Blowoff-type surface treating device

[Detailed Description of the Invention]

Field of the Invention This invention relates to the surface treatment device which can form a thin film by plasma-ization of organicity and inorganic compound gas under atmospheric pressure, Reactant gas is fed by the discharge section which made the high voltage electrode and earth electrode which covered the dielectric counter, and formed electric discharge space, Plasma excitation is carried out, it injects besides a discharge section, and the thin film according to a reactant gas kind is related with the blown off type surface treatment device which made possible formation or the in-line process that surface modification can be carried out, and the surface treatment for the fields. PRIOR ART the thin film of the composition in a material list side there are means, such as vacuum deposition, Ion Bray Tyng, sputtering, and CVD (chemicals vapor phase epitaxy), as drive rating today, and corresponding to the use or the object variously is formation -- or the surface treatment is carried out. As art of performing growth of thin film using gaseous plasma, there is plasma CVD and the method for film deposition according [ a reaction ] to each electric discharge plasma, such as a capacitive coupling type, a guidance knot pattern, and an ECR type, is used abundantly by the frequency band of the impression electric field. This is a method for forming thin film by plasma-izing of organicity and inorganic compound gas. For example, they are the method of carrying out plasma excitation of the hydrocarbon gas within a vacuum vessel, and carrying out precipitation formation of the amorphous carbon film on a silicon substrate or the glass substrate surface, and the method of forming the plasma polymerization film of unsaturated hydrocarbon, such as ethylene. Object of the Invention Each various above-mentioned methods for forming thin film and methods for film deposition by electric discharge plasma, and surface treatments are a reaction under a necessary vacuum atmosphere, and their vacuum device and reaction room equipment according to an all directions method are indispensable. There were problems, like the equipment component which could not put the large-sized equipment component into the necessary vacuum reaction room, or carried out complicated shape is difficult to form membranes, and have it. Generally it is difficult to perform necessary membrane formation for a material with a large area like sheet material with the low-pressure electric discharge plasma under a vacuum atmosphere, and also was not able to form membranes to sheet material continuously. Therefore, what is called an object for the in-line processes for performing the surface treatment of sheet material, such as a steel plate, vapor, glass, and plastics, and membrane formation and the surface treatment device for the fields were demanded under atmospheric pressure, for example. In view of this present condition, surface treatments, such as thin film formation and surface modification, and the surface treatment of complicated shape can carry out this invention easily at wide range planes, such as sheet material, under atmospheric pressure using gaseous plasma, and it is small and aims at offer of the easy surface treatment device for in-line processes of composition. Means for solving problem This invention uses gaseous plasma, in order to realize the above-mentioned object, and it is thin film formation under atmospheric pressure, As a result of examining many things about how to carry out surface modification, reactant gas is fed to the discharge section which made the high voltage electrode and earth electrode which covered the dielectric counter, and formed electric discharge space, The knowledge of carrying out plasma excitation, injecting besides a discharge section, and the surface modification of formation or a substrate being able to do the thin film according to a reactant gas kind is carried out, and this invention is completed. Namely, this invention, It has the singular number or a discharge section arranged for the electric discharge space formed between the high voltage electrode which made the dielectric cover or counter an electrode surface, and an earth electrode, [ multiple ] The reactant gas which consists of the monomer gas according to a membrane formation kind or gas for plasma according to processing, and inactive gas, The blow-off mouth which flowed from the gas induction by the side of the discharge section upper stream, passed through the above-mentioned electric discharge space, and was provided in the lower stream side of a discharge section, It is a blown off type surface treatment device which consists of composition spouted on the opposite processed material surface, passes through the electric discharge space which reactant gas impresses the high voltage between the above-mentioned electrodes, and carries out glow discharge near the atmospheric pressure, carries out plasma excitation, and is characterized by membrane formation or carrying out surface modification on the processed material surface. OPERATION As shown in Drawing 3, the commercial frequency on 1000 fine of the surface treatment device by this invention is R and F, From the high-voltage power supply to the microwave of a GHz level, and a necessary gas source, if needed, flow control is carried out and it mixes, Or it has the gas plasma gas spurting parts made to counter the induction and the material for membranes to be formed of the reactant gas feed unit which can carry out conveyance supply individually, and reactant gas, and comprises recovery playback equipment of the exhaust gas provided [ the discharge section and if needed ] attached the exhaust gas exhausting section provided if needed. In this invention, if a discharge section is the singular number or composition arranged, it can apply the electric discharge space formed between the high voltage electrode which made the dielectric cover or counter an electrode surface, and an earth electrode also to the electric discharge device which consists of which publicly known composition. [ multiple ] For example, as shown in an example, electrode shape should just be regular-intervals countering, such as parallel countering and circumference countering, ceramics, enamel, glass, mica, etc. can be used for dielectric material, and it is an electric discharge space gap. 0.5 mm ~ 15 mm is desirable, and may cope with gas volume increase by lamination of a countering electrode. In order to laminate a dielectric on an electrode, means, such as an individual assembly, ease, and simultaneous calcination, are employable. Also the wear-resistant film for preventing the outflow of wear of the dielectric by electric discharge, and an electrode, ion, and a molecule, Membranes can be easily formed to a dielectric and an electrode near the atmospheric pressure by introducing the reactant gas which consists of monomer gas selected according to the membrane formation kind, and inactive gas, for example, making 1500V~10kV alternating current voltage impress and discharge. In this invention, the neighborhood of atmospheric pressure is the atmosphere under atmospheric pressure, weak decompression, or pressurization, the atmosphere in which glow discharge is possible can be said, membranes can be formed under the weak decompression before and behind 400Torr, and diffused air pressing down can also form membranes. In this invention, although a simple substance or mixtures, such as helium, Ne, and Ar, can be suitably used for inactive gas, in order to maintain the glow discharge stable near the atmospheric pressure, it is preferred to use the rare gas mainly concerned with helium as dilution gas. The monomer gas mixed and introduced into inactive gas is although it is selected according to the membrane formation kind in which a material for membranes to be formed is demanded, For example, when 5i02 is formed In SiNx, mono-SilaneSiH4, DisilaneSi2H6, silicon tetrachloride 5iC14, oxygen 02, etc. can use mono-SilaneSiH4, DisilaneSi2H6, silicon tetrachloride 5iC14, nitrogen N2, hydrogen H2, and ammonia NH3 etc. In the case of the polyethylene membrane formation as membrane formation of an organic compound to others It is the fluorination ethylene system compound of 02F4.03F6 grade or CF3 in the case of C2H4, ethylene system hydrocarbon of C3H6 grade, and PTFE membrane formation. +H2 and C3F3 The mixture of methane series, such as +H2, and hydrogen, etc. can be used. Compared with the low-pressure method, the very high-speed membrane formation of the membrane formation which uses C2F4 especially was attained. Surface modification of a substrate can be performed by mixing and introducing the gas for plasma into inactive gas. For example, if plasma treatment is performed using the gas (for example, CF4+helium) which contains Flo Lynne in the substrate consisting of graphite and polyimide, surface modification can be performed on the surface which has water repellence like PTFE. Otherwise, wettability can be given to the surface if plasma treatment of oxygen is carried out to the plastic surface of a polyethylene Rensles phone. Although the mixture ratio of monomer gas or the gas for plasma, and inactive gas is arbitrary in the range which can maintain the glow discharge stable near the atmospheric pressure, it is preferred to make inactive gas concentration especially into about 90% or more about 65% or more. Two or more sorts of gas can also be used for the reactant gas to introduce. When the single pipe for mixture or a gas comrade reacts a carrier line at normal temperature according to a type of gas, it is necessary to carry out to two or more [ for individual ]. - Although the glow discharge under atmospheric pressure does not arise easily, since it has laminated the glass dielectric so that a high voltage electrode may be wrapped entirely, and it has introduced the above-mentioned inactive gas, by this invention, the stable glow discharge in the bottom of atmospheric pressure and its neighborhood atmosphere of it becomes possible in a discharge section at boat fishing. About plasma excitation of reactant gas, by this glow discharge, the inactive gas as dilution gas is excited and the plasma of a high energy excitation state is formed. Dissociation ionization is carried out in plasma, and reactant gas starts a chemical reaction, and deposits output on the solid surface. Although impression of the high voltage performs formation of this plasma, The alternating current voltage to impress is for inducing police box voltage on a dielectric, Although the high frequency voltage of a GHz level can be used from tens of Hz, and it can select suitably according to the quality on a ceramic protective film kind and the surface of processed, or the time of a surface treatment and it is suitably selected by electric discharge space, monomer gas or the gas for plasma, and inactive gas, The range of 1~10 kV, commercial frequency~30GHz, and 10W ~ several kilowatts is preferred. In the surface treatment by this invention, a multilayer film can be formed by changing reactant gas and performing membrane formation two or more times. In order to raise the degree of adhesion of membrane formation, the surface for membranes to be formed can also be heated and 200~800 degreeC of heating temperature is preferred. It is the indication of a Based <invention to a drawing. Drawings 1 a and b are eye squinting explanatory views showing one example of the surface treatment device by this invention, The vertical section explanation side figure and Drawing 4 showing other examples are an eye squinting explanatory view showing other examples, and Drawings 2 a and b illustrate the example which constituted Drawings [ 1 and 4 ] a and b in a torch type film deposition system and Drawing 2 a, and constituted b in the straight line blow-off type film deposition system here, respectively. DentistJ the torch type film deposition system (1) has carried out coaxial arrangement of the gas introducing pipe (7) at the cylindrical discharge section (2), and electric discharge space (6) is countering-arrangement-provided for an earth electrode (4) between electrodes cylindrical focusing on a high voltage electrode (3), a discharge section (2) covers a dielectric (5) to each electrode, and it comes out of it to it. A gas introducing pipe (7) connects one end of double pipe structure to a discharge section (2) so that A gas and B gas which react mutually at normal temperature can be supplied individually, it has connected the gas supply line (8X9) to the other end, and it is mixed in electric discharge space (6), and it serves as necessary reactant gas. After feeding inactive gas and monomer gas, mixing in the electric discharge space (6) currently maintained at this atmospheric pressure and making reactant gas, necessary voltage is impressed between a high voltage electrode (3) and an earth electrode (4), Glow discharge is carried out, plasma excitation of reactant gas occurs, and it becomes gaseous plasma, and spouts from a discharge section (2) tip. By making material for membranes to be formed counter at the tip of jet of this discharge section (2), the thin film according to a reactant gas kind can be formed on the surface. Composition 2 A straight line blow-off type film deposition system (10) is about the gas supply line (15) of double pipe structure to the blockade top end of a box-like discharge section (11), An exhaust pipe (18) is connected to the top other end, a pair of high voltage electrodes (12) and the earth electrode (13) which laminated dielectrics, such as glass, on the thin tabular electrode plane are for [ two or more pairs ] arranged via the insulation material separator which is not illustrated, and electric discharge space (14) is formed in the open lower end side. The inside of a discharge section (11) serves as double duct composition of the duct for A gas (16), and the duct for B gas (17) so that A gas and B gas from a gas supply line (15) can be supplied individually, and it is mixed in electric discharge space (14), and it serves as necessary reactant gas. Reactant gas is introduced in the electric discharge space (14) currently maintained at this atmospheric pressure, and necessary voltage is impressed between a high voltage electrode (12) and an earth electrode (13), Glow discharge can be carried out, plasma excitation of reactant gas can occur, and it can form the thin film according to a reactant gas kind on the sheet material (20) surface which was made opposite to a high voltage electrode (12) and an earth electrode (13), and has been arranged. Scar which provided exhaust gas after the reaction which blew off from electric discharge space (14) in the discharge section (11) opening lower end It is reversed by (19), between a discharge section (11) inner wall and the duct for B gas (17) is gone up, it is drawn from the exhaust pipe (18) of a discharge section (11) top end, and recovery and inactive gas are reproduced. Consumption store J A blown off type film deposition system (30) shown in Drawing 4, According to the width of sheet material (20), a necessary number is linearly arranged for the torch type film deposition system (31) of composition like the example of Drawings 1 a and b, It has connected with the gas supply line (32) of the double pipe composition which can supply A gas and B gas individually, The box type exhaust gas duct (34) arranged so that the torch type film deposition system (31) and gas supply line (32) of these plurality may be covered and a skirt (33) may contact the sheet material (20) surface is attached, It consists of composition that exhaust gas after being injected by the sheet material (20) surface and reacting from each torch type film deposition system (31) is collected. Membrane formation or a surface modification operation of this blown off type film deposition system (30) on sheet material (20) is the same as that of an above-mentioned torch type film deposition system (1) and a straight line blow-off type film deposition system (10). EXAMPLE Real Extravagance U In the film deposition system of Drawings 2 a and b which laminated the quartz dielectric on the high voltage electrode and the installation electrode, the SiNx film was formed in the silicon wafer surface according to the following conditions. ■ Reactant gas Ingredient helium 5iC14N2 H2 flow helium 5000cm /min■ electric discharge Atmospheric pressure, normal temperature 13.75 MHz (RF) 200W. ■ Dielectric Quartz board With the film deposition system by this invention, the membrane formation speed 5 neighborhood "of SiNx film was obtained. Covering intensity was also good and film thickness was also uniform. Real fan! Wandering In the film deposition system of Drawing 4 which laminated the enamel dielectric on the high voltage electrode and the installation electrode, the PTFE film was formed in the synthetic resin surface according to the following conditions. ■ Reactant gas Ingredient helium-TFE (tetrafluoro ethylene) flow helium 4500cm /rmnTFE 4-cm3/min■ electric discharge Atmospheric pressure, normal temperature 200 kHz 100W. ■ Dielectric Kapton (polyimide film) With the film deposition system by this invention, it was membrane formation speed 10 and obtained the PTFE film of ml meter. Covering intensity was also good and film thickness was also uniform. Past luck Drawing 1 a which consists of 7 mm of outside diameters which laminated and created the enamel dielectric to the high voltage electrode and the installation electrode Using the torch type film deposition system which consists of composition like b, as shown in Drawing 5, a sliding spacer (41) is passed to a torch type film deposition system (40) peripheral part, The inside of the small tube (42) 9 mm in inside diameter used for the heat exchanger for atomic power or the gas career for semiconductor manufacturing devices was made movable, and the SiNx film was formed in the small tube inner surface according to the same reactant gas as Example 1, and electric discharge conditions, moving a small tube (42). With the film deposition system by this invention, the membrane formation speed 5 pm/hr(7) SiN Engineering film was obtained. Covering intensity was also good and film thickness was also uniform. EFFECT OF THE INVENTION Since processed material does not need to be installed on an electrode as for the surface treatment device by this invention, Composition is easy, surface treatments, such as thin film formation, surface modification, etc. to sheet surfaces, such as a steel plate, vapor, glass, and plastics, or complicated shape, are possible, and since thin film formation can be carried out under atmospheric pressure, there is an advantage which can include in in-line one of a productive process, and does not choose an operation place.

[Brief Description of the Drawings]

The vertical section explanation side figure and Drawing 4 in which the eye squinting explanatory view showing one example of the surface treatment device according [ Drawings 1 a and b ] to this invention and Drawings 2 a and b show other examples are an eye squinting explanatory view showing other examples. Drawing 3 is a block diagram showing the incidental facilities of the surface treatment device by this invention. Drawing 5 is a vertical section explanation side figure showing the example of application of the surface treatment device by this invention. 1.31 ... a torch type film deposition system and 2, 11 ... discharge section, 3.12 ... high voltage electrode, 4, 13 ... An earth electrode, 5 ... A dielectric, 6.14 ... Electric discharge space, 7 ... a gas introducing pipe, 8.9, and 15, 32 ... gas supply line, 10 ... straight line blow-off type film deposition system, 16 ... duct for A gas, 17 ... duct for B gas, 19.33 ... skirt, 20 ... sheet material, 30 ... film deposition system, 34 ... exhaust gas duct, 41 ... sliding spacer, 42 ... small tube.