JP2008231471A - Film-forming method using progressive plasma, plasma-baked substrate, and apparatus for forming film with plasma - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-forming method using progressive plasma, which can form a film of adequate quality without embrittling a baked film, when baking a coating film formed on a substrate with plasma at a low temperature, and to provide an apparatus for forming the film with plasma. <P>SOLUTION: The film-forming method using the progressive plasma comprises the steps of: forming a surface film L on the surface of the substrate W from a film-forming material; placing the substrate in such a location as not to be sandwiched by electrodes (high-voltage electrode and low-voltage electrode) for forming plasma; passing the progressive plasma P so that the plasma can progress toward the film surface of the surface film L; and irradiating the surface film L with the progressive plasma P to bake the film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a progressive plasma film forming method in which baking processing is performed on a deposition target substrate by progressive plasma, a plasma sintered base material and a plasma film forming apparatus that have been subjected to plasma baking treatment by the progressive plasma film forming method.

  A transparent conductive film or a transparent electrode film formed on a transparent substrate is used for an image display device such as a liquid crystal display (LCD), a plasma display (PDP), and electroluminescence (EL), and a display panel such as a touch panel. ing.

  Conventionally, methods for forming the transparent conductive film and the transparent electrode film include a dry method and a wet method, and a high-quality fine film can be formed. Dry methods include vacuum deposition, ion plating, and sputtering. The wet method is a method of forming a film by a coating method, and includes a sol-gel method utilizing hydrolysis of a metal alkoxide and a condensation polymerization reaction.

  When film formation is performed by the dry method, a relatively high degree of vacuum is required, so that the manufacturing apparatus becomes expensive and the film formation cost increases. On the other hand, in the wet method, the coating apparatus is cheaper than the dry method, and continuous production is relatively easy, and it is used for forming the transparent conductive film and the transparent electrode film.

  When the transparent conductive film or the transparent electrode film is formed by a wet method, the conductive paint applied on the substrate contains a solvent, and therefore the substrate coated with the conductive paint is dried. There is a need. In order to increase the film forming time, the coating film substrate is generally heat-treated at a temperature of room temperature or higher, for example, 50 to 80 ° C.

  Since it is difficult to directly heat only the coating film of the coating film substrate with ordinary heating means, a hot plate is generally used as a simple drying device. Since the coating film substrate is placed on a hot plate and heat-conductive to the coating film through the substrate for drying treatment, the heat conduction efficiency is low and the temperature of the hot plate needs to be as high as about 150 ° C. There is. However, since heat transfer control is difficult, the coating film was overdried and cracks were generated in the film. In addition, since the substrate itself that is in contact with the hot plate is exposed to a high temperature of 150 ° C., the substrate is warped or distorted to cause thermal deformation, and in some cases, the substrate itself is overheated. There was a risk of damage.

  Unlike substrate heating by the hot plate, there is a surface treatment method using plasma as a method for directly performing film baking. In recent years, surface treatment methods using plasma have improved wettability, adhesion improvement, cleaning, sterilization, disinfection, biocompatibility improvement, etching, desmear treatment, unevenness, deburring, and surface modification of the surface of the workpiece. It is attracting attention that the characteristics of industrial products can be improved by performing the above. Plasma generation techniques used for the surface treatment include corona discharge, glow discharge, dielectric barrier discharge (DBD), RF discharge, microwave discharge, arc discharge, and the like. Furthermore, as a method for generating arc plasma, Czernichowski et al. Proposed a plasma generation method focusing on gliding arcs. Czemichowski: Gliding Arc. Applications to engineering and environment control, Pure and Applied Chemical, Vol. 666 (1994) pp. 1301-1310 (Non-Patent Document 1) and the like. A gliding arc is a phenomenon in which when an arc is generated by applying a high voltage to two electrodes whose distance between the electrodes increases along the direction of plasma travel, the arc moves in the opening direction between the electrodes. Yes.

In Patent Document 1, after forming a metal oxide film made of an amorphous material, a crystalline metal oxide thin film is formed as a post treatment by exposing to a low temperature plasma in a high frequency electric field at a temperature of 180 ° C. or lower. A plasma processing method is disclosed for manufacturing.
International Publication WO2003 / 031673 A. Czemichowski: Gliding Arc. Applications to engineering and environment control, Pure and Applied Chemical, Vol. 666 (1994) pp. 1301-1310

  According to the plasma processing method of Patent Document 1, it is possible to lower the temperature of the base material reforming process without using a hot plate and without performing an active heat treatment. However, in order to crystallize the film to be processed by applying plasma to the film to be processed in a high frequency electric field, when this processing method is applied to the baking treatment of the coating film such as the transparent conductive film or the transparent electrode film, a single crystal There was a problem that the film quality after firing was too brittle and the film quality after firing became brittle.

  Accordingly, an object of the present invention is to provide a progressive plasma capable of forming a film with a good film quality without causing embrittlement of the fired film when the firing process of the coating film applied to the substrate is performed at a low temperature using plasma. A film forming method and a plasma film forming apparatus are provided. Another object of the present invention is to provide a plasma fired substrate comprising a fired film having a film strength with excellent durability by the film forming treatment of the progressive plasma film forming method.

  The present invention has been proposed in order to solve the above-mentioned problems. In the first embodiment of the present invention, a substrate in which a surface film is formed on a substrate surface by a film forming material is sandwiched between plasma forming electrodes. It is a progressive plasma film-forming method in which the surface film is fired by circulating the progressive plasma that is installed at a position where it does not move and proceeds toward the surface film of the substrate.

  A second form of the present invention is a plume of pulse arc discharge generated in the first form by the progressive plasma at about atmospheric pressure, and the pulse arc discharge plume is a gliding arc method or a pen jet method. This is a progressive plasma film formation method.

  According to a third aspect of the present invention, there is provided a progressive plasma film forming method that controls the firing of the surface film by applying a bias voltage to the base material in the first or second aspect.

  A fourth aspect of the present invention is a progressive plasma film forming method according to the first, second, or third aspect, wherein the film forming material is a liquid material in which a film forming material and a solvent component are mixed.

  According to a fifth aspect of the present invention, there is provided a progressive plasma film forming method in which the film forming material is made of only a liquid film forming material in the first, second or third form.

  According to a sixth aspect of the present invention, in the fourth aspect, while the surface film is formed on the surface of the base material by the film forming material, the progressive plasma is circulated through the base material, and the solvent component is supplied. In this method, the surface film is fired while being evaporated or removed.

  According to a seventh aspect of the present invention, in any one of the first to fifth aspects, after the surface film is formed on the base material surface by the film forming material, the base material is sandwiched between plasma forming electrodes. This is a progressive plasma film forming method in which the surface film is baked by the progressive plasma, which is installed at a position that is not present.

  According to an eighth aspect of the present invention, in the sixth or seventh aspect, the substrate surface is irradiated with a purification plasma before the film formation of the base material by the film forming material. This is a progressive plasma film forming method for purifying a material.

  A ninth aspect of the present invention is a progressive plasma film forming method according to any one of the first to eighth aspects, wherein a surface film is formed on the substrate surface by an electrospray method.

  A tenth aspect of the present invention is the progressive plasma film forming method according to any one of the first to ninth aspects, wherein the surface film is formed on the substrate surface while the substrate is mechanically moved. is there.

  An eleventh aspect of the present invention is a progressive plasma film forming method according to the fourth or fifth aspect, wherein the liquid material has a surface energy of 60 dyn / cm or less.

  According to a twelfth aspect of the present invention, in the fourth aspect, the film-forming substance is composed of one or more of an organometallic compound, a metal inorganic acid salt, and a metal organic acid salt, and the film-forming substance is dissolved in the solvent. This is a progressive plasma film forming method.

  A thirteenth aspect of the present invention is the progressive plasma film-forming method according to the fourth aspect, wherein the film-forming substance comprises metal component-containing particles having a particle diameter of 1 nm to 500 nm.

  A fourteenth aspect of the present invention is a progressive plasma film forming method according to the thirteenth aspect, wherein a binder agent for bonding the metal component-containing particles is added as the film forming substance.

  According to a fifteenth aspect of the present invention, in the thirteenth or fourteenth aspect, the metal component-containing particles are made of one or more of metal oxide particles, metal nitride particles, metal carbide particles, a simple metal, and an alloy. This is a plasma film forming method.

  A sixteenth aspect of the present invention is the progressive plasma film forming method according to the thirteenth, fourteenth or fifteenth aspect, wherein the metal component-containing particles carry a carbon nanomaterial on the particle surface.

  According to a seventeenth aspect of the present invention, in any one of the thirteenth to sixteenth aspects, the film-forming substance includes the metal component-containing particles, an organic metal compound, a metal inorganic acid salt, and a metal organic acid salt. It is a progressive plasma film-forming method comprising one or more mixtures.

  An eighteenth aspect of the present invention is a plasma fired base material in which a surface film fired by the progressive plasma film forming method according to any one of the first to seventeenth aspects is formed on a base material surface.

  According to a nineteenth aspect of the present invention, there is provided a firing plasma generating means for generating a firing plasma, a progressing plasma introducing means for introducing the firing plasma as a progressing plasma traveling toward the substrate, and a film forming material. A film firing means for firing a surface film of the substrate by placing the substrate having a surface film formed on the substrate surface at a position not sandwiched between electrodes for plasma formation and circulating the progress plasma through the substrate. A progressive plasma film forming apparatus.

  A twentieth aspect of the present invention is the progressive plasma film forming apparatus according to the nineteenth aspect, wherein the plasma generation means is an atmospheric pressure pulse arc discharge means, and is a gliding arc discharge means or a pen jet discharge means.

  A twenty-first aspect of the present invention is a progressive plasma film forming apparatus according to the nineteenth or twentieth aspect, wherein a bias voltage applying means for applying a bias voltage to the substrate is provided to control firing of the surface film.

  According to a twenty-second aspect of the present invention, in the nineteenth, twentieth or twenty-first aspect, there is a film forming means for forming a surface film on a substrate surface by a film forming material, and the film is formed after the film forming means. This is a progressive plasma film forming apparatus provided with a firing means.

  According to a twenty-third aspect of the present invention, in the twenty-second aspect, there is provided a purifying plasma generating means for generating a purifying plasma for the base material surface, and before the film formation of the base material by the film forming material, It is a progress plasma film-forming apparatus which performs the purification process of the said base material by irradiating the base material surface with the said plasma for purification.

  In a twenty-fourth aspect of the present invention, in the twenty-second aspect, while the surface film is formed on the base material surface by the film forming means, the progressive plasma is circulated through the base material, and the solvent component is supplied. It is a progressive plasma film forming apparatus for firing the surface film while evaporating or removing.

  According to the first aspect of the present invention, the base material in which the surface film is formed on the base material surface by the film forming material is installed at a position not sandwiched between the plasma forming electrodes (high voltage electrode and low voltage electrode), Since the surface film is baked by circulating the progressing plasma traveling toward the surface film, the staying plasma staying in the electric field by the electrode is not used, but the action of the traveling plasma which is an electric fieldless plasma The surface film is fired. Accordingly, single crystallization due to the stagnant plasma, which is electric field plasma, can be polycrystallized by low-temperature treatment of the progressive plasma, and film formation with good film quality can be performed without causing brittleness of the fired film. It can be carried out. When plasma is formed by alternating current, alternating current pulse, or high frequency, the low voltage electrode is usually a grounded cathode. When plasma is formed by direct current or direct current pulse, the high voltage electrode is usually an anode and the low voltage electrode is a cathode. Of course, the reverse is also possible.

According to the second aspect of the present invention, the traveling plasma is a pulse arc discharge plume generated at about atmospheric pressure (0.5 to 1.5 atm), and the pulse arc discharge plume is a gliding arc method or Since it is obtained by the pen jet method, by generating the pulse arc discharge plume at a pressure around atmospheric pressure, it is not necessary to maintain a vacuum or high-pressure state in the plasma baking process of the surface film, and it is easily generated at low cost. It is possible to reduce the cost of film formation using the plasma. In addition, using the plasma generated by the grinding arc method or the pen jet method, it is possible to locally irradiate the processing site with plasma, and unnecessary heating is not required, and high-quality baking processing is performed. It can be carried out. Note that the pen jet method described in the following document is a kind of plasma processing apparatus that can irradiate the surface of an object to be processed only with the plume from a plasma injection pen type nozzle, similarly to the grinding arc method.
<Literature>: Jungo Toshifuji, Takashi Katsumata, Hirofumi Takikawa, Tateki Sakakibara, Ichiro Shimizu; "Cold arc-plasma jet under atomospheric pressure for surface modification", Surface and Coatings Technology vol. 171, (2003) pp. 302-306

  According to the third aspect of the present invention, since the bias voltage is applied to the base material to control the firing of the surface film, the constituent particles of the plasma are repelled from the base material by applying a bias potential. Thus, the influence of the progressive plasma on the base material can be reduced, and the surface film can be subjected to higher-quality low-temperature plasma firing without cracking the film or damaging the base material. It can be carried out.

  According to the fourth aspect of the present invention, since the film forming material is made of a liquid material in which a film forming material and a solvent component are mixed, the film does not crack or damage the substrate. A part or all of the solvent component may be heat-treated with progressive plasma to form a polycrystalline fired film containing the film-forming substance as a main component.

  When the film forming material is, for example, a conductive paint, the film forming material includes organometallic compounds, metal inorganic acid salts, metal oxide fine particles, metal / alloy fine particles (fine particles made of metal or alloy). In order to dissolve or disperse any one or two or more of these substances, an organic solvent and / or water is used as the solvent component.

  According to the fifth aspect of the present invention, since the film forming material is made of a liquid material composed only of a liquid film forming material, for example, an aqueous solution or an organic solvent liquid of the film forming material or a mixed solution thereof is used. It can be used to evaporate and remove solution components by the progressive plasma to form a polycrystalline fired film containing the film-forming substance as a main component.

  According to the sixth aspect of the present invention, while the surface film is formed on the base material surface by the film forming material, the progressive plasma is circulated through the base material to evaporate or remove the solvent component. Since the surface film is baked, the formation of the surface film and the baking are performed substantially simultaneously in parallel, and the solvent component is generated by the progressive plasma without causing cracks in the film or damaging the substrate. It is possible to form a hard film rich in durability by polycrystallizing while removing the carbon black, and to shorten and simplify the baking treatment.

  According to the seventh aspect of the present invention, after the surface film is formed on the base material surface by the film forming material, the base material is placed at a position not sandwiched between plasma forming electrodes, and the progressive plasma Since the surface film is baked, the surface film formed on the substrate surface is irradiated with the progressive plasma of electroless plasma without causing the film to crack or damage the substrate. It can be polycrystallized and reformed into a hard film rich in durability.

  According to the eighth aspect of the present invention, the substrate is purified by irradiating the substrate surface with a purification plasma before the film formation of the substrate by the film forming material. The substrate surface can be purified by irradiating the substrate without damaging the substrate by irradiating the substrate without irradiating the plasma for electric field-free plasma, and a high-quality film forming process can be performed.

  According to the ninth aspect of the present invention, since the surface film is formed on the substrate surface by the electrospray method, the thinned surface film can be formed even for a fine film pattern, and the thinned film is formed. Further, it is possible to form a high-quality thin film by firing with the progressive plasma without causing cracks in the surface film and without damaging the base material.

  According to the tenth aspect of the present invention, since the surface film is formed on the base material surface while mechanically moving the base material, the film thickness is more uniform as compared with the fixed arrangement of the base material. And a hard film rich in durability can be obtained by baking with the progressive plasma.

  In this embodiment, as the means for mechanically moving the base material, a vibration device that applies a vibration motion to the base material, a spinning device that applies a rotational motion to the base material, and a high speed of the base material in the X direction and / or Y direction. It is possible to use a shift device that moves with

  According to the eleventh aspect of the present invention, since the surface energy of the liquid material is 60 dyn / cm or less, the surface tension of the liquid material is small, and the liquid material is formed when the surface film is formed on the substrate surface. Is diffused over the entire surface of the base material, so that no small cavities (nests) are formed in the film, and a surface film having a uniform film thickness can be formed. Moreover, it has a low boiling point and is highly volatile. You can save time.

  According to the twelfth aspect of the present invention, the film-forming substance is composed of one or more of an organometallic compound, a metal inorganic acid salt, and a metal organic acid salt, and the film-forming substance is dissolved in the solvent. Without causing cracks in the film or damaging the substrate, heat treatment is performed by the progressive plasma to form a polycrystalline fired conductive film containing the film-forming substance as a main component. it can.

  According to the thirteenth aspect of the present invention, since the film-forming substance comprising metal component-containing particles having a particle diameter of 1 nm to 500 nm is used, the film has good sinterability and the electric conductivity of the formed film. Therefore, a high-quality fired conductive film can be formed. In particular, in the case of a transparent conductive film, transparency is further improved by using the film-forming substance composed of metal component-containing particles having the particle diameter. In addition, when the particle size of the metal component-containing particles is less than 1 nm, the crystallinity of the conductive film is lowered and the electric conductivity of the formed film is lowered, that is, the surface resistance is increased. Moreover, when a particle size exceeds 500 nm, the malfunction which sinterability and transparency fall will arise.

  According to the fourteenth aspect of the present invention, since the binder agent that binds the metal component-containing particles to each other is added as the film-forming substance, the gap between the metal component-containing particles is filled with the binder agent component. As a result, the bonding force between the particles is increased, the density of the film can be increased, and in addition to the improvement of the mechanical strength and the reduction of the electric resistance, there is an effect of further enhancing the transparency. In particular, when forming a transparent conductive film, a binder containing silica is used. For example, in the case of forming an ITO film, when silicon (Si) alkoxide is used as a binder, a silica thin film or ultrafine silica particles are interposed between ITO particles having an average particle diameter of 20 nm, and the gap is eliminated, resulting in high density. A transparent thin film can be realized.

  According to the fifteenth aspect of the present invention, the metal component-containing particles are composed of one or more of metal oxide particles, metal nitride particles, metal carbide particles, simple metals, and alloys, so that they are highly conductive and have high conductivity. A quality fired conductive film can be formed.

  According to the sixteenth aspect of the present invention, since the metal component-containing particles carry a carbon nanomaterial on the particle surface, the metal component-containing particles are interspersed with the carbon nanomaterial of the carbon nanomaterial. Thus, it is possible to form a high-quality fired conductive film rich in conductivity.

  According to the seventeenth aspect of the present invention, the film-forming substance is composed of the metal component-containing particles and a mixture of one or more of an organic metal compound, a metal inorganic acid salt, and a metal organic acid salt. By adjusting the mixing amount of the organometallic compound, the metal inorganic acid salt, and the metal organic acid salt with respect to the particles, the conductivity can be adjusted and controlled, and a high-quality fired conductive film can be formed.

  According to the plasma fired substrate of the eighteenth aspect of the present invention, the surface film baked by the progressive plasma film forming method according to any one of the first to seventeenth aspects is formed on the substrate surface. Without aggressive heat treatment using a direct heating device such as a plate, the modification of the base material is processed at low temperature by the progressive plasma, and is polycrystallized and has excellent durability. can do.

  According to the progressive plasma film forming apparatus of the nineteenth aspect of the present invention, the firing plasma generating means for generating the firing plasma and the progress for introducing the firing plasma as the proceeding plasma that proceeds toward the substrate. A substrate having a surface film formed on the surface of the substrate by a film introduction material and a plasma introduction means is installed at a position not sandwiched between electrodes for plasma formation, and the progress plasma is circulated through the substrate to Since it has a film baking means for baking the surface film, the surface plasma can be introduced by introducing the progressive plasma toward the substrate by the progressive plasma introducing means without using the staying plasma staying in the electric field generated by the electrode. The film can be baked by electroless plasma, and single crystallizing by the staying plasma, which is electric field plasma, does not occur, and low temperature treatment of the progressive plasma That polycrystalline becomes possible, it is possible to perform good film formation modification process without causing brittleness of the film.

  According to the progressive plasma deposition apparatus of the twentieth aspect of the present invention, the plasma generating means is an atmospheric pressure pulse arc discharge means, and further, it is a gliding arc discharge means or a pen jet discharge means. The pulse arc discharge plume is generated at a pressure around atmospheric pressure by the means or the pen jet discharge means, and it is not necessary to maintain a vacuum or high pressure state in the plasma baking process of the surface film, and plasma generated easily and at low cost The film formation processing cost can be reduced by using this, and high-quality baking processing can be performed without performing unnecessary heating by locally irradiating the processing target region with plasma.

  According to the progressive plasma film forming apparatus of the twenty-first aspect of the present invention, bias voltage applying means for applying a bias voltage to the substrate is provided to control the firing of the surface film. By applying a duct bias potential of about a degree to the base material by the bias voltage applying means, the constituent particles of the plasma are repelled from the base material, and the influence of the progressive plasma on the base material can be reduced, and the film Higher quality, low temperature plasma firing can be performed on the surface film without causing cracks or damaging the substrate.

  According to the progressive plasma film forming apparatus of the twenty-second aspect of the present invention, it has a film forming means for forming a surface film on the substrate surface with a film forming material, and the film baking means is disposed after the film forming means. Therefore, after forming a surface film on the surface of the base material by the film forming material, the base material is placed at a position not sandwiched between plasma forming electrodes, and the surface film is baked by the progressive plasma. The surface film formed on the base material surface is irradiated with the progressive plasma of electroless plasma, and is polycrystallized without causing the film to crack or damage the base material. It can be modified to a hard film rich in.

  According to the progressive plasma film forming apparatus of the twenty-third aspect of the present invention, the plasma generating means for purification for generating the plasma for purification of the substrate surface is provided, and before the film formation of the substrate by the film forming material, The substrate is purified by irradiating the substrate surface with the purification plasma. Therefore, the substrate surface is irradiated with the purification plasma of electroless plasma, and the substrate is subjected to the purification treatment. Can be purified without damaging the film, and a high-quality film formation process can be performed. The cleaning plasma may be shared by the baking plasma generating means.

  According to the progressive plasma film forming apparatus of the twenty-fourth aspect of the present invention, the progressive plasma is circulated through the base material while the surface film is formed on the base material surface by the film forming means, and the solvent Since the surface film is baked while evaporating or removing components, the formation and baking of the surface film are performed almost simultaneously, without causing cracks in the film or damaging the substrate. While removing the solvent component by the progressive plasma, it can be polycrystallized to form a durable hard film, and the firing process can be shortened and simplified.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

  FIG. 1 is a schematic configuration diagram of a plasma film forming apparatus according to the present invention. In the plasma film formation of the present embodiment, the base material W on which the surface film L is formed on the surface of the base material by the film forming material is placed at a position not sandwiched between the plasma forming electrodes of the plasma generator 2, and the film of the surface film L This is performed based on a progressing plasma film forming method in which the surface film L is baked by circulating and irradiating the progressing plasma P traveling toward the surface. Film baking by the progressive plasma P is performed after a surface film is formed on the substrate surface by a film forming apparatus described later.

The plasma film-forming apparatus of this embodiment introduces the plasma generated in the plasma generating unit 2 into the plasma baking unit 1 composed of a chamber from the plasma introduction port 3, and the substrate W disposed in the plasma baking unit 1. Is subjected to plasma baking.
The plasma generating unit 2 is composed of a plasma generator using a gliding arc (GA) method or a pen jet (PEN-JET) method, and uses a plume of pulsed arc discharge generated at about atmospheric pressure as the traveling plasma P.

  In the plasma baking part 1, the base material W which formed the surface film L as a to-be-fired processed material (work) is arrange | positioned. Plasma irradiation is performed so that the central axis of the plasma P in the straight direction substantially corresponds to the vertical axis of the surface film L. In order to increase the introduction efficiency of the plasma P, a magnetic field generator 6 for forming a focused magnetic field may be disposed on the outer periphery of the plasma baking unit 1. The plasma P can be narrowed in the direction of straight movement toward the center of the workpiece by the focused magnetic field formed by the magnetic field generator 6, plasma can be introduced into the film surface of the surface film L with high efficiency and uniformity, and plasma firing Quality improvement and efficiency improvement. Further, a magnetic field generator 5 for forming a focused magnetic field is also disposed in the plasma introduction path 4 between the plasma generator 2 and the plasma inlet 3 of the plasma baking unit 1, and plasma is generated by the focused magnetic field formed by the magnetic field generator 5. Thus, the narrowed plasma can be introduced into the plasma baking unit 1 and the plasma baking can be made uniform.

  Further, in order to further improve the film quality of the plasma treatment film, a bias potential applying potential generator 7 for applying a negative bias potential to the substrate W may be provided. The potential generating unit 7 is composed of a potential generating circuit for applying a DC bias, an RF bias, or a pulse bias. For example, a negative potential is intermittently applied using a unipolar pulse, or a positive / negative composite result is negative using a bipolar pulse. It can be applied by alternating current so as to be a potential. By applying a bias potential 8 to the base material W, the constituent particles of the plasma are repelled from the base material W, and the influence of the progressive plasma on the base material W can be reduced, the film is cracked or the base material is damaged. It is possible to perform higher-quality low-temperature plasma baking on the surface film L without causing the surface film L to flow.

In addition to the plasma P, the plasma firing unit 1 may be provided with a gas introduction system (not shown) including a film formation gas introduction device and a gas discharge device for using another film formation treatment gas. With this gas introduction system, the gas introduction flow rate in the plasma baking unit 1 is controlled to be constant. As the introduction gas, a rare gas such as Ar or He for maintaining a constant pressure can be used. N ₂ , H ₂ or N ₂ / H ₂ mixed gas may be used. Depending on the film processing conditions, for example, nitrogen, oxygen, hydrogen, carbon oxide gas (CO, CO ₂ ), hydrocarbon gas (C ₂ H ₂ , C ₂ H ₄ , CH _4, etc.) is used as the introduced gas. More than one species may be selected and used. In addition, a work placement table having a self-revolving mechanism for placing the substrate W inside the plasma baking unit 1 is provided, and the work placement table is rotated and moved sequentially for each process, so that the position where the plasma P is linearly introduced. The plurality of workpieces may be continuously subjected to plasma processing. Moreover, you may make it plasma-process to a base-material surface, moving the base material W mechanically. As means for mechanically moving the substrate, a vibration device for imparting vibration to the substrate, a spinning device for imparting rotational motion to the substrate, a shift device for moving the substrate at high speed in the X direction and / or Y direction, etc. Can be used.

  When the staying plasma staying between the electrodes of the plasma generator is directly applied to the substrate W, the staying plasma is an electric field plasma, so the surface film L is single-crystallized. Since the plasma P is introduced toward the base material W as the progress plasma without using the staying plasma, the surface film L can be baked by the electric fieldless plasma. Therefore, the surface film L can be polycrystallized by the low-temperature treatment of the progressive plasma, and a good film-forming reforming process can be performed without causing the film to become brittle.

  FIG. 2 is a schematic configuration diagram of a plasma film forming apparatus in which a pen jet method is applied to the plasma generator 2. This pen jet type plasma generating part is composed of an axial electrode 10 provided in the hollow part of the cylindrical guide body 9. A nozzle-like electrode 14 having a fine through hole 18 is provided on the distal end side of the guide body 9. A power source (not shown) is connected to one end side of the axial center electrode 10 via a capacitor 11, and the electrode 14 is connected to a ground 16. The tips of the electrode 14 and the axial electrode 10 are opposed to each other with a gap therebetween, and a plasma generation region is formed. An insulating portion 13 is provided inside the guide body 9 around the plasma generation region so as not to generate an unnecessary electric field. The axial electrode 10 is preferably set to about 0.5 mm to 3 mm in order to concentrate the electric field on the electrode tip surface.

  In the pen jet type plasma generating section, the working gas 12 is introduced from the opening of the guide body 9. As the working gas 12, a desired plasma can be generated by appropriately selecting from dry air, humidified air, helium, argon, oxygen, nitrogen, hydrogen, hydrogen sulfide, hydrocarbon gas and a mixed gas thereof according to the purpose. . Although not shown, the working gas can be supplied using a commercially available gas cylinder, compressor, blower, nitrogen gas supply device, or the like. The flow rate of the working gas is controlled using a commercially available valve, a mass flow controller, a rotameter, etc., and a regulator (not shown) for controlling the gas supply pressure is arranged.

  The working gas 12 flows between the side surface of the electrode 10 and the guide body 9 and is supplied to the plasma generation region. A high voltage pulse supplied from the power source is applied between the electrode 10 and the grounded nozzle electrode 14. The potential applied to the tip surface of the electrode 10 by the discharge from the capacitor 11 is held at a dischargeable potential. The applied high voltage pulse has a pulse width of, for example, about 2 μs and a pulse frequency of about 20 kHz. A voltage of 10 to 15 kV is applied to these inter-electrode gaps by the high voltage pulse, and the voltage of the inter-electrode gap is reduced to about 5 kV by arc discharge. The front end surface of the electrode 10 or the front end surface thereof and the vicinity thereof serve as a discharge surface, and the working gas 12 supplied to the plasma generation region is plasma by arc discharge between the electrode front end surface and the inner surface of the through hole 18 of the nozzle electrode 14. The plasma 15 is emitted from the lower end injection port of the through-hole 18 as progressing plasma, and is irradiated onto the surface of the base material 17 in which the surface film 19 is formed on the base material surface.

  In the plasma film forming apparatus having the above-described configuration of the pen jet type plasma generator, the plasma 15 with a sufficiently narrowed plasma flow is directly introduced toward the substrate 17 as a progressing plasma without using the staying plasma. The surface film L can be baked by electroless plasma. Therefore, the surface film L can be polycrystallized by the low-temperature treatment of the progressive plasma, and a good film-forming reforming process can be performed without causing the film to become brittle. Moreover, since the pulse arc discharge plume obtained by the pen jet method generates a pulse arc discharge plume at a pressure around atmospheric pressure, it is not necessary to maintain a vacuum or high pressure state in the plasma firing treatment of the surface film. In addition, it is possible to reduce the film formation processing cost by using plasma generated at low cost.

  FIG. 3 is a schematic configuration diagram of a plasma film forming apparatus in which a gliding arc method is applied to the plasma generator 2.

  The plasma generator 30 includes a plasma generator 39, a working gas supply path 31, a working gas supply means (not shown), and a voltage application means 32, and generates a plume of pulsed arc discharge at about atmospheric pressure by a gliding arc method. And used in the progressive plasma for firing of the present invention.

  A working gas supply path 31 is formed in the nozzle member 33, and a plasma generator 39 is formed in the nozzle member 33. The working gas supply means introduces the working gas 34 at or near atmospheric pressure into the working gas supply path 31 through the supply pipe 35, and the working gas 34 flows through the working gas supply path 31 and the electrodes 38 and 38 are arranged. It is supplied to the plasma generator 39 provided. As the working gas supply means, commercially available gas cylinders, compressors, blowers, nitrogen gas supply devices, and the like can be used.

  The electrodes 38 are disposed in the plasma generation unit 39 so that the distance between the electrodes increases along the traveling method of the working gas 34. Further, the electrodes 38 and 38 are installed so that the electrode tips 38 c and 38 c are located inside the injection port 40. When the voltage applied by the voltage applying means 32 reaches the dielectric breakdown voltage in the shortest gap 38a between the electrodes, the working gas supplied between the electrodes generates a spark at the shortest gap position 38b to generate plasma 41. The plasma 41 includes an arc column 36 which is a plasma in the current path portion and a plume 37 in a weakly ionized plasma state. As the voltage application means 32, a commercially available high voltage DC power supply, high voltage AC power supply, high voltage pulse power supply, or the like can be used.

  The arc column 36 is pushed out by the gas flow of the supplied working gas 34 and moves downstream along the electrodes 38 and 38. When the arc column 36 extends to a predetermined length, the discharge sustaining voltage of the arc column exceeds the applied voltage, and the arc column 36 self-extinguishes. At this time, the plume 37 is also pushed out by the gas flow and proceeds toward the injection port 40. A base material W1 on which a surface film L1 is formed is disposed immediately below the injection port 40. Since the electrode tips 38c and 38c are located on the inner side of the injection port 40, the arc column is cooled by the high-speed gas flow rate at the injection port, so that it is difficult for the arc column to come out of the injection port and the arc column 36 reaches The range is reduced. Therefore, generation | occurrence | production of an arc spot can be prevented and the baking process can be performed by irradiating the plume which is a weakly ionized plasma state to the surface film L1 with high efficiency.

  FIG. 4 is a schematic view of the nozzle member 33. An injection port 40 is formed in the nozzle member 33, and plasma is emitted from the injection port 40. (4A) shows the nozzle member 33 in which the slit and / or the working gas supply path are integrally formed, and the slit can be formed in the injection port 40. (4B) shows a nozzle member 33 having means for opening and closing the slit 42 (not shown), and the injection port 40 is composed of slit members 43 and 43. Slit surfaces 44, 44 are formed on the slit member. At least one of the slit members 43 can be freely moved by the opening / closing means, and the slit width can be controlled. Since the slit portion becomes high temperature, it is desirable to use heat resistant resin or ceramics for the slit member. (4C) shows the nozzle member 33 provided with slit members 43 and 43 having curved slit surfaces 44 and 44. Even when the slit surfaces 44 and 44 are formed in a curved shape to form the injection port 40, a plume in a weakly ionized plasma state is emitted from the injection port 40. Therefore, the shape of the injection port composed of the slit members 43 and 43 can be appropriately selected according to the environment in which the object to be fired is installed and the state and shape of the object to be fired.

  FIG. 5 is a schematic configuration diagram of the electrode 38 for the gliding arc. FIG. 5 shows gliding arc electrodes 38 and 38 in which the metal electrode is bent and the distance between the opposing electrode surfaces increases along the traveling direction of the working gas 34. The gliding arc electrodes 38, 38 need only have electrode pairs arranged in a divergent shape as described above, and electrodes having various shapes as shown below can be used. (5A) is a plasma generating unit 39 in which triangular electrodes 38 are provided. Further, (5B) shows electrodes 38, 38 having curved surfaces, and (5C) shows dog-shaped electrodes 38, 38. In the electrode pairs shown in (5A) to (5C), at least a part of the inter-electrode distance along the traveling direction of the working gas 34 is increased, and a gliding arc can be generated using these electrodes. .

  FIG. 6 is a schematic front view of the plasma injection port 40 to which the block member 45 is attached. In the figure, w is the width of the slit from which plasma is emitted. As shown in the figure, a plurality of block members 45 are attached to the slit members 43, 43, and plasma is emitted from a gap formed by the slit 42 and the block member 45. As the block member 45, a heat-resistant insulating material is used. For example, the block member is formed from a heat-resistant resin, high-resistance carbon, ceramic material, or the like.

  (6A) shows the slits 42 in which the thicknesses S of the block members 45 to be attached are all equal and the gaps d of the respective block members 45 are set at equal intervals. The position where the block member 45 is attached is not limited to the slit 42, but is disposed at or near the injection port 40 of the nozzle member to block the arc column and irradiate the object to be fired with the plume. If possible, the block member 45 can be disposed at a desired position. (6B) is set such that the gap d of the block member 45 is narrowed and the thickness S of the block member 45 is gradually increased as the mounting position of the block member 45 approaches the center position from the end side of the slit 42. ing. The sizes of the block members 45 do not have to be the same, and the gaps d between the block members need not be equally arranged. Therefore, since the arc column extends most at the center position between the electrodes, the gap d can be small at the center between the electrodes, and the gap d can be increased in the vicinity between the electrodes. Thus, a suitable shape and arrangement interval can be selected in accordance with the plasma injection shape.

  FIG. 7 is a schematic configuration diagram of the plasma generating unit 39 in which the block member 24 is disposed. In (7A) and (7B), a plurality of columnar or cylindrical block members 45 are arranged perpendicular to the direction in which the distance between the electrodes is increased at equal intervals. Since the arc column 36, which is the current path of the plasma 41, is blocked by the block member 45 and only the plume 37, which is weakly ionized plasma, is irradiated onto the surface film L1, generation of arc spots can be prevented and a suitable firing process can be performed. it can.

  FIG. 7B is a schematic configuration diagram of the plasma generation unit 39 in the comparative example in which the thickness and interval of the block member 45 are changed. When the block member 45 having a smaller diameter is used as compared with the block member 45 of (7A), when the applied voltage is increased, the arc column 36 bypasses the outside of the block member as shown in (7B). End up. Further, when the interval between the block members 45 is increased, the arc column 36 is easily pushed out by the working gas, so that the arc column reaches the surface film L1, and an arc spot is easily generated particularly on the conductive surface film L1. . Therefore, in order to suppress the occurrence of the arc spot, it is preferable to use the block member 45 having a large diameter and arrange it with a narrow bar interval. The diameter or width of the block member 45 is 0.1 to 10 mm, preferably 2 to 4 mm. The gap formed by the block members 45 is 0.1 to 5 mm, preferably 0.2 to 2 mm. In addition, the shape of each block material does not need to be the same. For example, thin block members and thick block members 45 can be alternately arranged.

  In the plasma film-forming apparatus provided with the plasma generating apparatus 32 having the above-described configuration, the surface film L1 can be subjected to plasma baking using progressive plasma composed of a plume of pulsed arc discharge generated at about atmospheric pressure. Therefore, it is not necessary to maintain a vacuum or high-pressure state, and it is possible to reduce the film forming process cost by using plasma generated easily and at low cost. In addition, it is possible to locally irradiate the site to be processed with plasma generated by the grinding arc method, and unnecessary heating is not required, and high-quality baking processing can be performed. In order to increase the power of the traveling plasma, a multi-torch type plasma generating apparatus in which a plurality of nozzle members 33 are bundled can be used.

  As a film forming material used for the plasma film forming apparatus of each of the above embodiments, a conductive paint can be used. The conductive paint is any one or two of metal component-containing materials such as organometallic compounds, metal inorganic acid salts, metal organic acid salts, metal oxide fine particles, and metal / alloy fine particles (fine particles made of metal or alloy). A paint obtained by dissolving or dispersing the above in an organic solvent and / or water. The metal component-containing material is not particularly limited as long as the material containing the metal element to be used is appropriately selected. In addition, since the coating film made of a conductive paint is dried at a predetermined temperature, for example, 50 to 80 ° C., if baking is performed using the progressive plasma, a drying process can be performed in a relatively short time.

  As the organometallic compound, for example, metal alkyl and metal aryl such as indium, tin, zinc, cadmium, gallium, antimony, and aluminum are preferably used, and metal acetylacetonate such as indium acetylacetonate is particularly suitable. .

  As the metal inorganic acid salt, for example, nitrates, hydrochlorides, sulfates, and phosphates containing one or more of indium, tin, zinc, cadmium, gallium, antimony, and aluminum are preferably used. . In place of the metal inorganic acid salt, a hydrate of the above-mentioned inorganic acid salt may be used.

  As the metal organic acid salt, a salt of a metal and a carboxylic acid such as a saturated aliphatic monocarboxylic acid, a saturated aliphatic dicarboxylic acid, an unsaturated fatty acid, a carbocyclic carboxylic acid, or a heterocyclic carboxylic acid is preferably used. Examples thereof include acetate, tartrate, formate, oxalate, 2-ethylhexanoate, and the like containing any one or more of indium, tin, zinc, cadmium, gallium, antimony, and aluminum.

  Examples of the metal oxide fine particles include fine particles such as indium oxide, zinc oxide, cadmium oxide, gallium oxide, antimony oxide, and aluminum oxide, or tin-added indium oxide (ITO) obtained by adding other metal elements to these oxides. ), Antimony-added zinc oxide (AZO), gallium-added zinc oxide (GZO), and the like are preferably used.

  In particular, the metal oxide constituting the transparent conductive film includes tin-added indium oxide (ITO), antimony-added tin oxide (ATO), zinc-added indium oxide (IZO), aluminum-added zinc oxide (AZO), and gallium-added zinc oxide. Fine particles such as (GZO) are preferably used.

  The average primary particle diameter of the metal oxide fine particles is 1 nm to 500 nm, preferably 1 nm to 100 nm, more preferably 1 nm to 30 nm. The reason for the preferred particle size is that when the average primary particle size of the metal oxide fine particles is less than 1 nm, the crystallinity of the transparent conductive film decreases, and as a result, the electrical conductivity of the film decreases (the surface resistance increases). This is because if the thickness exceeds 100 nm, the transparency and sinterability of the transparent conductive film decrease. Therefore, in particular, when the average primary particle size is 1 nm or more and 30 nm or less, the sinterability between the metal oxide fine particles is improved, and the densification of the coating film becomes easier, which is preferable.

  Examples of the metal / alloy fine particles include fine particles such as indium, tin, zinc, cadmium, gallium, antimony, and aluminum, or indium-tin alloy, indium-zinc alloy, antimony-tin alloy, zinc-aluminum alloy, zinc- Fine particles such as a gallium alloy are preferably used. The average primary particle diameter of these fine particles is from 1 nm to 500 nm, preferably from 1 nm to 100 nm, more preferably from 1 nm to 30 nm, for the same reason as the above metal oxide fine particles.

  The amount of the organic solvent and / or water used can be easily applied according to the organometallic compound, metal inorganic acid salt, metal organic acid salt, metal oxide fine particle, metal / alloy fine particle to be used, and has a desired film thickness. May be selected as appropriate. For example, when metal oxide fine particles or metal / alloy fine particles are dissolved or dispersed in an organic solvent and / or water, the amount of fine particles is preferably 1 to 10% by weight based on the total amount of the solvent. In addition to the organic solvent, the paint may contain a binder agent. The binder component of the binder agent is interspersed between the particles, increasing the bonding force between the particles, realizing high density of the film quality, improving the mechanical strength, lowering the electrical resistance, and further improving the transparency There is. For example, in the case of forming an ITO film, when a binder agent containing silica, such as Si alkoxide, is used as the binder agent, silica fine particles are interposed between ITO particles having an average particle diameter of 20 nm, so that the gap is eliminated and the density is high. A transparent thin film can be realized.

  The organic solvent may be appropriately selected according to the metal compound used, the metal inorganic acid salt, the metal organic acid salt, the metal oxide fine particles, and the metal / alloy fine particles, and is not particularly limited. Monohydric alcohols such as methanol, ethanol, 2-propanol and butanol, dihydric alcohols such as ethylene glycol, ketones such as acetone, methyl ethyl ketone and diethyl ketone, esters such as ethyl acetate, butyl acetate and benzyl acetate, Ether alcohols such as methoxyethanol and ethoxyethanol, ethers such as dioxane and tetrahydrofuran, amides such as N, N-dimethylformamide, aromatic hydrocarbons such as toluene and xylene can be used.

  As a method for applying the film forming material to the substrate, for example, a usual method such as a spin coating method, a spray coating method, an ink jet method, a dip method, a roll coating method, a screen printing method, or the like can be used. The thin film formation using the conductive paint is preferably performed by an electrospray deposition (ESD) method or an electrostatic mist spray method, which is one of spray coating methods.

  FIG. 8 shows a schematic configuration of a coating film forming apparatus by an ESD method. The coating film forming apparatus includes a glass capillary 200 filled with a film forming material 201, a current-carrying core material 202 for applying a high voltage to the liquid film-forming material 201 in the capillary 200, and a high voltage applied to the current-carrying core material 202. And a high-voltage power supply 213 for applying. A collimator electrode 207 to which a collimator potential is applied by a collimator power source 214 is disposed between the capillary 200 and the coating film forming substrate 211 via an insulator mask 209. A shield cover 205 is disposed above the collimator electrode 207. Openings 206, 208, and 210 are formed in the central portions of the shield cover 205, the collimator electrode 207, and the insulator mask 209, respectively.

  In the coating film forming apparatus having the above configuration, when a high voltage of several kV is applied between the capillary 200 and the substrate 211 by the high voltage power source 213 and the energizing core member 202, the film forming material 201 is formed from the tip 203 of the capillary 200 by static electricity. Is sprayed into the spray droplet group 204 toward the coating film portion of the substrate 211 to form a surface film 212 on the substrate surface. Since the ejected film forming material 201 component becomes droplets and is dispersed into finer droplets by its own charge, the spraying surface area is increased and the film is dried instantly to form a thin film. Can do. The positive ion particles contained in the spray droplet group 204 ejected from the tip end 203 of the capillary 200 try to diffuse near the collimator electrode 207 by the Coulomb repulsive force. The collimator power source 214 changes the collimator potential to the potential of the high voltage power source 213. By setting it to about 1/10, it can be repelled and narrowed down to the opening 208 side, and an efficient coating film formation can be performed. During spraying by the capillary 200, if a vibration is applied to the substrate 211 by a vibration device (not shown) or a rotational force is applied to the substrate 211 by a spinning device (not shown), film formation is performed. Smoothing and a more uniform coating film can be obtained. In this way, the substrate 211 on which the thinned surface film 212 is formed is subjected to plasma baking by the above-described plasma film forming apparatus, so that a progressive plasma of electroless plasma is irradiated and the surface film 212 is cracked. Without causing damage or damaging the base material 211, it can be polycrystallized and modified to a hard film with high durability, and thinning and improvement in film quality can be achieved.

  After the preliminary film formation for forming the surface film 212 on the base material surface by the film forming material 201, the base material surface is formed on the base material surface by the film forming material 201 in addition to the processing method for firing the surface film by the progressive plasma. While forming the surface film 212, the process position of the base material 211 may be made variable so that the base material 211 is irradiated with the progressive plasma at any time. When the substrate 211 is irradiated with the progressive plasma at any time in the coating process, the surface film 212 is baked while evaporating or removing the solvent component in the film forming material 201. Can be formed almost simultaneously and in parallel, without causing cracks in the film or damaging the base material, and can be polycrystallized to form a highly durable hard film. The firing process can be shortened and simplified.

  Like the ESD method, in the electrospray method, a liquid material is used as a film forming material, but the surface energy is preferably 60 dyn / cm or less. In the case of a liquid material containing alcohols or the like, if the surface energy is 60 dyn / cm or less, the surface tension of the liquid material is small, and the liquid material is based on the formation of the surface film on the substrate surface. Diffusion across the entire surface of the material does not produce a small cavity (nest) in the film, and a surface film with a uniform film thickness can be formed. Moreover, it has high boiling point due to its low boiling point and shortens the plasma firing time. it can.

  Although it does not specifically limit as a base material in this invention, A glass substrate and a plastic substrate (organic polymer compound substrate) can be used, As a shape, a flat plate, a film, a sheet | seat, etc. may be sufficient.

  A transparent plastic sheet or a transparent plastic film can be used for the plastic substrate. The material of the plastic substrate is not particularly limited. For example, cellulose acetate, polystyrene (PS), polyethylene terephthalate (PET), polyether, polyimide, epoxy, phenoxy, polycarbonate (PC), polyvinylidene fluoride, etc. Can be appropriately selected. Also, the thickness of the plastic substrate is not particularly limited, and a film of about 50 to 250 μm can be used for a film, and a sheet of about 10 mm can be used for a sheet.

  Each of the above substrates may be used alone or as a substrate having a laminated structure in which a plurality of substrates are bonded and integrated. When applying a conductive paint, it is preferable to clean the substrate with a cleaning liquid such as pure water or an organic solvent. When ultrasonic waves are applied to the cleaning liquid during cleaning, the cleaning power is increased and the cleaning effect is increased. Goes up. The film forming apparatus may be provided with a purifying plasma generating means for generating a purifying plasma on the substrate surface. That is, like the plasma baking, the cleaning plasma of the electroless plasma is generated, and the substrate surface is irradiated with the cleaning plasma before the substrate film is formed by the film forming material. By performing the purification treatment, the substrate can be purified without damaging the substrate, and a high-quality film formation treatment can be performed. As the cleaning plasma, the firing plasma P or the weakly ionized plasma plume 37 in each of the above embodiments may be shared.

  FIG. 9 shows an example of a configuration in which a series of processes of pretreatment, film formation, and plasma baking are continuously performed. This continuous processing system includes a pretreatment plasma device 51, a film formation device 52, a firing plasma device 53, and a substrate moving device (not shown). A continuous processing system composed of a part of these devices can also be put into practical use. The substrate moving device only needs to relatively move each component processing apparatus and the substrate to be processed 50, and may be unidirectional, reciprocating, or bi-directional. Each of the devices (the pretreatment plasma device 51, the film formation device 52, and the firing plasma device 53) may move relative to the substrate 50. The plasma 54 irradiated to the substrate 50 from the pretreatment plasma apparatus 51 is not limited to pulsed arc plasma (gliding arc, pen jet), but as its plasma generation source, RF plasma, barrier discharge, glow discharge, microwave discharge, etc. Can be used. As the film forming apparatus 52 for the continuous apparatus, a spray coating method, an inkjet method, a roll coating method, a screen printing method, an electrospray deposition (ESD) method, an electrostatic mist spray method, or the like can be used. The firing plasma 55 is preferably pulsed arc discharge plasma, and a gliding arc or a pen jet is used.

Next, an ITO film forming experiment by the plasma film forming method of the present invention will be described.
FIG. 10 shows a schematic configuration of a split type gliding arc apparatus used in this ITO film forming experiment. As shown in (10A) of FIG. 10, this gliding arc device includes a substantially C-shaped copper electrode 60, and a working gas 62 is supplied from an upper part of an electrode holder 61 to which the electrode 60 is attached. A power cable 63 is connected to the conductive electrode holder 61 to supply power to the electrode 60. A perforated slit plate 64 having a plurality of small holes 67 formed in a line is disposed at the open side outlet of the electrode 60. According to this gliding arc device, the arc column 65 is generated on the electrode 60 side by energization, and the plasma jet 66 can be ejected from each small hole 67. As shown in (10B) of FIG. 10, the diameter Q of the small hole 67 is about 1 mm, the length T of the small hole 67 is about 5 mm, and the interval P between the small holes 67 is about 2 mm. The depth H of the electrode 60 from the slit plate 64 is 25 mm, and the lateral length W of the slit plate 64 is 80 mm.

  FIG. 11 is a table showing ITO film formation conditions and resistance measurement results. * In the table is the plasma temperature measured with a K-type thermocouple. Three types of film formation (coating) methods were used: spin coating, dip coating, and ESD. As a film drying method, a hot plate and a plasma baking according to the present invention were compared.

  The ITO raw material chemical solution is 10 wt. % (Particle diameter about 20 nm), isopropyl alcohol 24 wt. %, Methanol 66 wt. It is a sample (ITO chemical solution) that was subjected to a dispersion treatment with a sand mill with a composition of% and made an ITO fine particle-dispersed paint.

The ESD film formation conditions were a working voltage of 9 kV and an ITO diluent flow rate of 30 μL / min. The ITO diluted chemical solution is obtained by diluting the ITO chemical solution with ethanol by 50 vol.%. The coating film after each film formation was subjected to hot plate drying (150 ° C., 5 min), hot plate baking (300 ° C., 5 ° C. min), and GA irradiation. The GA irradiation conditions are an output of 300 W, an operating gas of 40 L / min, and a processing time of 1 min and 5 min.
First, in hot plate heating, any of the spin coating method, the dip coating method, and the ESD method as a film forming (coating film) method cannot reduce the resistance value unless it is heated at a high temperature of 300 ° C., It was confirmed that the film quality deteriorated due to overheating or the effect on the substrate.

  In the GA treatment according to the present invention, a comparative experiment was conducted by performing plasma firing on the film forming substrate in an atmosphere (air) environment and a nitrogen atmosphere. In the atmospheric environment, it was confirmed that there was no film quality deterioration and no influence on the substrate as compared with hot plate heating, but no reduction in resistance value was observed. This is because the plasma baking effect is reduced because the ITO film is oxidized mainly by the influence of oxygen in the air. Therefore, we tried firing with nitrogen plasma using nitrogen as the working gas.

  The effect of reducing the resistance value by the non-oxidizing working gas is clear from the table of FIG. In particular, in the case of film formation by ESD, the surface resistance value is smaller than that in the case of 300 ° C. hot plate heating. This effect of reducing the resistance value is due to the fact that the progress of plasma GA can be sufficiently performed on the ITO film in a state where the oxidation of the film is sufficiently suppressed by the non-oxidizing nitrogen gas. By improving the irradiation efficiency, it is possible to shorten the plasma baking time. In addition, although the said resistance value reduction effect is acquired by the oxidation suppression effect | action only with nitrogen gas, you may mix a trace amount (refer FIG. 17 mentioned later) hydrogen gas with nitrogen gas. In this case, it is possible to sufficiently irradiate the progressive plasma with GA in a state in which film oxidation is further suppressed by the reducing action of hydrogen contained in the mixed gas.

  Therefore, the plasma film-forming apparatus of the present invention can produce a high-quality ITO film having high electrical conductivity, good film quality by using electroless plasma, and no damage to the substrate. Moreover, the film can be fired almost simultaneously with the thinning of the ITO film, and mass production of a high-quality fired film can be realized.

FIG. 12 is a cross-sectional photograph of an ITO sample film obtained by a firing experiment using plasma using a mixed gas of nitrogen N ₂ as a main operating gas and 0.25 vol.% Hydrogen H ₂ . In this experiment, the ESD film formation conditions were: a working voltage of 9.0 kV, a chemical flow rate of 30 μL / min, an ITO diluted chemical solution (ethanol 50 vol.% Diluted) obtained by diluting the ITO chemical solution used in the measurement of FIG. One time (traverse speed 2 mm / sec). The GA plasma irradiation conditions are an output of 300 W and a flow rate of 40 L / min. The plasma processing time is 3 min. In the experiment, the periphery of the plasma generation apparatus (griding arc apparatus) in FIG. 10 was covered with a cover member and sufficiently blocked so as not to enclose the surrounding air to prevent oxidation as much as possible. FIG. 12 shows a vertical cross section of an ITO sample film obtained by the main firing experiment. From this experimental result, an extremely small ITO film having a thickness of 450 nm and a resistance value of 2.7 kΩ / □ was obtained. This reduction in resistance does not cause film oxidation due to non-oxidizing nitrogen gas, and further sufficiently reduces the progress plasma GA against the ITO film substrate in a state where the oxidation is sufficiently suppressed by the reducing action of the hydrogen contained. Because it can be irradiated. In addition, the irradiation efficiency is improved and a plasma baking process can be performed in a short time. The oxidation may be prevented with only non-oxidizing nitrogen gas.

  As can be seen from the cross-sectional photograph in FIG. 12, in the case of the ESD method, the film surface has irregularities or small cavities (nests) compared to the spin coating method, dip coating method or ESD method. Yes. Therefore, the pretreatment of the base material itself is also subjected to plasma treatment.

FIG. 13 is a cross-sectional photograph of a sample when GA is used as a plasma for substrate purification, so-called pretreatment. The pretreatment GA irradiation conditions are an output of 300 W, a nitrogen working gas of 40 L / min, and a reciprocating traverse frequency of 2 (traverse speed of 2 mm / sec). The number of round trips of ESD is 0.5 (traverse speed 2 mm / sec), and other ESD film formation conditions are the same as those in FIG. GA plasma irradiation conditions during sintering are an output of 300 W and a flow rate of 40 L / min. A mixed gas of nitrogen N ₂ gas and 0.25 vol.% Hydrogen H ₂ is used as the working gas, and the processing time is 5 min. FIG. 13 shows a vertical cross section of the ITO sample film obtained by the main firing experiment. Also in this experiment, an extremely small ITO film having a thickness of 350 nm and a resistance value of 5.2 kΩ / □ was obtained. In addition, the surface of the base material is plasma-purified and flattened, and the film surface has no irregularities and no cavities (nests) compared to the cross-sectional photograph of FIG. 20, and a good film surface is formed. Therefore, the surface of the film is finely roughened by the plasma purification according to the present invention, and the wettability can be improved.

The ITO film was examined for vibration effects on the substrate in the ESD film formation and GA plasma firing process. FIG. 14 is a cross-sectional photograph of a sample when the same ITO diluted chemical solution as in FIGS. 12 and 13 is used and vibration is applied to the substrate using a vibration device having a vibration speed of 2000 rpm during plasma baking. The ESD film formation conditions are a use voltage of 13.0 kV and a chemical flow rate of 30 μL / min. The GA plasma irradiation conditions are an output of 300 W and a flow rate of 40 L / min. Nitrogen N ₂ gas is used as the working gas, and the processing time is 5 min. FIG. 14 shows a vertical cross section of the ITO sample film obtained by the main firing experiment. According to this experiment, an ITO film having a resistance value of 25.9 kΩ / □ was obtained. On the other hand, when the same film formation was performed without applying vibration by a vibration apparatus, an ITO film having a resistance value of 95.2 kΩ / □ was obtained. From this experiment, it can be seen that there is no significant change in the appearance of the film surface, but the resistance value can be slightly reduced by vibration.

FIG. 15 is a graph of experimental results when the amount of binder agent mixed is changed. The ITO chemical | medical solution used in the measurement of the said FIG. 11 was used for ITO chemical | medical agent. Si alkoxide was used as the binder agent. An ITO chemical solution mixed with a binder was formed by spin coating, and then irradiated with GA plasma. The GA plasma irradiation conditions are an output of 300 W, a flow rate of 40 L / min, an operating gas: hydrogen H ₂ 0.25 vol.% Mixed nitrogen N ₂ , and an irradiation time of 2 min. The film thickness is about 400 nm. The horizontal axis in FIG. 15 represents the volume mixing ratio of the binder agent. FIG. 15 shows that the sheet resistance value is minimized when the mixing ratio is 10 to 15%. That is, it can be seen that 10 to 15 vol.% Is the optimum mixing ratio of the binder.

  FIG. 16 is a sample cross-sectional photograph of the experiment of FIG. FIG. 16 (16a) is a cross-sectional photograph of a sample containing no binder agent. (16b) to (16f) are cross-sectional photographs of samples in which 5, 10, 12.5, 15, 20 vol. As is apparent from a comparison between the sample cross-sectional photograph (16a) not containing the binder agent and the sample cross-sectional photos (16b) to (16f) containing the binder agent, by including the binder agent, cavities, nests, etc. It can be seen that the silica thin film or the ultrafine silica particles have entered between the ITO particles. When the binder mixing rate is 10 to 15 vol.% ((16c) to (16e)), a silica film or ultrafine silica particles are interposed between ITO particles having an average particle diameter of 20 nm, so that the gap is eliminated and the density is increased. In addition, it is possible to realize an ITO thin film with good adhesion to the base material and better transparency. When the binder mixing rate is less than 10-15 vol.%, The nest increases and the resistivity increases. Also, if the binder mixing rate is larger than 10-15 vol.%, The silica binder formed from Si alkoxide covers the ITO fine particles, and the silica binder itself is electrically insulating, so there is no contact between the ITO fine particles. As a result, the overall conductivity is lowered, and the sheet resistance is increased.

FIG. 17 shows the results of examining the influence of the amount of mixed hydrogen on the main operating gas nitrogen. The same ITO chemical | medical solution as the experiment of the said FIGS. 12-16 was used for the ITO chemical | medical agent. Binder agent is not mixed. An ITO chemical solution was formed by spin coating and then irradiated with GA plasma. The GA plasma irradiation conditions are an output of 300 W, a flow rate of 40 L / min, and an irradiation time of 2 min. The film thickness is about 400 nm. The horizontal axis in FIG. 17 represents the volume mixing rate of H ₂ gas mixed in N ₂ gas. FIG. 17 shows that the sheet resistance value is minimized when the H ₂ mixing ratio is around 1 vol. That is, it can be seen that 1 vol.% Is the optimum mixing ratio of H ₂ gas. When a very small amount of H ₂ gas is mixed, the reduction action becomes effective, the oxidation of the film is suppressed, and the resistance is lowered. However, when the mixing amount is excessively large, the plasma is cooled, the plasma jet is deteriorated, the plasma does not reach the substrate, and the processing effect, that is, the resistance value reducing effect is lowered.

  The present invention is not limited to the above-described embodiments and modifications, and includes various modifications and design changes within the technical scope without departing from the technical idea of the present invention. Needless to say.

  According to the progressive plasma film forming method of the present invention, the surface film is baked by the action of the progressive plasma, which is an electric fieldless plasma, without using the staying plasma that stays in the electric field by the electrode, and single crystallization does not occur. Thus, polycrystallization can be achieved by low-temperature processing of the progress plasma, and film formation with good film quality can be performed without causing brittleness of the fired film. Therefore, with the progressive plasma film formation method and the progressive plasma film formation apparatus according to the present invention, surface treatment or modification such as improvement of conductivity, improvement of wettability, improvement of mechanical strength, etc. without damaging the substrate or the surface film. Quality can be suitably performed.

It is a schematic block diagram of the plasma film-forming apparatus which concerns on this invention. 1 is a schematic configuration diagram of a pen jet type plasma film forming apparatus according to the present invention. 1 is a schematic configuration diagram of a gliding arc type plasma film forming apparatus according to the present invention. It is the schematic of the nozzle member used for the plasma film-forming apparatus of FIG. It is a cross-sectional schematic diagram of the nozzle member. It is a cross-sectional schematic diagram of the nozzle member. It is a schematic block diagram of the electrode for no gliding arc used for the plasma film-forming apparatus of FIG. It is a schematic block diagram of the film forming apparatus by ESD method. It is a schematic block diagram which shows the structural example of a continuous processing apparatus. It is a schematic block diagram of the gliding arc apparatus used for the film-forming experiment of ITO. It is a table | surface which shows the ITO film-forming experiment result which carried out the plasma baking processing which concerns on this invention. It is a cross-sectional photograph of an ITO sample film obtained by a firing experiment using plasma in which nitrogen is the main working gas and a small amount of hydrogen is mixed. It is a sample cross-sectional photograph at the time of performing the pretreatment using plasma. It is a sample cross section photograph at the time of adding vibration to a substrate at the time of plasma baking. It is a sample cross section photograph at the time of adding vibration to a substrate at the time of plasma baking. It is a graph which shows the experimental result which changed the mixing amount of the binder agent with respect to ITO chemical | medical solution. It is a sample cross-sectional photograph by the mixing experiment of the binder agent of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plasma baking part 2 Plasma generation part 3 Plasma introduction port 4 Plasma introduction path 5 Magnetic field generator 6 Magnetic field generator 7 Potential generation part 8 for applying a bias potential Bias potential 9 Cylindrical guide body 10 Axis electrode 11 Capacitor 12 Working gas 13 Insulating part 14 Nozzle electrode 15 Plasma 16 Ground 17 Surface film 18 Through hole 19 Base material 30 Plasma generating device 31 Working gas supply path 32 Voltage application means 33 Nozzle member 34 Working gas 35 Supply pipe 36 Arc column 37 Plume 38 Electrode 38a Electrode Shortest gap 38b Shortest gap position 38c Electrode tip 39 Plasma generating portion 40 Ejection port 41 Plasma 50 Substrate for processing 51 Pretreatment plasma device 52 Film forming device 53 Plasma device for firing 54 Plasma 55 Plasma 60 Electrode 61 Electrode holder 62 Working gas 63 Power supply Bull 64 Slit plate 65 Arc column 66 Plasma jet 67 Small hole 200 Capillary 201 Film forming material 202 Conductive core material 203 Tip 204 Spray droplet group 205 Shield cover 206 Opening 207 Collimator electrode 208 Opening 209 Insulator mask 210 Opening 211 Base material 212 Surface film 213 High voltage power supply 214 Collimator power supply

Claims (24)

The surface film is formed by placing a base material having a surface film formed on the surface of the base material by a film forming material at a position not sandwiched between plasma forming electrodes, and circulating a progressing plasma traveling toward the surface film of the base material. Is a progressive plasma film-forming method characterized by firing. The progressive plasma film forming method according to claim 1, wherein the progressive plasma is a plume of a pulse arc discharge generated at about atmospheric pressure, and the pulse arc discharge plume is obtained by a gliding arc method or a pen jet method. The progressive plasma film-forming method according to claim 1, wherein a bias voltage is applied to the substrate to control firing of the surface film. The progressive plasma film-forming method according to claim 1, wherein the film-forming material comprises a liquid material in which a film-forming material and a solvent component are mixed. The progressive plasma film-forming method according to claim 1, wherein the film-forming material is made of a liquid material composed only of a liquid film-forming material. 5. The surface film is baked while forming the surface film on the surface of the base material with the film forming material, allowing the progressive plasma to flow through the base material, and evaporating or removing the solvent component. Progressive plasma deposition method. The surface film is formed on the surface of the base material by the film forming material, and then the base material is placed at a position not sandwiched between the plasma forming electrodes, and the surface film is baked by the progressive plasma. The progressive plasma film-forming method according to any one of the above. The progressive plasma film-forming method according to claim 6 or 7, wherein the substrate is purified by irradiating the substrate surface with a plasma for purification before the film formation of the substrate with the film-forming material. . The progressive plasma film-forming method according to claim 1, wherein a surface film is formed on the substrate surface by an electrospray method. The progress plasma film-forming method according to claim 1, wherein a surface film is formed on the surface of the base material while mechanically moving the base material. 6. The progressive plasma film forming method according to claim 4, wherein the liquid material has a surface energy of 60 dyn / cm or less. The progressive plasma film-forming method according to claim 4, wherein the film-forming substance is composed of one or more of an organometallic compound, a metal inorganic acid salt, and a metal organic acid salt, and the film-forming substance is dissolved in the solvent. The progressive plasma film-forming method according to claim 4, wherein the film-forming substance comprises metal component-containing particles having a particle diameter of 1 nm to 500 nm. The progressive plasma film-forming method according to claim 13, wherein a binder agent for bonding the metal component-containing particles is added as the film-forming substance. The progressive plasma film-forming method according to claim 13 or 14, wherein the metal component-containing particles are composed of one or more of metal oxide particles, metal nitride particles, metal carbide particles, simple metals, and alloys. The progressive plasma film-forming method according to claim 13, wherein the metal component-containing particles carry a carbon nanomaterial on the particle surface. The progressive plasma film-forming method according to any one of claims 13 to 16, wherein the film-forming substance comprises the metal component-containing particles, an organic metal compound, a metal inorganic acid salt, and a mixture of one or more metal organic acid salts. . A plasma fired base material, wherein a surface film fired by the progressive plasma film forming method according to claim 1 is formed on a base material surface. A firing plasma generating means for generating a firing plasma, a progressing plasma introducing means for introducing the firing plasma as a progressing plasma that progresses toward the base material, and a surface film is formed on the surface of the base material by a film forming material. A traveling plasma component comprising: a film firing means for firing the surface film of the substrate by placing the substrate at a position not sandwiched between electrodes for plasma formation and circulating the traveling plasma through the substrate. Membrane device. 20. The progressive plasma film forming apparatus according to claim 19, wherein the plasma generating means is an atmospheric pressure pulse arc discharge means, and further is a gliding arc discharge means or a pen jet discharge means. The progressive plasma film-forming apparatus according to claim 19 or 20, wherein a bias voltage applying means for applying a bias voltage to the substrate is provided to control firing of the surface film. The progressive plasma film-forming apparatus according to claim 19, 20 or 21, further comprising a film-forming unit that forms a surface film on a substrate surface with a film-forming material, and the film-baking unit is disposed after the film-forming unit. A purification plasma generating means for generating a purification plasma of the substrate surface, and before the film formation of the substrate by the film-forming material, the substrate plasma is irradiated with the purification plasma; The progressive plasma film-forming apparatus of Claim 22 which performs the purification process of a material. 23. The surface film is fired while the surface film is formed on the surface of the base material by the film forming means and the progressive plasma is circulated through the base material to evaporate or remove the solvent component. Progressive plasma deposition system.