JPH1129873A - Method and apparatus for forming laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and apparatus for forming a laminated film in which various different thin films are continuously and rapidly deposited on a substrate surface under a pressure near atmospheric pressure. A plurality of sets of opposed electrodes each having a solid dielectric disposed on at least one facing surface are adjacent to each other, and a processing gas is introduced between the opposed electrodes of each set to produce a pressure near the atmospheric pressure. Voltage rise time between pairs of counter electrodes is 100μ
In the following, a glow discharge plasma is generated by applying a pulsed electric field having an electric field intensity of 1 to 100 kV / cm, and the base material is continuously passed between the plural sets of counter electrodes. And

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a laminated film in which thin films of the same type or different types are continuously deposited on the surface of a substrate by using glow discharge plasma under a pressure near atmospheric pressure. , And an apparatus for forming the same.

[0002]

2. Description of the Related Art Substrates made of plastic, metal, paper, fiber, etc. are widely used as household and industrial materials, but their surfaces have specific functions such as electrical properties, optical properties, and mechanical properties. If given, the application will be further expanded and will have a great added value.

Conventionally, methods for imparting a specific function to the surface of a substrate include a vacuum deposition method, a sputtering method, an ion beam method, an ion plating method, and a plasma CVD method using a glow discharge under reduced pressure. Etc. are known. However, these methods are all performed in a vacuum system, require large-scale equipment such as a vacuum chamber and a large-sized vacuum pump, and have various limitations in production.

In order to form a thin film on the surface of a long base material in a vacuum system, there are two types of production, a batch system and a continuous system. In the batch method, thin film formation is performed in a decompression and closed system, and a roll in which a base material is rolled in a long length is placed in a vacuum chamber, and a thin film is formed on the surface while unwinding the base material from the roll. Is done. In this method, the vacuum must be released and formed each time the raw material is carried in or the product is carried out, and the size of the equipment limits the diameter of the substrate roll and the capacity of the thin film raw material, etc. Production efficiency is also reduced.

In the continuous method, a differential evacuation method is used to obtain a reduced pressure state, and the evacuation is gradually performed from the atmospheric pressure to a reduced pressure to continuously maintain the degree of vacuum necessary for forming a thin film. A thin film is formed in the space defined. In this method, it is easy to carry in the roll base material and replenish the raw materials, but it is necessary to exhaust the air more than the inflow of air into the thin film forming apparatus and maintain the degree of vacuum, so a large capacity vacuum pump is required. Therefore, it is inevitable that the facilities become huge.

[0006] Further, when a plurality of functions are given to one base material or more advanced functions are added, an attempt has been made to laminate a plurality of kinds of thin films. However, in the case of industrially forming a multilayer film, in the batch method, the cycle of vacuum formation, thin film formation, and vacuum release must be repeated for each layer type, which is extremely inefficient. Not realistic. In the continuous method, large-scale equipment is required even for a single layer, and it is difficult to introduce a process for forming a multilayer film.
Furthermore, in the continuous method, it is difficult to cope with various kinds in a small amount in terms of capital investment, and it is extremely difficult to cope with an application in which a specific function is individually added to a base material.

Various methods have been proposed for forming a laminated film as described above. For example, Japanese Patent Application Laid-Open Nos. 2-181701 and 3-518202 disclose an electron gun in a vacuum evaporation method. There has been proposed a method of forming a laminated film on the surface of a base material by controlling the incident angle of the film and the angle between a vapor deposition roll and a vapor deposition source, but the continuous method using a differential pumping method has not been changed. To do so, the capital investment becomes excessively large, so it was necessary to adopt the batch method while recognizing that it was extremely inefficient.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and various kinds of thin films are continuously formed on a substrate surface under a pressure near atmospheric pressure. It is an object of the present invention to provide a method of manufacturing a laminated film deposited at a high speed and a continuous manufacturing apparatus thereof.

[0009]

Means for Solving the Problems The method for forming a laminated film according to the invention described in claim 1 of the present application (hereinafter referred to as the first invention) is as follows.
A plurality of sets of counter electrodes each having a solid dielectric disposed on at least one of the opposing surfaces are adjacent to each other, and a processing gas is introduced between the counter electrodes of each set to a pressure close to the atmospheric pressure. By applying a pulsed electric field having a voltage rise time of 100 μs or less and an electric field intensity of 1 to 100 kV / cm, a glow discharge plasma is generated, and a substrate is continuously formed between the plurality of sets of counter electrodes. Characterized by passing through.

The invention described in claim 2 of the present application (hereinafter referred to as “second
The method of forming a laminated film according to the first aspect of the present invention is characterized in that, in the pulsed electric field of the first aspect, the frequency is 0.5 to 100 kHz.
z, the pulse duration is 1 to 1000 μs.

The invention according to claim 3 of the present application (hereinafter referred to as the third
The method for forming a laminated film according to the first invention or the second invention
In the pulsed electric field of the present invention, a DC voltage supply unit capable of supplying a high voltage DC, and a pulse for converting the high voltage DC into a high voltage pulse by a semiconductor element having a turn-on time and a turn-off time of 500 ns or less. It is characterized in that a pulsed electric field is applied by a high-voltage pulse power supply composed of a control unit.

The invention according to claim 4 of the present application (hereinafter referred to as the fourth
The method of forming a laminated film according to the first, second or third invention is characterized in that the processing gas introduced into any one or more of the plurality of sets of the counter electrodes is a metal element-containing gas. It is characterized by including.

[0013] The invention according to claim 5 of the present application (hereinafter referred to as the fifth invention)
In the apparatus for forming a laminated film according to the present invention, a plurality of pairs of opposed electrodes each having a solid dielectric disposed on at least one facing surface are adjacent to each other, and the base material continuously runs between the plurality of pairs of opposed electrodes. And a processing gas supply unit for supplying a processing gas between the counter electrodes at a gas speed equal to or higher than the running speed of the base material in a direction opposite to the running direction of the base material for each set. And a high-voltage pulse power supply adapted to apply a pulsed electric field between the opposing electrodes.

In the above inventions, the first to fourth inventions relate to a method for forming a laminated film, and the fifth invention relates to a forming apparatus for forming a laminated film. Therefore, the forming method and the forming apparatus of the above invention are
Since they have common items that are closely related to each other, they are collectively referred to as the present invention, and when it is necessary to distinguish them, they are referred to as the method of the present invention or the apparatus of the present invention.

The present invention will be outlined. A state in which a plurality of pairs of counter electrodes each having a solid dielectric disposed on at least one of the opposing surfaces are adjacent to each other, and a processing gas of the same or different type is introduced between the counter electrodes for each pair, and a pressure near the atmospheric pressure is established. By applying a predetermined pulsed electric field to each pair of opposed electrodes, a glow discharge plasma depending on the processing gas is generated, and a thin film is formed on a base material passing through the glow discharge plasma. Here, by continuously running the base material between a plurality of sets of counter electrodes, thin films depending on the processing gas of each set are sequentially and continuously deposited, and a laminated film is formed.

Therefore, the area in which each set of the counter electrodes is housed constitutes a separate small-unit discharge plasma processing apparatus, and the processing gas is supplied to the apparatus so that the processing gas has a pressure near the atmospheric pressure. The substrate is continuously moved in the space between the counter electrodes by a known method, and is successively introduced into the next small-unit discharge plasma processing apparatus. As described above, a plurality of sets of the discharge plasma processing apparatus in each small unit are installed adjacent to each other so that the base material can run continuously, and the processing is performed under a pressure near the atmospheric pressure in the apparatus. The inlet and outlet of the base material need only be sealed in a confidential state to the extent that gas leakage can be tolerated, and a large-scale exhaust device such as a process performed in a vacuum system is not required.

Hereinafter, the discharge plasma processing apparatus of each small unit will be described. In the present invention, the pressure under the atmospheric pressure means a pressure of 13.3 to 106.4 kPa, and the pressure is easily adjusted and the apparatus is simplified.
A range of 103.74 kPa is preferred.

It is known that under a pressure close to the atmospheric pressure, a stable plasma discharge state is not maintained except for a specific gas such as helium, ketone, etc., and an instantaneous transition to an arc discharge state occurs. However, when a pulsed electric field is applied, a cycle in which the discharge is stopped before the transition to the arc discharge and the discharge is started again is realized, and a stable glow discharge plasma (hereinafter simply referred to as a discharge plasma) is generated. be able to.

According to the method of applying a specific pulsed electric field of the present invention, discharge plasma can be generated regardless of the type of gas existing in the plasma generation space. Conventionally, it has been necessary to perform the treatment using discharge plasma under a known low-pressure condition or under a specific gas atmosphere in a closed container protected from the outside air. The system can be implemented in a low airtight system that prevents free flowing of gas, and a high-density plasma state can be realized.

In the present invention, the electric field strength is 1 to 100 k.
V / cm, the rise time is 100 μs or less,
By applying a pulse electric field having a steep rise, gas molecules existing in the plasma generation space are efficiently excited. Applying a pulse electric field with a slow rise corresponds to the stepwise application of energies with different magnitudes.First, the excitation of molecules that ionize with low energy, that is, molecules with a small first ionization potential, takes precedence. When the next higher energy is applied, already ionized molecules are excited to a higher level,
It is difficult to efficiently ionize molecules present in the plasma generation space. In contrast, the rise time is 100
A pulse electric field of less than μs is equivalent to applying energy to molecules existing in space all at once, increasing the absolute number of ionized molecules in space and increasing the plasma density. Become.

The manufacturing method of the present invention is performed in an apparatus in which a plurality of sets of opposing electrodes are arranged adjacent to each other and a solid dielectric is provided on at least one opposing surface of the opposing electrodes.
Therefore, the discharge plasma processing apparatus of each small unit of the present invention,
If the above conditions are satisfied, the arrangement of the solid dielectrics of all the counter electrodes need not be the same. The portion where the discharge plasma is generated is between the solid dielectric and the electrode when a solid dielectric is installed on one of the electrodes, and between the solid dielectrics when the solid dielectric is installed on both of the electrodes. Space.

Examples of the electrodes include electrodes made of simple metals such as copper and aluminum, alloys such as stainless steel and brass, and intermetallic compounds. The counter electrode preferably has a structure in which the distance between the counter electrodes is substantially constant in order to avoid occurrence of arc discharge due to electric field concentration. Examples of an electrode structure that satisfies this condition include a parallel plate type, a cylindrical opposed plate type, a spherical opposed plate type, a hyperboloid opposed plate type, and a coaxial cylindrical structure.

The solid dielectric is provided on one or both of the opposing surfaces of the electrodes. At this time, the electrode on the side on which the solid dielectric is placed is in close contact with the electrode, and the opposing surface of the contacting electrode is completely covered. If there is a portion where the electrodes directly face each other without being covered by the solid dielectric, an arc discharge occurs therefrom.

Examples of the solid dielectric include plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, metal oxides such as silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide, and double oxides such as barium titanate. Can be

The shape of the solid dielectric may be a sheet or a film, but preferably has a thickness of 0.05 to 4 mm. If it is too thick, a high voltage is required to generate discharge plasma, and if it is too thin, dielectric breakdown occurs when a voltage is applied, causing arc discharge.

The solid dielectric has a relative dielectric constant of 2 or more (2
In a 5 ° C. environment, the same applies hereinafter). Specific examples of the dielectric having a relative dielectric constant of 2 or more include polytetrafluoroethylene, glass, and a metal oxide film. Further, in order to stably generate high-density discharge plasma, it is preferable to use a fixed dielectric having a relative dielectric constant of 10 or more. Although the upper limit of the relative permittivity is not particularly limited, it is known that the actual material is about 18,500. As a solid dielectric having a relative dielectric constant of 10 or more, a metal oxide film mixed with 5 to 50% by weight of titanium oxide and 50 to 95% by weight of aluminum oxide, or
It consists of a metal oxide film containing zirconium oxide,
It is preferable to use a film having a thickness of 10 to 1000 μm.

The distance between the electrodes is determined in consideration of the thickness of the solid dielectric, the magnitude of the applied voltage, the purpose of utilizing plasma, and the like, and is preferably 1 to 50 mm. 1m
If it is less than m, the distance between the electrodes is too small to pass through the substrate or the like, and if it exceeds 50 mm, it is difficult to generate uniform glow discharge plasma.

In the present invention, the electric field applied between the electrodes is pulsed, the voltage rise time is 100 μs or less, and the electric field intensity is 1 to 100 kV / cm.
It is characterized by having been done.

FIG. 1 shows an example of a pulse voltage waveform. Waveforms (A) and (B) are impulse waveforms, waveform (C) is a square wave waveform, and waveform (D) is a modulation waveform. Although FIG. 1 shows an example in which voltage application is repeated positive and negative, a so-called one-sided waveform in which a voltage is applied to either the positive or negative polarity side may be used.

The pulse voltage waveform in the present invention is not limited to the above-mentioned waveform, but the shorter the rise time of the pulse, the more efficiently the ionization of the gas at the time of plasma generation. If the rise time of the pulse exceeds 100 μs, the discharge state easily shifts to an arc and becomes unstable, so that a high-density plasma state due to a pulse electric field cannot be expected. Further, it is better that the rise time is short. However, there is a limitation in a device that has an electric field intensity that is large enough to generate plasma at normal pressure and generates an electric field with a fast rise time. It is difficult to achieve a pulsed electric field with a rise time of less than 40 ns. The rise time is more preferably 50 ns to 5 μs. Here, the rise time means a time during which the voltage change is continuously positive.

Also, the fall time of the pulse electric field is preferably steep, and is 100 μm similar to the rise time.
The time scale is preferably equal to or less than s. For example, in the power supply device used in the embodiment of the present invention, the rise time and the rise time can be set to the same time, although it differs depending on the pulse electric field generation technique.

Further, modulation may be performed using pulses having different pulse waveforms, rise times, and frequencies.

The frequency of the pulse electric field is 0.5 kHz to 1
Preferably, it is 00 kHz. If the frequency is less than 0.5 kHz, the plasma density is low and the processing takes too much time. If the frequency exceeds 100 kHz, arc discharge is likely to occur. More preferably, the frequency is 1 kHz or more. By applying such a high-frequency pulsed electric field, the processing speed can be greatly improved.

The pulse duration in the pulse electric field is preferably 1 to 1000 μs. 1 μs
When the discharge time is less than 1,000 μs, the discharge becomes unstable.
When it exceeds, it is easy to shift to arc discharge. More preferably, it is 3 μs to 200 μs. Here, one pulse duration is an example shown in FIG.
It refers to the time during which a pulse is continuous in a pulse electric field composed of repetition of FF. In the case of the intermittent pulse as shown in FIG. 2A, the pulse duration is equal to the pulse width time, but in the case of the pulse having the waveform as shown in FIG. Say time including.

Further, in order to stabilize the discharge, it is preferable to have an OFF time lasting at least 1 μs within a discharge time of 1 ms.

The above discharge is performed by applying a voltage.
Although the magnitude of the voltage is appropriately determined, in the present invention,
The electric field strength between the electrodes is set in a range of 1 to 100 kV / cm. If it is less than 1 kV / cm, it takes too much time for the treatment, and if it exceeds 100 kV / cm, arc discharge is likely to occur. In applying the pulse voltage, a direct current may be superimposed.

FIG. 3 shows a block diagram of a power supply when such a pulsed electric field is applied. FIG. 4 shows an equivalent circuit diagram of the power supply. In FIG. 4, SW is a semiconductor element functioning as a switch. By using a semiconductor element having a turn-on time and a turn-off time of 500 ns or less as the switch, the electric field strength as described above is 1 to 100 kV / cm, and the rise time and fall time of the pulse are 100 μs or less. Such a high voltage and high speed pulsed electric field can be realized.

Hereinafter, the principle of the power supply will be briefly described with reference to the equivalent circuit diagram of FIG. + E is a positive DC voltage supply unit, and -E is a negative DC voltage supply unit. SW1
Reference numerals 4 to 4 denote switch elements composed of the high-speed semiconductor elements as described above. D1 to D4 indicate diodes. I _{1 to} I ₄ indicate the direction of current flow.

[0039] First, when turned ON SW1, load of the positive polarity is charged in the flow direction current I _1. Then, the SW1 is turned OFF, by turning ON the SW2 instantaneously, the electric charge charged is charged in the direction of I ₃ through SW2 and D4. Next, when the switch SW3 is turned on after the switch SW2 is turned off, the load having the negative polarity causes the current I ₂
Charge in the direction of flow. Next, the SW3 is turned OFF, by turning ON the SW4 instantaneously, the electric charge charged is charged in the direction of I ₄ through SW4 and D2. By repeating the above series of operations, the output pulse of FIG. 5 can be obtained. Table 1 shows this operation table.

[0040]

[Table 1]

The advantages of this circuit are that even if the load impedance is high, the charged electric charge can be reliably discharged by operating SW2 and D4 or SW4 and D2, and the high-speed operation is possible. High-speed charging can be performed using SW1 and SW3, which are turn-on switch elements. Therefore, a pulse signal having a very fast rise time and fall time as shown in FIG. 5 can be obtained.

In the discharge obtained by the above method,
The discharge current density between the counter electrodes is 0.2 to 300 mA / c.
m ² is preferred.

The discharge current density is a value obtained by dividing a value of a current flowing between electrodes by discharge by an area in a direction orthogonal to a current flow direction in a discharge space. When used, it corresponds to a value obtained by dividing the current value by the facing area. In the present invention, a pulse-shaped current flows to form a pulsed electric field between the electrodes. In this case, the maximum value of the pulse current, that is, the peak-peak value is divided by the above area.

In a glow discharge under a pressure near the atmospheric pressure,
As shown below, it has been revealed by the present inventors that the discharge current density reflects the plasma density and is a value that affects the production of the laminated film. By setting the thickness in the range of 0.2 to 300 mA / cm ² , uniform discharge plasma can be generated, and a good production result of the laminated film can be obtained.

The substrate used in the present invention includes plastics such as polyethylene, polypropylene, polystyrene, polycarbonate, polyethylene terephthalate, polyphenylene sulphite, polyether ether ketone, polytetrafluoroethylene, and acrylic resin, glass, ceramic, and metal. And the like. The shape of the substrate is not particularly limited. However, since the treatment is performed continuously, the substrate is suitable for a long substrate such as a plate, a film, and a pipe.

In the present invention, an arbitrary thin film can be laminated by selecting a gas (hereinafter referred to as a processing gas) existing in the discharge plasma generation space.

By using a fluorine-containing compound gas as the processing gas, a fluorine-containing group can be formed on the surface of the substrate to lower the surface energy and obtain a water-repellent surface.

Examples of the fluorine element-containing compound include fluorine-carbon compounds such as propylene hexafluoride (CF ₃ CFCF ₂ ) and octafluorocyclobutane (C ₄ F ₈ ).
From the viewpoint of safety, propylene hexafluoride and octafluorocyclobutane that do not generate harmful gas, hydrogen fluoride, are used.

By performing the treatment in an atmosphere of a monomer having a hydrophilic group and a polymerizable unsaturated bond in the molecule,
A hydrophilic polymer film can also be deposited. As the hydrophilic group, a hydroxyl group, a sulfonic acid group, a sulfonate group,
Examples include a hydrophilic group such as a primary, secondary, or tertiary amino group, an amide group, a quaternary ammonium base, a carboxylic acid group, and a carboxylic acid group. Further, a hydrophilic polymer film can be similarly deposited by using a monomer having a polyethylene glycol chain.

The monomers include acrylic acid, methacrylic acid, acrylamide, methacrylamide, N, N
-Dimethylacrylamide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, sodium styrenesulfonate, allyl alcohol, allylamine, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, and the like. At least one
Seeds can be used.

Further, as the processing gas, a metal-containing gas can be suitably used. As the metal, for example, Al, Sb,
As, Bi, B, Ca, Cd, Cr, Co, Cu, G
a, Ge, Au, In, Ir, Hf, Fe, Pb, L
i, Na, Mg, Mn, Hg, Mo, Ni, P, Pt,
Po, Rh, Se, Si, S, Ta, Te, Sn, T
Metals such as i, W, V, Y, Zr, Zn and the like can be mentioned. Examples of the gas containing the metal include metal organic compounds, metal-halogen compounds, metal-hydrogen compounds, metal-halogen compounds, metal alkoxides and the like. Processing gas may be used.

More specifically, the case where the metal is Si will be described as an example. Tetramethylsilane [Si (C
H ₃ ) ₄ ], dimethylsilane [Si (CH ₃ )
₂ H ₂ ], tetraethylsilane [Si (C ₂ H ₅ ) ₄ ]
Organometallic compounds such as silicon tetrafluoride (SiF ₄ ), silicon tetrachloride (SiCl ₄ ), and silicon chloride (SiH ₂ Cl ₂ )
Metal silane compounds such as monosilane (SiH ₄ ), disilane (SiH ₃ SiH ₃ ), and trisilane (SiH ₃ S)
metal hydrides such as iH ₂ SiH ₃ ); metal alkoxides such as tetramethoxysilane [Si (OCH ₃ ) ₄ ] and tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ]; At least one of these can be used, including other metals. In the above metal-containing gas,
In consideration of safety, it is preferable that there is no danger of ignition, explosion, or the like in a room temperature, such as a metal alkoxide or a metal halide, in terms of safety. In view of corrosiveness and generation of harmful gas, a metal alkoxide is preferably used. You.

If the metal-containing gas is a gas, it can be directly introduced into the discharge space. If the gas is a liquid or solid, it may be introduced into the discharge space via a vaporizer.

From the viewpoint of economy and safety, it is preferable to carry out the treatment in an atmosphere diluted with a diluent gas rather than in the atmosphere of the treatment gas alone. Examples of the diluent gas include rare gases such as helium, neon, argon, and xenon, and nitrogen gas, and at least one of them is used. When a diluent gas is used, the ratio of the processing gas is preferably 1 to 10% by volume.

As described above, as the atmosphere gas (processing gas), a compound having more electrons is more advantageous in increasing the plasma density and performing high-speed processing. Therefore, argon and / or nitrogen are preferable in that they are easily available, inexpensive, and can be processed at a high speed.

FIG. 6 shows an example of an apparatus for continuously producing a laminated film according to the present invention, and the production method of the present invention will be specifically described below. As shown in FIG. 6, the apparatus of the present invention mainly includes a high-voltage pulse power supply unit 10, a plurality of small-unit discharge plasma processing apparatuses 20, 21, 22, 23, and an unwinding roll 8.
0 and a take-up roll 81, and the discharge plasma processing apparatuses 20, 21, 22, and 23 of each small unit are respectively
Upper electrodes 30, 31, 32, 33, lower electrodes 40, 4
1, 42, 43, processing gas supply units 50, 51, 52,
53, solid dielectrics 70, 71, 72, 73, 74, 7
5, 76, and 77.

The dotted line portion in FIG. 6 indicates that a plurality of small-unit discharge plasma processing apparatuses are arranged, but in FIG. The processing apparatus is represented by four small-unit discharge plasma processing apparatuses 20, 21, 22, and 23, and upper and lower electrodes, solid dielectrics, processing gas supply units, and the like are denoted by corresponding reference numerals. . For solid dielectrics, 70-73
Are lower electrodes 40 to 43, and 74 to 77 are upper electrodes 30 to
Reference numeral 33 denotes a solid dielectric mounted, and it is necessary that the solid dielectric is mounted on at least one of the counter electrodes.

The various processing gases 90 to 93 are supplied to the counter electrodes (ie, 30/40, 31/41, 32/42, 33/33) of the adjacent small unit discharge plasma processing apparatuses 20 to 23.
43) An arbitrary type is selected and introduced according to the purpose at a pressure close to the atmospheric pressure every interval, and a pulsed electric field is applied to each electrode under the above-described conditions, and the type of the processing gas is selected. Discharge plasma is generated in accordance with
0 is brought into contact, various thin films are deposited on the base material, and a multilayer laminated film 61 is formed. The type of processing gas introduced into each small-unit discharge plasma processing apparatus differs depending on the purpose, and may be the same or different.

The processing gas introduced between the counter electrodes of each set can be introduced by a known method. However, in order to form and deposit a thin film uniformly and effectively on the surface of the substrate, the traveling gas of the substrate is used. It is preferable that the processing gas is continuously contacted at a gas speed equal to or higher than the traveling speed of the base material under a pressure close to the atmospheric pressure from a direction opposite to the direction.

Therefore, the processing gas supply section is provided with a gas flow arranged so that a desired processing gas is continuously contacted from the direction opposite to the traveling direction of the substrate at a gas speed higher than the traveling speed of the substrate. It has a generating mechanism. As the gas flow generation mechanism,
A method of blowing out a processing gas by a slit or nozzle-shaped gas supply device, a method of providing a hole for supplying a processing gas in a desired direction to an electrode facing a substrate processing surface and blowing out the same, a pump, a blower, a blower Supply between electrodes using
Circulating method and the like can be mentioned.

More specifically, the processing gas supply unit 5
The reference numerals 0, 51, 52, and 53 are arranged as shown in FIG. 6, and the processing gas is supplied in a direction opposite to the traveling direction of the substrate. As a method of supplying the processing gas, as shown in FIG. 7, the processing gas 90 is brought into contact with the turbo plasma blower 100 at a gas speed equal to or higher than the traveling speed of the base material for each small-unit discharge plasma processing apparatus. It may be configured to circulate at the same time.

In the present invention, as shown in FIG.
The high-voltage pulse power supply unit 10 is commonly used as a power supply for the discharge plasma processing apparatus in each small unit, but in the method of the present invention, the individual units are independent as long as the conditions for generating the discharge plasma are satisfied. You can use the power supply.

[0063]

According to the method of forming a laminated film of the present invention, as described above, a plurality of regions are provided in an atmosphere having different types of gas compositions so that the pressure is controlled to be close to the atmospheric pressure. A stable high-density plasma is generated by applying a pulsed electric field to the substrate, and at the same time, a substrate is successively supplied to each of the regions to deposit various thin films on the surface of the substrate. By changing the type of gas in the above region, a plurality of thin films having various characteristics corresponding to the type of gas can be simultaneously and continuously laminated at high speed.

Further, since the apparatus for forming a laminated film of the present invention is constructed as described above, processing can be performed at normal pressure, and a large vacuum pump and a large decompression vessel are not required. It does not require such large equipment. Therefore, supply of the substrate,
The substrate and the gas composition can be freely changed, and various laminated films can be manufactured economically.

[0065]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following embodiment, a high-voltage pulse power supply (manufactured by Heiden Laboratories, semiconductor element: IXYS, model number IXBH40N1) according to the equivalent circuit diagram of FIG.
60-627G).

Example 1 In an apparatus having four small-unit discharge plasma processing apparatuses adjacent to each other (the apparatus shown in FIG. 6 excluding the dotted lines), processing gas supply units 50 to 53 were used. A device having a slit-shaped gas outlet was used as an apparatus for forming a laminated film. In addition, the upper electrodes 30 to 33 and the lower electrodes 40 to 43 of the small-unit discharge plasma processing apparatus have a width of 35 mm.
A material having a size of 0 × 150 mm in length and coated with aluminum oxide having a thickness of 1.5 mm by thermal spraying as solid dielectrics 70 to 77 on opposite surfaces of both electrodes was used.

The substrate 60 has a thickness of 50 μm and a width of 300 mm.
Polyethylene terephthalate film (Lumirror T50 manufactured by Toray Industries, Inc., contact angle 70 °, hereinafter referred to as PET film) was used.

In the above-described apparatus for forming a laminated film, the P
The ET film was introduced into the discharge plasma processing apparatus of each small unit via the unwinding roll 80 and the winding roll 81 at a traveling speed of 10 m / min, and the various conditions shown in Table 2 (processing gas composition, total flow rate) (Electric field waveform, rise time, peak value, frequency, pulse duration, discharge current density), a processing gas excited by discharge plasma was brought into contact with one surface of the PET film to form a laminated film.

The processing gas is supplied to the processing gas supply unit 50.
To 53, and between each electrode at a total flow rate of 30 SLM. 4 vol% of tetraiso-propoxytitanate [Ti (i-OP)
r) Nitrogen gas containing ₄ ], processing gas supply units 51 and 53
2% by volume of tetraethoxysilane [Si (OC ₂ H
₅ ) Using ₄ ) and nitrogen gas containing 2% by volume of oxygen gas, the first to fourth layers are counted in the order of lamination on the PET film, and titanium oxide (TiO 2) is used for the first and third layers. ₂ ) A thin film of silicon oxide (SiO ₂ ) was laminated on the thin film, the second layer and the fourth layer to form a four-layer laminated film of a PET film.

The refractive index and the film thickness of each layer of the obtained laminated film were measured by an ellipsometer (BVA- manufactured by Mizojiri Optical Industrial Co., Ltd.).
36 VW) and the results are summarized in Table 2. Further, when the reflectance of the PET four-layer laminated film was measured with a spectrophotometer (U-3000, manufactured by Hitachi, Ltd.), the average visible light (wavelength: 400 to 700 nm) reflectance was about 7% for the PET film alone. However, since it was 0.2%, it was clear that the antireflection function was provided.

[0071]

[Table 2]

Example 2 In order to make the thin film of the third layer tin oxide (SnO ₂ ), 1% by volume of 4 methyl tin [Sn (C
H ₃ ) ₄ ] and nitrogen gas containing 4% by volume of oxygen gas were introduced, and a pulsed electric field under various conditions shown in Table 2 was applied between the upper electrode 32 and the lower electrode 42 to generate discharge plasma. Except for the above, a laminated film was manufactured in the same manner as in Example 1.

When the surface resistance of the obtained third laminated film was measured and found to be 10 ⁸ Ω / □, the laminated film having an antistatic function and an antireflection function (reflectance: 0.3%) was obtained. It was a membrane. Further, as shown in Table 2, the titanium oxide film of the first layer and the silicon oxide films of the second and fourth layers have the same refractive index and the same refractive index as those of the first embodiment.
It had a film thickness.

Comparative Example 1 In the continuous manufacturing apparatus used in Example 1, the si
When a continuous electric field of n waves was applied, no uniform discharge plasma was generated under the gas atmosphere of the processing gas of Example 1. Therefore, the helium gas (H
e) In this atmosphere of helium gas at atmospheric pressure, a laminated film was formed in the same manner as in Example 1. The obtained thin film had a sticky surface, and a strong thin film could not be obtained. Table 2 shows the refractive index and film thickness of the obtained laminated film.

As described above, according to the method of forming a laminated film of the present invention, a plasma having a higher density can be obtained as compared with the comparative example, and a thin film having a larger film thickness can be obtained as compared with the comparative example. The generation rate is high, and a high-quality laminated film can be formed.

[0076]

The method for forming a laminated film according to the present invention is configured as described above, so that the processing gas can be selected according to the purpose under the pressure near the atmospheric pressure, thereby obtaining the surface of the base material. The thin films having various functions can be stacked at high speed and continuously. Therefore, the method of the present invention can be used to produce various functional films such as an antireflection film, a light selective transmission film, an infrared reflection film, an antistatic film, an electromagnetic wave sealing film, and a semiconductor device material.

Further, the continuous production apparatus for a laminated film according to the present invention does not require a decompression system as in the prior art, so that a large exhaust device is not required, and the loading and unloading of raw materials and products is facilitated. Therefore, it is extremely useful from the viewpoint of production operability and economy of production equipment.

[0078]

[Brief description of the drawings]

FIG. 1 is a voltage waveform diagram showing an example of a pulse electric field.

FIG. 2 is an explanatory diagram of a pulse duration.

FIG. 3 is a block diagram of a power supply that generates a pulse electric field.

FIG. 4 is an equivalent circuit diagram of a power supply that generates a pulse electric field.

FIG. 5 is a diagram of an output pulse signal corresponding to an operation table of a pulse electric field.

FIG. 6 is an example of an apparatus for continuously producing a laminated film according to the present invention.

FIG. 7 is a diagram showing an example of a gas flow generation mechanism in a small-unit discharge plasma processing apparatus.

[Explanation of symbols]

Reference Signs List 10 High-voltage pulse power supply unit 20, 21, 22, 23 Discharge plasma processing device in small unit 30, 31, 32, 33 Upper electrode 40, 41, 42, 43 Lower electrode 50, 51, 52, 53 Processing gas supply unit Reference Signs List 60 base material 61 laminated film 70, 71, 72 to 77 solid dielectric 80 unwinding roll 81 take-off roll 90, 91, 92, 93 processing gas 100 turbo blower

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08J 7/00 306 C08J 7/00 306 H01L 21/31 H01L 21/31 C D06M 10/00 G

Claims (5)

[Claims] 1. A plurality of sets of opposed electrodes each having a solid dielectric disposed on at least one opposed surface are adjacent to each other, and a processing gas is introduced between the opposed electrodes of each set so as to be at a pressure near atmospheric pressure. Voltage rise time between each pair of counter electrodes is 100μ
In the following, a glow discharge plasma is generated by applying a pulsed electric field having an electric field intensity of 1 to 100 kV / cm, and the base material is continuously passed between the plural sets of counter electrodes. A method for forming a laminated film. 2. In a pulsed electric field, the frequency is 0.5 to 100 kHz and the pulse duration is 1 to 1000.
2. The method according to claim 1, wherein the value is set to μs. 3. A DC voltage supply unit capable of supplying a high voltage DC, and a turn-on time and a turn-off time of 50 hours.
The pulsed electric field is applied by a high-voltage pulse power supply comprising a pulse control unit that converts the high-voltage direct current into a high-voltage pulse by a semiconductor element having a duration of 0 ns or less. Of forming a laminated film. 4. The laminated film according to claim 1, wherein the processing gas introduced into any one or more of the plurality of sets of the counter electrodes includes a metal element-containing gas. Method. 5. A base material comprising a plurality of sets of counter electrodes each having a solid dielectric disposed on at least one of the opposing surfaces, wherein the base material runs continuously between the plurality of sets of counter electrodes. A traveling unit, a processing gas supply unit for supplying a processing gas between the counter electrodes at a gas speed equal to or higher than a traveling speed of the substrate from a direction opposite to a traveling direction of the substrate for each set, and between the opposing electrodes. An apparatus for forming a laminated film, comprising: a high-voltage pulse power supply adapted to apply a pulsed electric field to the substrate.