JP4244574B2 - Thin film forming equipment - Google Patents

Description

【００７０】
【発明の効果】
表１の結果からも明らかなように、本発明の薄膜形成装置によれば、電極の放電面の汚れのみならず、ガス供給ノズルの汚れも防止することができて、収率や製膜速度を向上することができる。
【図面の簡単な説明】
【図１】大気圧プラズマ処理装置のガス導入部及び電極部の一例を示す断面図である。
【図２】反応性ガス流路出口外壁先端の形状の例を示す図である。
【図３】反応性ガス流路出口外壁先端の形状の他の例を示す図である。
【図４】高圧印加用電極の一例を示す図である。
【符号の説明】
１ 基材
２ａ、２ｂ 印加電極
３ａ、３ｂ、７ 金属母体
４ａ、４ｂ、６ 誘電体
５ アース電極
８ 高周波電源
１０ ガス導入部
１１ 反応性ガス流路（通路）
１２ａ、１２ｂ 不活性（放電）ガス流路（通路）
１３ａ、１３ｂ 保温制御システム
１４ａ、１４ｂ 反応性ガス流路を構成する仕切り（反応性ガス通路壁）
１４１ａ、１４１ｂ 反応性ガス流路出口外壁
１５ａ、１５ｂ 不活性ガス通路壁[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thin film forming apparatus capable of suppressing contamination by reaction products.
[0002]
[Prior art]
For semiconductor devices and various devices for display, recording and photoelectric conversion, highly functional thin films such as electrode films, dielectric protective films, semiconductor films, transparent conductive films, antireflection films, optical Various materials provided with an interference film, a hard coat film, an undercoat film, a barrier film, and the like are used.
[0003]
In the production of such highly functional thin films, conventionally, a dry film forming method using a vacuum such as a sputtering method, a vacuum vapor deposition method, an ion plating method or the like has been used. Not only is the equipment cost high, but continuous production is not possible and the film-forming speed is low, which has the problem of low productivity.
[0004]
As a method for overcoming the disadvantages of low productivity due to the use of these vacuum devices, Japanese Patent Application Laid-Open No. 61-238961, etc., generates a discharge plasma under atmospheric pressure, and obtains a high treatment effect by the discharge plasma. Plasma processing methods have been proposed.
[0005]
The atmospheric pressure plasma treatment method can form a film on the surface of a substrate with a uniform composition, physical properties, and distribution. Further, since the treatment can be performed under atmospheric pressure or near atmospheric pressure, vacuum equipment is not required, equipment costs can be reduced, continuous production can be supported, and the film forming speed can be increased.
[0006]
Further, examples of applications in which a thin film is formed on a substrate by discharging at atmospheric pressure or a pressure near atmospheric pressure to excite a reactive gas to form a thin film on a substrate are disclosed in JP-A-11-61406 and JP-A-11-133205, JP-A-11-133205. 2000-121804, 2000-147209, 2000-185362, etc. (hereinafter also referred to as atmospheric pressure plasma method).
[0007]
Further, JP-A-6-330326 proposes a method of forming a metal oxide film by adding a small amount of metal alkoxide or the like during atmospheric pressure plasma discharge.
[0008]
In the above atmospheric pressure plasma method, dirt related to the plasma processing adheres to the portion of the processing portion where the electrode base material is not in contact, and the plasma discharge becomes unstable or adheres to the base material as the processing proceeds. As a result, there was a problem that the quality of the thin film to be produced varied, and the finished product had defects such as streak-like unevenness and spot-like unevenness. If this happens during production, production will be temporarily suspended, the electrodes, etc. cleaned, and conditions for starting production and warm-up will increase, resulting in increased loss time and reduced production efficiency. .
[0009]
[Problems to be solved by the invention]
The present inventors placed a substrate between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof, and applied a high frequency voltage exceeding 100 kHz in a reaction gas atmosphere to perform plasma discharge treatment, thereby In addition, we succeeded in forming a uniform and high-quality thin film quickly. However, continuous production not only shortens the dirt occurrence time of the electrode, but also the degree of dirt becomes severe, and if the dirty electrode is used as it is, the formability of the thin film on the base material is significantly inferior, Deterioration of the quality of the thin film, unevenness of the film thickness, and a decrease in the strength of the thin film are clearly seen. In addition, the number of times that dirt is cleaned increases and productivity is greatly reduced.
[0010]
Therefore, in order to supply the reactive gas to the discharge space so that the reactive gas does not directly touch the electrode part, the base material is placed so as to cover the discharge surface of one of the counter electrodes, and the reactive gas (raw material gas) and The gas supply means was configured to supply the discharge gas not containing the source gas individually to the discharge space, thereby preventing deposits on the electrode portion.
[0011]
FIG. 1 is a sectional view showing an example of a gas introduction part and an electrode part of such an atmospheric pressure plasma processing apparatus.
[0012]
In the figure, reference numeral 1 denotes a base material on which a thin film is formed. Reference numerals 2a and 2b denote high-voltage application electrodes, and the surfaces of the metal bases 3a and 3b are covered with dielectrics 4a and 4b, respectively, and preferably have heat exchange means such as water inside. At a position facing the application electrodes 2a and 2b, the ground electrode 5 covered with the dielectric 6 is disposed on the metal base 7, and the base material contacts and is transported. Reference numeral 8 denotes a high-frequency power source for applying a high-frequency voltage between the application electrodes 2 a and 2 b and the ground electrode 5, and the ground electrode 5 is grounded by a ground 9.
[0013]
Reference numeral 10 denotes a gas introduction part, which has a reactive gas passage 11 at the center thereof, and discharge gas passages 12a and 12b around it. The reactive gas passageway has an outlet so that the reactive gas does not directly contact the application electrodes 2a, 2b. Is the mark It is provided at substantially the same position as the bottom of the additional electrodes 2a, 2b. The reactive gas passage 11 and the discharge gas passages 12a and 12b are separated by the reactive gas passage walls 14a and 14b, and the discharge gas passages 12a and 12b are separated from the outside by the discharge gas passage walls 15a and 15b.
[0014]
However, even if the source gas and the discharge gas are supplied separately, if both gases are mixed in the discharge space or before being introduced into the discharge space, the source gas is not applied to the electrode side that is not covered with the base material. The product formed by the activation energy of the discharge is deposited on the discharge surface of the electrode.
[0015]
Further, mixing with the discharge gas dilutes the raw material gas concentration on the base material side and reduces the raw material to be used for film formation, which causes a problem of lowering the yield and film formation speed.
[0016]
The present invention has been made in view of the above circumstances, and its purpose is to introduce individually introduced source gas and discharge gas into the discharge space so as not to mix as much as possible, and to clean the discharge surface of the electrode. This is to suppress the yield and improve the film forming speed.
[0017]
[Means for Solving the Problems]
In order to introduce the individually introduced raw material gas and discharge gas into the discharge space as much as possible, the inventor is important to join the gas layers (interfacial formation process). As a result of obtaining knowledge that the shape of the confluence portion has a great influence, the present inventors have found a gas supply port end shape that forms a smooth flow path without gas convection and vortices at the confluence.
[0018]
That is, the above object of the present invention is to
1) a discharge space in which the first electrode and the second electrode are arranged to face each other; a voltage application unit that applies a voltage between the electrodes; and a gas introduction unit that introduces a gas into the discharge space;
Under or near atmospheric pressure A thin film forming apparatus for activating the gas introduced into the discharge space by the voltage applying means and forming a thin film by exposing a substrate to the activated gas;
The gas introduction means has a discharge gas flow path for introducing a discharge gas, and a reactive gas flow path for introducing a reactive gas,
The discharge gas flow path and the reactive gas flow path are partitioned by a partition member,
The discharge gas and the reactive gas flow at the junction of the discharge gas flow and the reactive gas flow in the vicinity of the outlet of the gas introduction means to the discharge space. Form an interface A thin film forming apparatus, characterized in that
2) The reactive gas channel outlet outer wall tip is configured to have a slope with a sharp tip on the first electrode side of the partition constituting the channel,
3) The tip of the partition member is further configured to align the direction of the flow after the combination of the reactive gas flow and the discharge gas flow with the direction of the surface of the base material to be processed,
4) The reactive gas channel outlet outer wall tip expands in the outer circumferential direction with respect to the partition constituting the channel;
5) The thickness β of the expanding portion of the reactive gas flow path outlet outer wall tip is 10 mm or less,
6) The reactive gas flow path outlet outer wall tip is formed by notching a partition constituting the flow path,
7) The reactive gas flow path outlet outer wall front end is configured to have an inclined portion whose front end expands on the first electrode side of the partition constituting the flow path,
8) When the angle formed by the surface facing the first electrode and the surface facing the second electrode of the inclined portion where the tip extends is α °, α ≦ 60.
Is achieved.
[0019]
Details of the present invention will be described below.
The present invention is a reactive gas flow channel outlet outer wall tip of the gas introduction means, Making sure that the discharge gas and the reactive gas are not substantially mixed at the junction of the discharge gas flow and the reactive gas flow in the vicinity of the outlet of the gas introduction means to the discharge space; The flow direction at the contact point on the discharge space inflow side is aligned with the direction of the substrate surface to be treated.
[0020]
2 and 3 show examples of the shape of the outer wall tip of the reactive gas flow channel outlet. Specifically, the members shown by the reactive gas passage walls 14a and 14b in FIG. 1 are the “partitions constituting the reactive gas flow path” in the present invention.
[0021]
In FIG. 2A, the ends of the reactive gas flow channel outlet outer walls 141a and 141b expand in the outer circumferential direction with respect to the partitions 14a and 14b constituting the flow channel. When the length of the outlet outer wall is L and the thickness is β, L is preferably 70 mm or less, and β is preferably 10 mm or less.
[0022]
FIG. 2B shows another example in which the tips of the reactive gas flow channel outlet outer walls 141a and 141b expand in the outer peripheral direction with respect to the partitions 14a and 14b constituting the flow channel. The discharge gas flow path side has a curved surface or an inclination. The curved surface and the inclination may be any as long as the gas flow direction is aligned with the direction of the substrate surface, but the flow rate fluctuation of the discharge gas is reduced by matching the shape of the corner of the first electrode as much as possible. It is preferable to do this.
[0023]
FIG. 2C shows an example in which the front end of the reactive gas flow channel outlet outer wall is formed by cutting out the partitions 14a and 14b constituting the flow channel. Note that “notched and formed” as used herein is not limited to concrete notching, but includes a case where a recess is formed by polishing, or a case where it is formed by molding using a mold.
[0024]
FIG. 3A shows an example in which the tips of the reactive gas flow channel outlet outer walls 141a and 141b have slopes 142a and 142b with sharp tips on the first electrode side of the partitions 14a and 14b constituting the flow channel. It is shown. Here, the sharp end means that the radius of curvature of the outlet outer walls 141a and 141b is 3 mm or less or the taper is 3 mm or less with processing accuracy.
[0025]
FIG. 3 (b) shows an inclination in which the tips 141a and 141b of the outer walls of the reactive gas flow channel outlet are extended toward the first electrodes of the partitions 14a and 14b constituting the flow channel. portion This is an example having 143a and 143b. The inclined portions 143a and 143b whose front ends expand have a surface facing the second electrode 5 and a surface (slope) facing the discharge gas flow path. In this example, the application (first) electrodes 2a and 2b Corner Shape , Inclination of the partitions 14a and 14b portion 143a, 143b Slope of In Along Has a slope, With the slopes of the inclined parts 143a and 143b A discharge gas flow path is formed. Inclination that this tip expands Angle formed by the surface facing the first electrode and the surface facing the second electrode When α is α °, there is a workability limitation, but α is preferably as small as possible, and α ≦ 60 is preferable.
[0026]
It is preferable that the partitions 14a and 14b constituting the reactive gas flow path have a portion made of a heat-resistant material so as to be insulative and heatable so that no discharge occurs in the flow path.
[0027]
Examples of such a material include a heat insulating resin, a heat-resistant sliding resin, an inorganic composite material, etc., and examples of the heat insulating resin include a fluorinated resin such as polyester, polyimide, polyethylene imide, and Teflon (R), and a polyether ether. Examples include ketone (PEEK), polysulfone, polyethersulfone (PES), polyparapentic acid resin, polyphenylene oxide, polycarbonate, polyarylate resin, and epoxy resin.
[0028]
The heat-resistant sliding resin is polyimide resin, polyamide resin, polyamide polyimide resin, tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene-hexafluoride. Propylene copolymer (FEP), high temperature nylon resin, polyphenylene sulfide resin (PPS), trifluoroethylene chloride resin (CTFP), modified phenol resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyether A resin such as ether ketone (PEEK) with a filler such as glass fiber, glass bead, graphite, carbon fiber, fluororesin, molybdenum disulfide, and titanium oxide. For example, graphite-containing polyimide resin, graphite-containing nylon resin, PT E-filled acetal resin, a PTFE-filled phenolic resin and the like.
[0029]
The inorganic composite material is a reinforcing material such as glass fiber or aramid fiber and an inorganic binding composite material such as cement or calcium silicate. For example, Miorex, Myonite, PEG-677, Rosnaboard, Vesthermo manufactured by Nikko Kasei Co., Ltd. , Calphone, Micalex, Hemisar, Lumiboard, Ricobest, Nitron R, TC board, Mica D581 (Damma), Bragra, S4000 (Branden Burger), DME insulation board, etc.
[0030]
In addition, glass made of alumina, zirconia, silicon nitride, titanium nitride, silicon carbide, mullite, aluminum nitride, cermet, etc., ceramic, soot, etc. can be used. Examples of glass include quartz glass, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, chalcogenide glass, halide glass, non-glass Examples thereof include a crystalline alloy, oxynitride glass, oxyhalide glass, calcohalide glass, and Pyrex (R) glass.
[0031]
As materials of the partitions 14a and 14b constituting the reactive gas flow path, plasma resistance, rigidity, workability and the like are required in addition to insulation and heat resistance, and fibers such as glass are hybrid-molded with a thermoplastic resin. A compression member made of fiber such as glass is also preferably used. The thermoplastic resin is not particularly limited. For example, polypropylene, propylene / ethylene block copolymer, propylene / ethylene random copolymer, polyolefin resin such as high density polyethylene, polystyrene, rubber-modified impact-resistant polystyrene. , Polystyrene containing a syndiotactic structure, styrene resin such as ABS resin, AS resin, polyvinyl chloride resin, polyamide resin, polyester resin, polyacetal resin, polycarbonate resin, polyphenylene sulfide, polyaromatic ether or A thioether resin, a polyaromatic ester resin, a polysulfone resin, an acrylate resin, or the like can be employed. These can be used alone or in combination of two or more. There is no restriction | limiting in particular as a fiber used, It selects from the various fiber which has an expansibility at the time of melt-kneading. For example, inorganic fibers such as glass fibers and carbon fibers, copper fibers, brass fibers, steel fibers, stainless steel fibers, aluminum fibers, aluminum alloy fibers, titanium alloy fibers and other metal fibers, boron fibers, silicon carbide fibers, alumina fibers, chips. Ceramic fibers such as silicon carbide fibers and zirconia fibers, aramid fibers, polyoxymethylene fibers, aromatic polyester fibers, polyamide fibers, polyarylate fibers, polyphenylene sulfide fibers, polysulfone fibers, and organic fibers such as ultrahigh molecular weight polyethylene fibers Can be illustrated. In addition, these fibers can also use together 2 or more types of inorganic fiber, organic fiber, etc., for example.
[0032]
When the partitions 14a and 14b constituting the reactive gas flow path are heated (see 13a and 13b), a heat exchange medium such as water vapor may be passed, or a heater may be used.
[0033]
FIG. 4 shows an example of a high voltage application electrode that can be used in the present invention.
FIG. 4 is a perspective view showing an example of an electrode fixed in a prismatic shape. When the counter electrode for high voltage application is taken as an example, the fixed application electrodes 2a and 2b and the hollow metal bases 3a and 3b are shown. The stainless steel pipe is composed of a combination in which ceramics are thermally sprayed and then sealed with a dielectric material 4a, 4b that is sealed with an inorganic material.
[0034]
Examples of the metal base of the application electrode and the ground electrode include metals such as silver, platinum, stainless steel, titanium, aluminum, and iron. Stainless steel is used from the viewpoint of processing and reducing the thermal expansion difference from the dielectric. Alternatively, a titanium metal is preferable.
[0035]
In addition, the dielectric is preferably an inorganic material, such as silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadium. Glass such as acid salt glass can be used. Of these, borate glass is easy to process. It is also preferable to use a highly heat-resistant ceramic with high hermeticity by thermal spraying. Examples of the ceramic material include alumina-based, zirconia-based, silicon nitride-based, and silicon carbide-based ceramics. Of these, alumina-based ceramics are preferable, and alumina-based ceramics are particularly Al. ₂ O _Three Is preferably used. The thickness of the alumina ceramic is preferably about 1 mm, and the volume resistivity is 10 ⁸ Ω · cm or more is preferable.
[0036]
The ceramic is preferably sealed with an inorganic material, whereby the durability of the electrode can be improved. After coating the alumina-based ceramics and applying a sol that is a sealant, a silicon compound that is cured by a sol-gel reaction (preferably alkoxysilane), and then gelled and cured, Ceramic sealing can be performed by forming a strong three-dimensional bond to form a silicon oxide having a uniform structure.
[0037]
Moreover, it is preferable to perform energy treatment in order to promote the sol-gel reaction. By applying energy treatment to the sol, a three-dimensional bond of metal-oxygen-metal can be promoted. The energy treatment is preferably plasma treatment, heat treatment at 200 ° C. or lower, and UV treatment.
[0038]
In a method of manufacturing an electrode by coating a dielectric on a metal base material at a high temperature, at least the dielectric on the side in contact with the substrate is polished and further, thermal expansion between the metal base material and the dielectric of the electrode It is necessary to make the difference as small as possible. Therefore, in the manufacturing method, the surface of the base material is lined with an inorganic material by controlling the amount of bubbles mixed as a layer capable of absorbing stress. It is preferable that the glass is obtained by a melting method, and the amount of bubbles mixed in the lowermost layer in contact with the conductive metal base material is set to 20 to 30% by volume, and the subsequent layer and the subsequent layers are set to 5% by volume or less, thereby being dense and A good electrode without cracks and the like can be produced.
[0039]
In addition, as a method for coating the metal base material of the electrode with a dielectric, ceramic spraying is performed densely to a porosity of 10% by volume or less, and a sealing process is performed with an inorganic material that is cured by a sol-gel reaction. Preferably, heat curing and UV curing are good for promoting the sol-gel reaction. Further, when the sealing liquid is diluted, and coating and curing are repeated several times in succession, the mineralization is further improved and a dense electrode without deterioration. Can do.
[0040]
Although it is possible to discharge at an applied voltage of 1 kHz or more, a preferable range is more than 100 kHz and 150 MHz or less. The high frequency power supply that can be used is not particularly limited. For example, the high frequency power supply (200 kHz), the same (800 kHz), the same (2 MHz) manufactured by Pearl Industry, the high frequency power supply (13.56 MHz) manufactured by JEOL, and the product manufactured by Pearl Industry. A high frequency power supply (150 MHz) or the like can be used.
[0041]
Voltage discharge output is 1 W / cm ² ~ 50W / cm ² It is preferable that the plasma density of the discharge plasma can be increased.
[0042]
In order to suppress the deterioration of the uniformity of the coating formed by the gas leakage from the discharge space to the width direction of the substrate (the direction orthogonal to the transport direction), the insulating side plate is It is preferable to provide it.
[0043]
The gas used in the present invention is a discharge gas and a reactive gas for forming a thin film. It is preferable to contain 0.01-50 volume% of reactive gas with respect to all the gas supplied. According to the present invention, a thin film having a thickness of 1 to 1000 nm is obtained.
[0044]
The discharge gas is a gas containing 90% by volume or more of an inert gas, which is a gas necessary for discharging, and does not contain a raw material gas described later. Examples of the inert gas include helium, neon, argon, krypton, xenon, radon and the like, which are Group 18 elements of the periodic table, and nitrogen gas. In the present invention, helium and argon are preferably used.
[0045]
The discharge gas according to the present invention may contain a reaction promoting gas, which will be described later, depending on the type of source gas contained in the reactive gas.
[0046]
As the reactive gas, there is a reaction gas for reacting a raw material gas containing an element that is a raw material of the thin film and the raw material gas, and the raw material gas varies depending on the type of thin film to be provided on the substrate, for example, By using an organic fluorine compound, a low refractive index layer or an antifouling layer useful for an antireflection layer or the like can be formed. By using a silicon compound, a low refractive index layer or a gas barrier useful for an antireflection layer or the like can be formed. Layers can also be formed. Further, by using an organometallic compound containing a metal such as Ti, Zr, Sn, Si or Zn, a metal oxide layer or a metal nitride layer can be formed. A useful medium refractive index layer or high refractive index layer can be formed, and a conductive layer or an antistatic layer can also be formed. Preferred examples of the source gas substance include organic fluorine compounds and metal compounds.
[0047]
The organic fluorine compound of the source gas is preferably a gas such as fluorocarbon or fluorinated hydrocarbon. For example, tetrafluoromethane, hexafluoroethane, 1,1,2,2-tetrafluoroethylene, 1,1,1 , 2,3,3-hexafluoropropane, hexafluoropropene and other fluorocarbon compounds; 1,1-difluoroethylene, 1,1,1,2-tetrafluoroethane, 1,1,2,2,3- Fluorinated hydrocarbon compounds such as pentafluoropropane; Fluorinated chlorinated hydrocarbon compounds such as difluorodichloromethane and trifluorochloromethane; 1,1,1,3,3,3-hexafluoro-2-propanol, 1,3-difluoro Fluorinated alcohols such as 2-propanol and perfluorobutanol; vinyl trifluoroacetate, 1,1,1-tri Le Oro ethyl trifluoroacetate, etc. fluorinated carboxylic acid esters of; acetyl fluoride, hexafluoroacetone, 1,1,1-trifluoro fluoride ketones such as acetone and the like.
[0048]
As the metal compound of the source gas, Al, As, Au, B, Bi, Ca, Cd, Cr, Co, Cu, Fe, Ga, Ge, Hg, In, Li, Mg, Mn, Mo, Na, Ni , Pb, Pt, Rh, Sb, Se, Si, Sn, V, W, Y, Zn, Zr, and other metal compounds or organometallic compounds.
[0049]
Among these, examples of the silicon compound include alkyl silanes such as dimethylsilane and tetramethylsilane; silicon such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, and ethyltriethoxysilane. Examples include organosilicon compounds such as alkoxides; silicon hydrogen compounds such as monosilane and disilane; halogenated silicon compounds such as dichlorosilane, trichlorosilane, and tetrachlorosilane; and other organosilanes.
[0050]
Examples of metal compounds other than silicon as the source gas include organometallic compounds, metal halide compounds, metal hydrogen compounds, and the like. As the organic component of the organometallic compound, an alkyl group, an alkoxide group, and an amino group are preferable, and tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetradimethylaminotitanium, and the like can be preferably exemplified. In addition, examples of the metal halide compound include titanium dichloride, titanium trichloride, and titanium tetrachloride, and examples of the metal hydrogen compound include monotitanium and dititanium.
[0051]
Examples of the reaction promoting gas include oxygen gas, hydrogen gas, water vapor, hydrogen peroxide gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ozone gas, NOx (nitrogen oxide), and ammonia. This reaction promoting gas may be placed on the discharge gas side, on the reactive gas side, or on both sides.
[0052]
There are no particular limitations on the substrate on which atmospheric pressure plasma treatment can be performed in the present invention, as long as a thin film can be formed on the surface thereof, such as a film-like material or a three-dimensional shape such as a lens shape.
[0053]
The material constituting the substrate is not particularly limited, but a resin can be preferably used because it is under atmospheric pressure or a pressure near atmospheric pressure and because it is a low-temperature plasma discharge.
[0054]
For example, when the thin film according to the present invention is an antireflection film, the substrate is preferably a cellulose ester such as a cellulose triacetate film, polyester, polycarbonate, polystyrene, and further gelatin, polyvinyl alcohol (PVA), acrylic on these. A resin, polyester resin, cellulose-based resin, or the like can be used. Further, these base materials have an antiglare layer or a clear hard coat layer coated with a resin layer formed by polymerizing a component containing an ethylenically unsaturated monomer on a support, a back coat layer, an antistatic layer. Can be used. In this case, it is preferable to use a cellulose ester film from the viewpoint of obtaining a laminate having a low reflectance, and cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable as the cellulose ester, particularly cellulose acetate butyrate, Cellulose acetate propionate is preferably used.
[0055]
Specific examples of the support (also used as a base material) include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, cellulose diacetate films, cellulose acetate butyrate films, Cellulose acetate propionate film, cellulose acetate phthalate film, cellulose triacetate, cellulose ester film such as cellulose nitrate, or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene series Film, polycarbonate film, norbornene resin film, polymethylpen Film, polyetherketone film, polyimide film, polyethersulfone film, polysulfone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film or polyarylate film Can be mentioned.
[0056]
These materials can be used alone or in combination as appropriate. Among these, commercially available products such as ZEONEX (manufactured by Nippon Zeon Co., Ltd.) and ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.) can be preferably used. Furthermore, even for materials with a large intrinsic birefringence, such as polycarbonate, polyarylate, polysulfone, and polyethersulfone, conditions such as solution casting and melt extrusion, as well as stretching conditions in the longitudinal and lateral directions are set as appropriate. Can be obtained. Moreover, the support body which concerns on this invention is not limited to said description. A film thickness of 10 to 1000 μm is preferably used.
[0057]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. In this embodiment, the “partition constituting the reactive gas flow path” is referred to as a nozzle for convenience.
[0058]
Example 1
[Preparation of base film]
On one side of a cellulose ester film with a thickness of 80 μm
30 parts by mass of acetone
45 parts by mass of ethyl acetate
10 parts by mass of isopropyl alcohol
Diacetylcellulose 0.5 parts by mass
Ultrafine silica 2% acetone dispersion (Aerosil 200V:
Nippon Aerosil Co., Ltd.) 0.1 parts by mass
The composition consisting of was coated by extrusion so that the wet film thickness was 13 μm, and then dried in a drying section set at 80 ° C. to provide a backcoat layer.
[0059]
Then on the other side of the cellulose ester film
60 parts by mass of dipentaerythritol hexaacrylate monomer
Dipentaerythritol hexaacrylate dimer 20 parts by mass
20 parts by mass of dipentaerythritol hexaacrylate trimer or higher component
4 parts by weight of dimethoxybenzophenone photoinitiator
50 parts by mass of ethyl acetate
50 parts by mass of methyl ethyl ketone
50 parts by mass of isopropyl alcohol
The composition consisting of is extruded and coated to a wet film thickness of 13 μm, and then dried in a drying section set at 80 ° C., and then 120 mJ / cm ² And a clear hard coat layer having a dry film thickness of 4 μm and a center line average surface roughness (Ra) of 15 nm was provided to prepare a base film.
[0060]
(Formation of high refractive index layer)
A sample was obtained by subjecting the base film to plasma discharge treatment under the following conditions using a thin film forming apparatus having a gas introduction part and an electrode part shown in FIG.
[0061]
<Equipment conditions>
1) The electrodes 2a and 2b are made of stainless steel SUS316, using a rod-shaped metal base formed by processing 20 mm squares and 120 mm long corners with a radius of curvature of 3 mm. Using a 20 mm flat metal matrix, alumina ceramic is spray-coated on the surface until it becomes 1 mm, a coating solution in which an alkoxysilane monomer is dissolved in an organic solvent is applied to the alumina ceramic coating, dried, and then heated at 150 ° Then, each of those sealed to form a dielectric was used.
[0062]
2) The nozzles 14a and 14b are made of the above-described Rossner board, and FIG. 1 (a 2 mm thick flat plate), FIG. 2 (a) (L = 3 mm, β = 2 mm), and the left view of FIG. 2 (b). (Surface having a curvature radius of 3 mm, L ′ = 3 mm) and the shape of FIG. 3A (γ = 1 mm), the slit gap was 2 mm. The gap between the nozzle outer wall and the electrodes 2a and 2b was set to about 4 mm, and the temperature was 60 ° C.
[0063]
<Gas conditions>
Discharge gas: helium gas 99.0%, hydrogen gas 1.0%
Flow rate 0.5L / min · cm
Reactive gas: Tetraisopropoxytitanium 0.1% was vaporized with a Lintex vaporizer and mixed in 99.9% helium gas.
[0064]
Flow rate 0.25L / min · cm
<Gas supply method>
A discharge gas is introduced into the discharge gas passages 12a and 12b arranged in a slit shape, and a reactive gas is introduced into the reactive gas passage 11 while the ground electrode 5 and the application electrodes 2a and 2b are supplied with a pearl as a high-frequency power source 8. Using industrial high frequency power supply, frequency 13.56MHz, discharge output 20W / cm ² Applied. Here, the base film (100 mm × 100 mm sheet) was moved back and forth in FIG. 1 at a traveling speed of 0.3 m / sec, and the gap between the ground electrode 5 and the applied electrodes 2a and 2b was 4 mm. I went to set.
[0065]
Moreover, the base material which comprises each electrode was made into the jacket specification, and the 80 degreeC cooling water was circulated at 5 L / min.
[0066]
<Observation of electrode surface contamination and evaluation of formed film>
After performing plasma treatment for 10 hours continuously, visually observe the surface of each electrode, visually observe the presence of condensation and other deposits,
○: No occurrence was observed
△: Slight condensation is recognized, but practical problems are low
×: Condensation or deposits are recognized, and there is a slight problem in practice
<Observation of nozzle dirt>
○: No occurrence was observed
×: Condensation or deposits are recognized at the tip, and there is a practical problem
The evaluation was performed according to the criteria.
[0067]
Also 100nm TiO ₂ The 20 substrate sheets on which the film was formed were observed to evaluate the film quality.
[0068]
The results obtained as described above are shown in Table 1.
[0069]
[Table 1]

[0070]
【The invention's effect】
As is apparent from the results in Table 1, according to the thin film forming apparatus of the present invention, not only the discharge surface of the electrode but also the gas supply nozzle can be prevented, and the yield and film forming speed can be prevented. Can be improved.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a gas introduction part and an electrode part of an atmospheric pressure plasma processing apparatus.
FIG. 2 is a diagram showing an example of the shape of a reactive gas flow path outlet outer wall tip.
FIG. 3 is a view showing another example of the shape of the outer wall tip of the reactive gas flow channel outlet.
FIG. 4 is a diagram illustrating an example of a high voltage application electrode.
[Explanation of symbols]
1 Base material
2a, 2b Applied electrode
3a, 3b, 7 Metal matrix
4a, 4b, 6 dielectric
5 Ground electrode
8 High frequency power supply
10 Gas introduction part
11 Reactive gas flow path (passage)
12a, 12b Inactive (discharge) gas flow path (passage)
13a, 13b Thermal insulation control system
14a, 14b Reactive gas flow path partitions (reactive gas passage walls)
141a, 141b Reactive gas flow path outlet outer wall
15a, 15b inert gas passage wall

Claims (8)

A discharge space in which the first electrode and the second electrode are arranged to face each other, a voltage applying means for applying a voltage between the electrodes, and a gas introducing means for introducing a gas into the discharge space,
A thin film forming apparatus for forming a thin film by activating the gas introduced into the discharge space by the voltage applying means and exposing a substrate to the activated gas under atmospheric pressure or a pressure in the vicinity thereof. ,
The gas introduction means has a discharge gas flow path for introducing a discharge gas, and a reactive gas flow path for introducing a reactive gas,
The discharge gas flow path and the reactive gas flow path are partitioned by a partition member,
The tip of the partition member is configured such that the discharge gas and the reactive gas form an interface at the junction of the discharge gas flow and the reactive gas flow in the vicinity of the outlet of the gas introduction means to the discharge space. A thin film forming apparatus.   2. The thin film formation according to claim 1, wherein the tip of the outer wall of the reactive gas flow channel outlet has an inclination with a sharp tip on the first electrode side of the partition constituting the flow channel. apparatus.   The tip of the partition member is further configured to align the direction of the flow of the reactive gas flow and the discharge gas flow after merging with the direction of the substrate surface to be treated. The thin film forming apparatus described.   The thin film forming apparatus according to claim 3, wherein a distal end of the reactive gas flow channel outlet outer wall expands in an outer peripheral direction with respect to a partition constituting the flow channel.   5. The thin film forming apparatus according to claim 4, wherein a thickness β of an enlarged portion of the distal end of the outer wall of the reactive gas flow channel outlet is 10 mm or less.   The thin film forming apparatus according to claim 3, wherein a tip of the outer wall of the reactive gas flow channel outlet is formed by cutting out a partition constituting the flow channel.   The thin film formation according to claim 3, wherein the tip of the outer wall of the reactive gas flow channel outlet has an inclined portion whose tip extends on the first electrode side of the partition constituting the flow channel. apparatus.   The thin film according to claim 7, wherein α ≦ 60, where α is an angle formed between a surface facing the first electrode and a surface facing the second electrode of the inclined portion where the tip extends. Forming equipment.

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