WO2005116293A1 - Thin film forming equipment and thin film forming method - Google Patents

Abstract

Thin film forming equipment is provided for generating high density plasma maintaining stable discharge conditions and for manufacturing an excellent quality thin film. A matching box is provided between a plurality of second power supplies (HF) and high frequency electrodes for matching impedance. An impedance absolute value and a phase value are automatically adjusted by at least one matching box during operation of the equipment, the impedance absolute value is fixed by other matching box and only the phase value is automatically adjusted.

Description

 Specification

 Thin film forming apparatus and thin film forming method

 Technical field

 The present invention relates to an apparatus and a method for forming a thin film using an atmospheric pressure plasma discharge process.

 Background art

 [0002] Atmospheric pressure plasma CVD (Chemical Vapor Deposition) for obtaining a high-quality thin film using a mixed gas of a discharge gas and a thin film forming gas by using an atmospheric pressure plasma discharge process has been known. . Atmospheric pressure plasma CVD is being considered for practical use in forming deposited films in photoconductors for semiconductor devices, electrophotographic elements, various electronic elements, and optical elements.

 For example, an atmospheric pressure plasma processing apparatus for performing an atmospheric pressure plasma discharge process includes an atmospheric pressure plasma processing apparatus 1 using one high frequency power supply, and FIG. FIG. The atmospheric pressure plasma processing apparatus 1 is connected to a power supply D which is a high-frequency power supply via a matching unit 11 for adjusting impedance, and is connected to a high-frequency electrode 12 composed of a metal base material 122 and a dielectric 121 so as to be grounded. In this configuration, a metal base material 132 and an electrode 13 made of a dielectric material 131 on which a base material 14 is disposed are opposed to each other.

 [0004] In the atmospheric pressure plasma processing apparatus 1, a gas mixture near the atmospheric pressure composed of a discharge gas and a thin film-forming gas is supplied between the high-frequency electrode 12 and the electrode 13 by a gas supply device (not shown). By applying a high-frequency voltage from D, a thin film is formed on the substrate 14.

[0005] Further, as shown in FIG. 1 (b), the atmospheric pressure plasma processing apparatus includes an atmospheric pressure plasma processing apparatus la which is a high frequency power supply and has two power supplies having different frequencies. The difference between the atmospheric pressure plasma processing apparatus la and the atmospheric pressure plasma processing apparatus 1 here is that the atmospheric pressure plasma processing apparatus la is connected to an electrode 13 on which a base material 14 is disposed by means of an LF matching unit 15 that boosts the voltage to an electrode 13. 1 This is the point where the power supply LF is connected. With the above configuration, the atmospheric pressure plasma processing apparatus la has a higher plasma density in the vicinity of the base material 14 and can form a better quality thin film. [0006] The output of the power of the atmospheric pressure plasma processing apparatus is partially returned to the power as a reflected wave if the impedance of the power and the impedance of the plasma viewed from the electrodes are not the same, Can not be sent to In a plasma processing apparatus, it is necessary to maintain a constant power consumption in a plasma and maintain a stable plasma state in order to form a high-quality thin film having a uniform thickness at the time of film formation.

 [0007] Therefore, the atmospheric pressure plasma apparatus is provided with a matching box (matching box) for making the impedance the same, and is adjusted so that the impedance becomes the same in advance by a preliminary experiment or the like. The matching device is equipped with a mechanism that automatically adjusts according to the impedance on the plasma side, which fluctuates depending on the power supply voltage, gas temperature, pressure, supply amount, and the like.

 [0008] Therefore, as shown in FIG. 3, the matching device 11 in the atmospheric pressure plasma processing apparatus 1 and la adjusts the absolute value adjusting variable capacitor 21 for adjusting the absolute value of the impedance, and adjusts the phase of the impedance. The phase adjustment variable capacitor 22, coil 23, and the absolute value adjustment variable capacitor 21 and coil 23 are automatically adjusted from the voltage value and current value between the power supply and the electrode to adjust the impedance of the power supply and the impedance of the plasma viewed from the electrode. A control box 24 for making the same is attached, and an output from a power supply is sent to a maximum as a plasma output (for example, see Patent Document 1).

 [0009] In addition to the atmospheric pressure plasma processing apparatus between the pair of opposing electrodes, there is an apparatus using a plurality of pairs of electrodes. In the impedance adjustment in this case, the transmitted wave from the adjacent electrode is mixed in the reflected wave, and the transmitted wave and the reflected wave cannot be measured separately. Up the bow I.

 [0010] As a result, there is a problem that the operating state becomes unstable. As a solution, impedance matching is performed only at the beginning of the step in the vacuum plasma processing or when the reflection becomes abnormally large. Methods and the like are known (see Patent Document 2). Patent Document 1: Japanese Patent Application Laid-Open No. 2003-268557

 Patent Document 2: JP-A-8-96992

[0011] Certainly, the above technique is an effective method for forming a thin film by plasma processing between a plurality of sets of electrodes. However, the formation of high-quality thin films is still insufficient, and realizing a more stable plasma state has been a major issue. Therefore, the present invention has been made in such an industrial demand, and it is possible to generate high-density plasma while maintaining a stable discharge state, and to form a thin film capable of forming a good-quality thin film. It is to provide a device.

 Disclosure of the invention

 [0013] In order to solve the above problem, the following configuration is achieved.

 (1) Between the plurality of electrode pairs for generating plasma at or near atmospheric pressure and an AC power supply for supplying AC power to the electrode pair, an output impedance of the AC power supply and the plurality of electrodes are provided. A plurality of impedance matching devices for matching each input impedance of the pair are interposed, and based on the AC power supply or the voltage between the electrode pairs and the AC power supply or the current flowing between the electrode pairs, In a thin film forming apparatus provided with automatic adjustment means for automatically adjusting a plurality of impedance matching devices, the automatic adjustment means may use one of the plurality of impedance matching devices for any one of the impedance matching devices. For other impedance matching devices, the variable capacitor for absolute value adjustment is fixed, and the impedance is automatically adjusted using only the variable capacitor for phase adjustment. And said one of the impedance matching device, configured thin film forming apparatus so as to automatically adjust impedance by the absolute value adjusting variable capacitor and a phase adjusting variable capacitor scratch.

 (2) In the invention described in the above (1), the impedance matching device has a variable capacitance capacitor for adjusting an absolute value of impedance, and the automatic adjusting means forms a thin film for adjusting the capacitance of the variable capacitance capacitor. apparatus.

 (3) In the invention described in the above (1) or (2), high-frequency AC power is supplied to one electrode of the electrode pair, and AC power supplied to the one electrode is supplied to the other electrode. Thin film forming apparatus to which AC power of a relatively low frequency is supplied.

 (4) In the invention according to any one of the above (1) to (3), the plurality of pairs of electrodes are a planar electrode in which one electrode is provided integrally in a planar shape, and the other electrode Is a thin film forming apparatus comprising a plurality of individual electrodes provided separately and separately opposed to said one electrode.

(5) In the invention according to any one of (1) to (4), the plurality of pairs of electrodes are One electrode is a roll-type electrode provided so as to be rotatable in the circumferential direction, and the other electrode is a plurality of individual electrodes provided separately and opposed to the outer peripheral surface of the one electrode. Puru thin film forming equipment.

 (6) A method for realizing the thin film formation according to the invention described in the above (1) is provided. Brief Description of Drawings

 [0014] [Fig. L] (a) is a longitudinal sectional view of a thin film forming apparatus using an atmospheric pressure plasma process with one power source, and (b) is a thin film forming apparatus using an atmospheric pressure plasma process with two power sources. FIG.

 [FIG. 2] (a) is a longitudinal sectional view of a thin film forming apparatus for performing atmospheric pressure plasma processing on a substrate on a flat plate in the present invention, and (b) is an atmospheric pressure plasma on a substrate on a film in the present invention. It is a longitudinal section of a thin film formation device by processing.

 FIG. 3 is a diagram showing an internal configuration of a matching device 11.

 BEST MODE FOR CARRYING OUT THE INVENTION

First, an outline of an embodiment of the present invention will be described.

 In the present invention, the plasma discharge treatment is performed at or near atmospheric pressure, and the pressure at or near atmospheric pressure is about 20 kPa to: about L10 kPa, which is a good value according to the present invention. In order to obtain the effect, 93 kPa to 104 kPa is preferable.

 In the thin film forming apparatus of the present invention, the gas supplied between the opposed electrodes (discharge space) is at least a discharge gas excited by an electric field, and a plasma state or an excited state by receiving the energy to form a thin film. Contains a thin film forming gas to be formed.

 [0018] The discharge condition in the present invention is that the first high-frequency electric field and the second high-frequency electric field are superimposed on the discharge space, and the frequency f of the second high-frequency electric field is higher than the frequency f of the first high-frequency electric field.

 1 2 and the electric field strength V of the first high-frequency electric field, the electric field strength V of the second high-frequency electric field, and the discharge

 1 2 The relationship between the starting electric field and the electric field strength IV is

 V≥IV> V

 1 2

 Or, satisfy V> IV≥V.

 1 2

 [0019] The frequency f of the second high-frequency electric field is 0.8 MHz or more and 200 MHz or less and the second high frequency

 2

The electric field strength V of the wave electric field is 0.5 kVZmm or more, and The frequency ^ of the first high-frequency electric field is 1 kHz or more and 500 kHz or less, and the electric field strength V force of the first high-frequency electric field is 4 kVZmm or more.

 More preferably, within the above range, the frequency f of the first high-frequency electric field is 50 kHz or more and 100 kHz or less, the electric field strength of the first high-frequency electric field V force lOkVZmm or more, and the frequency f of the second high-frequency electric field f force ^ MHz or more 50 MHz Hereinafter, the electric field strength V of the second high-frequency electric field is 1.

 twenty two

8kVZmm or more!

[0020] High frequency refers to a high frequency of 0.5 kHz or more.

 When the superimposed high-frequency electric fields are both sine waves, a component is obtained by superimposing the frequency f of the first high-frequency electric field and the frequency f of the second high-frequency electric field higher than the frequency f.

 1 2

 Has a frequency f

 A higher frequency f on a sine wave of 1

 The sine wave of 2 overlaps.

 In the present invention, the intensity of the electric field at the start of discharge refers to the intensity of discharge occurring in a discharge space (such as the configuration of electrodes) and reaction conditions (such as gas conditions) used in an actual thin film forming apparatus. Refers to the lowest possible electric field strength. The discharge starting electric field intensity varies depending on the kind of gas supplied to the discharge space, the dielectric material of the electrode, the distance between the electrodes, and the like. In the same discharge space, the discharge starting electric field intensity is dominated by the discharge starting electric field intensity of the discharge gas.

 [0023] When the high-frequency electric field as described above is applied to the opposing electrodes, that is, applied to the same discharge space, a discharge capable of forming a thin film is generated, and a thin film of high quality and uniform thickness is formed. Generates high-density plasma required for

 [0024] The force described for the superposition of the continuous wave such as the sine wave is not limited to this. If both the first high-frequency electric field V and the second high-frequency electric field V are pulse waves,

 1 2

 Either the high-frequency electric field V or the second high-frequency electric field V is a continuous wave and the other

 1 2

 The high frequency electric field may be a pulse wave. Further, it may have a third electric field.

As a specific apparatus for applying the high-frequency electric field of the present invention to the same discharge space, a first high-frequency electric field having a frequency f and an electric field strength V is applied to a first electrode constituting a counter electrode. Connect the first power supply to be applied, and connect the second electrode to the second electrode with frequency f and electric field strength V

 twenty two

The use of an atmospheric pressure plasma discharge treatment device connected to a second power supply for applying a high-frequency electric field (see Fig. 1 (b)). [0026] The above-mentioned atmospheric pressure plasma discharge treatment apparatus includes a gas supply means for supplying a discharge gas and a thin film forming gas between opposed electrodes. Further, it is preferable to have an electrode temperature control means.

 Further, the first power supply of the atmospheric pressure plasma discharge treatment apparatus according to the present invention is higher than the second power supply.

V, preferably having the ability to apply high frequency electric field strength.

Applying the high-frequency electric fields V and V from such two power supplies is equivalent to the first high-frequency electric field V

 1 2

 Is required to start the discharge of a discharge gas having a discharge starting electric field strength, and the plasma density is increased by the high frequency and high power density of the second high-frequency electric field V.

 2

 Necessary for forming a dense, high-quality thin film.

Further, by increasing the output density of the first high-frequency electric field V, the output density of the second high-frequency electric field V can be improved while maintaining the uniformity of the discharge. With this,

 2

 Uniform high-density plasma can be generated, and further improvement in film forming speed and film quality can be achieved.

 FIGS. 2 (a) and 2 (b) are longitudinal sectional views showing an example of an atmospheric pressure plasma discharge treatment apparatus of a type for treating a substrate between a plurality of counter electrodes useful in the present invention. In the atmospheric pressure plasma discharge treatment apparatus in which the substrate is treated between a plurality of counter electrodes, the number is preferably 10 or less, more preferably 2 to 5.

 As shown in FIG. 2 (b), the atmospheric pressure plasma processing apparatus 2a according to the present invention includes a plurality of second power supplies HF1 to HF3 as second power supplies, dielectrics 121a to 121c, and a metal base material 122a. , And a matching device 11a-: Lie connected between the second power supply and the electrode for matching impedance with the electrodes arranged in close proximity to each other, and a first power supply as the first power supply. (1) a power source LF, a dielectric material 131, a metal base material 132, which are arranged opposite to the electrodes so as to form a discharge space, and constitute a roll-type electrode capable of transporting a film-shaped substrate by rotating. LF matching device 15 connected between first power supply and electrode 13 to boost the voltage, film-like base material 14 placed on top of roll-type electrode and subjected to plasma treatment, and discharge space A gas supply device 16 for supplying a mixed gas of a rare gas and a thin film to the gas.

[0032] The matching devices l la to l lc (see Fig. 3) were connected to the variable capacitor 21 for absolute value adjustment and the variable capacitor 22 for phase adjustment to maximize the power output from the power supply through preliminary experiments. Is set in advance so as to be sent. Then, during operation of the apparatus, the absolute value adjusting variable capacitor 21 and the phase adjusting variable capacitor 22 are automatically adjusted by the control box 24 in any one of the matching devices l la to l lc. In other matching devices, only the absolute value adjusting variable capacitor 21 is fixed, and the phase adjusting variable capacitor 22 is automatically adjusted by the control box 24.

[0033] Thereby, due to the influence of the electrodes arranged close to each other, the automatic adjustment cannot be performed, and the unstable state does not continue. In addition, a single matching device automatically adjusts the absolute value of the impedance, which makes it possible to cope with fluctuations in the plasma state due to fluctuations in the gas inflow, etc., and stabilizes the formation of multiple thin films simultaneously. You can do it.

 [0034] In addition, by using a roll-type electrode, a plasma treatment can be continuously performed on a film-shaped substrate.

 Further, the atmospheric pressure plasma processing apparatus 2 shown in FIG. 2 (a) is configured by connecting a plate electrode 13 to a first power supply LF which is a first power supply of the atmospheric pressure plasma processing apparatus 2a, This is a device that performs plasma processing on 14.

 [0036] Thereby, a plurality of thin films can be simultaneously and stably formed on a hard base material by plasma treatment.

The first power supply (high-frequency power supply) installed in the atmospheric pressure / atmospheric pressure plasma discharge treatment apparatus of the present invention includes:

 Applied power supply symbol Manufacturer Frequency Product name

 A1 Shinko Electric 3kHz SPG3 -4500

 A2 Shinko Electric 5kHz SPG5 -4500

 A3 Kasuga Electric 15kHz AGI-023

 A4 Shinko Electric 50kHz SPG50-4500

 A5 Heiden Laboratory 100kHz * PHF— 6k

 A6 Pearl Industry 200kHz CF-2000-200k

A7 Pearl Industry 400kHz CF-2000-400k and other commercially available products can be used, and any of them can be used. [0038] As the second power supply (high-frequency power supply),

 Applied power supply symbol Manufacturer Frequency Product name

 B1 Knoll Industrial 800kHz CF-2000 -800k

 B2 Pearl Industrial 2MHz CF-2000-2M

 B3 Knole 13.56MHz CF—5000—13M

 B4 Knoll Industrial 27MHz CF-2000- 27M

 Commercially available products such as B5 Pearl Industry 150MHz CF-2000-150M can be mentioned, and any of them can be preferably used. Note that, among the above power supplies, the asterisk (*) is the high-frequency power supply from Hyden Laboratory, Inc. (100 kHz in continuous mode). Others are high-frequency power supplies that can apply only continuous sine waves.

[0039] In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field to an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, of the electric power applied between the opposing electrodes, the first electrode (first high-frequency electric field) supplies an electric power (output density) of 1 WZcm ² or more to excite the discharge gas. Energy to the thin film forming gas to form a thin film.

[0041] The upper limit value of the power supplied to the first electrode is preferably 50 WZcm ² , more preferably 20 WZcm ² . The lower limit is preferably 1.2 W / cm ² . Note that the discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (output density) of 1 WZcm ² or more also to the second electrode (second high-frequency electric field), the output density can be further improved. As a result, uniform and high-density plasma can be generated, and further improvement in film forming speed and improvement in film quality can be achieved. The power of the second high-frequency electric field is preferably 5 WZcm ² or more. The upper limit is 50 WZcm ² .

 Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called continuous mode, and an intermittent oscillation mode called pulse mode in which ONZOFF is performed intermittently.Either of these may be adopted, but at least the second electrode side (the second high frequency For the electric field, a continuous sine wave is preferable because a denser and higher quality film can be obtained.

[0044] The electrodes used in such a thin film formation method using atmospheric pressure plasma have a high performance even in terms of structure. It must be able to withstand severe conditions. Such an electrode is preferably a metal base material coated with a dielectric.

[0045] The dielectric coated electrode used in the present invention! One of the characteristics that preferably has characteristics between various metallic base materials and dielectrics is one of the characteristics. The difference in the linear thermal expansion coefficient between the metallic base material and the dielectric is 10 × 10 — Combination of less than ⁶ Z ° C. Preferably below 8 X 10- ⁶ Z ° C, even more preferably not more than 5 X 10- ⁶ Z ° C, more preferably 2 X 10- ⁶ Z ° C hereinafter. The linear thermal expansion coefficient is a physical property value of a known material.

 [0046] The combination of a conductive metallic base material and a dielectric material having a difference in linear thermal expansion coefficient within this range is as follows: 1: The metallic base material is pure titanium or a titanium alloy, and the dielectric material is a ceramic. Sprayed coating 2: Metallic base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metallic base material is stainless steel, dielectric is ceramic sprayed coating 4: Metallic base material is stainless steel, Dielectric material is glass lining 5: Metallic base material is ceramic and iron composite material, dielectric material is ceramic sprayed coating 6: Metallic base material is ceramic and iron composite material, dielectric material is glass lining 7: Metallic The base material is a composite material of ceramics and aluminum, and the dielectric is a ceramic sprayed coating. 8: The metal base material is a composite material of ceramics and aluminum, and the dielectric is glass lining. . From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are particularly preferable, and 1 is particularly preferable.

 [0047] In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or titanium alloy as the metallic base material and using the dielectric material as described above, it is possible to use the electrode for a long time under severe conditions where deterioration of the electrode during use, especially cracks, peeling, and falling off, etc. will not occur. Can withstand.

[0048] The metallic base material of the electrode useful in the present invention is titanium alloy or titanium metal containing 70% by mass or more of titanium. In the present invention, if the content of titanium in the titanium alloy or the titanium metal is 70% by mass or more, it can be used without any problem. /, Prefer things. As titanium alloys or titanium metals useful in the present invention, those generally used as industrial pure titanium, corrosion-resistant titanium, high-strength titanium and the like can be used. Examples of industrial pure titanium include TIA, TIB, TIC, and TID, all of which have very few iron, carbon, nitrogen, oxygen, and hydrogen atoms. The titanium content is 99% by mass or more. T15PB can be preferably used as the corrosion resistance titanium alloy, which contains lead in addition to the above-mentioned contained atoms, and has a titanium content of 98% by mass or more. As the titanium alloy, in addition to the above-mentioned atoms except for lead, T64, Τ325, Τ525, ΤΑ3 and the like containing aluminum and also containing vanadium and tin can be preferably used. The content is 85% by mass or more. These titanium alloys or titanium metals are made of a stainless steel, for example, having a coefficient of thermal expansion smaller than that of AISI316 by about 1/2, as a metallic base material, and a later-described dielectric applied on the titanium alloy or titanium metal. The combination can withstand high temperature and long time use.

 [0049] On the other hand, as the properties required of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferably used. And glass lining materials such as silicate glass and borate glass. Among them, those formed by spraying ceramics described later and those provided by glass lining are preferred. In particular, a dielectric provided by spraying alumina is preferable.

 [0050] Alternatively, as one of specifications capable of withstanding high power as described above, the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, and more preferably more than 0% by volume. Less than 5% by volume. The porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment coated on a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved by the dielectric having a low porosity. As a dielectric material having such voids but having a low porosity, there can be mentioned a ceramic sprayed film having a high density and a high adhesion by an atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform a sealing treatment.

The above-mentioned atmospheric plasma spraying method is a technique in which fine powders such as ceramics, wires and the like are charged into a plasma heat source and sprayed as molten or semi-molten fine particles onto a metal base material to be coated to form a film. It is. The plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further applied with energy to emit electrons. The spray speed of this plasma gas is higher than that of conventional arc spraying or flame spraying. Since the material collides with the metal base material at a high speed, a high-density coating film having high adhesion strength can be obtained. For details, reference can be made to the thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A-2000-301655. According to this method, the porosity of the dielectric body (ceramic sprayed film) to be coated as described above can be obtained.

[0052] Another preferable specification that can withstand high power is that the thickness of the dielectric is 0.5 to 2 mm. This variation in film thickness is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

[0053] In order to further reduce the porosity of the dielectric, a sprayed film of ceramics or the like is used as described above.

Further, it is preferable to perform a sealing treatment with an inorganic compound. Among the inorganic compounds, metal oxides are preferred, and those containing silicon oxide (SiO 2) as a main component are particularly preferable.

 [0054] The inorganic compound for the pore-sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for the sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

 Here, to promote the sol-gel reaction, it is preferable to use energy treatment. Examples of the energy treatment include thermal curing (preferably at 200 ° C. or lower) and ultraviolet irradiation. Further, as a sealing treatment method, when the sealing liquid is diluted, and coating and curing are repeated several times sequentially, the inorganic material can be further improved, and a dense electrode without deterioration can be obtained.

 [0056] When a ceramic sprayed film is coated with a metal alkoxide or the like of the dielectric-coated electrode according to the present invention as a sealing liquid and then subjected to a sealing treatment in which it is cured by a sol-gel reaction, the cured metal oxide is used. The content of the substance is preferably 60 mol% or more. When alkoxysilane is used as the metal alkoxide of the sealing solution, the content of SiO (X is 2 or less) after curing is preferably 60 mol% or more. The SiO content after curing is measured by analyzing the tomography of the dielectric layer by XPS (X-ray photoelectron spectroscopy).

In the electrode according to the thin film forming apparatus of the present invention, the maximum height (R) of the surface roughness defined by JIS B 0601 on at least the side of the electrode which is in contact with the substrate is set to be 10 m or less. Adjustment is preferable from the viewpoint of obtaining the effects described in the present invention, but more preferably, the maximum value of the surface roughness is 8 m or less, particularly preferably 7 m or less. In this way, the thickness of the dielectric and the gap between the electrodes can be kept constant, the discharge state can be stabilized, and the heat shrinkage can be achieved by polishing the dielectric surface of the dielectric coated electrode. Distortion and cracks due to differences and residual stress can be eliminated, and high accuracy and durability can be greatly improved. Polishing of the dielectric surface is preferably performed on at least the dielectric in contact with the substrate. Further, the center line average surface roughness (Ra) specified in JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 m or less.

 [0058] Another preferable specification of the dielectric-coated electrode used in the present invention that withstands large power is that the heat-resistant temperature is 100 ° C or higher. It is more preferably at least 120 ° C, particularly preferably at least 150 ° C. The upper limit is 500 ° C. Note that the heat-resistant temperature refers to the highest temperature that can withstand a state in which dielectric breakdown does not occur and a normal discharge can be performed with respect to a voltage used in atmospheric pressure plasma processing. Such a heat-resistant temperature is determined by applying the above-described ceramic spraying or a dielectric provided with a layered glass lining having a different amount of bubbles mixed therein, or a range of a difference in linear thermal expansion coefficient between the metallic base material and the dielectric. It can be achieved by appropriately combining the means for appropriately selecting the materials within.

 Next, the gas supplied to the discharge space will be described.

 The supplied gas contains at least a discharge gas and a thin film forming gas. The discharge gas and the thin film forming gas may be supplied as a mixture, or may be supplied separately.

 [0061] The discharge gas is a gas that can generate plasma capable of forming a thin film. Examples of the discharge gas include nitrogen, a rare gas, air, hydrogen gas, and oxygen, and these may be used alone as a discharge gas or may be used as a mixture. In the present invention, nitrogen is preferable as the discharge gas. 50 to 50% of discharge gas: It is preferable that LOO volume% is nitrogen gas. At this time, the discharge gas other than nitrogen preferably contains a rare gas in an amount of less than 50% by volume. The amount of the discharge gas is preferably 90 to 99.9% by volume based on the total amount of gas supplied to the discharge space.

[0062] The thin film forming gas itself is activated by dissociation or excitation and becomes chemically active on the substrate. It is a raw material that is deposited on to form a thin film.

 Next, a gas supplied to a discharge space for forming a thin film used in the present invention will be described. Basically, a discharge gas and a thin film forming gas. Further, an additive gas may be added. The discharge gas preferably contains 90 to 99.9% by volume of the total gas supplied to the discharge space.

 [0064] The thin film forming gas used in the present invention includes an organometallic compound and a halogen metal compound.

And a metal hydride compound.

[0065] Organometallic compounds useful in the present invention are preferably those represented by the following general formula (I).

[0066] R MR R General formula (I)

 lx 2y 3z

 In the formula, M is a metal, R is an alkyl group, R is an alkoxy group, R is a j8-diketone complex group,

 one two Three

 a group selected from a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketoxoxy group (ketoxoxy complex group), where x + y + z = m, where 0 to m, or x = 0 to m-1, y = 0 to m, z = 0 to m, each of which is 0 or a positive integer. Examples of the alkyl group for R include a methyl group, an ethyl group, a propyl group, and a

 1

 And the like. As the alkoxy group for R, for example, methoxy group, ethoxy

 2

 Group, propoxy group, butoxy group, 3,3,3-trifluoropropoxy group and the like. Further, a hydrogen atom of an alkyl group may be substituted with a fluorine atom. R of β—

3 As a group selected from a diketone complex group, a β-ketocarboxylic ester complex group, a β-ketocarboxylic acid complex group and a ketoxoxy group (ketoxoxy complex group), a β-diketone complex group such as 2,4 pentanedione Cetylacetone or acetacetone), 1,1,1,5,5,5hexamethyl- 2,4 pentanedione, 2,2,6,6-tetramethylenole 3,5 heptanedione, 1,1,1- Examples of j8-ketocarboxylic acid ester complex groups include, for example, methyl acetate acetate, ethyl acetate acetate, propyl acetate acetate, propyl acetate acetate, ethyl trifluoroacetate, and trifluoroacetate. Examples of methyl 13-ketocarboxylic acids include acetoacetic acid and trimethylacetovinegar. As can be exemplified, and also Ketokishi, for example, Asetokishi group (or Asetokishi group), propionic - Ruokishi group, Buchiriro alkoxy group, Atari Roy Ruo alkoxy group and a methacryloyloxy Ruo alkoxy group. these The number of carbon atoms of the above group is preferably 18 or less, including the organometallic compounds described in the above examples. In addition, as shown in the examples, it may be a straight-chain or branched one or a hydrogen atom substituted with a fluorine atom.

 [0067] From the viewpoint of handling in the present invention, organometallic compounds having at least one or more oxygen atoms in the molecule, which are preferred for safe organometallic compounds, are preferred. Such compounds include organometallic compounds containing at least one alkoxy group of R,

 23 A metal compound having at least one group selected from a ketone complex group, a β-ketocarboxylic ester complex group, a β-ketocarboxylic acid complex group, and a ketoxoxy group (ketoxoxy complex group) is preferable.

 [0068] Specific organometallic compounds will be described later.

 [0069] In the present invention, the gas supplied to the discharge space may be mixed with an additive gas that promotes a reaction of forming a thin film, in addition to a discharge gas and a thin film-forming gas. Examples of the additive gas include oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and ammonia. Among them, components selected from oxygen, carbon monoxide and hydrogen are preferred. Mixing is preferred. The content is preferably 0.01 to 5% by volume with respect to the total amount of the gas, whereby the reaction is promoted, and a dense and high-quality thin film can be formed.

 [0070] The thickness of the formed oxide or composite compound thin film is preferably in the range of 0.1 to: LOOO nm.

 In the present invention, as the metal of the organometallic compound, the metal halide, and the metal hydride used in the thin film forming gas, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti , V, Cr, Mn, Fe ゝ Co, Ni ゝ Cu, Zn, Ga ゝ Ge ゝ Rb ゝ Sr ゝ Y, Zr ゝ Nb ゝ Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Examples include Hf, Ta, W, Tl, Pb, Bi 、 Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like.

The thin film forming apparatus of the present invention can obtain various highly functional thin films by using a metal compound such as an organometallic compound, a halogen metal compound, or a metal hydride compound together with a discharge gas. . Examples of the thin film of the present invention are shown below, but the present invention is not limited thereto. [0073] Electrode film Au, Al, Ag, Ti, Ti, Pt, Mo, Mo—Si

 Dielectric protective film SiO, SiO, Si N, Al O, Al O, Y O

 2 3 4 2 3 2 3 2 3

 Transparent conductive film In O, SnO

 2 3 2

 Elect mouth chromic film WO, IrO, MoO, V O

 3 2 3 2 5

 Phosphor film ZnS, ZnS + ZnSe, ZnS + CdS

 Magnetic recording film Fe—Ni, Fe—Si—Al, y—FeO, Co, FeO, Cr, SiO, AIO

 2 3 3 4 2 3 Superconductive film Nb, Nb—Ge, NbN

 Solar cell membrane a—Si, Si

 Reflective film Ag, Al, Au, Cu

 Selective absorption membrane ZrC— Zr

 Selective permeable membrane In O, SnO

 2 3 2

 Anti-reflective coating SiO, TiO, SnO

 2 2 2

 Shadow Mask Cr

 Abrasive film Cr ゝ Ta ゝ Pt ゝ TiC ゝ TiN

 Alkaline film Al, Zn, Cd ゝ Ta ゝ Ti, Cr

 Heat resistant film W, Ta, Ti

 Lubrication film MoS

 2

 Decorative film Cr, Al, Ag, Au, TiC, Cu

 The nitriding degree of the nitride, the oxidation degree of the oxide, the sulfide degree of the sulfide, and the carbonization degree of the carbide are merely examples, and the composition ratio with the metal may be changed as appropriate. In addition, the thin film may contain impurities such as a carbon compound, a nitrogen compound, and a hydrogen compound in addition to the metal compound.

[0074] In the present invention, particularly preferred metals of the metal compound are Si (silicon), Ti (titanium), Sn (tin), Zn (zinc), In (indium) and A1 (aluminum). Of these metal compounds that bind to metals, the organometallic compounds represented by the above general formula (I) are preferable.

 [0075] Examples of the organometallic compound will be described later.

Here, the antireflection film (layer) and the antireflection film in which the antireflection film is laminated, and the transparent conductive film among the high-performance films will be described in detail. [0077] The antireflection layer of the antireflection film among the high-performance films according to the present invention is formed by laminating a thin film of a medium refractive index layer, a high refractive index layer, and a low refractive index layer.

 In the gas material for forming an anti-reflection layer thin film according to the present invention, a titanium compound forming a high refractive index layer, a tin compound forming a middle refractive index layer, and a silicon compound forming a low refractive index layer will be described. . An antireflection film having an antireflection layer is obtained by laminating each refractive index layer directly or via another layer on a substrate. In order to stack the three layers of the discharge treatment device in the order of medium refractive index layer, high refractive index layer, and low refractive index layer, three units can be arranged in series and processed continuously. It is suitable for forming the thin film of the present invention. Instead of laminating, winding may be performed after each layer processing, and the layers may be sequentially processed and laminated. In the present invention, in the case where an antifouling layer is provided on the antireflection layer, another one of the above-mentioned atmospheric pressure plasma discharge treatment apparatuses may be continuously installed, and four antifouling layers may be arranged and the antifouling layer is finally laminated. Good. Before providing the anti-reflection layer, a hard coat layer or an anti-glare layer may be provided in advance by coating on the base material, or a knock coat layer may be provided in advance by coating on the back side.

 The gas for forming an antireflection layer thin film of the antireflection film according to the present invention can be used without limitation as long as it is a compound capable of obtaining an appropriate refractive index. Titanium conjugate as a reactive gas, and a mixture of a tin compound or a titanium compound and a silicon compound (or a layer formed of a titanium compound for forming a high refractive index and a low refractive index layer as a medium refractive index layer thin film forming gas). The low refractive index layer thin film forming gas may preferably be a silicon compound, a fluorine compound, or a mixture of a silicon compound and a fluorine compound. . In order to adjust the refractive index, two or more of these compounds may be used as a thin film forming gas for forming any of the layers.

[0080] The tin compound used in the gas for forming a medium refractive index layer thin film useful in the present invention is an organic tin compound, a tin hydride compound, a halogenated tin, and the like. Tin, butyltin tris (2,4-pentanedionate), tetraethoxytin, methyltriethoxytin, getyl ethoxytin, triisopropylethoxytin, ethylethyl Xin tin, methinolemethoxy tin, isopropinole isopropoxy tin, tetrabutoxy tin, jetoxy tin, dimethoxy tin, diisopropoxy tin, dibutoxy tin, dibutylyloxy tin, getyl tin, tetrabutyl tin, tin bis (2,4-pentanedionate ), Ethyl ethyl acetate acetate, ethoxy tin (2,4-pentanedionate), dimethyltin di (2,4-pentanedionate), diacetomethinorea acetate tin, diacetoxy tin, dibutoxy dia Examples of halogenated tins such as cetoxytin and diacetoxytin diacetoacetonate include tin dichloride and tin tetrachloride, all of which can be preferably used in the present invention. Further, two or more of these thin film forming gases may be mixed and used at the same time. In this way, Sani匕錫layer formed in order to be able to lower the surface specific resistance value 10 ^u Q Zcm ² or less, are also useful as anti-static layer.

[0081] Examples of the titanium conjugate used in the high refractive index layer thin film forming gas useful in the present invention include an organic titanium conjugate, a titanium hydrogen compound, a halogen titanium, and the like. For example, triethoxytitanium, trimethoxytitanium, triisopropoxytitanium, tributoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, methyldimethoxytitanium, ethyltriethoxytitanium, methyltriisopropoxytitanium, triethyltitanium, triisopropyltitanium , Tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, tetradimethylamino titanium, dimethyl titanium di (2,4-pentanedionate), ethyl titanium tri (2,4-pentanedionate), titanium tris (2,4 -pen Dionylonate), titanium tris (acetomethyl acetate), triacetoxytitanium, dipropoxypropionyloxytitanium, etc., dibutylyloxytitanium, titanium hydrogen compounds such as monotitanium hydrogen compounds, dititanium hydrogen compounds, etc. Examples thereof include titanium trichloride and titanium titanium tetrachloride, all of which can be preferably used in the present invention. In addition, two or more of these thin-film forming gases can be mixed and used at the same time.

Examples of the silicon compound used in the low-refractive index layer thin film forming gas useful in the present invention include an organic silicon compound, a silicon hydride compound, a halogenated silicon compound, and the like. For example, tetraethylsilane, tetramethylsilane, tetraisobutyl silane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, Examples of silicon hydrogen compounds such as tetrabutoxy silane, dimethinoresimethoxy silane, ethynole ethoxy silane, ethynole silane di (2,4-pentanedionate), methyl trimethoxy silane, methyl triethoxy silane, and ethyl triethoxy silane Examples of the halogenated silicon compound such as tetrahydrosilane, hexahydrogendisilane and the like include tetrachlorosilane, methyltrichlorosilane and getyldichlorosilane, all of which can be preferably used in the present invention. . Further, the above-mentioned fluorine compounds can be used. Two or more of these thin film forming gases can be mixed and used at the same time. For fine adjustment of the refractive index, two or more of these tin compounds, titanium compounds and silicon compounds may be appropriately mixed and used at the same time.

 [0083] The above-mentioned organotin compound, organotitanium compound or organosilicon compound is preferably a metal hydrogen compound or an alkoxy metal from the viewpoint of handling. Alkoxy metals are preferably used because they are small. In order to introduce the above-mentioned organotin compound, organotitanium compound or organosilicon compound between electrodes which are discharge spaces, both may be in a gas, liquid or solid state at normal temperature and normal pressure. I do not care. In the case of gas, it can be directly introduced into the discharge space, but in the case of liquid or solid, it is used after being vaporized by heating, decompression, ultrasonic irradiation or the like. When an organotin compound, an organic titanium compound, or an organosilicon compound is used after being vaporized by heating, a metal alkoxide such as tetraethoxy metal or tetraisopropoxy metal which is liquid at ordinary temperature and has a boiling point of 200 ° C or less is used. It is suitably used for forming an anti-reflection film. The alkoxy metal may be used after being diluted with a solvent. In this case, the alkoxy metal may be vaporized into a rare gas by a vaporizer or the like and used as a mixed gas. As the solvent, organic solvents such as methanol, ethanol, isopropanol, butanol, n-xane and the like and a mixed solvent thereof can be used.

[0084] From the viewpoint of forming a uniform thin film on the base material by the discharge plasma treatment using the thin film forming gas, the content in the total gas is preferably 0.0110% by volume. , the more preferred are 0.01 1 volume ^_0/0.

The medium refractive index layer can be obtained by appropriately mixing the silicon compound, the titanium compound or the tin compound according to the target refractive index. Can be. [0086] The preferable refractive index and film thickness of each refractive index layer are, for example, 1.6 to 1.8 as a refractive index and about 50 to 70 nm as a film thickness for a tin oxide layer as a medium refractive index layer. The high refractive index titanium oxide layer has a refractive index of 1.9 to 2.4, the film thickness is about 80 to 150 nm, and the low refractive index silicon oxide layer has a refractive index of 1.3 to 1.5. The thickness is about 80 to 120 nm.

 Next, the formation of a thin film having a transparent conductive film as another example of the high-performance film according to the present invention will be described.

 [0088] The metal component of the organometallic compound used for forming the anti-reflection layer described above slightly differs in that it forms a thin film having transparency and conductivity such as indium. Almost the same components are used.

 [0089] Preferably, the metal of the organometallic compound for forming the transparent conductive film is at least one metal selected from indium (In), zinc (Zn) and tin (Sn) forces.

 [0090] In the present invention, preferred examples of the preferred organometallic compound include indium tris (2,4 pentanedionate), indium tris (hexafluoropentanedionate), indium triacetate acetate, and triacetate. Xindium, jetethoxyacetoxyindium, triisopolopoxyindium, diethoxyindium (1,1,1-trifluoropentanedionate), tris (2,2,6,6-tetramethyl-3,5 heptane Dionate) indium, ethoxyindium bis (acetomethyl acetate), di (n) butyltin bis (2,4 pentane dionate), di (n) butyldiacetoxytin, di (t) butino Examples include resiacetoxytin, tetraisopropoxytin, tetra (i) butoxytin, and bis (2,4 pentanedionate) zinc. These organometallic compounds are generally commercially available (for example, from Tokyo Chemical Industry Co., Ltd.).

[0091] In the present invention, in addition to the above-mentioned organometallic compound having at least one oxygen atom in the molecule, the transparent conductive film is formed in order to further enhance the conductivity of the transparent conductive film formed from the organometallic compound. It is preferable that the organic metal compound as a thin film-forming gas, which is preferable to dope a film, and an organic metal compound gas for doping be mixed and used at the same time. Examples of the gas for forming a thin film of an organometallic compound or a fluorine compound used for doping include triisopropoxyaluminum and tris (2,4 pentanedionate). ) Nickel, bis (2,4 pentanedionate) manganese, isopropoxyboron, tri (n) butoxyantimony, tri (n) butylantimony, di (n) butylbis (2,4 pentanedionate) tin, di (n) Butyldiacetoxytin, di (t) butinoresiacetoxytin, tetraisopropoxytin, tetrabutoxytin, tetrabutyltin, di (2,4 pentanedionate), propylene hexafluoride, octafluoride Examples thereof include cyclobutane and methane tetrafluoride.

[0092] The ratio of the organometallic compound necessary for forming the transparent conductive film to the gas for forming a thin film for doping varies depending on the type of the transparent conductive film to be formed. For example, tin is used for indium oxide. In the ITO film obtained by doping, it is necessary to adjust the amount of the thin film-forming gas so that the atomic ratio of the ratio of In to Sn is in the range of 100: 0.1 to: LOO: 15. You. It is preferable to adjust the ratio to 100: 0.5 to: L00: 10. In a transparent conductive film (called an FTO film) obtained by doping fluorine to tin oxide, the atomic ratio of the ratio of Sn to F in the obtained FTO film is 100: 0.01 to: L00: 50. It is preferable to adjust the quantity ratio of the thin film-forming gas so as to fall within the range. In O ZnO-based amorphous transparent conductive film

 twenty three

 Therefore, it is preferable to adjust the amount ratio of the thin film forming gas so that the atomic ratio of the ratio of In to Zn is in the range of 100: 50 to L00: 5. In: Sn ratio, 311: ratio and 111: 211 ratio

It can be determined by XPS measurement.

[0093] In the present invention, the transparent conductive thin film forming gas is used in an amount of 0.01 to 10 volumes with respect to the mixed gas.

% Is preferable.

[0094] In the present invention, the obtained transparent conductive film is, for example, an oxide of SnO, InO, ZnO.

 2 2 3

 Film or Sb-doped SnO, F-doped SnO (FTO), A1-doped ZnO, Sn-doped In O (IT

 2 2 2 3

O) Complex oxides doped with dopants such as O) can be mentioned, and an amorphous film mainly containing at least one of these forces is preferable. In addition, non-oxide films such as chalcogenide, LaB, TiN, and TiC, metal films such as Pt, Au, Ag, Cu, and CdO

 6

 A transparent conductive film can be given.

 The thickness of the formed oxide or composite oxide transparent conductive film is preferably in the range of 0.1 to: LOOO nm.

[0096] The substrate used in the present invention will be described.

[0097] The substrate used in the present invention may have a plate-like, sheet-like, or film-like planar shape. There is no particular limitation as long as a thin film such as a three-dimensional one such as a lens or a molded article such as a lens can be formed on its surface. There is no limitation on the form or material of the substrate as long as the substrate is exposed to the mixed gas in a plasma state in a stationary state or a transported state and a uniform thin film is formed. As the morphology, a planar shape or a three-dimensional shape may be a glass plate, a resin film, or the like. Various materials such as glass, resin, pottery, metal, and nonmetal can be used. Specifically, glass includes a glass plate and a lens, and resin includes a resin lens, a resin film, a resin sheet, and a resin plate.

 [0098] Since the resin film can be continuously transferred between the electrodes or in the vicinity of the electrodes of the atmospheric pressure plasma discharge treatment apparatus according to the present invention to form a transparent conductive film, the resin film can be used in a vacuum system such as sputtering. It is suitable for mass production, which is not a batch type, and is suitable as a production system with continuous high productivity.

 [0099] The material of the molded product such as a resin film, a resin sheet, a resin lens, and a resin molded product is, for example, cellulose paste acetonate, cellulose paste diacetate, cellulose acetate butyl acetate, or cellulose acetate butyrate. Such as cellulose esters, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl alcohol copolymer, and syndiotactic polystyrene. , Polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone, polysulfone, polyetherimide, polyamide, fluorine resin, polymethyl Ruatalylate, atarilate copolymer and the like can be mentioned.

[0100] These materials can be used alone or in an appropriate mixture. Among them, ZEONEX ZENOA (manufactured by ZEON Corporation) and amorphous cyclopolyolefin resin film

It is preferable to use commercially available products such as ARTON (manufactured by JSR Corporation), Pure Ace of polycarbonate film (manufactured by Teijin Limited), and Co-Katak KC4UX and KC8UX of cellulose triacetate film (manufactured by Ko-Riki Co., Ltd.). Can be. Furthermore, even for materials having a large intrinsic birefringence such as polycarbonate, polyacrylate, polysulfone, and polyethersulfone, conditions such as solution casting film formation and melt extrusion film formation, as well as in the vertical and horizontal directions. What can be used can be obtained by appropriately setting the stretching conditions and the like.

 [0101] Among these, a cellulose ester film that is nearly optically isotropic is preferably used for the optical element of the present invention. As the cellulose ester film, as described above, cellulose triacetate film and cellulose acetate propionate are one of those preferably used. As the cellulose triacetate film, commercially available Co-Katak KC4 UX and the like are useful.

 [0102] The surface of these resins coated with gelatin, polybutyl alcohol, acrylic resin, polyester resin, cellulose ester resin or the like can also be used. An antiglare layer, a clear hard coat layer, a barrier layer, an antifouling layer and the like may be provided on the thin film side of these resin films. Further, an adhesive layer, an alkali barrier coat layer, a gas barrier layer, a solvent-resistant layer, and the like may be provided as necessary.

 [0103] The substrate used in the present invention is not limited to the above description. The film thickness of the film is preferably 10 to: LOOO μm, more preferably 40 to 200 μm. Example

 [0104] The present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.

 [0105] The present example is an experiment of plasma treatment of a film by a roll rotating electrode and a plurality of electrodes placed opposite to the roll rotating electrode (see FIG. 2 (b)).

[0106] With the configuration shown in Fig. 2 (a), the same experiment was performed on a flat base material, and similar results were obtained. This example shows that a continuous verification experiment could be performed.

[0107] In this example, stainless steel SUS316 was used as the electrode base material, and the dielectric material was sprayed with a single layer of alumina ceramic on the discharge surface of the electrode facing the electrode, and then the alkoxysilane monomer was applied. A coating solution dissolved in an organic solvent was applied to the ceramic coating, dried, and then heated at 150 ° C.

[0108] A film substrate was placed on the electrode system thus prepared, and a SiO film was formed.

 2

 went. In addition, it was assumed that the temperature of the electrode of the metal base material to be formed could be controlled by circulating warm water.

[0109] The mixed gas for forming the SiO film is as follows: Discharge gas: Nitrogen gas

 Reaction gas: oxygen gas (0.1 to 21% based on the volume of nitrogen gas)

 Film forming gas: tetraethoxysilane vapor

 Was used.

 [0110] In the apparatus having the same configuration as described above, the impedance absolute value and the phase adjustment of only one matching device are automatically variable, and the other matching devices have the fixed impedance absolute value and only the phase is adjusted (this application). An experiment in which the absolute value of the impedance and the phase adjustment were automatically varied for all matching devices (Comparative 1), and an experiment in which the absolute value of the impedance was fixed for all the matching devices and only the phase adjustment was automatically varied. (Comparison 2) was performed, and the results shown in Table 1 were obtained.

 [0111] The setting outputs of HF1 to HF3 were set at 300, 1000, and 2000W. The reflection power was measured from the current and voltage between the power supply and the electrodes. The measured value and the maximum measured value are described.

[0112] [Table 1]

As shown in Table 1, in the experiment according to the present invention, the reflected power was The value of was small and the fluctuation was small. In addition, since uniform and stable discharge was performed in all the electrodes, a uniform, high-quality thin film could be formed on the base material.

 [0114] In Comparison 1, the range of fluctuation increased as the output became higher. In addition, the discharge situation is constantly changing, and there is very little force that can instantaneously match, for example, the state where all electrodes can be matched. For this reason, the thin film on the substrate was non-uniform.

 [0115] Comparative 2 has the same fluctuation range as Comparative 1, and the discharge state does not fluctuate frequently, but once matching cannot be achieved, it cannot be dealt with, and the state of mismatch continues. For this reason, although the thin film on the substrate is somewhat uniform, it has been difficult to form a film having a desired thickness.

 As described above, in the present embodiment, at least one matching device 11 is provided between the plurality of second power sources HF and the high-frequency electrodes 12 and matches the impedance during operation of the device. Automatically adjusts the absolute value of the impedance and the phase value, and the other matching device 11 fixes the absolute value of the impedance and automatically adjusts only the phase value.

 [0117] Therefore, it is possible to perform impedance matching that copes with impedance mismatch due to the interaction between adjacent electrodes and also to cope with fluctuations in the plasma state, and to form a thin film by more stable plasma processing. it can. Industrial applicability

According to the inventions described in the above configurations (1), (2), (3), and (6), in a thin film forming apparatus using atmospheric pressure plasma, uniformity and high accuracy do not cause a large deviation in matching. A good quality thin film can be formed. Further, even at the time of high output, the alignment does not largely deviate, so that a thin film can be formed quickly, and productivity can be improved. In addition, different electrodes can be precisely formed by a plurality of electrodes at once, and the number of production steps can be reduced.

 [0119] According to the invention described in the above (4), by arranging the apparatus in a plane, the plasma treatment can be performed even on a plane rigid base material.

[0120] According to the invention as set forth in the above (5), by using a roll-type electrode, a plasma treatment can be performed on a film-shaped substrate, and by rotating the roll-type electrode, Can be subjected to continuous plasma processing.

Claims

The scope of the claims

 [1] Between a plurality of electrode pairs for generating plasma at or near atmospheric pressure and an AC power supply for supplying AC power to the electrode pair, the output impedance of the AC power supply and the plurality of electrodes A plurality of impedance matching devices for matching with each input impedance of the pair are interposed, and based on the voltage between the AC power supply or the electrode pair and the current flowing between the AC power supply or the electrode pair, In the thin film forming apparatus provided with automatic adjustment means for automatically adjusting the plurality of impedance matching devices, the automatic adjustment means may include any one of the plurality of impedance matching devices. Other impedance matching devices except the matching device fix the variable capacitor for absolute value adjustment and automatically adjust the impedance only with the variable capacitor for phase adjustment. And said one of the impedance matching device, configured thin film-shaped formation device to automatically adjust the impedance by the absolute value adjusting variable capacitor and a phase adjusting variable capacitor scratch.

 [2] The thin film forming apparatus according to claim 1, wherein the impedance matching device has a variable capacitance capacitor for adjusting an absolute value of impedance, and the automatic adjusting means has a capacitance of the variable capacitance capacitor. To adjust the thin film forming equipment.

 [3] The thin film forming apparatus according to claim 1, wherein high-frequency AC power is supplied to one electrode of the electrode pair, and AC power supplied to the one electrode is supplied to the other electrode. Thin film forming apparatus to which AC power of a relatively low frequency is supplied.

 4. The thin film forming apparatus according to claim 1, wherein the plurality of pairs of electrodes are planar electrodes in which one electrode is integrally provided in a planar shape, and the other electrode is the one electrode. A thin film forming apparatus comprising a plurality of individual electrodes provided separately and opposed to each other.

 [5] In the thin film forming apparatus according to claim 1, the plurality of pairs of electrodes are roll-type electrodes in which one electrode is provided rotatably in a circumferential direction, and the other electrode is the one electrode. A thin film forming apparatus comprising a plurality of individual electrodes provided separately and separately from each other so as to face an outer peripheral surface of an electrode.

[6] The method for forming a thin film according to claim 1, wherein the plurality of impedances are Other impedance matching devices except for one of the impedance matching devices have a variable capacitor for absolute value adjustment fixed, the impedance is automatically adjusted only by the variable capacitor for phase adjustment, and the one impedance matching device is used. The matching device is a thin film forming method that automatically adjusts the impedance using a variable capacitor for absolute value adjustment and a variable capacitor for phase adjustment.