supply section 5 with respect to the line segment L in the third direction. Move (rotate). After that, the bolt 43B is inserted through another hole 411B in the fixed plate 41B and the hole 421A in the movable plate 42B and screwed into them. As a result, the movable plate 42B is fixed again to the fixed plate 41B.
  • the amount of movement of the center 30A and the amount of movement of the center 30B are the same. Then, the distance between the center 30A of the magnetic field generating member 3A and the gas supply section 5 and the distance between the center 30B of the magnetic field generating member 3B and the gas supply section 5 are the same.
  • the angle X2 between the second line segment L1 connecting the center 30A of the magnetic field generating member 3A and the axis 21A of the film forming roll 2A and the line segment L is, for example, 1 degree or more, preferably , 5 degrees or more and, for example, 45 degrees or less, preferably 35 degrees or less. If the angle X2 is equal to or greater than the lower limit described above, the physical properties of the film 102 can be successfully adjusted. If the angle X2 is equal to or less than the upper limit described above, it is possible to suppress a decrease in film formation rate.
  • the angle X2 is, for example, a multiple of ⁇ regarding the hole 411A of the fixing plate 41A.
  • the angle Y2 formed by the above-described line segment L and the second line segment L1 connecting the center 30B of the magnetic field generating member 3B and the axis 21B of the film forming roll 2B is the same as the above-described angle X2.
  • the angle Y2 is, for example, 1 degree or more, preferably 5 degrees or more, and is, for example, 45 degrees or less, preferably 35 degrees or less. If the angle X2 is equal to or greater than the lower limit described above, the physical properties of the film 102 can be successfully adjusted. If the angle X2 is equal to or less than the upper limit described above, it is possible to suppress a decrease in film formation rate.
  • the angle Y2 is, for example, a multiple of ⁇ described above for the hole 411B of the fixing plate 41B.
  • the film 102 made of silicon oxynitride is manufactured using the plasma CVD apparatus 1 after adjusting the arrangement of the pair of magnetic field generating members 3A and 3B.
  • the Si content ratio can be increased with respect to the film 102 manufactured using the plasma CVD apparatus 1 before adjustment and made of silicon oxynitride. That is, by adjusting the arrangement of the pair of magnetic field generating members 3A and 3B described above, the film 102 in which the Si content ratio is adjusted is manufactured.
  • This plasma CVD apparatus 1 includes a pair of position adjusting members 4A and 4B for adjusting the positions of the pair of magnetic field generating members 3A and 3B, respectively.
  • a pair of position adjusting members 4A and 4B are arranged to adjust the distance between the center 30A of one magnetic field generating member 3A and the gas supply section 5 and the distance between the center 30B of the other magnetic field generating member 5B and the gas supply section 5.
  • the positions of the pair of magnetic field generating members 3A and 3B are adjusted so that the distances are the same. Therefore, the physical properties of the film 102 can be changed according to the application and purpose.
  • the centers 30A and 30B of the magnetic field generating members are located at the gas supply section with respect to the line segment L connecting the axes 21A and 21B of the pair of film forming rolls 2A and 2B. 5 side. Therefore, the physical properties of the film 102 can be changed. For example, the water vapor barrier property of the film 102 made of silicon oxynitride is enhanced, and the light transmittance is enhanced.
  • the film 102 In the first method, if the angle X1 formed by the second line segment L1 connecting the center 30A of the magnetic field generating member 3A and the axis 21A of the film forming roll 2A and the line segment L is 1 degree or more, the film 102 The physical properties can be adjusted successfully. If the angle X1 is 45 degrees or less as described above, it is possible to suppress a decrease in the film formation rate.
  • the film 102 In the first method, if the angle Y1 between the third line segment L2 connecting the center 30B of the magnetic field generating member 3B and the axis 21B of the film forming roll 2B and the line segment L is 1 degree or more, the film 102 The physical properties can be adjusted successfully. If the angle Y1 is 45 degrees or less as described above, it is possible to suppress a decrease in the film formation rate.
  • the position adjusting members 4A and 4B rotate the magnetic field generating members 3A and 3B about the shafts 21A and 21B of the film forming rolls 2A and 2B. Easy to adjust.
  • the centers 30A and 30B of the magnetic field generating members are located at the gas supply section with respect to the line segment L connecting the axes 21A and 21B of the pair of film forming rolls 2A and 2B. 5 is placed on the opposite side. Therefore, the physical properties of the film 102 can be changed. For example, the Si content ratio in the film 102 made of silicon oxynitride can be increased.
  • the film 102 In the second method, if the angle X2 formed by the second line segment L1 connecting the center 30A of the magnetic field generating member 3A and the axis 21A of the film forming roll 2A and the line segment L is 1 degree or more, the film 102 The physical properties can be adjusted successfully. If the angle X2 is 45 degrees or less as described above, it is possible to suppress a decrease in the film formation rate.
  • the film 102 In the second method, if the angle Y2 formed by the third line segment L2 connecting the center 30B of the magnetic field generating member 3B and the axis 21B of the film forming roll 2B and the line segment L is 1 degree or more, the film 102 The physical properties can be adjusted successfully. If the angle Y2 is 45 degrees or less as described above, it is possible to suppress a decrease in film formation rate.
  • the plasma CVD apparatus 1 described above can reliably adjust the positions of the pair of magnetic field generating members 3A and 3B by the pair of position adjusting members 4A and 4B.
  • the hole 421A of the movable plate 42A has a larger diameter than the rod 431A of the bolt 43A and the hole 411A of the fixed plate 41A. .
  • the hole 421A is smaller than the head 432A of the bolt 43A.
  • the inner surface of the hole 421A of the movable plate 42A does not have to be internally threaded.
  • the axis of the hole 421A and the axis of the hole 411A match.
  • the bolt 43A and the hole 411A are screwed together.
  • the movable plate 42A is fixed to the fixed plate 41A by tightening in the second direction by the fixed plate 41A and the head 432A.
  • the magnetic field generating member 3A is moved by a multiple of the angle ⁇ (that is, the angle X1) with respect to the hole 411 of the fixed plate 41A, and then the movable plate 42A is moved as shown in FIGS. 7A and 7B. It is slightly moved (rotated) with respect to the fixed plate 41A. For example, the inner peripheral surface of the hole 421A of the movable plate 42A is brought into contact with the rod portion 431A. The magnetic field generating member 3A interlocks with the movement (rotation) of the movable plate 42A. After that, the bolt 43A is screwed onto the fixing plate 41A.
  • the angle ⁇ that is, the angle X1
  • the configuration and operation of the position adjustment member 4B and the operation of the magnetic field generation member 3B are the same as the configuration and operation of the position adjustment member 4A and the operation of the magnetic field generation member 3A, respectively.
  • the magnetic field generating member 3A can be moved (rotated) at angles smaller than the angles ⁇ and ⁇ with respect to the holes 411A and 411B.
  • each of the plurality of holes 411A in the fixed plate 41A has a larger diameter than the rod portion 431A of the bolt 43A and the hole 421A of the movable plate 42A.
  • the inner surface of each of the plurality of holes 411A in the fixing plate 41A does not have to be internally threaded.
  • the position adjusting member 4A has a nut 44A.
  • the nut 44A is arranged on the side opposite to the movable plate 42A with respect to the fixed plate 41A in the second direction.
  • the inner surface of the nut 44A has the same diameter as the outer surface of the rod portion 431A of the bolt 43A.
  • the bolt 43A and the nut 44A are screwed together.
  • the movable plate 42A is fixed to the fixed plate 41A by tightening in the second direction by the nut 44A and the head 432A.
  • the magnetic field generating member 3A is moved by a multiple of the angle ⁇ (that is, the angle X1) with respect to the hole 411 of the fixed plate 41A, and then the movable plate 42A is fixed as shown in FIG. It is slightly moved (rotated) with respect to the plate 41A.
  • the rod portion 431A is brought into contact with the inner peripheral surface of the hole 411A.
  • the magnetic field generating member 3A interlocks with the movement (rotation) of the movable plate 42A. After that, the bolt 43A is screwed onto the nut 44A.
  • the configuration and operation of the position adjustment member 4B and the operation of the magnetic field generation member 3B are the same as the configuration and operation of the position adjustment member 4A and the operation of the magnetic field generation member 3A, respectively.
  • the fixing plate 41A has one hole 411A.
  • the hole 411A is an elongated hole extending in the circumferential direction.
  • the yoke 31A is a flat plate.
  • the first surface 311A and the second surface 312A of the yoke 31A are parallel.
  • the number of magnets 32A is preferably an odd number (specifically, 3).
  • the magnets 321A and 322A positioned at both ends are shorter than the magnet 323A positioned at the center. That is, the length of the magnet 323A extending perpendicularly from the first surface 311A is longer than the length of the magnets 321A and 322A extending perpendicularly from the first surface 311A.
  • the shortest distance from one longitudinal end of the magnet 323A to the film forming roll 2A and the shortest distance from one longitudinal end of the magnets 321A and 322A to the film forming roll 2A are substantially the same.
  • the center 30A is located at the central portion in the length direction of the magnet 323A.
  • the magnetic field generating member 3B has the same configuration as the magnetic field generating member 3A described above.
  • the centers 30A and 30B of the pair of magnetic field generating members 3A and 3B are The angle X2 and the angle Y2 may be different as long as they are arranged on the opposite side of the gas supply unit 5 with respect to the line segment L.
  • the plasma CVD apparatus 1 has a pair of position adjusting members. 4A and 4B may not be provided. In this modification, the positions of the pair of magnetic field generating members 3A and 3B are adjusted in advance.
  • the plasma CVD apparatus 1 can be arranged at the pair of positions
  • the adjusting members 4A and 4B may not be provided. In this modification, the positions of the pair of magnetic field generating members 3A and 3B are adjusted in advance.
  • Example 1 A plasma CVD apparatus 1 of one embodiment shown in FIG. 1 was prepared. Each of the angles ⁇ and ⁇ was 10 degrees. Also, the centers 30A and 30B of the pair of magnetic field generating members 3A and 3B were located on the line segment L.
  • a film 102 made of silicon oxynitride with a thickness of 83.0 nm was formed on the surface 101S of a substrate 101 made of COP with a thickness of 50 ⁇ m. Film formation conditions are described below.
  • Running speed of base material 101 2.0 m/min Flow rate of TSA gas 30ml/m Oxygen gas flow rate 550ml/m Nitrogen gas flow rate 550ml/m Applied power to the film forming rolls 2A and 2B 1.0 kW
  • Example 2 In the plasma CVD apparatus 1 of Example 1, as shown in FIG. 4, the positions of the pair of magnetic field generating members 3A and 3B are adjusted by rotating the movable plates 42A and 42B of the pair of position adjusting members 4A and 4B. did.
  • the centers 30A and 30B of the pair of magnetic field generating members 3A and 3B were located on the gas supply section 5 side (upstream side in the gas supply direction) with respect to the line segment L.
  • Each of the angles X1, Y1 was 10 degrees.
  • the position-adjusted plasma CVD apparatus 1 was used to form a film 102 made of silicon oxynitride with a thickness of 81.5 nm.
  • the film formation conditions are the same as in the first embodiment.
  • Example 3 In the same manner as in Example 2, the positions of the pair of magnetic field generating members 3A and 3B are adjusted by rotating the movable plates 42A and 42B in the pair of position adjusting members 4A and 4B.
  • a film 102 made of silicon oxynitride was formed with a thickness of 79.2 nm.
  • Each of the angles X1, Y1 was 20 degrees.
  • Example 4 In the same manner as in Example 2, the positions of the pair of magnetic field generating members 3A and 3B are adjusted by rotating the movable plates 42A and 42B in the pair of position adjusting members 4A and 4B.
  • a film 102 made of silicon oxynitride was formed with a thickness of 75.9 nm.
  • Each of the angles X1, Y1 was 30 degrees.
  • Example 5 In the plasma CVD apparatus 1 of Example 1, as shown in FIG. 5, the positions of the pair of magnetic field generating members 3A and 3B are adjusted by rotating the movable plates 42A and 42B of the pair of position adjusting members 4A and 4B. did.
  • the centers 30A and 30B of the pair of magnetic field generating members 3A and 3B were located on the opposite side of the line segment L from the gas supply section 5 (downstream side in the gas supply direction).
  • Each of the angles X2, Y2 was 30 degrees.
  • the position-adjusted plasma CVD apparatus 1 was used to form a film 102 made of silicon oxynitride with a thickness of 82.6 nm.
  • the film formation conditions are the same as in the first embodiment.
  • Water vapor barrier property The water vapor barrier property of the film 102 was evaluated. The water vapor barrier property of the film 102 was measured using a water vapor transmission rate evaluation device based on the mocon method (differential pressure method). Model 3/34 from mocon was used as a water vapor transmission rate evaluation device.
  • Transmittance Y Value The transmittance Y value of the film 102 was evaluated using a spectrophotometer (Agilent Cary 7000).
  • the atomic proportions [atom %] of Si atoms, N atoms, and O atoms were measured by X-ray photoelectron analysis (ESCA).
  • X-ray photoelectron analysis Quantera SXM manufactured by ULVAC-PHI was used.
  • a plasma CVD apparatus is used in a method of forming a film on a substrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un dispositif de dépôt chimique en phase vapeur par plasma (1) comprenant une paire de rouleaux de formation de film (2A, 2B), une paire d'éléments de génération de champ magnétique (3A, 3B), une paire d'éléments de réglage de la position (4A, 4B) et une partie d'alimentation en gaz (5). Les deux rouleaux de formation de film (2A, 2B) sont disposés de façon à être séparés l'un de l'autre et opposés l'un à l'autre. Les deux éléments de génération de champ magnétique (3A, 3B) sont disposés à l'intérieur respectivement des deux rouleaux de formation de film (2A, 2B). Les deux éléments de génération de champ magnétique (3A, 3B) génèrent des champs magnétiques avec la paire de rouleaux de formation de film (2A, 2B). Les deux éléments de réglage de la position (4A, 4B) ajustent respectivement la position des deux éléments de génération de champ magnétique (3A, 3B). La partie d'alimentation en gaz (5) amène un gaz de formation de film entre les deux rouleaux de formation de film (2A, 2B). Les deux éléments de réglage de la position (4A, 4B) sont conçus de façon à régler la position des deux éléments de génération de champ magnétique (3A, 3B) de telle sorte que la distance entre la partie d'alimentation en gaz et l'un des éléments de génération de champ magnétique (3A, 3B) soit identique à la distance entre la partie d'alimentation en gaz et l'autre élément de génération de champ magnétique (3A, 3B).
PCT/JP2023/001507 2022-02-16 2023-01-19 Dispositif de dépôt chimique en phase vapeur par plasma et procédé de fabrication de film WO2023157553A1 (fr)

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JP2022022256 2022-02-16

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008196001A (ja) * 2007-02-13 2008-08-28 Kobe Steel Ltd プラズマｃｖｄ装置
JP2011080104A (ja) * 2009-10-05 2011-04-21 Kobe Steel Ltd プラズマｃｖｄ装置
JP2012126969A (ja) * 2010-12-16 2012-07-05 Kobe Steel Ltd プラズマｃｖｄ装置
JP2014156632A (ja) * 2013-02-15 2014-08-28 Kobe Steel Ltd プラズマｃｖｄ装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008196001A (ja) * 2007-02-13 2008-08-28 Kobe Steel Ltd プラズマｃｖｄ装置
JP2011080104A (ja) * 2009-10-05 2011-04-21 Kobe Steel Ltd プラズマｃｖｄ装置
JP2012126969A (ja) * 2010-12-16 2012-07-05 Kobe Steel Ltd プラズマｃｖｄ装置
JP2014156632A (ja) * 2013-02-15 2014-08-28 Kobe Steel Ltd プラズマｃｖｄ装置

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