WO2013073443A1

WO2013073443A1 - Plasma modification and film formation apparatus

Info

Publication number: WO2013073443A1
Application number: PCT/JP2012/078966
Authority: WO
Inventors: 建典笹井
Original assignee: 東海ゴム工業株式会社
Priority date: 2011-11-18
Filing date: 2012-11-08
Publication date: 2013-05-23
Also published as: JP2013108116A

Abstract

A plasma modification and film formation apparatus (1) is provided with a chamber (10), substrate (F) transport means (20, 200, 201), an electron cyclotron resonance (ECR) plasma generating device (3) that modifies a surface of the substrate (F), and a film formation device (6) that forms a thin film on said surface of the substrate (F). The ECR plasma generating device (3) is provided with: a rectangular waveguide tube (31) that transmits microwaves; a slot antenna (32) having a slot (320) through which said microwaves pass; a dielectric part (33) covering the slot (320), and having a surface (330) on the plasma-generating-region side which is parallel to the incident direction of the microwaves that enter from the slot (320); a support plate (34) disposed on the rear surface of the dielectric part (33); and a permanent magnet (35) disposed on the rear surface of the support plate (34). The ECR plasma generating device (3) generates ECR plasma (P1). The plasma modification and film formation apparatus (1) is capable of continuously performing modification of and film formation on the surface of the substrate (F) in a single low-pressure chamber (10).

Description

Plasma reforming deposition system

The present invention relates to a plasma reforming film forming apparatus capable of continuously performing reforming of the surface of a substrate and film formation on the surface in one chamber.

Mobile devices such as smartphones, PHS (Personal Handyphone System), tablet PCs (Personal Computers), mobile notebook PCs, and other mobile devices such as small game machines and electronic paper are becoming increasingly popular with the arrival of the ubiquitous society. ing. In addition, there is an increasing need for these mobile devices to be lighter, thinner, flexible, and to prevent damage due to dropping, impact, and the like. For this reason, demands for touch panels, organic EL (Electro Luminescence) devices, etc. using functional resin films in which functional thin films are laminated on a resin substrate are increasing instead of glass display units that are widely used at present. . Furthermore, in the solar cell market, flexible, lightweight and thin organic thin-film solar cells using functional resin films are in the spotlight.

JP 2009-224269 A JP 2005-197371 A JP 2007-184259 A JP 2009-275251 A

However, a product using a functional resin film has a problem that its lifetime is shorter than that of a conventional glass product. One possible cause is a nodule (bloomed granular lump) derived from the resin component on the surface of the resin substrate. That is, when the functional thin film is formed on the resin base material, if there is a nodule on the surface of the resin base material, the thin film is formed unevenly along the nodule. If the thin film has irregularities, the electric field concentrates on the convex portions and the device is easily damaged.

As an example, a flexible organic EL device will be described. FIG. 7 shows a cross-sectional view of the organic EL device. As shown in FIG. 7, the organic EL device 8 includes a hard coat layer 80, a resin base material 81, a front gas barrier film 82, an anode 83, a hole transport layer 84, and an electron transport from the front to the rear. Luminescent layer 85, cathode 86, and rear gas barrier layer 87.

The light emission principle of the organic EL device 8 will be briefly described. When a voltage is applied to the anode 83 and the cathode 86, holes (holes) are generated from the anode 83 and electrons are generated from the cathode 86, respectively. The holes pass from the anode 83 through the hole transport layer 84 and enter the electron transport light emitting layer 85. On the other hand, electrons enter the electron transporting light emitting layer 85 from the cathode 86. In the electron-transporting light-emitting layer 85, light is emitted by combining holes and electrons. Here, the hard coat layer 80, the resin base material 81, the front gas barrier film 82, the anode 83, and the hole transport layer 84 disposed in front of the electron transporting light emitting layer 85 are transparent. For this reason, the emitted light can be viewed from the front of the organic EL device 8.

In the organic EL device 8, the gas barrier film 82 and the anode 83 are formed on the rear surface of the resin substrate 81 by sputtering, CVD (Chemical Vapor Deposition), or the like. However, if the gas barrier film 82 and the anode 83 are formed while a nodule having a large particle diameter is present on the rear surface of the resin base material 81, the unevenness of the film increases along the nodule. Then, the electric field concentrates on the convex portion of the anode 83, and the electron transporting light emitting layer 85 deteriorates due to the influence, and the light is not emitted.

In order to reduce the unevenness of the thin film to be formed, it is desirable to refine or remove the nodules on the surface of the resin substrate before film formation. Therefore, the present inventor examined a method of modifying the surface of the resin base material by irradiating microwave plasma. However, in the conventional methods as described in

Patent Documents

1 and 2, for example, microwave plasma is generated under a pressure of 5 Pa or more. That is, it is difficult to generate microwave plasma under a lower pressure. On the other hand, film formation by sputtering or the like is preferably performed under a low pressure of about 0.3 to 1 Pa in order to suppress the intrusion of impurities and maintain the film quality. Therefore, conventionally, since the pressure at which microwave plasma can be generated is different from the pressure at the time of film formation, it is necessary to perform the reforming process and the film forming process in separate chambers (for example, Patent Document 1). FIG. 7 and FIG. 8).

In this case, a device for supplying and discharging gas, a substrate transport device, and the like are required for each chamber. For this reason, equipment costs increase and manufacturing costs increase. Further, while the base material after the modification treatment is transported to the film forming chamber, impurities may adhere to the surface and the base material may be contaminated.

Incidentally, as an attempt to maintain the plasma under a low pressure, Patent Document 1 discloses a mode in which a magnet is disposed on the chamber side of the dielectric part. However, when a magnet is arranged on the chamber side of the dielectric part, the magnet is exposed to the generated plasma and the microwave propagating on the surface of the dielectric part. For this reason, the temperature of a magnet rises and magnetism will fall. Therefore, it is difficult to stably generate the microwave plasma under a low pressure. Further, Patent Document 3 discloses a mode in which a hollow hole is formed on the chamber side of the dielectric part. However, according to this aspect, it is difficult to generate the microwave plasma uniformly. In addition, it is difficult to produce stably under low pressure.

The present invention has been made in view of such a situation, and in one low-pressure chamber, plasma modification that can continuously perform the modification of the surface of the substrate and the film formation on the surface. It is an object to provide a film formation apparatus.

(1) In order to solve the above-mentioned problems, a plasma-modified film-forming apparatus of the present invention includes a chamber, a transport unit disposed in the chamber and transporting a substrate, and electron cyclotron resonance (ECR) using microwaves. And a film forming apparatus for forming a thin film on the surface of the substrate, and the plasma is generated in the one chamber. A plasma-modified film forming apparatus capable of continuously modifying the surface of the substrate and forming a film on the surface, wherein the ECR plasma generating apparatus is a rectangular waveguide that transmits microwaves. A wave tube, a slot antenna disposed on one surface of the rectangular waveguide, and having a slot through which the microwave passes, and a surface of the plasma generation region side disposed to cover the slot of the slot antenna. Is a dielectric part parallel to the incident direction of the microwave incident from the slot, a support plate disposed on the back surface of the dielectric part and supporting the dielectric part, and disposed on the back surface of the support plate. A permanent magnet for forming a magnetic field in the plasma generation region, and generating plasma while generating ECR by the microwave propagating from the dielectric part into the magnetic field.

In the plasma modified film forming apparatus of the present invention, the surface modification treatment of the substrate is performed using an ECR plasma generating apparatus. According to the ECR plasma generation apparatus, high-density plasma can be stably generated even under a low pressure of 1 Pa or less. The reason for this will be described below. In the ECR plasma generation apparatus of the present invention, 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”.

First, the configuration of the plasma generator in the conventional microwave plasma generator will be described. FIG. 6 is a perspective view of a conventional plasma generation unit. As shown in FIG. 6, the 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 right opening of the waveguide 90. That is, the slot antenna 91 forms the right wall of the waveguide 90. The slot antenna 91 is formed with a plurality of slot-like slots 910. The dielectric part 92 is disposed on the right surface (chamber side) of the slot antenna 91 so as to cover the slot 910. The microwave transmitted from the front end of the waveguide 90 passes through the slot 910 and enters the dielectric portion 92 as indicated by the white arrow Y1 in the horizontal direction in the drawing. The microwave incident on the dielectric portion 92 propagates along the right surface 920 of the dielectric portion 92 as indicated by the white arrow Y2 in the front-rear 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 right 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 right 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.

Next, the configuration of the plasma generation unit in the ECR plasma generation apparatus of the present invention will be described. FIG. 3 is a perspective view of a plasma generation unit in the ECR plasma generation apparatus of the present invention. FIG. 3 is a diagram showing an embodiment of the plasma generation unit (see the embodiment described later). FIG. 3 does not limit the ECR plasma generation apparatus of this invention at all.

As shown in FIG. 3, the plasma generation unit 30 includes a waveguide 31, a slot antenna 32, a dielectric unit 33, a support plate 34, and a permanent magnet 35. A tubular body 51 that transmits microwaves is connected to the left of the rear end of the waveguide 31. The slot antenna 32 is disposed so as to close the upper opening of the waveguide 31. That is, the slot antenna 32 forms the upper wall of the waveguide 31. The slot antenna 32 is formed with a plurality of slot-like slots 320. The dielectric portion 33 is disposed on the upper surface of the slot antenna 32 so as to cover the slot 320.

The microwave transmitted from the tube part 51 passes through the slot 320 and enters the dielectric part 33 as indicated by the vertical arrow Y1 in the vertical direction in the drawing. The microwave incident on the dielectric portion 33 propagates mainly along the right surface 330 of the dielectric portion 33 as indicated by the white arrow Y2 in the front-rear direction in the drawing. Thereby, microwave plasma is generated. Here, the incident direction of the microwave incident on the dielectric portion 33 from the slot 320 is parallel to the right surface 330 (surface on the plasma generation region side) of the dielectric portion 33. Since the microwave is incident along the generated microwave plasma, the microwave that is the plasma source easily propagates to the microwave plasma.

Further, eight permanent magnets 35 are arranged on the left side of the dielectric portion 33 via the support plate 34. Each of the eight permanent magnets 35 has an N pole on the right side and an S pole on the left side. Magnetic field lines M are generated from each permanent magnet 35 to the right. Thereby, a magnetic field is formed on the right side (plasma generation region) of the dielectric portion 33.

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 to the right 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 0.0875T. 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, the high-density ECR plasma P1 is generated on the right side of the dielectric portion 33.

As described above, according to the ECR plasma generation apparatus of the present invention, the microwave is incident along the generated microwave plasma, and the plasma density is increased by using the ECR. Plasma can be generated even under an extremely low pressure of 0.1 Pa or less. That is, when the ECR plasma generation apparatus of the present invention is used, high-density plasma can be stably generated even under a low pressure in which film formation is performed. Therefore, the reforming process and the film forming process, which conventionally had to be performed in separate chambers due to the difference in processing pressure, can be performed continuously in one low-pressure chamber. Thereby, the gas supply, discharge device, substrate transport device, and the like, which are conventionally required for each of the reforming and film forming chambers, can be combined into one. Therefore, the equipment cost can be reduced. In addition, since the modification and the film formation are continuously performed in the same chamber, there is little possibility that impurities will adhere to the surface of the modified substrate. That is, the base material is not easily contaminated. For this reason, a thin film with less unevenness can be formed.

In addition, according to the ECR plasma generation apparatus of the present invention, it is possible to generate a plasma having a large energy with a low potential. Thereby, a large modification effect can be obtained while suppressing roughening and deformation of the substrate.

Further, according to the ECR plasma generation apparatus of the present invention, long plasma can be generated by arranging slots in the longitudinal direction using a long rectangular waveguide. Therefore, even when the substrate has a large width and a large area, the modification treatment can be easily performed.

According to the plasma modified film-forming apparatus of the present invention, the nodules on the surface of the resin base material can be refined by the modification treatment. For this reason, the unevenness | corrugation of the thin film formed after that can be made small. Therefore, for example, if the resin substrate for an organic EL device is modified and formed using the plasma modified film forming apparatus of the present invention, the unevenness of the formed gas barrier film or anode can be reduced. Can do. As a result, the electric field concentration on the convex part of the anode can be suppressed, and the deterioration of the electron transporting light emitting layer can be suppressed.

(2) Preferably, in the configuration of (1) above, the pressure in the chamber is set to 0.05 Pa or more and 3 Pa or less to perform reforming and film formation.

By setting the inside of the chamber to a high vacuum state of 0.05 Pa or more and 3 Pa or less, the plasma for sputtering film formation can be stabilized and intrusion of impurities can be suppressed. In sputter deposition, the mean free path of the target particles can be increased. Thereby, the film quality of the formed thin film improves.

(3) Preferably, in the configuration of the above (1) or (2), the support plate of the ECR plasma generation apparatus includes a support plate cooling means for suppressing a temperature increase of the permanent magnet. Better.

The permanent magnet is arranged on the back 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. According to this configuration, the temperature rise of the permanent magnet is suppressed by the support plate cooling means. For this reason, there is little possibility that the magnetism of a permanent magnet will be lost. Therefore, according to this configuration, a stable magnetic field can be formed.

(4) Preferably, in any one of the above configurations (1) to (3), the film forming apparatus includes a target and a magnetic field forming unit for forming a magnetic field on the surface of the target, and a magnetron It is better to have a configuration that is a magnetron sputtering film forming apparatus in which the target is sputtered by plasma generated by electric discharge, and the sputtered particles that are ejected adhere to the surface of the substrate to form a thin film.

Examples of the film forming method by sputtering include a bipolar sputtering method and a magnetron sputtering method. In particular, according to the magnetron sputtering method, secondary electrons jumping out of the target are captured by the magnetic field generated on the target surface. For this reason, it is difficult for the temperature of the base material to rise. In addition, since ionization of the gas is promoted by the captured secondary electrons, the deposition rate can be increased. Therefore, according to this configuration, the deformation of the base material due to heat is small, and a thin film can be formed relatively quickly. In the magnetron sputtering film forming apparatus of this configuration, it is desirable to employ a DC (direct current) magnetron sputtering method (including a DC pulse method).

(5) Preferably, in the configuration of (4), the magnetron sputtering film forming apparatus further includes the ECR plasma generation apparatus, and the ECR plasma generation apparatus causes an ECR between the base material and the target. It is better to have a configuration in which plasma is irradiated.

In a magnetron sputter deposition apparatus, a high voltage of several hundred volts is often applied to a target in order to stabilize the generated plasma. When the applied voltage is high, particles having a large particle size such as cluster particles may be ejected from the target. When particles having a large particle diameter adhere to the substrate, irregularities are generated on the surface of the formed film. When the film surface has large irregularities, oxygen or the like is likely to be adsorbed in the recesses, which may deteriorate the film itself or the partner material in contact with the film. Moreover, there exists a possibility that a counterpart material may deteriorate by a convex part.

As a result of extensive research conducted by the present inventor to solve such problems, film formation by plasma generated by magnetron discharge (hereinafter referred to as “magnetron plasma” as appropriate) is performed while irradiating microwave plasma. For example, it came to the standpoint that the applied voltage can be lowered. The magnetron sputtering film forming apparatus of the present configuration based on such a viewpoint includes the above-described ECR plasma generating apparatus. That is, in the magnetron sputtering film forming apparatus of this configuration, film formation by magnetron plasma is performed while irradiating ECR plasma. By irradiating the ECR plasma between the substrate and the target, the magnetron plasma can be stably maintained even when the applied voltage is lowered. Thereby, jumping out of a target having a large particle diameter such as cluster particles from the target can be suppressed. As a result, the variation in the particle diameter of the sputtered particles is suppressed, and the unevenness on the surface of the formed thin film can be reduced. Moreover, when ECR plasma is irradiated, sputtered particles are miniaturized. For this reason, a finer thin film can be formed.

(6) Preferably, in any one of the above configurations (1) to (5), the conveying means may include a roll member.

When the substrate is transported by a roll member, for example, the chamber can be reduced in size as compared with a case where the substrate is transported linearly using a conveyor or the like.

(7) Preferably, in the configuration of (6) above, the roll member may have a roll cooling means for lowering the temperature of the outer peripheral surface.

According to the configuration of (6) above, the substrate is conveyed while being supported on the outer peripheral surface of the roll member. The substrate is irradiated with ECR plasma. At this time, the temperature of the substrate tends to rise. When the temperature of the base material increases, the base material may be deformed or damaged. In this regard, according to the present configuration, the temperature of the outer peripheral surface of the roll member can be lowered by the roll cooling means. Therefore, the temperature rise of the conveyed base material can be suppressed. Thereby, the deformation | transformation and damage of the base material by a heat | fever can be suppressed.

It is a horizontal direction sectional view of the plasma modification film-forming device of an embodiment. It is sectional drawing to which the ECR plasma generation apparatus vicinity of FIG. 1 was expanded. It is a perspective view of the plasma generation part in the ECR plasma generation apparatus. It is sectional drawing to which the magnetron sputtering film-forming apparatus vicinity of FIG. 1 was expanded. It is a perspective view of the plasma production | generation part of the ECR plasma production | generation apparatus which comprises the same magnetron sputter film-forming apparatus. It is a perspective view of the plasma generation part in the conventional microwave plasma generation apparatus. It is sectional drawing of an organic EL device.

1: Plasma reforming film forming apparatus, 10: processing chamber (chamber), 11: supply chamber, 12: winding chamber, 101, 102: opening.
20: processing roll (conveying means), 21: supply roll, 22: winding roll, 200, 201: guide roll (conveying means), 210, 220: guide roll.
3: ECR plasma generator, 30: Plasma generator, 31: Waveguide (rectangular waveguide), 32: Slot antenna, 33: Dielectric part, 34: Support plate, 35: Permanent magnet, 320: Slot, 330: right side, 340: refrigerant passage (support plate cooling means), 341: cooling pipe.
4: ECR plasma generator, 40: plasma generator, 41: waveguide (rectangular waveguide), 42: slot antenna, 43: dielectric, 44: support plate, 45: permanent magnet, 420: slot, 430: Left side, 440: Refrigerant passage (support plate cooling means), 441: Cooling pipe.
50: Microwave transmission part, 51: Tube part, 52: Microwave power supply, 53: Microwave oscillator, 54: Isolator, 55: Power monitor, 56: EH matching device.
6: magnetron sputter deposition apparatus, 60: sputter unit, 61: target, 62: backing plate, 63a to 63c: permanent magnet (magnetic field forming means), 64: cathode, 65: earth shield, 66: DC pulse power supply.
F: Base material, F ′: Film formation film, M: Magnetic field lines, P1: ECR plasma, P2: Magnetron plasma.

Hereinafter, embodiments of the plasma modified film forming apparatus of the present invention will be described.

<Overall configuration>
First, the overall configuration of the plasma modified film forming apparatus of this embodiment will be described. FIG. 1 shows a cross-sectional view in the left-right direction of the plasma modified film forming apparatus of this embodiment. In FIG. 1, the front side and the back side are the front-rear direction. As shown in FIG. 1, the plasma modified film forming apparatus 1 includes a processing chamber 10, a processing roll 20, two guide rolls 200 and 201, an ECR plasma generating apparatus 3, a magnetron sputter film forming apparatus 6, A supply chamber 11 and a winding chamber 12 are provided.

The supply chamber 11 is made of stainless steel and has a rectangular parallelepiped box shape. The supply chamber 11 is disposed on the left side of the processing chamber 10. An opening 101 through which the substrate F can pass is formed in a partition wall that partitions the supply chamber 11 and the processing chamber 10. In the supply chamber 11, a supply roll 21, a guide roll 210, and a microwave transmission unit 50 of the ECR plasma generation apparatus 3 described later are disposed. Both the supply roll 21 and the guide roll 210 have a cylindrical shape that is long in the front-rear direction. A motor (not shown) is connected to the supply roll 21. Further, the base material F is wound around the supply roll 21. The substrate F is a long polyethylene terephthalate (PET) film. When the supply roll 21 rotates counterclockwise by driving the motor, the base material F is guided by the guide roll 210 and sent to the processing chamber 10.

The winding chamber 12 is made of stainless steel and has a rectangular parallelepiped box shape. The winding chamber 12 is disposed on the right side of the processing chamber 10. The partition wall that partitions the winding chamber 12 and the processing chamber 10 is formed with an opening 102 through which the processed substrate F (deposition film F ′) can pass. In the winding chamber 12, a winding roll 22, a guide roll 220, and a microwave transmission unit 50 of the ECR plasma generation apparatus 4 to be described later are arranged. The winding roll 22 and the guide roll 220 both have a columnar shape that is long in the front-rear direction. A motor (not shown) is connected to the winding roll 22. When the take-up roll 22 rotates counterclockwise by driving the motor, the film formation film F ′ sent from the processing chamber 10 is guided by the guide roll 220 and taken up by the take-up roll 22.

The processing chamber 10 is made of stainless steel and has a rectangular parallelepiped box shape. A gas supply hole is formed in a rear wall (not shown) of the processing chamber 10. The gas supply hole is connected to a downstream end of a gas supply pipe for supplying argon (Ar) gas into the processing chamber 10. An exhaust hole (not shown) is formed in the lower wall of the processing chamber 10. A vacuum exhaust device (not shown) for exhausting the gas inside the processing chamber 10 is connected to the exhaust hole. The processing chamber 10 is included in the chamber of the present invention.

The treatment roll 20 has a long cylindrical shape in the front-rear direction. The processing roll 20 is disposed near the center in the processing chamber 10. A rotation shaft is disposed at the center of the processing roll 20 in the axial direction. The processing roll 20 can rotate counterclockwise around the rotation axis. A base material F is supported on the outer peripheral surface of the processing roll 20. The processing roll 20 has a built-in cooling pipe (not shown). As the coolant circulates through the cooling pipe, the outer peripheral surface of the processing roll 20 is cooled. The coolant and the cooling pipe are included in the roll cooling means of the present invention.

The two guide rolls 200 and 201 each have a columnar shape that is long in the front-rear direction. The guide roll 200 is disposed on the upper left side of the processing roll 20. Similarly, the guide roll 201 is disposed on the upper right side of the processing roll 20. The two guide rolls 200 and 201 are arranged in parallel to the processing roll 20 and spaced apart from each other at a predetermined interval. The guide roll 200 can rotate clockwise around the rotation axis. The guide roll 200 conveys the base material F sent from the supply chamber 11 to the processing roll 20. The guide roll 201 can rotate clockwise around the rotation axis. The guide roll 201 conveys the processed substrate F (deposition film F ′) sent from the processing roll 20 to the winding chamber 12. The processing roll 20 and the guide rolls 200 and 201 are included in the roll member and the conveying unit of the present invention.

The ECR plasma generator 3 is disposed on the left side of the processing roll 20. The ECR plasma generation apparatus 3 includes a plasma generation unit 30 and a microwave transmission unit 50. The ECR plasma generator 3 generates ECR plasma P1 and modifies the surface of the substrate F with the ECR plasma P1. Details of the ECR plasma generation apparatus 3 will be described later.

The magnetron sputtering film forming apparatus 6 is disposed below the processing roll 20. The magnetron sputtering film forming apparatus 6 includes a sputtering unit 60 and an ECR plasma generation apparatus 4. The magnetron sputtering film forming apparatus 6 forms a thin film on the surface of the substrate F by sputtering with the magnetron plasma P2 of the sputtering unit 60 while irradiating the ECR plasma P1 with the ECR plasma generating apparatus 4. Details of the magnetron sputtering film forming apparatus 6 will be described later.

<ECR plasma generator>
Next, the configuration of the ECR plasma generation apparatus 3 will be described. FIG. 2 is an enlarged cross-sectional view of the vicinity of the ECR plasma generation apparatus of FIG. FIG. 3 is a perspective view of a plasma generation unit in the ECR plasma generation apparatus. As shown in FIGS. 2 and 3, the ECR plasma generation apparatus 3 includes a plasma generation unit 30 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 unit 51 is connected to the left side of the waveguide 31 of the plasma generation unit 30 through a waveguide hole formed in the left wall of the processing chamber 10.

The plasma generation unit 30 includes a waveguide 31, a slot antenna 32, a dielectric unit 33, a support plate 34, and a permanent magnet 35. As shown in FIG. 3, the waveguide 31 is made of aluminum and has a rectangular parallelepiped box shape opening upward. The waveguide 31 extends in the front-rear direction. The waveguide 31 is included in the rectangular waveguide in the present invention. The tube part 51 and the waveguide 31 are sealed so that the internal pressure is atmospheric pressure or a high vacuum state of 0.01 Pa or less. For this reason, plasma is not generated inside the tube portion 51 and the waveguide 31.

The slot antenna 32 is made of aluminum and has a rectangular plate shape. The slot antenna 32 closes the opening of the waveguide 31 from above. That is, the slot antenna 32 forms the upper wall of the waveguide 31. Four slots 320 are formed in the slot antenna 32. The slot 320 has a long hole shape extending in the front-rear direction. The slot 320 is disposed at a position where the electric field is strong.

The dielectric portion 33 is made of quartz and has a rectangular parallelepiped shape. The dielectric portion 33 is disposed on the right side of the upper surface of the slot antenna 32. The dielectric portion 33 covers the slot 320 from above. As described above, the right surface 330 of the dielectric portion 33 is disposed in parallel to the incident direction Y1 of the microwave incident from the slot 320. The right surface 330 is included in the surface of the dielectric portion 33 on the plasma generation region side.

The support plate 34 is made of stainless steel and has a flat plate shape. The support plate 34 is disposed on the upper surface of the slot antenna 32 so as to be in contact with the left surface (back surface) of the dielectric portion 33. A refrigerant passage 340 is formed in the support plate 34. The refrigerant passage 340 has a U shape extending in the front-rear direction. The front end of the refrigerant passage 340 is connected to the cooling pipe 341. The refrigerant passage 340 is connected to a heat exchanger and a pump (both not shown) outside the processing chamber 10 via a cooling pipe 341. The coolant circulates in the path of the refrigerant passage 340 → the cooling pipe 341 → the heat exchanger → the pump → the cooling pipe 341 → the refrigerant passage 340 again. The support plate 34 is cooled by the circulation of the coolant. The refrigerant passage 340 and the cooling liquid are included in the support plate cooling means of the present invention.

The permanent magnet 35 is a neodymium magnet and has a rectangular parallelepiped shape. Eight permanent magnets 35 are arranged on the left surface (back surface) of the support plate 34. The eight permanent magnets 35 are arranged in series in the front-rear direction. Each of the eight permanent magnets 35 has an N pole on the right side and an S pole on the left side. Magnetic field lines M are generated from each permanent magnet 35 to the right. Thereby, a magnetic field is formed in the plasma generation region on the right side of the dielectric portion 33.

<Magnetron sputtering deposition system>
Next, the configuration of the magnetron sputtering film forming apparatus 6 will be described. FIG. 4 is an enlarged cross-sectional view of the vicinity of the magnetron sputtering film forming apparatus of FIG. FIG. 5 is a perspective view of the plasma generation unit of the ECR plasma generation apparatus constituting the magnetron sputtering film forming apparatus. As shown in FIGS. 4 and 5, the magnetron sputtering film forming apparatus 6 includes a sputtering unit 60 and an ECR plasma generation apparatus 4.

The sputter unit 60 includes a target 61, a backing plate 62, permanent magnets 63a to 63c, and a cathode 64. The cathode 64 is made of stainless steel and has a rectangular parallelepiped box shape opening upward. An earth shield 65 is disposed around the cathode 64, the target 61, and the backing plate 62. The cathode 64 is disposed on the lower surface of the processing chamber 10 via the earth shield 65. The cathode 64 is connected to a DC pulse power supply 66.

The permanent magnets 63a to 63c are arranged inside the cathode 64. Each of the permanent magnets 63a to 63c has a rectangular parallelepiped shape extending in the front-rear direction. The permanent magnets 63a to 63c are spaced apart from each other in the left-right direction and arranged so as to be parallel to each other. Regarding the permanent magnet 63a and the permanent magnet 63c, the upper side is the S pole and the lower side is the N pole. As for the permanent magnet 63b, the upper side is the N pole and the lower side is the S pole. A magnetic field is formed on the upper surface of the target 61 by the permanent magnets 63a to 63c. The permanent magnets 63a to 63c are included in the magnetic field forming means in the present invention.

The backing plate 62 is made of copper and has a rectangular plate shape. The backing plate 62 is disposed so as to cover the upper opening of the cathode 64.

The target 61 is a composite oxide (ITO) of indium oxide and tin oxide, and has a rectangular thin plate shape. The target 61 is disposed on the upper surface of the backing plate 62. The target 61 is disposed so as to face the lower surface of the processing roll 20.

The ECR plasma generation apparatus 4 includes a plasma generation unit 40 and a microwave transmission unit 50. The configuration of the microwave transmission unit 50 is as described in the ECR plasma generation apparatus 3. The configuration of the plasma generation unit 40 is the same as the configuration of the plasma generation unit 30 of the ECR plasma generation apparatus 3. Hereinafter, the configuration of the plasma generation unit 40 will be briefly described.

As shown in FIG. 5, the plasma generation unit 40 includes a waveguide 41, a slot antenna 42, a dielectric unit 43, a support plate 44, and a permanent magnet 45. The waveguide 41 extends in the front-rear direction. The waveguide 41 is included in the rectangular waveguide in the present invention. The waveguide 41 is sealed so that the internal pressure becomes atmospheric pressure or a high vacuum state of 0.01 Pa or less. For this reason, similarly to the ECR plasma generation apparatus 3 described above, plasma is not generated inside the tube body portion 51 and the waveguide 41. The slot antenna 42 closes the opening of the waveguide 41 from above. Four slots 420 are formed in the slot antenna 42. The dielectric portion 43 is disposed on the upper left side of the slot antenna 42. The dielectric part 43 covers the slot 420 from above. The left surface 430 of the dielectric part 43 is disposed in parallel to the incident direction Y1 of the microwave incident from the slot 420. The left surface 430 is included in the surface of the dielectric part 43 on the plasma generation region side.

The support plate 44 is disposed on the upper surface of the slot antenna 42 so as to be in contact with the right surface (back surface) of the dielectric portion 43. A refrigerant passage 440 is formed inside the support plate 44. The front end of the refrigerant passage 440 is connected to the cooling pipe 441. The refrigerant passage 440 is connected to a heat exchanger and a pump (both not shown) outside the processing chamber 10 via a cooling pipe 441. The support plate 44 is cooled by circulation of the coolant through the refrigerant passage 440 and the cooling pipe 441. The refrigerant passage 440 and the coolant are included in the support plate cooling means of the present invention. Eight permanent magnets 45 are arranged on the right surface (back surface) of the support plate 44. Magnetic lines of force M are generated from each permanent magnet 45 toward the left. Thereby, a magnetic field is formed in the plasma generation region on the left side of the dielectric portion 43.

<Movement>
Next, the movement of the plasma modified film forming apparatus 1 will be described. First, an evacuation apparatus (not shown) is operated to exhaust the gas inside the processing chamber 10 from the exhaust hole, thereby reducing the pressure inside the processing chamber 10. Next, argon gas is supplied into the processing chamber 10 from the gas supply pipe, and the pressure in the processing chamber 10 is set to about 0.1 Pa. In this state, the motors of the

rolls

20, 21, 22, 200, 201, 210, and 220 are driven to transport the substrate F from the supply roll 21 to the processing chamber 10.

Then, the microwave power sources 52 of the two

ECR plasma generators

3 and 4 are 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 microwaves reflected from the

plasma generation units

30 and 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 microwave that has passed through the tube body 51 propagates inside the waveguide 31 of the plasma generator 30. Similarly, it propagates inside the waveguide 41 of the plasma generation unit 40.

Microwave propagating inside the waveguide 31 enters the slot 320 of the slot antenna 32. Then, as indicated by the hollow arrow Y 1 in FIG. 3, the light passes through the slot 320 and enters the dielectric portion 33. The microwave incident on the dielectric portion 33 propagates mainly along the right surface 330 of the dielectric portion 33, as indicated by the white arrow Y2 in the figure. Due to the strong electric field of the microwave, the argon gas in the processing chamber 10 is ionized, and microwave plasma is generated on the right side of the dielectric portion 33. 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. 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 0.0875T, which 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, the high-density ECR plasma P1 is generated on the right side of the dielectric portion 33. With this ECR plasma P1, the surface of the substrate F conveyed by the processing roll 20 is modified. Similarly to the plasma generation unit 30, high-density ECR plasma P <b> 1 is also generated on the left side of the dielectric unit 43 of the plasma generation unit 40.

In the sputter unit 60, the DC pulse power supply 66 is turned on and a voltage is applied to the cathode 64. The magnetron discharge generated thereby ionizes the argon gas, and magnetron plasma P <b> 2 is generated above the target 61. Then, the target 61 is sputtered by magnetron plasma P2 (argon ions), and sputtered particles are sputtered from the target 61. The sputtered particles that have jumped out of the target 61 scatter toward the upper base material F and adhere to the modified surface of the base material F, thereby forming an ITO film. At this time, the ECR plasma P1 is irradiated from the plasma generation unit 40 between the base material F and the target 61 (including the magnetron plasma P2 generation region).

The modified and film-formed substrate F, that is, the film-forming film F ′, is guided by the guide rolls 201 and 220, conveyed from the processing chamber 10 to the winding chamber 12, and taken up by the winding roll 22. It is done.

<Effect>
Next, the function and effect of the plasma modified film forming apparatus of this embodiment will be described. In the plasma modified film forming apparatus 1 of the present embodiment, the surface modification process of the substrate F is performed using the ECR plasma generation apparatus 3. According to the ECR plasma generation apparatus 3, high-density plasma can be stably generated even under a low pressure of about 0.3 to 1 Pa in which film formation is performed. Therefore, the reforming process and the film forming process, which conventionally had to be performed in separate processing chambers due to the difference in processing pressure, can be performed continuously in one processing chamber 10. Thus, the gas supply, discharge device, base material transport device, and the like, which are conventionally required for each processing chamber for reforming and film formation, can be combined into one. Therefore, the equipment cost can be reduced. In addition, since the modification and the film formation are continuously performed in the same processing chamber 10, there is little possibility that impurities adhere to the surface of the modified substrate F. That is, the base material F is hardly contaminated. For this reason, a thin film with less unevenness can be formed.

In the plasma reforming film forming apparatus 1, the substrate F is transported by the processing roll 20 or the like. Therefore, compared with the case where it conveys linearly using a conveyor etc., the process chamber 10 can be reduced in size. Here, a coolant is circulated through the cooling pipe inside the processing roll 20. Thereby, the outer peripheral surface of the processing roll 20 is cooled. Therefore, the temperature rise of the conveyed base material F can be suppressed and the deformation | transformation and damage of the base material F by a heat | fever can be suppressed.

According to the plasma-modified film forming apparatus 1, nodules on the surface of the PET substrate F are refined by the modification process. For this reason, the unevenness | corrugation of the ITO film | membrane formed after that is small. Therefore, if the film formation film F ′ is used in an organic EL device, the electric field concentration on the convex portion of the anode can be suppressed, and the deterioration of the electron transporting light emitting layer can be suppressed.

Further, according to the ECR plasma generation apparatus 3, it is possible to generate the ECR plasma P1 having a large energy with a low potential. Thereby, a large modification effect can be obtained while suppressing roughening and deformation of the substrate F. The waveguide 31 has a long box shape extending in the front-rear direction. And the slot 320 is arrange | positioned in series in the front-back direction. Thereby, the long ECR plasma P1 can be generated. Therefore, even when the base material F has a large width and a large area, the modification treatment can be easily performed. The eight permanent magnets 35 are arranged on the left surface of the support plate 34. Inside the support plate 34, the coolant circulates through the refrigerant passage 340. Thereby, the support plate 34 is cooled. Therefore, the temperature of the permanent magnet 35 is unlikely to increase. That is, the possibility that the magnetism of the permanent magnet 35 is lost is small. Therefore, a stable magnetic field is formed even during plasma generation.

In the plasma modified film forming apparatus 1, film formation on the surface of the substrate F is performed using a magnetron sputtering film forming apparatus 6. The magnetron sputtering film forming apparatus 6 includes a sputtering unit 60 and an ECR plasma generation apparatus 4. Thereby, sputter film formation by magnetron plasma P2 can be performed while irradiating ECR plasma P1.

In the sputter unit 60, secondary electrons that have jumped out of the target 61 are captured by the magnetic field generated on the surface of the target 61. For this reason, the temperature of the base material F hardly rises. Therefore, the deformation of the base material F due to heat is small. Further, since the ionization of argon gas is promoted by the captured secondary electrons, the film forming speed is high.

Further, by irradiating the ECR plasma P1, the magnetron plasma P2 can be stably maintained even when the applied voltage is lowered. Thereby, the jumping out of the target 61 with particles having a large particle diameter such as cluster particles can be suppressed. As a result, the variation in the particle diameter of the sputtered particles is suppressed, and the unevenness on the surface of the formed thin film can be reduced. Further, when the ECR plasma P1 is irradiated, the sputtered particles are miniaturized. For this reason, a finer thin film can be formed. Further, by setting the inside of the processing chamber 10 to a high vacuum state of about 0.1 Pa, the magnetron plasma P2 can be stabilized, the intrusion of impurities can be suppressed, and the average free path of the target particles can be lengthened. Thereby, the film quality of the formed thin film improves.

In the ECR plasma generation apparatus 4, the waveguide 41 has a long box shape extending in the front-rear direction. The slots 420 are arranged in series in the front-rear direction. Thereby, according to the ECR plasma generator 4, the long ECR plasma P1 can be generated. Therefore, the ECR plasma generation apparatus 4 is suitable for forming a large area thin film.

<Others>
The embodiment of the plasma modified film forming apparatus of the present invention has been described above. However, the embodiment of the plasma modified film forming apparatus is not limited to the above embodiment. Various modifications and improvements that can be made by those skilled in the art are also possible.

For example, in the above embodiment, a magnetron sputtering film forming apparatus is used as the film forming apparatus. However, the film formation apparatus may be an apparatus that performs sputtering without forming a magnetic field (such as a bipolar sputtering apparatus) or a plasma CVD apparatus. Further, it is not always necessary to irradiate ECR plasma during film formation. That is, the film forming apparatus may be configured without using the ECR plasma generating apparatus. In addition, when an ECR plasma generation apparatus is used as the film formation apparatus, an ECR plasma generation apparatus that performs a modification process may also be used.

When using a magnetron sputter deposition apparatus, the material and shape of the backing plate of the sputtering part and the cathode are not particularly limited. For example, 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. For the cathode, metals such as aluminum can be used in addition to stainless steel. Further, the configuration of the magnetic field forming means for forming a magnetic field on the surface of the target is not limited to the above embodiment. When a permanent magnet is used as the magnetic field forming means, the type and arrangement of the permanent magnet may be determined as appropriate. For example, the N pole and S pole of each permanent magnet may be the reverse of the above embodiment.

The substrate transport means is not limited to the system using the roll member as in the above embodiment. The transfer means may be any means that can transfer the base material so that the reforming process and the film forming process can be continuously performed in one chamber. Moreover, even when using a roll member, the structure and arrangement | positioning form of a roll member are not limited.

In the above embodiment, the plasma modified film forming apparatus is configured to include a supply chamber and a winding chamber in addition to the processing chamber. However, the supply chamber and the winding chamber are not necessarily required. The plasma reforming film forming apparatus may be configured only from a processing chamber (chamber) that performs the reforming process and the film forming process on the base material. The material and shape of the chamber are not particularly limited. For example, the chamber may be made of a metal material. Among metal materials, it is desirable to adopt a material having high conductivity.

In the above embodiment, ITO was used as the target of the magnetron sputtering film forming apparatus. However, the target material is not particularly limited, and may be appropriately determined according to the type of thin film to be formed. Of course, the type of thin film to be formed is not limited. Similarly, the substrate may be appropriately selected according to the application. Besides the PET film of the above embodiment, for example, polyethylene naphthalate (PEN) 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 such as cycloolefin polymer A film or the like can be used.

In the ECR plasma generator, 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.

Further, the material and shape of the support plate are not particularly limited. In the said embodiment, the refrigerant path and the cooling fluid were arrange | positioned as a cooling means for support plates. However, the structure of the support plate cooling means is not particularly limited. The support plate may not have support plate cooling means.

Further, the shape, type, number, arrangement form, etc. of the permanent magnet that forms the magnetic field on the right side or the left side (plasma generation region) of the dielectric part 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.

In the above embodiment, microwaves with a frequency of 2.45 GHz were used for generating ECR plasma. However, the frequency of the microwave is not particularly limited. It may be 8.35 GHz, 1.98 GHz, 915 MHz, or the like.

In the above embodiment, the reforming and film forming processes were performed under a pressure of about 0.1 Pa. However, the processing pressure is not limited to the pressure. The modification and the film formation process may be performed under an optimum pressure as appropriate. As the gas to be supplied, in addition to argon, helium (He), neon (Ne), krypton (Kr), xenon (Xe) and other rare gases, nitrogen (N ₂ ), oxygen (O ₂ ), hydrogen ( H ₂ ) or the like may be used. Two or more kinds of gases may be mixed and used.

The plasma-modified film forming apparatus of the present invention is useful for forming a transparent conductive film used for, for example, a touch panel, a display, LED (light emitting diode) illumination, a solar cell, electronic paper, and the like.

Claims

A chamber;
A conveying means disposed in the chamber for conveying the substrate;
An ECR plasma generation apparatus for generating plasma by electron cyclotron resonance (ECR) using microwaves and modifying the surface of the substrate by the plasma;
A film forming apparatus for forming a thin film on the surface of the substrate;
A plasma-modified film-forming apparatus capable of continuously performing the modification of the surface of the substrate and the film formation on the surface in one chamber,
The ECR 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;
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;
A plasma reforming film forming apparatus, wherein plasma is generated while ECR is generated by the microwave propagating from the dielectric part into the magnetic field.
The plasma-modified film forming apparatus according to claim 1, wherein the pressure in the chamber is set to 0.05 Pa or more and 3 Pa or less to perform reforming and film forming.
3. The plasma reforming film forming apparatus according to claim 1, wherein the support plate of the ECR plasma generation apparatus has a support plate cooling means for suppressing a temperature rise of the permanent magnet.
The film forming apparatus includes a target and a magnetic field forming unit for forming a magnetic field on the surface of the target. The target is sputtered by plasma generated by magnetron discharge, and the sputtered particles ejected from the substrate are The plasma modified film forming apparatus according to any one of claims 1 to 3, which is a magnetron sputtering film forming apparatus for forming a thin film by adhering to the surface.
The magnetron sputter deposition apparatus further includes the ECR plasma generation apparatus,
The plasma modified film forming apparatus according to claim 4, wherein the ECR plasma generation apparatus irradiates ECR plasma between the substrate and the target.
The plasma reforming film forming apparatus according to any one of claims 1 to 5, wherein the transport means includes a roll member.
The plasma reforming film forming apparatus according to claim 6, wherein the roll member has a roll cooling means for lowering the temperature of the outer peripheral surface.