JP2014070236A - Magnetron sputter film deposition apparatus, magnetron sputter film deposition method, and film member manufactured using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a magnetron sputter film deposition apparatus and a magnetron sputter film deposition method that can form a thin film having superior gas barrier properties and small surface unevenness, and to provide a film member having a gas barrier film which has superior gas barrier properties and small surface unevenness.SOLUTION: A magnetron sputter film deposition apparatus 1 includes a base material 20, a backing plate 31, a target 30, a magnetron sputter cathode 3 having a magnet member 32, and a microwave plasma generation device 4 irradiating the part between the base material 20 and the target 30 with a microwave plasma. The plasma density between the base material 20 and the target 30 is larger nearby the target 30 than nearby the base material 20, and electron cyclotron resonance (ECR) is caused on a surface of the target 30. The target 30 is sputtered with a generated ECR plasma P2 and flying-out sputter particles are stuck on a surface of the base material 20 to form a thin film.

Description

  The present invention relates to a magnetron sputtering film forming apparatus using a microwave plasma generating apparatus capable of generating high-density plasma under a low pressure, a magnetron sputtering film forming method, and a film member manufactured using the same.

  Development of flexible electronics such as a touch panel using a functional resin film, an organic EL (Electro Luminescence) device, and a thin-film solar cell is progressing. A product using a functional resin film has advantages such as light weight, thinness, and flexibility, but also has a problem that its lifetime is shorter than that of a conventional glass substrate product. The functional resin film is configured by laminating a functional thin film on a base resin film. For this reason, the functional thin film is likely to be deteriorated when oxygen or water vapor in the air enters the functional thin film through the base material or gas or a volatile component contained in the base material comes out as an outgas. For example, in a flexible organic EL device, when oxygen or water vapor in the air enters the hole transport layer and the electron transporting light emitting layer through the substrate, the hole transport layer and the electron transporting light emitting layer are deteriorated. Thereby, there exists a possibility that a brightness | luminance may fall or it may stop light-emission. Therefore, a gas barrier film is interposed between the base material and the anode to prevent oxygen or water vapor that has passed through the base material from entering the hole transport layer or the electron transport light emitting layer (for example, patents). Reference 1).

JP 2006-297694 A JP-A-2005-197371 Japanese Patent Laid-Open No. 7-6998 JP 2003-301268 A Japanese Patent Laid-Open No. 5-25625 JP 2002-69637 A JP 2007-169705 A

  As the gas barrier film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or the like is known. However, the gas barrier property (low permeability of oxygen, water vapor and outgas) of the conventional gas barrier film is not sufficient. For this reason, deterioration of the functional thin film cannot be suppressed.

  Usually, the gas barrier film is formed by sputtering, CVD (Chemical Vapor Deposition) or the like. Examples of the film forming method by sputtering include a bipolar sputtering method and a magnetron sputtering method. Among these, a DC (direct current) magnetron sputtering method (including a DC pulse method) is frequently used from the viewpoint of film formation speed and the like. However, the DC magnetron sputtering method has a problem that plasma is not stabilized or plasma is not generated unless a constant high voltage is applied to the target. For this reason, usually, a high voltage of several hundred volts is applied to the target. When the applied voltage is high, the frequency with which particles having a very large particle size such as cluster particles are ejected from the target increases. When particles having a large particle diameter and large variations adhere to the substrate, large irregularities are generated on the surface of the formed film. If the unevenness of the gas barrier film is large, oxygen, moisture or the like is adsorbed in the concave portion, or electrolysis concentrates on the convex portion, thereby deteriorating the functional thin film. Therefore, in order to achieve a product life that can withstand practical use in a functional resin film, it is extremely important to improve the performance of the gas barrier film and reduce the surface roughness.

  The present invention has been made in view of such circumstances, and provides a magnetron sputter film forming apparatus and a magnetron sputter film forming method capable of forming a thin film having excellent gas barrier properties and small surface irregularities. Is an issue. It is another object of the present invention to provide a film member having a gas barrier film that has excellent gas barrier properties and small surface irregularities.

  (1) In order to solve the above problems, a magnetron sputtering film forming apparatus of the present invention includes a base material, a backing plate having a facing surface facing the base material, a target disposed on the facing surface, and the backing plate. A magnetron sputtering cathode having a magnet member disposed on the opposite side of the target across the substrate, and a microwave plasma generator for irradiating microwave plasma between the base material and the target, from the target A magnetron sputtering film forming apparatus for forming a thin film by attaching sputtered sputtered particles to the surface of the substrate, wherein the microwave plasma generating apparatus includes a rectangular waveguide for transmitting microwaves and the rectangular waveguide. A slot antenna having a slot disposed on one surface of the tube and through which the microwave passes, and the slot of the slot antenna. And a surface of the plasma generation region side is provided with a dielectric part parallel to the incident direction of the microwave incident from the slot, and the plasma density between the substrate and the target is The electron cyclotron resonance (ECR) occurs on the surface of the target that is larger in the vicinity of the target than in the vicinity of the substrate.

  As a result of intensive research on film formation by the DC magnetron sputtering method, the present inventor found that if magnetron sputtering is performed while irradiating with microwave plasma, the particle diameter is reduced by applying energy to the particles ejected from the target. It was possible to reduce the unevenness on the surface of the film. However, in general, magnetron sputtering is performed under a constant low pressure in which magnetron plasma (plasma generated by magnetron discharge) is stable in order to suppress intrusion of impurities and maintain film quality. The pressure during film formation is preferably about 0.5 to 1.0 Pa. On the other hand, a general microwave plasma generation apparatus generates microwave plasma under a relatively high pressure of 5 Pa or more (see, for example, Patent Document 2). For this reason, when a conventional microwave plasma generator is used, it is difficult to generate microwave plasma under a low pressure of 1 Pa or less in which magnetron sputtering is performed. The reason is considered as follows.

  FIG. 12 is a perspective view of a microwave plasma generation unit in a conventional microwave plasma generation apparatus. As illustrated in FIG. 12, the microwave plasma generation unit 9 includes a waveguide 90, a slot antenna 91, and a dielectric unit 92. The slot antenna 91 is disposed so as to close the front opening of the waveguide 90. That is, the slot antenna 91 forms the front wall of the waveguide 90. The slot antenna 91 is formed with a plurality of slot-like slots 910. The dielectric portion 92 is disposed on the front surface (chamber side) of the slot antenna 91 so as to cover the slot 910. The microwave transmitted from the right end of the waveguide 90 passes through the slot 910 and is incident on the dielectric portion 92 as indicated by a white arrow Y1 in the front-rear direction in the drawing. The microwave incident on the dielectric portion 92 propagates along the front surface 920 of the dielectric portion 92 as indicated by the white arrow Y2 in the left-right direction in the drawing. Thereby, the microwave plasma P is generated.

  Here, the incident direction (arrow Y1) of the microwave that enters the dielectric portion 92 from the slot 910 and the front surface 920 of the dielectric portion 92 are orthogonal to each other. For this reason, the microwave incident on the dielectric part 92 is blocked by the generated microwave plasma P and propagates through the front surface 920 of the dielectric part 92 by changing the traveling direction by 90 ° (arrow Y2). As described above, since the microwave is perpendicularly incident on the generated microwave plasma P, the microwave that is the plasma source is difficult to propagate to the microwave plasma P. For this reason, it is considered that plasma generation under low pressure is difficult.

  In view of this, the present inventor has focused on the incident direction of the microwave with respect to the generated microwave plasma, and has developed a microwave plasma generating apparatus capable of generating microwave plasma even under a low pressure of 1 Pa or less. FIG. 4 is a perspective view of a microwave plasma generation unit in the microwave plasma generation apparatus of the present invention. FIG. 4 is a diagram illustrating an embodiment of a microwave plasma generation unit. FIG. 4 is not intended to limit the microwave plasma generation apparatus of the present invention.

  As shown in FIG. 4, the microwave plasma generation unit 40 includes a waveguide 41, a slot antenna 42, a dielectric part 43, and a dielectric part fixing plate 44. A tubular body 51 that transmits microwaves is connected to the left end of the waveguide 41. The slot antenna 42 is disposed so as to close the upper opening of the waveguide 41. That is, the slot antenna 42 forms the upper wall of the waveguide 41. The slot antenna 42 is formed with a plurality of slots 420 having a long hole shape. The dielectric portion 43 is disposed on the upper surface of the slot antenna 42 so as to cover the slot 420.

  The microwave transmitted from the tube part 51 passes through the slot 420 and enters the dielectric part 43 as indicated by the vertical arrow Y1 in the vertical direction in the drawing. The microwave incident on the dielectric portion 43 propagates mainly along the front surface 430 of the dielectric portion 43 as indicated by the white arrow Y2 in the left-right direction in the drawing. Thereby, the microwave plasma P1 is generated. Here, the incident direction of the microwave incident on the dielectric part 43 from the slot 420 is parallel to the front surface 430 (surface on the plasma generation region side) of the dielectric part 43. Since the microwave is incident along the generated microwave plasma, the microwave that is the plasma source easily propagates to the microwave plasma P1. For this reason, it is considered that plasma can be generated even under a low pressure of 1 Pa or less.

  As described above, according to the microwave plasma generation apparatus of the present invention, microwave plasma can be generated even under a low pressure of 1 Pa or less by making the microwave incident along the generated microwave plasma. Therefore, when the microwave plasma generation apparatus of the present invention is used, film formation by magnetron sputtering can be performed while irradiating microwave plasma under a low pressure. Thereby, since an applied voltage can be lowered | hung, the jumping out from the target of a particle | grain with a large particle diameter like a cluster particle is suppressed. Further, by performing magnetron sputtering under a low pressure, it is possible to suppress the intrusion of impurities and to increase the mean free path of the target particles. Thereby, the film quality of the formed thin film improves.

  Further, according to the magnetron sputtering film forming apparatus of the present invention, the plasma density near the target is larger than the plasma density near the substrate, and electron cyclotron resonance (ECR) occurs on the surface of the target. Further, by irradiating the target with microwave plasma, the electron density on the target surface is increased. By generating ECR on the target surface, the electron density on the target surface increases and the kinetic energy of electrons increases, resulting in an increase in sputtering energy. As a result, the number of sputtered particles jumping out of the target increases, and the particle size also increases. As a result, the film forming speed increases. And the sputtered particle | grains produced | generated are refined | miniaturized by the microwave plasma irradiated between a base material and a target, a particle diameter is adjusted, and it becomes a comparatively flat film | membrane. Therefore, according to the magnetron sputtering film forming apparatus of the present invention, it is possible to form a thin film with high density, small unevenness, and extremely high gas barrier properties at high speed. In addition, since the sputtering energy is higher than when no ECR is generated on the target surface, the deposition rate is significantly increased. Moreover, by making the plasma density near the base material smaller than the vicinity of the target, damage to the base material due to plasma can be reduced, and thermal deformation of the base material can be suppressed.

  (2) Preferably, in the configuration of the above (1), the microwave plasma generation device is further disposed on the back surface of the dielectric portion and supports the dielectric portion, and on the back surface of the support plate. And a permanent magnet that forms a magnetic field in the plasma generation region, and is preferably configured to irradiate microwave plasma while generating ECR from the microwave propagating into the magnetic field from the dielectric portion. .

  In the microwave plasma generation apparatus of this configuration, the surface on the plasma generation region side is referred to as “front surface”, and the surface facing away from the surface is referred to as “back surface”. In this configuration, microwaves are incident along the generated microwave plasma (configuration (1) above), and microwave plasma is irradiated while generating ECR. Below, an example of the microwave plasma production | generation part in the microwave plasma production | generation apparatus of this structure is demonstrated.

  FIG. 5 is a perspective view of a microwave plasma generation unit in the microwave plasma generation apparatus of this configuration. In FIG. 5, the members corresponding to those in FIG. FIG. 5 is a diagram illustrating an embodiment of a microwave plasma generation unit (see the embodiment described later). For convenience of explanation, here, a slit plate disposed on the surface side of the dielectric portion in the embodiment described later is omitted. FIG. 5 is not intended to limit the microwave plasma generation apparatus of the present invention.

  As shown in FIG. 5, the microwave plasma generation unit 40 includes a waveguide 41, a slot antenna 42, a dielectric part 43, a support plate 45, and a permanent magnet 46. Eight permanent magnets 46 are arranged behind the dielectric part 43 via a support plate 45. Each of the eight permanent magnets 46 has an N pole on the front side and an S pole on the rear side. Magnetic field lines M are generated from each permanent magnet 46 toward the front. Thereby, a magnetic field is formed in front of the dielectric part 43 (plasma generation region).

Electrons in the generated microwave plasma perform a clockwise turning motion with respect to the direction of the magnetic force line M in accordance with the cyclotron angular frequency _ωce . On the other hand, the microwave propagating in the microwave plasma excites a clockwise circular polarization called an electron cyclotron wave. When the electron cyclotron wave propagates forward and its angular frequency ω matches the cyclotron angular frequency ω _ce , the electron cyclotron wave is attenuated and wave energy is absorbed by the electrons. That is, ECR occurs. For example, when the frequency of the microwave is 2.45 GHz, ECR occurs at a magnetic flux density of 87.5 mT. Electrons whose energy has been increased by ECR collide with surrounding neutral particles while being restrained by the magnetic lines of force M. Thereby, neutral particles are ionized one after another. Electrons generated by ionization are also accelerated by ECR and further ionize neutral particles. In this way, high-density ECR plasma P1 _ECR is generated in front of the dielectric portion 43.

  As described above, according to the microwave plasma generation apparatus of the present configuration, the microwave is incident along the generated microwave plasma and the plasma density is increased by using the ECR. Can generate plasma even under an extremely low pressure of 0.01 Pa or less. Therefore, when the microwave plasma generating apparatus having this configuration is used, it is possible to perform film formation by magnetron sputtering while irradiating ECR plasma under low pressure or extremely low pressure. Thereby, the plasma density of the target surface can be increased. The sputtered particles that have jumped out of the target are refined by high-density ECR plasma that is irradiated between the base material and the target. Therefore, according to the magnetron sputtering film forming apparatus of this configuration, it is possible to form a thin film with higher density, less unevenness, and extremely high gas barrier properties.

  Note that Patent Document 3 discloses a microwave plasma generation apparatus that generates ECR by microwaves. In the microwave plasma generator of Patent Document 3, a magnetic field is formed by an air-core coil. However, if an air-core coil is used, it is restricted by the coil diameter or the like, and thus plasma cannot be generated over a long and wide area. In this regard, according to the microwave plasma generation apparatus of this configuration, a long ECR plasma can be generated by arranging slots in the longitudinal direction using a long rectangular waveguide. Therefore, a large-area thin film can be formed by incorporating it into a magnetron sputtering film forming apparatus.

  Further, Patent Document 4 discloses a magnetron sputtering film forming apparatus using ECR. In the magnetron sputtering film forming apparatus of Patent Document 4, a magnet is disposed on the back side of a base material to be formed, and ECR plasma is generated near the surface of the base material. However, if a magnet is disposed on the back side of the base material, the thickness of the thin film formed tends to vary. In addition, there is a problem that the thin film is easily colored. Moreover, in the magnetron sputter film-forming apparatus of patent document 4, the microwave is radiated | emitted from the helical antenna. For this reason, it is difficult for the microwave to propagate uniformly throughout the plasma generation region. In addition, there is no directivity from the antenna to the plasma generation region due to the magnetic field. Furthermore, since the plasma density in the vicinity of the target cannot be increased, no ECR occurs on the surface of the target.

  In this regard, in the microwave plasma generation apparatus of the present invention, a permanent magnet is disposed on the back surface side of the dielectric portion, and the microwave is propagated along the surface of the dielectric portion. That is, no permanent magnet is disposed in the vicinity of the base material. Therefore, in the thin film formed by the magnetron sputtering film forming apparatus of the present invention, thickness variations and coloring problems are unlikely to occur.

(3) Preferably, in the configuration of the above (1) or (2), the magnet member may be configured to form a magnetic field satisfying the following formula (I) on the surface of the target.
B ≧ f · 2πm / e (I)
[B: magnetic flux density (T), f: microwave frequency (Hz), m: electron mass (kg), e: electron charge (C)]
According to this configuration, ECR can be reliably generated on the surface of the target.

  (4) Preferably, in the configuration of (3) above, when the frequency of the microwave is 2.45 GHz, the magnet member forms a magnetic field having a magnetic flux density of 87.5 mT or more on the surface of the target. Better to do.

  When the frequency of the microwave is 2.45 GHz, the magnetic flux density that satisfies the above formula (I) is 87.5 mT or more. Therefore, according to this configuration, ECR can be reliably generated on the surface of the target.

  (5) Preferably, in any one of the configurations (1) to (4), the slot antenna is configured to be disposed on the H surface of the rectangular waveguide.

  A slot is formed in the slot antenna. Even if a slot is provided on the E surface of the rectangular waveguide, it is difficult to control the microwave radiation energy. According to this configuration, since the slot is provided at a specific position on the H plane of the rectangular waveguide, the microwave radiation energy can be easily controlled, and high-density plasma can be generated.

  (6) Preferably, in any one of the configurations (1) to (5), the microwave plasma generation apparatus further includes a slit plate disposed on the surface side of the dielectric portion and having a slit, It is preferable that the microwave plasma generated on the surface of the dielectric portion is irradiated through the slit.

  According to this configuration, the irradiation direction of microwave plasma (including ECR plasma) can be adjusted by adjusting the size of the slit and the position to be formed. That is, by adjusting the size of the slit and the position to be formed, the microwave plasma can be irradiated so that the plasma density near the target becomes larger than the plasma density near the substrate. Thereby, ECR can be efficiently generated on the surface of the target while suppressing thermal deformation or the like of the base material.

  (7) Preferably, in any one of the configurations (1) to (6), the magnet member includes a central magnet disposed in a central portion of the backing plate, and the central magnet so as to surround the central magnet. A peripheral magnet disposed on the peripheral edge of the backing plate, the polarity at the target side end of the central magnet is N pole, and the polarity at the target side end of the peripheral magnet is S pole It is better to have a configuration.

  The microwave plasma irradiated from the microwave plasma generator is attracted to the south pole of the magnet member disposed on the magnetron sputter cathode. In the magnetron sputtering cathode, the peripheral magnet is disposed so as to surround the central magnet. For this reason, the peripheral magnet is closer to the microwave plasma generator than the central magnet. Here, the microwave plasma is irradiated near the target surface. Therefore, when the polarity at the end on the target side of the peripheral magnet is the S pole, the microwave plasma can be easily attracted toward the target, and the generation of ECR on the target surface can be promoted.

  (8) Preferably, in any one of the configurations (1) to (7), the magnet member may be configured to form an equilibrium magnetic field on the surface of the target.

  The magnetic field formed on the target surface by the magnet member may be in an equilibrium state or a non-equilibrium state. In the equilibrium state, since the magnetic field is closed on the target surface, the generated plasma tends to stay on the target surface. On the other hand, in the non-equilibrium state, part of the magnetic lines of force extend in the direction of the base material, so that the plasma on the target surface easily diffuses to the vicinity of the base material along the magnetic field lines. As a result, the substrate may be damaged by the plasma. In this respect, according to the present configuration, damage to the base material due to plasma can be reduced, and thermal deformation or the like of the base material can be suppressed.

  (9) Preferably, in any one of the configurations (1) to (8), the film formation on the base material is performed under a pressure of 0.01 Pa to 5 Pa.

  As described above, the microwave plasma generation apparatus can generate stable plasma even under a low pressure of 1 Pa or less. In addition, by irradiating microwave plasma, stable plasma is generated under a low pressure even in a strong magnetic field near the target. As shown in a later example, a thin film having a high gas barrier property can be formed at a high film formation rate by performing sputter film formation under a low pressure.

  (10) The magnetron sputtering film forming method of the present invention uses the magnetron sputtering film forming apparatus having any one of the constitutions (1) to (9), and the inside of the chamber of the magnetron sputter film forming apparatus has a predetermined degree of vacuum. A thin film is formed on the surface of the substrate by introducing a gas into the chamber and sputtering the target with ECR plasma generated on the surface of the target under a predetermined pressure. And a film forming step.

  According to the magnetron sputtering film forming method of the present invention, by forming ECR on the target surface and sputtering the target with ECR plasma, it is possible to form a thin film with high density, small unevenness, and extremely high gas barrier properties. In addition, since the sputtering energy is higher than when no ECR is generated on the target surface, a thin film with high gas barrier properties can be formed at a high deposition rate. Further, since the plasma density in the vicinity of the base material is smaller than that in the vicinity of the target, damage to the base material due to plasma can be reduced, and thermal deformation of the base material can be suppressed.

  (11) The film member of the present invention has a base material made of a resin film and a gas barrier film disposed on at least one side of the base material, and the gas barrier film has the structure of (10) above. It is formed by a magnetron sputtering film forming method.

  The film member of the present invention has excellent gas barrier properties and small surface irregularities. Therefore, when the film member of the present invention is used, for example, in an organic EL device, entry of oxygen, water vapor, and outgas to the hole transport layer and the electron transporting light emitting layer can be suppressed. Moreover, since there are few surface unevenness | corrugations, the concentration of electrolysis etc. is hard to produce, and deterioration of a hole transport layer or an electron transport light emitting layer can be suppressed. As a result, the product life can be extended.

  A gas barrier film | membrane may be arrange | positioned only at one among the front and back both sides of a base material, and may be arrange | positioned at both sides. When the gas barrier film is disposed on both the front and back sides of the substrate, the low permeability of oxygen and water vapor can be further improved. For example, when the gas barrier films are arranged on both the front and back sides of the substrate, the magnetron sputtering film formation may be performed once for each of the front and back surfaces of the substrate. An intermediate layer may be disposed between the base material and the gas barrier film.

1 is a cross-sectional view in the left-right direction of a magnetron sputtering film forming apparatus according to a first embodiment of the present invention. It is a front-back direction sectional drawing of the same magnetron sputter film-forming apparatus. It is a top view of the magnet member in a magnetron sputter cathode. It is a perspective view of the 1st microwave plasma generation part in a microwave plasma generator. It is a perspective view of the 2nd microwave plasma generation part in a microwave plasma generator. 4 is an SPM photograph of an AlON film of Comparative Example 1. 2 is a SPM photograph of the AlON film of Example 1. 5 is a graph showing film formation rates of Examples 1 and 2 and Comparative Example 2. It is a graph which shows the relationship between the film-forming time in each film member of Examples 1, 2 and Comparative Example 2, and a gas permeation ratio. 4 is a graph showing the relationship between reaction pressure, gas permeation ratio, and film formation rate in the film member of Example 1. 6 is a graph showing the relationship between the output of microwave plasma and the gas transmission ratio in the film member of Example 1. It is a perspective view of the microwave plasma production | generation part in the conventional microwave plasma production | generation apparatus.

  Hereinafter, embodiments of a magnetron sputtering film forming apparatus, a magnetron sputtering film forming method, and a film member of the present invention will be described.

<First embodiment>
[Magnetron sputtering deposition system]
First, the configuration of the magnetron sputtering film forming apparatus of this embodiment will be described. FIG. 1 is a cross-sectional view in the left-right direction of the magnetron sputtering film forming apparatus of this embodiment. FIG. 2 shows a cross-sectional view in the front-rear direction of the magnetron sputtering film forming apparatus. FIG. 3 shows a top view of the magnet member in the magnetron sputtering cathode. FIG. 5 is a perspective view of a microwave plasma generation unit in the microwave plasma generation apparatus. For convenience of explanation, the thickness and length of members are exaggerated in each drawing. In FIG. 3, the magnet member is shown hatched.

  As shown in FIGS. 1 and 2, the magnetron sputtering film forming apparatus 1 includes a chamber 8, a base material 20, a base material support member 21, a magnetron sputter cathode 3, and a microwave plasma generation device 4. ing.

The chamber 8 is made of aluminum and has a rectangular parallelepiped box shape. A carrier gas supply hole 80 is formed in the left wall of the chamber 8. The carrier gas supply hole 80 is connected to a downstream end of a gas supply pipe (not shown) for supplying argon (Ar) gas into the chamber 8. A first gas supply hole 81 and a second gas supply hole 82 are formed in the right wall of the chamber 8. A downstream end of a gas supply pipe (not shown) for supplying nitrogen (N ₂ ) gas into the chamber 8 is connected to the first gas supply hole 81. Similarly, a downstream end of a gas supply pipe (not shown) for supplying oxygen (O ₂ ) gas into the chamber 8 is connected to the second gas supply hole 82. An exhaust hole 83 is formed in the lower wall of the chamber 8. A vacuum exhaust device (not shown) for exhausting the gas inside the chamber 8 is connected to the exhaust hole 83.

  The substrate support member 21 includes a table portion 210 and a pair of leg portions 211. The table part 210 is made of stainless steel and has a hollow rectangular plate shape. The table portion 210 is filled with a cooling liquid. The table unit 210 is cooled by circulating the coolant. The pair of leg portions 211 are arranged on the upper surface of the table portion 210 so as to be separated in the left-right direction. Each of the pair of leg portions 211 is made of stainless steel and has a cylindrical shape. The outer peripheral surfaces of the pair of leg portions 211 are covered with an insulating layer. The table part 210 is attached to the upper wall of the chamber 8 via a pair of leg parts 211.

  The substrate 20 is a polyethylene naphthalate (PEN) film and has a rectangular shape. The base material 20 is attached to the lower surface of the table unit 210.

  The magnetron sputtering cathode 3 includes a target 30, a backing plate 31, a magnet member 32, a case 33, and an earth shield 34.

  The case 33 is made of stainless steel and has a rectangular parallelepiped box shape opening upward. The length of the case 33 in the left-right direction is 1000 mm, and the length in the front-rear direction is 100 mm. The case 33 is connected to a DC pulse power source 35.

  The backing plate 31 is made of copper and has a rectangular plate shape. The thickness of the backing plate 31 is 10 mm. The backing plate 31 is disposed so as to cover the upper opening of the case 33. The upper surface of the backing plate 31 is included in a facing surface that faces the substrate 20. On the lower surface of the backing plate 31, a groove portion 310 that accommodates the upper end portion of the magnet member 32 is formed. The depth of the groove part 310 is 5 mm.

  The target 30 is made of aluminum and has a rectangular thin plate shape. The thickness of the target 30 is 6 mm. The target 30 is disposed on the upper surface of the backing plate 31. The target 30 is disposed to face the base material 20. The distance from the target 30 to the base material 20 is 100 mm.

  The magnet member 32 is disposed inside the case 33. As shown in FIG. 3, the magnet member 32 has 18 central magnets 320 and 38 peripheral magnets 321. The center magnet 320 and the peripheral magnet 321 are both neodymium magnets. Each of the central magnets 320 has a rectangular parallelepiped shape with a width of 25 mm, a length of 50 mm, and a thickness of 30 mm. The center magnet 320 is arranged in a straight line extending in the left-right direction at the center of the case 33. Each upper end of the central magnet 320 is accommodated in a groove 310 formed on the lower surface of the backing plate 31. The polarity of the upper end of the central magnet 320 is N pole, and the polarity of the lower end is S pole. Each of the peripheral magnets 321 has a rectangular parallelepiped shape having a width of 15 mm, a length of 50 mm, and a thickness of 30 mm. The peripheral portion magnet 321 is arranged in a ring shape on the peripheral portion of the case 33. The peripheral magnet 321 is disposed so as to surround the central magnet 320. Each upper end of the peripheral magnet 321 is accommodated in a groove 310 formed on the lower surface of the backing plate 31. The polarity of the upper end of the peripheral magnet 321 is the S pole, and the polarity of the lower end is the N pole.

  An equilibrium magnetic field M <b> 1 is formed on the upper surface of the target 30 by the central magnet 320 and the peripheral magnet 321. The magnetic flux density on the upper surface of the target 30 is 320 mT at the center and 190 mT at the periphery.

  The ground shield 34 is disposed so as to surround the case 33, the target 30, and the backing plate 31. An earth shield 34 is interposed between the lower peripheral edge of the case 33 and the lower wall of the chamber 8.

  The microwave plasma generation device 4 includes a microwave plasma generation unit 40 and a microwave transmission unit 50. The microwave transmission unit 50 includes a tube unit 51, a microwave power source 52, a microwave oscillator 53, an isolator 54, a power monitor 55, and an EH matching unit 56. The microwave oscillator 53, the isolator 54, the power monitor 55, and the EH matching unit 56 are connected by the tube part 51. The tube part 51 is connected to the rear side of the waveguide 41 of the microwave plasma generation part 40 through a waveguide hole formed in the rear wall of the chamber 8.

  The microwave plasma generation unit 40 includes a waveguide 41, a slot antenna 42, a dielectric part 43, a support plate 45, a permanent magnet 46, and a slit plate 47. As shown in FIG. 5, the waveguide 41 is made of aluminum and has a rectangular parallelepiped box shape opening upward. The waveguide 41 extends in the left-right direction. The waveguide 41 is included in the rectangular waveguide in the present invention. The slot antenna 42 is made of aluminum and has a rectangular plate shape. The slot antenna 42 closes the opening of the waveguide 41 from above. That is, the slot antenna 42 forms the upper wall of the waveguide 41. The slot antenna 42 is disposed on the H surface of the waveguide 41. Four slots 420 are formed in the slot antenna 42. The slot 420 has a long hole shape extending in the left-right direction. The slot 420 is disposed at a position where the electric field is strong.

  The dielectric portion 43 is made of quartz and has a rectangular parallelepiped shape. The dielectric part 43 is disposed on the front side of the upper surface of the slot antenna 42. The dielectric part 43 covers the slot 420 from above. As described above, the front surface 430 of the dielectric portion 43 is disposed in parallel to the incident direction Y1 of the microwave incident from the slot 420. The front surface 430 is included in the surface on the plasma generation region side in the dielectric portion.

  The support plate 45 is made of stainless steel and has a flat plate shape. The support plate 45 is disposed on the upper surface of the slot antenna 42 so as to be in contact with the rear surface (back surface) of the dielectric portion 43. A refrigerant passage 450 is formed inside the support plate 45. The refrigerant passage 450 has a U shape extending in the left-right direction. The right end of the refrigerant passage 450 is connected to the cooling pipe 451. The refrigerant passage 450 is connected to a heat exchanger and a pump (both not shown) outside the chamber 8 via a cooling pipe 451. The coolant circulates in the path of the refrigerant passage 450 → the cooling pipe 451 → the heat exchanger → the pump → the cooling pipe 451 → the refrigerant passage 450 again. The support plate 45 is cooled by the circulation of the coolant.

  The permanent magnet 46 is a neodymium magnet and has a rectangular parallelepiped shape. Eight permanent magnets 46 are arranged on the rear surface (back surface) of the support plate 45. The eight permanent magnets 46 are arranged in series continuously in the left-right direction. Each of the eight permanent magnets 46 has an N pole on the front side and an S pole on the rear side. Magnetic field lines M are generated from each permanent magnet 46 toward the front. Thereby, a magnetic field is formed in the plasma generation region in front of the dielectric part 43.

  The slit plate 47 is made of stainless steel and has a flat plate shape extending in the left-right direction. The slit plate 47 is disposed so as to cover the front of the dielectric portion 43. The slit plate 47 is supported by the front wall of the waveguide 41 and the mounting member 48. A slit 470 extending in the left-right direction is formed near the center of the slit plate 47. The slit 470 has a long hole shape with a width of 25 mm.

[Magnetron sputtering film forming method]
Next, a film forming method using the magnetron sputter film forming apparatus 1 will be described. In this embodiment, an aluminum oxynitride film (AlON film) as a gas barrier film is formed on the surface of the PEN film (base material). The magnetron sputtering film forming method of this embodiment includes a pressure reducing process and a film forming process. In the decompression step, a vacuum exhaust device (not shown) is operated to exhaust the gas inside the chamber 8 from the exhaust hole 83, and the inside of the chamber 8 is brought into a decompressed state of about 0.008 Pa.

In the film forming process, first, Ar gas as a carrier gas is supplied into the chamber 8. Subsequently, N ₂ gas as a source gas is supplied into the chamber 8. Thereby, the pressure in the chamber 8 is set to about 0.4 Pa. Further, O ₂ gas as a raw material gas is supplied into the chamber 8 as necessary.

  Next, the microwave power source 52 is turned on. When the microwave power source 52 is turned on, the microwave oscillator 53 generates a microwave having a frequency of 2.45 GHz. The generated microwave propagates in the tubular body portion 51. Here, the isolator 54 suppresses the microwave reflected from the microwave plasma generation unit 40 from returning to the microwave oscillator 53. The power monitor 55 monitors the output of the generated microwave and the output of the reflected microwave. The EH matching device 56 adjusts the amount of reflected microwaves. The microwaves that have passed through the tube part 51 propagate inside the waveguide 41. The microwave propagating inside the waveguide 41 enters the slot 420 of the slot antenna 42. Then, as indicated by a hollow arrow Y1 in FIG. The microwave that has entered the dielectric portion 43 propagates mainly along the front surface 430 of the dielectric portion 43, as indicated by a hollow arrow Y2 in FIG. Due to the strong electric field of the microwave, the argon gas is ionized and a microwave plasma is generated in front of the dielectric portion 43. The generated microwave plasma passes through the slit 470 and is irradiated in the forward direction and the target 30 direction.

  Electrons in the microwave plasma perform a clockwise turning motion with respect to the direction of the magnetic field line M according to the cyclotron angular frequency. On the other hand, the microwave propagating through the microwave plasma excites the electron cyclotron wave. The angular frequency of the electron cyclotron wave is a magnetic flux density of 87.5 mT and matches the cyclotron angular frequency. This causes ECR. Electrons whose energy has been increased by ECR collide with surrounding neutral particles while being restrained by the magnetic lines of force M. Thereby, neutral particles are ionized one after another. Electrons generated by ionization are also accelerated by ECR and further ionize neutral particles. In this way, ECR plasma is generated.

Next, the DC pulse power supply 35 is turned on, and a voltage is applied to the magnetron sputtering cathode 3. The magnetic flux density on the upper surface of the target 30 is 320 mT at the center and 190 mT at the periphery. Thereby, ECR is generated on the upper surface of the target 30 by magnetron discharge and irradiated microwave plasma, and ECR plasma P2 is generated. The density of the ECR plasma P2 is greater near the target 30 than near the substrate 20. The target 30 is sputtered by the generated ECR plasma P2 (argon ions), and sputtered particles are knocked out of the target 30. The sputtered particles that have jumped out of the target 30 scatter toward the base material 20 while reacting with the N ₂ gas and the O ₂ gas, and adhere to the lower surface of the base material 20. The ECR plasma is irradiated on the sputtered particles even while heading toward the substrate 20. In this way, an AlON film is formed on the lower surface of the substrate 20. The film member consisting of the base material 20 (PEN film) and the AlON film is included in the film member of the present invention.

[Function and effect]
Next, the effects of the magnetron sputtering film forming apparatus, the magnetron sputtering film forming method, and the film member of this embodiment will be described.

  In the microwave plasma generation apparatus 4 of the present embodiment, the front surface 430 of the dielectric part 43 is disposed perpendicular to the slot antenna 42. Thereby, the incident direction Y1 of the microwave that enters the dielectric portion 43 from the slot 420 is parallel to the front surface 430 of the dielectric portion 43. In this case, the microwave is incident along the generated microwave plasma. Therefore, the microwave that is the plasma source is easily propagated to the microwave plasma.

  A magnetic field is formed in front of the dielectric portion 43. The magnetic field lines M extend forward from the dielectric part 43. As the microwave propagates from the dielectric part 43 into the magnetic field, ECR is generated. Thereby, ECR plasma is generated in front of the dielectric portion 43. As described above, according to the microwave plasma generation apparatus 4, the microwave is incident along the generated microwave plasma and the plasma density is increased by using ECR, so that even under a low pressure of about 0.4 Pa. ECR plasma can be generated.

  According to the magnetron sputtering film forming apparatus 1, ECR occurs on the upper surface of the target 30. For this reason, the electron density on the upper surface of the target 30 increases, the kinetic energy of electrons increases, and the sputtering energy increases. As a result, sputtered particles having a relatively large particle size and a small variation in particle size are generated. The generated sputtered particles are refined by ECR plasma irradiated between the base material 20 and the target 30. Therefore, according to the magnetron sputter deposition apparatus 1, it is possible to form an AlON film that is dense and has small irregularities and extremely high gas barrier properties. Further, since the sputtering energy is higher than when no ECR is generated on the upper surface of the target 30, the film formation rate can be increased. Moreover, the plasma density near the base material 20 is smaller than the plasma density near the target 30. Therefore, damage to the base material 20 due to plasma is small, and thermal deformation or the like of the base material 20 is suppressed.

  A balanced magnetic field M <b> 1 is formed on the upper surface of the target 30 by the central magnet 320 and the peripheral magnet 321. In this case, the ECR plasma P <b> 2 generated on the upper surface of the target 30 is difficult to diffuse in the direction of the base material 20. Therefore, thermal deformation of the base material 20 due to plasma can be suppressed. The magnetic flux density on the upper surface of the target 30 is 320 mT at the center and 190 mT at the periphery. The microwave frequency used in the microwave plasma generator 4 is 2.45 GHz. Therefore, ECR is reliably generated on the upper surface of the target 30. The polarity at the upper end of the peripheral magnet 321 close to the microwave plasma generation device 4 is the S pole. Therefore, the microwave plasma irradiated from the microwave plasma generator 4 can be drawn toward the target 30. Thereby, the production | generation of ECR can be accelerated | stimulated.

  In the microwave plasma generation unit 40, a slit plate 47 is disposed in front of the dielectric unit 43. The slit plate 47 is formed with a long slit 470 having a width of 25 mm. By passing the microwave plasma generated on the front surface 430 of the dielectric part 43 through the slit 470, the ECR plasma can be irradiated in the direction of the target 30 instead of in the direction of the substrate 20. Thereby, the plasma density near the target 30 can be made larger than the plasma density near the substrate 20. As a result, it is possible to efficiently generate ECR on the upper surface of the target 30 while suppressing thermal deformation or the like of the base material 20.

  In the microwave plasma generation apparatus 4, the waveguide 41 has a long box shape extending in the left-right direction. The slots 420 are arranged in series in the left-right direction. Therefore, according to the microwave plasma generation apparatus 4, it is possible to generate a long ECR plasma. Therefore, according to the magnetron sputtering film forming apparatus 1, a long and large AlON film can be formed. The eight permanent magnets 46 are arranged behind the dielectric part 43. Then, the microwave is propagated in the magnetic field formed in front of the dielectric part 43. For this reason, the microwave easily propagates uniformly throughout the plasma generation region. Further, the eight permanent magnets 46 are disposed on the rear surface of the support plate 45. A refrigerant passage 450 is formed inside the support plate 45. The support plate 45 is cooled by circulating the coolant through the coolant passage 450. For this reason, it is difficult for the temperature of the permanent magnet 46 to rise. Therefore, there is little possibility that the magnetism of the permanent magnet 46 will decrease due to the temperature rise. Therefore, a stable magnetic field is formed even during plasma generation.

  The AlON film formed by the magnetron sputtering film forming method of this embodiment is dense, has small surface irregularities, and has extremely high gas barrier properties. Therefore, the manufactured film member is suitable for an organic EL device or the like.

<Second embodiment>
The difference between the magnetron sputtering film forming apparatus of this embodiment and the magnetron sputtering film forming apparatus of the first embodiment is that a non-equilibrium magnetic field is formed on the upper surface of the target by reducing the magnetic force by reducing the width of the central magnet This is the point. Therefore, only the differences will be described here.

  Also in the magnetron sputter cathode of this embodiment, the magnet member has 18 center magnets and 38 peripheral magnets as in the first embodiment (see FIG. 3 above). . In this embodiment, a rectangular parallelepiped neodymium magnet having a width of 15 mm, a length of 50 mm, and a thickness of 30 mm was used as the central magnet. Thereby, a non-equilibrium magnetic field is formed on the upper surface of the target. The magnetic flux density on the upper surface of the target is 240 mT at the center and 180 mT at the periphery.

  The magnetron sputtering film forming apparatus and magnetron sputtering film forming method of this embodiment have the same functions and effects as those of the magnetron sputtering film forming apparatus and magnetron sputtering film forming method of the first embodiment with respect to common parts. doing. In the magnetron sputtering film forming apparatus of this embodiment, a non-equilibrium state is formed on the upper surface of the target by breaking the magnetic force balance between the central magnet and the peripheral magnet. In this case, since part of the magnetic force lines extend in the direction of the base material, the plasma generated on the target surface diffuses to the vicinity of the base material along the magnetic force lines. Therefore, according to the magnetron sputtering film forming apparatus and the magnetron sputtering film forming method of this embodiment, the film forming speed can be further increased.

<Others>
The embodiments of the magnetron sputtering film forming apparatus and the magnetron sputtering film forming method of the present invention have been described above. However, the embodiments of the magnetron sputtering film forming apparatus and the magnetron sputtering film forming method are not limited to the above-described forms. Various modifications and improvements that can be made by those skilled in the art are also possible.

  For example, in the above embodiment, the magnet member in the magnetron sputtering cathode is constituted by the central magnet and the peripheral magnet. However, the magnet member only needs to be able to form a magnetic field in which ECR is generated on the surface of the target, and the configuration, arrangement, type, number, size, and the like of the magnet member are not particularly limited. For example, instead of a neodymium magnet, a samarium cobalt magnet may be used as the magnet. In the said embodiment, the polarity of the target side edge part of a center part magnet was made into N pole, and the polarity of the target side edge part of a peripheral part magnet was made into S pole. However, you may arrange | position a center part magnet and a peripheral part magnet so that polarity may respectively be reversed. Further, the magnetic flux density on the target surface may be changed according to the frequency of the microwave. In the above embodiment, microwaves having a frequency of 2.45 GHz are used for generating microwave plasma. However, the frequency of the microwave is not limited to the 2.45 GHz band, and any frequency band may be used as long as it is a frequency band of 300 MHz to 100 GHz. Examples of the frequency band in this range include 8.35 GHz, 1.98 GHz, 915 MHz, and the like.

  In the above embodiment, the slit plate is disposed in front of the dielectric part of the microwave plasma generation part. In this case, the slit width is not limited to the above embodiment. The irradiation direction of microwave plasma (ECR plasma) may be adjusted by adjusting the slit width. Moreover, it is not necessary to arrange a slit plate. For example, the microwave plasma may be irradiated in the target direction by changing the angle of the microwave plasma generation unit.

  In the above embodiment, a permanent magnet is disposed on the back surface side of the dielectric portion, and microwave plasma is irradiated while generating ECR. However, as shown in FIG. 4, the microwave plasma generation unit that does not include a permanent magnet may be used to irradiate microwave plasma without generating ECR.

  The material of the slot antenna, the number of slots, the shape, the arrangement, etc. are not particularly limited. For example, the material of the slot antenna may be a nonmagnetic metal, and may be stainless steel or brass in addition to aluminum. Further, the slots may be arranged in two or more rows instead of one row. The number of slots may be odd or even. Further, the slots may be arranged in a zigzag shape by changing the arrangement angle of the slots. The material and shape of the dielectric part are not particularly limited. As a material of the dielectric portion, a material having a low dielectric constant and hardly absorbing microwaves is desirable. For example, aluminum oxide (alumina) other than quartz is suitable.

  The shape, type, number, arrangement form, and the like of the permanent magnet that forms a magnetic field in front of the dielectric portion (plasma generation region) are not particularly limited as long as ECR can be generated. For example, only one permanent magnet may be disposed, or a plurality of permanent magnets may be disposed in two or more rows.

  The permanent magnet is disposed on the back surface side of the dielectric part via the support plate. For this reason, when generating plasma, the temperature of the permanent magnet is likely to rise. When the temperature of the permanent magnet is equal to or higher than the Curie temperature, the magnetism is lost. For this reason, in the said embodiment, in order to suppress the temperature rise of a permanent magnet, the refrigerant path and the cooling fluid were arrange | positioned as a cooling means of a support plate. However, the structure of the cooling means for the support plate is not particularly limited. The material and shape of the support plate are not particularly limited. Moreover, the support plate does not need to have a cooling means.

In the above embodiment, an AlON film was formed by using aluminum as a target and introducing Ar gas, N ₂ gas, and O ₂ gas into the chamber. However, the type of thin film to be formed is not particularly limited. What is necessary is just to select suitably also about the material and gas composition of a target according to the kind of thin film to form. For example, when an indium oxide-tin oxide composite oxide (ITO) is used as a target and Ar gas is introduced into the chamber, an ITO film can be formed. In the above embodiment, the film was formed under a pressure of about 0.4 Pa. However, the pressure during film formation is not particularly limited. The film formation may be performed under an optimum pressure as appropriate in consideration of stable generation of plasma and a film formation speed.

  What is necessary is just to select suitably also about a base material according to a use. In addition to the PEN film of the above embodiment, for example, polyethylene terephthalate (PET) film, polyphenylene sulfide (PPS) film, polyamide (PA) 6 film, PA11 film, PA12 film, PA46 film, polyamide MXD6 film, PA9T film, polyimide ( PI film, polycarbonate (PC) film, fluororesin film, ethylene-vinyl alcohol copolymer (EVOH) film, polyvinyl alcohol (PVA) film, polyethylene (PE), polypropylene (PP), polyolefin film such as cycloolefin polymer Etc. can be used.

  The material and shape of the chamber, the substrate support member, the backing plate in the magnetron sputtering cathode, and the case are not particularly limited. For example, the chamber may be made of metal, and it is desirable to employ a highly conductive material. The table portion of the substrate support member may not be cooled. A nonmagnetic conductive material may be used for the backing plate. Among these, a metal material such as copper having high conductivity and heat conductivity is desirable. The case can be made of metal such as aluminum in addition to stainless steel.

  Next, the present invention will be described more specifically with reference to examples.

<Surface condition of AlON film>
(1) Example 1
An AlON film was formed on the surface of the PEN film using the magnetron sputtering film forming apparatus of the first embodiment. Hereinafter, the reference numerals of the members correspond to those in FIGS. 1 to 3 and FIG. As the PEN film, “Teijin (registered trademark) Tetron (registered trademark) film Q65FA (thickness: 200 μm)” manufactured by Teijin DuPont Films Ltd. was used.

First, in the decompression step, a vacuum exhaust device (not shown) was operated to exhaust the gas inside the chamber 8 from the exhaust hole 83, and the inside of the chamber 8 was brought into a decompressed state of about 0.008 Pa. Next, in the film forming process, Ar gas is supplied, the internal pressure of the chamber 8 is set to 0.7 Pa, and then the output of the microwave oscillator 53 is set to 1.2 kW for cleaning the lower surface of the base material 20. Microwave plasma treatment was performed for 0.5 minutes. Thereafter, the output of the microwave oscillator 53 was once turned off, and N ₂ gas and O ₂ gas were supplied while adjusting the flow rate, so that the internal pressure of the chamber 8 was 0.42 Pa. The output of the microwave oscillator 53 is 1.2 kW, and the ECR plasma is irradiated. The output of the DC pulse power supply 35 (“RPG-100, Pulsed DC Plasma Generator” manufactured by Japan MKS Co., Ltd.) is 2 kW, the frequency is 100 kHz, and the pulse. A voltage was applied to the magnetron sputter cathode 3 under the condition of a width of 3056 ns to perform sputter film formation.

(2) Comparative Example 1
The configuration of the magnetron sputtering cathode 3 was changed, and an AlON film was formed without irradiating ECR plasma. Differences from the magnetron sputtering cathode 3 used in Example 1 are as follows. First, a magnet having a lower magnetic force than that of the above embodiment was used as the magnet member 32. Next, by not forming the groove portion 310 on the lower surface of the backing plate 31, the magnet member 32 was disposed 5 mm below the above embodiment. By doing so, an equilibrium magnetic field having a magnetic flux density of 50 mT at the central portion and a magnetic flux density of 20 mT at the peripheral portion was formed on the upper surface of the target 30. And the pressure at the time of film-forming was 0.7 Pa, the voltage was applied to the magnetron sputter cathode 3 on the same conditions as the said Example 1, and sputter film-forming was performed for 5 minutes.

(3) Evaluation of surface state The surface of the AlON film of Example 1 and Comparative Example 1 was observed with a scanning probe microscope (SPM). FIG. 6 shows an SPM photograph of the AlON film of Comparative Example 1. FIG. 7 shows an SPM photograph of the AlON film of Example 1.

  6 and 7, it can be seen that the AlON film of Example 1 (FIG. 7) has finer and more uniform film quality than the AlON film of Comparative Example 1 (FIG. 6). Specifically, the particle diameter of the AlON film of Example 1 was about 65 to 110 nm. Moreover, when the surface roughness was measured (JIS B0601: 2001), they were Ra = 1.8 nm and Rz = 15.8 nm. On the other hand, the particle diameter of the AlON film of Comparative Example 1 was as large as about 100 to 350 nm. The surface roughness was Ra = 2.7 nm and Rz = 53.0 nm.

<Deposition rate>
In addition to Example 1, an AlON film was further formed by the following method, and the film formation rates were compared.

(1) Example 2
An AlON film was formed on the surface of the PEN film in the same manner as in Example 1 except that the magnetron sputtering film forming apparatus of the second embodiment provided with a magnetron sputtering cathode in which a non-equilibrium magnetic field was formed was used. The film formation time was 3 minutes.

(2) Comparative Example 2
In the magnetron sputtering film forming apparatus used in Example 1, the configuration of the magnetron sputtering cathode 3 was changed, and the width of the slit 470 of the microwave plasma generation unit 40 was changed to 5 mm to form an AlON film. The difference from the magnetron sputter cathode 3 used in Example 1 is the same as in Comparative Example 1 above. In the magnetron sputtering film forming apparatus of this configuration, no ECR occurs on the upper surface of the target 30. The flow rate of the supplied N ₂ gas and O ₂ gas was adjusted, the pressure during film formation was set to 0.7 Pa, and sputter film formation was performed for 5 minutes in the same manner as in Example 1 above.

Table 1 shows the film forming conditions of Examples 1 and 2 and Comparative Example 2.

(3) Evaluation of film forming speed The film forming speed was calculated from the thickness of the formed AlON film and the film forming time. In FIG. 8, the film-forming speed | velocity of Example 1, 2 and the comparative example 2 is shown with a graph. As shown in FIG. 8, compared with Comparative Example 2, the film formation rates of Examples 1 and 2 were significantly increased. This is presumably because in Examples 1 and 2, ECR was generated on the upper surface of the target, so that the sputtering energy was increased. In Example 2, although the film formation rate was high, some thermal deformation of the substrate was observed.

<Gas barrier properties>
The gas permeability of the film members (PEN film / AlON film) obtained by the film forming methods of Examples 1 and 2 and Comparative Example 2 was measured. In Example 1 and Comparative Example 2, various AlON films were formed by changing the film formation time. The gas permeability was measured according to JIS K7126-1: 2006, Annex 2. Helium (He) gas was used for the measurement, and He gas was supplied from the PEN film side. FIG. 9 shows the relationship between the film formation time and the gas transmission ratio in each film member. Here, the “gas transmission ratio” is the transmission ratio of each film member when the transmittance of the PEN film is 100%. It shows that gas barrier property is so high that the value of a gas permeation | transmission ratio is small.

  As shown in FIG. 9, in Example 1 and Comparative Example 2, when film members having the same gas permeation ratio are compared with each other, Example 1 has a film formation time of about 1 as compared with Comparative Example 2. It can be seen that it is shortened to / 5. Further, when film members having the same film formation time were compared with each other, the gas permeation ratio in Example 1 was about ¼ that in Comparative Example 2. That is, according to the film forming method of Example 1, it can be seen that the gas barrier property of the AlON film is greatly improved as compared with the film forming method of Comparative Example 2. Similarly, when Example 2 and Comparative Example 2 are compared, it can be seen that in the film forming method of Example 2, the film forming time is shortened and the gas barrier property is improved. From the above, it was confirmed that the AlON film having excellent gas barrier properties can be formed in a short time according to the magnetron sputtering film forming apparatus and the magnetron sputtering film forming method of the present invention.

<Influence of pressure during film formation>
In the film forming method of Example 1, an AlON film was formed by changing the pressure (reaction pressure) at the time of film formation, and the influence of the pressure on the gas permeation ratio of the film member and the film formation rate was examined. The results are shown in FIG.

  As shown in FIG. 10, when compared at pressures of 0.4 Pa, 0.5 Pa, and 0.7 Pa, when the pressure becomes 0.7 Pa, the film formation rate decreases and the gas permeation ratio increases (that is, the gas barrier property is increased). It was confirmed that the

<Influence of microwave plasma output>
In the film forming method of Example 1, the output of microwave plasma was changed to 1.4 kW, the film formation time was set to 2 minutes, an AlON film was formed, and the output of microwave plasma relative to the gas transmission ratio of the film member The influence of was investigated. The results are shown in FIG.

  As shown in FIG. 11, when the output of the microwave plasma was increased, the gas transmission ratio was decreased. That is, it was confirmed that the gas barrier property of the AlON film is improved when the output of the microwave plasma is increased.

  The magnetron sputtering film forming apparatus and the magnetron sputtering film forming method of the present invention include, for example, a gas barrier film and a transparent conductive film in a functional resin film used for a touch panel, display, LED (light emitting diode) illumination, solar cell, electronic paper, etc. It is useful for the formation of etc.

1: Magnetron sputtering film forming apparatus.
20: base material, 21: base material support member, 210: table portion, 211: leg portion.
3: magnetron sputtering cathode, 30: target, 31: backing plate, 32: magnet member, 33: case, 34: earth shield, 35: DC pulse power supply, 310: groove, 320: center magnet, 321: peripheral magnet .
4: Microwave plasma generator, 40: Microwave plasma generator, 41: Waveguide (rectangular waveguide), 42: Slot antenna, 43: Dielectric part, 44: Dielectric part fixing plate, 45: Support Plate: 46: Permanent magnet, 47: Slit plate, 48: Mounting member, 420: Slot, 430: Front surface, 450: Refrigerant passage, 451: Cooling pipe, 470: Slit.
50: Microwave transmission part, 51: Tube part, 52: Microwave power supply, 53: Microwave oscillator, 54: Isolator, 55: Power monitor, 56: EH matching device.
8: Chamber, 80: Carrier gas supply hole, 81: First gas supply hole, 82: Second gas supply hole, 83: Exhaust hole.
M: magnetic field lines, M1: equilibrium magnetic field, P1: microwave plasma, P1 _ECR : ECR plasma, P2: ECR plasma.

Claims (11)

A substrate;
A magnetron sputter cathode having a backing plate having an opposing surface facing the substrate, a target disposed on the opposing surface, and a magnet member disposed on the opposite side of the target across the backing plate;
A microwave plasma generator for irradiating microwave plasma between the substrate and the target;
A magnetron sputter deposition apparatus for forming a thin film by adhering sputtered particles jumping out of the target to the surface of the substrate,
The microwave plasma generation apparatus includes:
A rectangular waveguide for transmitting microwaves;
A slot antenna disposed on one surface of the rectangular waveguide and having a slot through which the microwave passes;
A dielectric part that is disposed so as to cover the slot of the slot antenna and whose surface on the plasma generation region side is parallel to the incident direction of the microwave incident from the slot;
With
2. A magnetron sputter deposition apparatus characterized in that a plasma density between the substrate and the target is larger near the target than near the substrate, and electron cyclotron resonance (ECR) occurs on the surface of the target. The microwave plasma generation apparatus further includes a support plate disposed on the back surface of the dielectric portion and supporting the dielectric portion;
A permanent magnet disposed on the back surface of the support plate to form a magnetic field in the plasma generation region;
With
The magnetron sputtering film forming apparatus according to claim 1, wherein microwave plasma is irradiated while generating ECR by the microwave propagating from the dielectric part into the magnetic field. The magnetron sputtering film forming apparatus according to claim 1, wherein the magnet member forms a magnetic field satisfying the following formula (I) on a surface of the target.
B ≧ f · 2πm / e (I)
[B: magnetic flux density (T), f: microwave frequency (Hz), m: electron mass (kg), e: electron charge (C)]   4. The magnetron sputtering film forming apparatus according to claim 3, wherein, when the frequency of the microwave is 2.45 GHz, the magnet member forms a magnetic field having a magnetic flux density of 87.5 mT or more on the surface of the target.   The magnetron sputtering film forming apparatus according to claim 1, wherein the slot antenna is disposed on an H surface of the rectangular waveguide. The microwave plasma generation apparatus further includes a slit plate disposed on the surface side of the dielectric part and having a slit,
The magnetron sputtering film forming apparatus according to any one of claims 1 to 5, wherein the microwave plasma generated on the surface of the dielectric portion is irradiated through the slit.   The magnet member includes a central magnet disposed at a central portion of the backing plate, and a peripheral magnet disposed at a peripheral portion of the backing plate so as to surround the central magnet. The magnetron sputter deposition apparatus according to any one of claims 1 to 6, wherein the polarity of the target side end of the magnet is N pole, and the polarity of the target side end of the peripheral magnet is S pole.   The magnetron sputtering film forming apparatus according to claim 1, wherein the magnet member forms an equilibrium magnetic field on a surface of the target.   The magnetron sputtering film forming apparatus according to any one of claims 1 to 8, wherein the film formation on the substrate is performed under a pressure of 0.01 Pa or more and 5 Pa or less. Using the magnetron sputtering film forming apparatus according to any one of claims 1 to 9,
A depressurization step for maintaining the inside of the chamber of the magnetron sputter deposition apparatus at a predetermined degree of vacuum;
A film forming step of forming a thin film on the surface of the substrate by introducing a gas into the chamber and sputtering the target with ECR plasma generated on the surface of the target under a predetermined pressure;
A magnetron sputtering film forming method characterized by comprising: A base material made of a resin film, and a gas barrier film disposed on at least one side of the base material,
The film member is formed by the magnetron sputtering film forming method according to claim 10.