JP4747658B2 - Film forming apparatus and film forming method - Google Patents

Description

  The present invention relates to a plasma CVD film-forming apparatus (hereinafter referred to as a film-forming apparatus) and a plasma CVD film-forming method (hereinafter referred to as a film-forming method), and in particular, stabilizes a thin film uniformly on a substrate surface under reduced pressure. The present invention relates to a film forming apparatus and a film forming method.

  Conventionally, in order to form a thin film on a substrate by plasma CVD, a method using capacitively coupled plasma and inductively coupled plasma is known (Non-Patent Document 1).

Plasma Electronics Ohmsha, Hideo Sakurai, 1st edition, 1st edition, issued on August 25, 2000, page 106

  On page 106, line 8 of this document, it is described that capacitively coupled plasma can easily generate large-diameter plasma, which can be applied to substrates such as ceramics such as wafers and glass, resin plates, plastic films, metal plates, and metal foils. On the other hand, capacitively coupled plasma is widely used in the field of thin film formation.

  In this document, FIG. 6.3 and page 106, lines 13 to 14, when capacitively coupled plasma is used for thin film formation, two electrodes for plasma discharge are used. It arrange | positions on the sheet | seat of a sheet | seat, and film-forming is performed in this state.

  However, when a film is formed by such a method, there is a problem that, particularly by disposing a semiconductor or an insulating film-forming substrate on the electrode, it is difficult to flow plasma, that is, discharge impedance increases. there were. In this case, there is a problem that it is difficult to generate plasma discharge or the stability of plasma discharge is deteriorated.

  Further, when the discharge impedance increases, the discharge voltage increases and the discharge current decreases even when the same power is applied. As a result, film formation rate decreases (productivity decrease), film stress increases, damage to the substrate (electric charge-up occurs, poor adhesion due to strong etching of the substrate, substrate coloring occurs Etc.), and deterioration of film quality becomes a problem.

Furthermore, since the discharge impedance differs depending on the base material, there arises a problem that the film thickness and film quality of the formed film differ, and it is necessary to optimize the film forming conditions for each type of base material.
The above problem is that, for example, when an insulating film such as SiO ₂ or TiO ₂ is formed, the discharge impedance is further increased due to poor decomposability of the film forming material, and the film forming becomes unstable. There's a problem.
On the other hand, there may be a problem that the film forming impedance is small. When the discharge impedance is small, the discharge voltage is small, the discharge current is large, the effect of ion implantation into the substrate is small, and as a result, the adhesion of the film is insufficient, and film peeling may occur.

  The present invention has been made in view of the above problems, and an object thereof is to provide a film forming apparatus and a film forming method capable of stably forming a uniform and high-quality thin film on the surface of a substrate. It is in.

In order to achieve the above-described object, a first invention is a film forming apparatus for forming a thin film on a substrate under reduced pressure by a plasma CVD method, and a chamber and a gas supply unit for supplying a gas into the chamber A set of electrodes that are movably arranged on the same surface side of the base material in the chamber and are electrically placed at a floating level, an AC power source connected to the two electrodes, and the 2 Adjusting means for adjusting the distance between the two electrodes, and measuring means for measuring the plasma discharge impedance, the electrode is provided with an auxiliary wing formed of an insulating material on the surface, the adjusting means, The film forming apparatus is characterized in that the distance between the electrodes is adjusted so that the discharge impedance measured using the measuring means is constant.
A second invention is a film forming apparatus for forming a thin film on a base material under reduced pressure by a plasma CVD method, wherein the chamber, a gas supply unit for supplying gas into the chamber, A pair of electrodes that are movably arranged on the same surface side of the substrate and are electrically placed at a floating level, an AC power source connected to the two electrodes, and a distance between the two electrodes are adjusted. An adjustment unit; a measurement unit that measures plasma discharge impedance; a drum that is provided in the chamber and winds the base material; and a transport mechanism that transports the base material. A chamber and an exhaust chamber, wherein the electrode is provided in the exhaust chamber, and the adjusting means adjusts the distance between the electrodes so that the discharge impedance measured using the measuring means is constant. DOO is a film forming apparatus according to claim.
According to a third aspect of the present invention, there is provided a film forming apparatus for forming a thin film on a substrate under reduced pressure by a plasma CVD method, wherein the chamber, a gas supply unit for supplying a gas into the chamber, A pair of electrodes that are movably arranged on the same surface side of the substrate and are electrically placed at a floating level, an AC power source connected to the two electrodes, and a distance between the two electrodes are adjusted. An adjustment unit; a measurement unit that measures plasma discharge impedance; a drum that is provided in the chamber and winds the base material; and a transport mechanism that transports the base material. A substrate charging chamber is provided in the substrate transport chamber upstream of the film forming chamber, and the adjusting means measures the discharge impedance measured using the measuring means. Is constant A film forming apparatus characterized by intoxicated adjusting the distance between the electrodes.

  Here, the electrical floating level refers to the state in which the electrodes are designed and installed using insulating parts and insulating coatings so that insulation is maintained from chambers and film deposition equipment parts installed at the ground level. Means. Despite being designed so that the insulation of the electrode is ensured, the refrigerant required for cooling the electrode is used, and this refrigerant and the piping for circulating supply of the refrigerant have some conductivity The case where a resistance of 10 kΩ to 1000 MΩ is provided between the electrode and the ground based on the ground level (ground level) due to the above is also included in the present invention.

You may further comprise the drum which is provided in the said chamber and winds the said base material, and the conveyance mechanism which conveys the said base material.
The base material may be held in the chamber so as to have a straight free span portion, and film formation may be performed on the free span portion of the base material.
The gas supply unit may be electrically in a floating level, and the gas supply unit may be attached to the electrode side of the base material and supply gas toward the base material surface.

The electrode may have a flat plate shape, a curved surface shape, or a cylindrical shape.
The electrode may have a polygonal cross section perpendicular to the rotation axis, and the polygon may be a regular polygon. Alternatively, the polygon may be a triangle or more and 20 or less.
The electrode may have a rotation axis and rotate, and a cross section perpendicular to the rotation axis may be circular or polygonal.
The rotation speed of the electrode is set between 0.1 rotations per minute and 30000 rotations per minute.
The one set of electrodes may have the same or different rotation directions.

An auxiliary wing may be provided on the surface of the electrode, and the auxiliary wing may be formed of an insulating material.
The electrode may include a magnet that concentrates and forms plasma in the vicinity of the substrate. The magnet may be fixed to the substrate without rotating simultaneously with the electrode.
The magnet has a horizontal magnetic flux density on the substrate surface of 10 gauss to 10,000 gauss, and the magnet has a magnetron structure.
The power supply preferably has a frequency of 10 Hz to 27.12 MHz.
In this film forming apparatus, a plurality of sets of electrodes composed of the one set of electrodes may be installed on both sides of the substrate.

The substrate may be installed at an electrical ground level or may be installed at an electrical floating level. Further, when the base material is at an electrically floating level, a constant DC voltage may be applied to the base material.
The film forming pressure in the vicinity of the substrate may be between 0.1 Pa and 100 Pa.
The chamber may have a film forming chamber and an exhaust chamber. It is desirable that the degree of vacuum in the exhaust chamber is higher in the range of 10 times or more and 10,000 times or less than the degree of vacuum at the time of film formation in the film forming chamber.

The film forming apparatus may further include a substrate transport mechanism. In this case, the substrate is placed on a substrate holding component such as an insulating tray or carrier. Further, the film forming apparatus may include a load lock chamber adjacent to the chamber.
The drum may be installed electrically at a ground level or may be installed electrically at a floating level. Further, when the drum is at an electrically floating level, a constant DC voltage may be applied to the drum.

The chamber may have a film forming chamber and a substrate transfer chamber. In this case, the deposition pressure in the deposition chamber may be between 0.1 Pa and 100 Pa, and the degree of vacuum in the base material transfer chamber is 10 times higher than the degree of vacuum in the deposition chamber deposition. It may be high in the range of 10000 times or less.
The chamber may include a film formation chamber and an exhaust chamber, and the electrode may be provided in the exhaust chamber. It is desirable that the degree of vacuum in the exhaust chamber is higher in the range of 10 times or more and 10,000 times or less than the degree of vacuum at the time of film formation in the film forming chamber.

A base material charge removing unit that removes base material charge generated by film formation may be provided in the base material transfer chamber downstream of the film formation chamber. The base material charge removing unit may be a plasma discharge device.
A plasma discharge treatment apparatus may be provided in the base material transfer chamber upstream of the film formation chamber.
The base material charge removing unit may be provided in the base material transfer chamber upstream of the film forming chamber.

The drum may be formed of a material containing at least one of stainless steel, aluminum, iron, copper, and chromium, and may have a surface average roughness Ra of 0.1 nm to 10 nm.
You may further have a temperature adjustment means to maintain the said drum at the fixed temperature between -20 degreeC and 200 degreeC.
The drum may have an electrically insulating region at both ends. The insulating region is formed of one or more oxide films, nitride films, or oxynitride films of Al, Si, Cr, Ta, Ti, Nb, V, Bi, Y, W, Mo, Zr, and Hf. Alternatively, any one of a polyimide resin, a fluororesin, and a mica may be coated with a coating film.

A roll provided in the chamber and in contact with the substrate after film formation may further be provided, and the roll may have a cooling mechanism or may be installed at an electrical ground level.
The roll may include a base material charge removal unit that removes base material charge generated by film formation. The roll may have a base neutralization mechanism before the roll, and the roll is installed at a floating level. May be.
The base material charge removing unit may be a plasma discharge device.

A fourth invention is a film forming method for forming a thin film on a substrate under reduced pressure by a plasma CVD method, wherein gas is supplied into the chamber and moved to the same surface side of the substrate in the chamber. Power is supplied from an AC power source to a pair of electrodes that are arranged and electrically placed at a floating level, plasma is generated, impedance of plasma discharge is measured, and the discharge impedance is constant. while adjusting the distance between the electrodes, a thin film was formed on the substrate, wherein the electrode is a film forming method comprising Rukoto aileron made of an insulating material on the surface is provided.

A fifth invention is a film forming method for forming a thin film on a base material under reduced pressure by a plasma CVD method, wherein the base material is wound around a drum provided in the chamber, and gas is supplied into the chamber. In the chamber, it is arranged to be movable on the same surface side of the substrate, and power is supplied from an AC power source to a pair of electrically floating level electrodes, plasma is generated, and impedance of plasma discharge is measured. And forming a thin film on the substrate while adjusting the distance between the electrodes so that the discharge impedance is constant , the chamber having a film forming chamber and an exhaust chamber, a film forming method comprising Rukoto provided in an exhaust chamber.

A sixth invention is a film forming method for forming a thin film on a base material under reduced pressure by a plasma CVD method, wherein the base material is wound around a drum provided in the chamber, and gas is supplied into the chamber. In the chamber, it is arranged to be movable on the same surface side of the substrate, and power is supplied from an AC power source to a pair of electrically floating level electrodes, plasma is generated, and impedance of plasma discharge is measured. Then, a thin film is formed on the substrate while adjusting the distance between the electrodes so that the discharge impedance is constant, and the chamber includes a film forming chamber and a substrate transfer chamber. The film forming method is characterized in that a base material charge removing portion is provided in the base material transport chamber upstream of the film chamber.

  According to the present invention, the film is formed while adjusting the distance between the electrodes. Therefore, the discharge impedance is set optimally, a good quality film is uniformly formed on the substrate, the film formation input power is increased, and the film formation is performed. It is possible to improve the film speed, improve productivity, and stably form a film without abnormal discharge for a long time.

Hereinafter, a film forming apparatus and a film forming method according to an embodiment of the present invention will be described in detail with reference to the drawings.
1A and 1B are diagrams showing a film forming apparatus 1 according to the first embodiment. FIG. 2A is a perspective view of FIG. 1, and FIG. 2B is a top view of FIG.

A film forming chamber 4 is formed in the chamber 3, and gas supply units 7-1, 7-2 and 7-3 are provided in the film forming chamber 4. The gas supply units 7-1, 7-2, and 7-3 are gas storage units 5-1, 5-2, 5- through the flow rate controllers 8-1, 8-2, and 8-3 for each supply gas type. 3 is connected. The gas reservoirs 5-1, 5-2, and 5-3 hold a film-forming gas. The gas reservoir 5-1 includes, for example, TEOS (tetraethoxysilane Si (OC ₂ H ₅₎ that is a film-forming raw material. ₄ ) is stored, the gas storage section 5-2 stores oxygen (O ₂ ) which is a decomposable oxidizing gas, and the gas storage section 5-3 stores argon (Ar) which is an ionizing gas for discharge. .

  In the chamber 3, a base material holder 11 is provided on the support portion 9, and a base material 13 is held on the base material holder 11. Although not shown, a temperature adjusting medium pipe for circulating a coolant and a heat medium in the base material holder 11 and the support portion 9 for the purpose of cooling or heating the substrate during film formation to maintain a constant temperature. May be provided. Examples of the substrate 13 include a wafer, ceramics such as glass, a resin plate, a plastic film, a metal plate, a metal foil, paper, a nonwoven fabric, and a fiber.

  Electrode units 15-1 and 15-2 having electrodes 35-1 and 35-2 installed at a pair of electrically floating levels on the surface side of the base material 13 are installed. -2 is connected to a power source 17 capable of applying power at a constant frequency. Power is supplied from the power source 17 to emit plasma 16 toward the base material 13. The chamber 3 is provided with an evacuation pump 21 via a pressure adjustment valve 19.

As shown in FIG. 2A, the electrode unit 15-1 and the electrode unit 15-2 have a cylindrical shape, and a part of the surface of the cylindrical shields 21-1, 21-2 is made of an insulating material. Covered with.
These shields have an effect of preventing abnormal discharge outside a desired film formation region. For this purpose, these shields are preferably made of an electrically insulating material.

The electrode 35-1 held inside the electrode unit 15-1 is provided with gears 27-1 and 27-3 at both ends. The motor 27-1 is connected to the gear 27-1 through a belt 25-1. Is provided.
The gear 27-3 is provided with a motor 23-2 via a belt 25-2.
On the other hand, the electrode 35-2 held inside the electrode unit 15-2 is provided with gears 27-2 and 27-4 at both ends. The gear 27-2 is connected to the motor 23 via a belt 25-1. -1 is provided.
The gear 27-4 is provided with a motor 23-3 via a belt 25-3.

That is, the electrode 35-1 can be rotated in the directions A1 and B1 in FIG. 1 by the motor 23-1 or the motor 23-2.
Similarly, the electrode 35-2 can be rotated in the C1 and D1 directions of FIG. 1 by the motor 23-1 or the motor 23-3.

  The rotation speed of these electrodes is preferably set to 0.1 to 30000 rotations / minute. If the rotation speed is lower than 0.1 rotation / minute, the effect of cooling the electrode cannot be obtained, and if it is 30000 rotation / minute or more, the rotation mechanism becomes complicated and there is a problem that the device becomes expensive. The rotation speed of these electrodes is more preferably 1 to 1000 revolutions per minute, more preferably 1 to 100 revolutions per minute. At these rotational speeds, the maximum effect can be obtained in terms of discharge stability and device cost.

  In general, it is preferable to use the same size and the same structure for the electrodes and electrode units used as a set.

  2A and 2B, the ends of the electrode unit 15-1 and the electrode unit 15-2 are connected to rails 22-1 and 22-2, and the rails 22-1, 22-2, It can move in the E direction and the F direction on 22-2.

As shown in FIG. 1, the electrodes 35-1 and 35-2 are connected to a power source 17, and when power is supplied from the power source 17, plasma 16 is generated from the electrodes 35-1 and 35-2.
Details of the structures of the electrode units 15-1 and 15-2 will be described later.

  The gas supply units 7-1, 7-2, and 7-3 are arranged so that the jet ports thereof are directed to the surface of the base material 13. For this reason, the film-forming gas can be uniformly diffused and supplied to the surface of the base material 13, and uniform film formation can be performed on a large area portion of the base material 13.

The power supply 17 has a frequency of 10 Hz to 27.12 MHz. At a frequency of 10 Hz or higher, the decomposability of the film-forming raw material becomes good, and plasma discharge and film formation are possible. On the other hand, at a frequency higher than 27.12 MHz, the power supply and its matching circuit become expensive and the apparatus cost increases.
More preferably, 10 kHz to 500 kHz, 13.56 MHz, and 27.12 MHz are preferable.

  When a film-forming power source of 10 kHz to 500 kHz is used, the film-forming material is highly efficient in causing decomposition necessary for film formation, and a high-quality film is obtained because the film-forming material driving effect on the substrate 13 is high. It is done. Further, at 13.56 MHz and 27.12 MHz, the decomposition efficiency that causes decomposition necessary for film formation of the film formation material is further increased, the gas reactivity is increased, and high-quality film formation with high density and high adhesion becomes possible. . Since these power supplies are frequencies that are allowed to be used industrially even in the high frequency band, there are advantages that many such power supplies are commercially available and are inexpensive.

  As a method for controlling the power source 17, there is an impedance control method in which the input impedance control or the discharge impedance indicating the difficulty of the flow of electricity, which is a value obtained by dividing the discharge voltage value by the discharge current value, is controlled. In the input power control, the film formation input power of the power source 17 is made constant, and the film formation can be performed while stabilizing the plasma discharge, and the film formation can be performed stably, simply, and inexpensively.

  In the impedance control, when the response is fast and the impedance changes in the film formation for a long time (for example, the composition of the CVD film formation gas changes due to the influence of moisture that starts to be released when the inner wall of the chamber 3 is warmed by discharge). As a result, when the impedance changes), there is an effect of maintaining this constant.

Alternatively, the discharge voltage value and the discharge current value can be used alone or in combination as a method for simpler control.
As a method for monitoring and controlling the discharge impedance, discharge current, and discharge voltage, a method using a monitor mechanism or a discharge stabilization circuit possessed by a film forming power source is the simplest.

  An optical method may be used as a control method for stable film formation of the power supply 17. For example, a plasma emission monitor may be installed, the emission intensity of a specific element in the plasma may be monitored, and process control for making the emission intensity constant may be performed. Process control methods in this case include control of the amount of supply gas such as film forming source gas, decomposable gas, oxidizing gas, discharge gas and ionized gas, control of the amount of film forming gas and additive gas, Film formation conditions such as film pressure and substrate temperature may be controlled.

The base material 13 may be installed at an electrical ground level. When the base material 13 is installed at the ground level, the charged charges accumulated on the surface of the base material 13 are transmitted to the base material holder 11 and released to the ground level, and as a result, stable film formation is possible.
In this case, it can be realized by using a metal conductive material for the substrate holder 11 or the holder support.

  Further, the base material 13 may be placed at an electrically floating level, that is, an insulation potential. By setting the potential of the base material 13 to a floating level, it is possible to prevent power leakage, increase the power for film formation, and increase the efficiency of use for film formation.

  Here, the electric floating level is a base material or a base material holder using an insulating part or an insulating coating so that the insulating property is maintained from the chamber 3 or other film forming apparatus parts installed at the earth level. Means the state where it is designed and installed.

  Although the base material holder 11 is designed to ensure insulation, a refrigerant or heat medium necessary for cooling or heating the base material 13 and the base material holder 11 is used. 10 kΩ to 1000 MΩ between the substrate 13 and the earth or between the substrate holder 11 and the earth on the basis of the earth level (ground level) due to the fact that the piping for circulating and supplying these media has some conductivity The present invention also includes the case of having the above resistance.

  Specifically, a method using an insulating material such as ceramic, mica, fluororesin, polyimide resin having insulating properties, plasma resistance and heat resistance for the substrate holder 11 or the substrate holder support, or a substrate holder , A method using a surface-treated material made of the ceramic, mica, fluororesin, polyimide resin on the surface of the substrate holder support, the insulating ceramics, mica, between the chamber 3 and the substrate holder 11, The method of inserting the member which consists of a fluororesin and a polyimide resin is mention | raise | lifted.

  Ceramic materials include inorganic oxide films such as aluminum oxide, silicon oxide, titanium oxide, and chromium oxide, inorganic nitride films such as aluminum nitride, silicon nitride, titanium nitride, and chromium nitride, aluminum oxynitride, silicon oxynitride, and oxide Examples thereof include inorganic oxynitride films such as titanium nitride and chromium oxynitride.

  The gas supply units 7-1, 7-2, and 7-3 may be electrically floating. In this case, it is possible to prevent the deposition power from leaking to the gas supply units 7-1, 7-2, 7-3, the deposition power can be increased, and the utilization efficiency for deposition is high. It will be a thing.

  Moreover, before the gas is supplied into the chamber 3 in the gas supply units 7-1, 7-2, and 7-3, it is possible to avoid film formation from occurring at the pipe supply port and blocking the supply port.

Here, the structure of the electrode unit 15-1 and the electrode unit 15-2 will be described in detail. FIG. 3 is an enlarged view of the electrode unit 15-1 in FIG. 1, and FIGS. 4 and 5 are modifications of FIG. 6 is a sectional view of the electrode unit 15-1, and FIG. 7 is a modification of FIG. Further, FIGS. 8, 9 and 10 are modifications of the electrode unit 15-1.
In addition, since the structure of the electrode unit 15-2 is the same as that of the electrode unit 15-1, description is abbreviate | omitted.

  As shown in FIG. 3, the electrode unit 15-1 has a cylindrical shape, and a part of the surface is covered with a cylindrical shield 21-1.

As shown in FIG. 4, only the end of the electrode unit 15-1a may be covered with the shields 22a and 22b.
For the plasma discharge forming portion, a V-shaped or U-shaped shield notch may be provided as shown in FIGS. 24-1 and 24-2.

In addition to the shield 21-1, as shown in FIG. 5, side shields 23-1, 23-2 may be provided at the end of the electrode unit 15-1.
The side shields 23-1 and 23-2 have groove portions 25-1 and 25-2, and end portions of the shield 21-1 are fitted into the groove portions 25-1 and 25-2.

  The shields 21-1, 22-1 and 22-2 and the side shields 23-1 and 23-2 are preferably made of an insulating material having excellent plasma resistance, heat resistance, and workability. Specifically, a fluororesin material, a polyimide resin material, an inorganic oxide material, an inorganic nitride material, an inorganic oxynitride material, or a material provided with these coating films is preferably used.

  The electrode unit 15-1 may have a polygonal shape. In this case, in order to stably perform discharge formation and film formation so that the discharge voltage and current are not uneven, the electrode cross-sectional shape is A regular polygon is preferable.

  Further, the electrode unit 15-1 may have a flat plate shape.

Next, the internal structure of the electrode unit 15-1 will be described.
As shown in FIG. 6, a cylindrical electrode 35-1 is provided on the surface of the electrode unit 15-1, and a fixed shaft 27 for supporting the entire electrode unit is provided inside the electrode unit 15-1. It has been.
Electrode cooling water 29 for cooling the electrode 35-1 flows between the electrode 35-1 and the fixed shaft 27.

  The electrode 35-1 is electrically conductive for supplying electric power, has excellent plasma resistance, has heat resistance, has high cooling efficiency with cooling water (high thermal conductivity), is a non-magnetic material, and has excellent workability. It is preferable to manufacture using an excellent material. Specifically, aluminum, iron, copper, and stainless steel are preferably used.

  Further, as shown in FIG. 7, a base 28 may be provided inside the electrode unit 15-1c, and magnets 29-1, 29-2, 29-3 may be provided on the base 28. The magnets 29-1, 29-2, and 29-3 are installed so that the plasma 16 from the electrode 35-1 is concentrated on the surface of the base material 13.

In the electrode unit 15-1c, only the electrode 35-1 may be rotated in the cross-sectional shape shown in FIG. That is, the pedestal 28, the cooling water pipe 31, and the magnets 29-1, 29-2, 29-3 are fixed and installed at positions facing the substrate surface, and the plasma 16 formed is continuously formed on the substrate surface. It is possible to form a plasma CVD film.
The pedestal 28 is provided with cooling water pipes 31-1, 31-2, and the magnets 29-1, 29-2, 29-3 are cooled inside the cooling water pipes 31-1, 31-2. Cooling water is flowing.

By providing the magnets 29-1, 29-2, and 29-3, the reactivity in the vicinity of the surface of the substrate 13 is increased, and a high-quality film can be formed at high speed.
The magnets 29-1, 29-2, and 29-3 of the electrode unit 15-1c have a horizontal magnetic flux density at the surface position of the base material 13 of 10 gauss to 10000 gauss. If the horizontal magnetic flux density on the surface of the substrate 13 is 10 gauss or more, the reactivity in the vicinity of the surface of the substrate 13 can be sufficiently increased, and a high-quality film can be formed at high speed.

On the other hand, an expensive magnet or a magnetic field generating mechanism is required to increase the horizontal magnetic flux density on the surface of the base material 13 to more than 10,000 Gauss.
The arrangement structure of the magnets 29-1, 29-2, 29-3 of the electrode 35-1c is a magnetron structure. With the magnetron structure, ions and electrons formed during plasma CVD film formation continuously rotate according to the magnetron structure.

  For this reason, for example, when plasma CVD film formation is performed on a large-area substrate 13 having a size of 300 mm × 300 mm or more, decomposition products of film formation materials such as electrons and ions are spread over the entire surface of the electrode unit 15-1c. Evenly diffused and uniform and stable film formation is possible even when the substrate 13 has a large area.

  In addition, there is no accumulation of thermoelectrons and ions locally on the electrode unit 15-1c such as the electrode 35-1, the magnets 29-1, 29-2, and 29-3, and the heat resistance of the constituent members is low. Therefore, it is possible to manufacture parts at a low cost, and it is possible to suppress the occurrence of problems such as thermal deformation, the formation of holes in the structure, and the occurrence of cracks.

On the other hand, as shown in FIG. 8, a plate-like auxiliary blade 33-1 may be provided on the surface of the electrode unit 15-1d.
By providing the auxiliary blade 33-1, it becomes possible to efficiently remove unreacted decomposition products and by-products that are retained in the vicinity of the surface of the electrode unit 15-1d.

  When TEOS (tetraethoxysilane) is used as a film forming raw material, oxygen is used as an oxidizing gas, and argon as an ionizing gas for discharge is used, water, carbon monoxide, carbon dioxide, and a hydrocarbon substance are generated as by-products, If these by-products are present in the vicinity of the substrate, they are used as film-forming reaction materials. As a result, the reaction system gas is not controlled, and a poor film quality and a sparse film are formed. In order to form a simple film, it is necessary to efficiently remove by-products from the vicinity of the substrate.

The auxiliary blade 33-1 is made of an electrically insulating material.
If the auxiliary blade 33-1 is electrically insulative, it is not electrically coupled, so that discharge discharge does not increase and plasma discharge and film formation can be performed stably.

  The shape of the auxiliary wings may be a bent shape like the auxiliary wings 33-2 and 33-3 shown in FIGS.

  Next, a schematic operation of the film forming apparatus 1 will be described. The substrate 13 is placed on the substrate holder 11, the vacuum exhaust pump 21 is operated, the pressure adjustment valve 19 is opened, and the film forming chamber in the chamber 3 is evacuated. The film forming gas is supplied from the gas storage units 5-1, 5-2, and 5-3 while controlling the flow rate by the flow rate controllers 8-1, 8-2, and 8-3, respectively, and mixed uniformly. The gas is supplied to the gas supply units 7-1, 7-2, and 7-3 in the film chamber, and the film forming gas is jetted uniformly toward the base material 3. The opening degree of the pressure adjusting valve 19 is adjusted to set the desired degree of vacuum in the film forming chamber.

Usually, in this plasma CVD film forming apparatus and film forming method, in order to stably form plasma and form a film having a desired sufficient density and adhesion, the film forming pressure ( The degree of vacuum) is adjusted by adjusting the opening degree of the pressure adjusting valve 19, and the film is formed while being set and maintained at a degree of vacuum between 0.1 Pa and 100 Pa.
Electric power is supplied from the power source 17 to the electrodes 35-1 and 35-2 at a constant frequency, plasma 16 is emitted from the electrodes 35-1 and 35-2 toward the base material 13, and a thin film is formed on the base material 13. The By-products generated during the film formation are exhausted by the vacuum exhaust pump 21.

  The electrodes 35-1 and 35-2 are rotating during film formation, but the rotation direction is the same in order to enable stable discharge and film formation without disturbing the plasma discharge. It is preferable.

During film formation, the distance between the electrode units 15-1 and 15-2 is adjusted so that the discharge impedance is constant.
Specifically, the discharge impedance at the time of film formation is electrically measured and monitored in real time, and the electrode units 15-1 and 15-2 are not shown in FIG. Move in E direction or F direction in (a).

  As the electrical monitoring method of the discharge impedance, the method of using the discharge voltage (output voltage) and discharge current (output current) of the film forming power source and dividing the discharge voltage value by the discharge current value and using it as the discharge impedance is the most. It is a simple and accurate method. Using this monitor value, the distance between the electrodes is adjusted.

That is, when the actual discharge impedance is smaller than the set value, the electrode units 15-1 and 15-2 are moved so as to narrow the distance between the electrode units 15-1 and 15-2.
On the contrary, when the actual discharge impedance is larger than the set value, the electrode units 15-1 and 15-2 are moved so as to increase the distance between the electrode units 15-1 and 15-2.

In order to make the control method simpler, a method of monitoring only the discharge voltage or only the discharge current may be used.
In any case, in order to distinguish from abnormal discharge that occurs instantaneously, it is possible to use in combination with an arcing monitor held by the power source to distinguish abnormal discharge from abnormal discharge. When an abnormal discharge is detected, it is preferable that the discharge signal during this period is not excessively used for adjusting the distance between the electrodes.

  Another method for recognizing abnormal discharge and preventing the distance between electrodes from being sensitively adjusted is to perform an average value of the discharge voltage value or discharge current value over time or similar statistical calculation processing, and use this value as the average value. And the distance between the electrodes may be adjusted.

  In this way, the discharge impedance is always kept constant during film formation. In particular, when the film formation time is long, for example, heat generated by the process is accumulated in the chamber or the film formation unit, and the temperature rises, so that moisture comes out of the chamber inner wall and parts or is released from the base material. As the amount of moisture increases or decreases, there arises a problem that the atmosphere of the film forming chamber, specifically, the gas composition changes over time.

  In addition, when the film formation is not performed properly and stably due to the supply stability of the film forming raw material gas and the instability of the applied power, there arises a problem that the discharge impedance is not stable. In these cases, an important point in the process is that the film forming raw material is appropriately decomposed and reacted with an oxidizing gas to form a film. Even when these supply gases and input power become unstable, the process is controlled so that the discharge impedance is constant in order to properly decompose the film forming raw material and supply an appropriate amount of oxidizing gas. It is preferable.

  Thus, according to the first embodiment, the discharge impedance during film formation is electrically measured and monitored in real time, and the distance between the electrode units 15-1 and 15-2 is adjusted. Therefore, the discharge impedance can always be kept constant, the ion implantation effect on the base material 13 can be adjusted, the adhesion of the film can be increased, the damage to the base material can be reduced, and a high quality film can be formed. Become.

  In addition, according to the first embodiment, the substrate is not deposited on the electrode and is not electrically coupled, so that it is not electrically coupled, so that an increase in impedance of plasma discharge can be prevented, and plasma formation can be easily performed. It becomes possible to perform discharge and plasma CVD film formation stably for a long time. In addition, since the discharge impedance does not increase, in plasma CVD film formation, the film formation speed is improved (productivity improvement), the film stress is reduced, and damage to the base material is reduced (the occurrence of electrical charge-up is suppressed, the base material) It is possible to improve adhesion by reducing etching and reduce substrate coloring.

  In addition, the rotation of the electrode enables efficient cooling of the electrode surface. In particular, when a magnet is installed inside the electrode, the magnet is sequentially cooled onto the surface of the electrode facing the substrate where the plasma is concentrated. The electrode surface appears, and the plasma discharge during film formation is dramatically stabilized. Further, since the electrode is sufficiently cooled, the input power can be increased. Further, since the cooling efficiency of the electrode is improved, abnormal discharge such as arcing caused by scattering of foreign matters such as particles adhering to the electrode surface is eliminated, and as a result, a dense film having no defect can be formed.

  Since the cylindrical electrode is excellent in the cooling efficiency, it is possible to design the size compactly compared to the flat plate type electrode. It is possible to increase the exhaust conductance, and to efficiently remove by-products staying in the vicinity of the surface. As a result, a dense and high-quality film can be formed.

Next, a film forming apparatus 101 according to the second embodiment of the present invention will be described.
FIG. 11 is a diagram showing the film formation apparatus 101, in which a partition wall 105 is provided in the chamber 103, and a film formation chamber 107 and an exhaust chamber 109 are formed by the partition wall 105.
The gas supply units 113-1, 113-2, and 113-3 are gas storage units 111-1, 111-2, and 111- for each supply gas type via the flow rate controllers 114-1, 114-2, and 114-3. 3 and a gas for film formation whose flow rate is individually controlled from 111-1, 111-2, and 111-3 are supplied from the gas reservoir.

The support portion 115 provided in the chamber 103 is provided with a coupling portion 117 made of an electrically insulative component, and a base material holder 119 is provided on the support portion 115. The substrate holder 119 supports the substrate 121.
In the chamber 103, electrode units 123-1 and 123-2 having electrodes 149-1 and 149-2 installed at an electrically floating level are provided. The electrodes 149-1 and 149-2 are connected to a power source 125. Connected.

The structure of the electrode units 123-1 and 123-2 is the same as that of the electrode units 15-1 and 15-2 in the first embodiment, and the electrode 149-1 can rotate in the directions A2 and B2 in FIG. .
Similarly, the electrode 149-2 can rotate in the directions C2 and D2 in FIG.
Similarly to the electrode units 15-1 and 15-2, the electrode units 123-1 and 123-2 can adjust the distance between the electrode units by moving on a rail (not shown).

  A vacuum exhaust pump 131-1 is provided on the exhaust chamber 109 side via a pressure adjustment valve 129-1, and a vacuum exhaust pump 131-2 is provided on the film formation chamber 107 side via a pressure adjustment valve 129-2.

  In the film forming apparatus 101, a partition wall 105 is provided in a chamber 103, and the chamber 103 is divided into a film forming chamber 107 and an exhaust chamber 109. The pressures in the film formation chamber 107 and the exhaust chamber 109 are different. In order to stably form plasma in the film formation chamber 107 and form a film having a desired sufficient density and adhesion, the film formation pressure (degree of vacuum) in the film formation chamber is set to the pressure adjusting valve 131-2. By adjusting the degree of opening, the degree of vacuum between 0.1 Pa and 100 Pa is set and maintained, and film formation is performed. The exhaust chamber 109 preferably has a high degree of vacuum that is 10 to 10,000 times the degree of vacuum during film formation in the film formation chamber 107.

In this way, by separating the film formation chamber 107 and the exhaust chamber 109, by-products generated during film formation can be efficiently exhausted from the vicinity of the surface of the substrate 121.
In order to exhaust the by-product efficiently, the exhaust chamber 109 needs to be at least 10 times higher in vacuum than the film formation chamber 107. Further, since an expensive exhaust system is required to make the vacuum degree of the exhaust chamber 109 10,000 times higher than that of the film forming chamber 107, it is preferably 10,000 times or less.

  The potentials of the electrodes 149-1 and 149-2 and the base material 121 in the film formation apparatus 101 can be the same as those in the film formation apparatus 1.

  Here, when the base material 121 is in an electrically floating level, a direct current potential is applied to the base material 121 using a direct current power source (not shown), and the effect of implanting the ionized film forming material onto the base material 121 is strengthened or weakened. It is possible to install a mechanism to In order to enhance the ionization implantation effect, it is preferable to apply a minus potential of minus 10 V to minus 3000 V to the base material 121, and in order to weaken the ionization implantation effect, a plus potential of plus 10 V to plus 3000 V is preferably imparted to the substrate 121. .

The coupling portion 117 is a mechanism necessary for applying a potential to the base material 121 in this way, and between the chamber 103, the base material 121, and the base material holder 119 in order to bring the base material holder 119 into an electrically floating level. It is an electrically insulating member installed in
Even when the base material holder 119 is set to the electrically floating level, the coupling portion 117 is not necessary if no potential is applied to the base material 121.

  Moreover, although it is expensive and complicated in terms of equipment, AC power having a frequency of 10 Hz to 27.12 MHz may be applied to the base material 121. In addition, you may perform in this Embodiment that direct current potential is applied to the base material 121 in this way.

Next, a film forming apparatus 201 according to the third embodiment of the present invention will be described.
FIG. 12 is a view showing a film forming apparatus 201. In this film forming apparatus 201, electrode units 215-1, 215-2, 215-3, and 215-4 are arranged on both sides of a base material 213.

  Gas supply units 207-1, 207-2, 207-3, 207-4, 207-5, and 207-6 are provided in the chamber 203. The gas supply units 207-1, 207-2, and 207-3 are supplied to the gas storage units 205-1, 205-2, and 205- via the flow rate controllers 240-1, 240-2, and 240-3 for each supply gas type. The gas supply units 207-4, 207-5, and 207-6 are connected to the gas storage units 205-4 and 205 via the flow rate controllers 240-4, 240-5, and 240-6 for each supply gas type. -5, 205-6.

  The gas storage units 205-1, 205-2, 205-3, 205-4, 205-5, and 205-6 store a film forming gas. That is, the gas storage units 205-1, 205-2, and 205-3 correspond to the gas storage units 5-1, 5-2, and 5-3 in FIG. Similarly, the gas storage units 205-4, 205-5, and 205-6 correspond to the gas storage units 5-1, 5-2, and 5-3.

The base material 213 is held by the base material holder 211. Electrode units 215-1 and 215-2 having electrodes 230-1 and 230-2 are provided on one side of the substrate 213, and the electrodes 230-1 and 230-2 are connected to a power source 217-1.
In addition, electrode units 215-3 and 215-4 having electrodes 230-3 and 230-4 are provided on the opposite surface side of the substrate 213, and the electrodes 230-3 and 230-4 are connected to a power source 217-2. The

  The electrode surfaces of these electrodes 230-1, 230-2, 230-3, and 230-4 are electrically placed at a floating level.

The structure of the electrode units 215-1, 215-2, 215-3, and 215-4 is the same as that of the electrode units 15-1 and 15-2 in the first embodiment, and the electrode 230-1 is the same as A3 in FIG. The electrode 230-2 can rotate in the C3 and D3 directions of FIG.
Similarly, the electrode 230-3 can rotate in the A4 and B4 directions in FIG. 12, and the electrode 230-4 can rotate in the C4 and D4 directions in FIG.
Also, the electrode units 215-1, 215-2, 215-3, and 215-4, like the electrode units 15-1 and 15-2, adjust the distance between the electrode units by moving on a rail (not shown). Is possible.

Next, a schematic operation of the film forming apparatus 201 will be described.
The film forming gas stored in the gas storage units 205-1, 205-2, and 205-3 is individually adjusted in flow rate by the flow rate controllers 240-1, 240-2, and 240-3, and is supplied to the gas supply unit 207-. 1, 207-2, and 207-3 are emitted toward one side of the substrate 213. Power is supplied from the power source 217-1 to the electrodes 230-1 and 230-2, and plasma 216 is generated. At this time, the electrodes 230-3 and 230-4 rotate.

  Similarly, the film forming gas is released from the gas supply units 207-4, 207-5, and 207-6 toward the opposite surface side of the substrate 213. In order to stably form plasma and to form a film having a desired sufficient density and adhesion, the opening pressure of the pressure adjusting valve 219 is adjusted to the film forming pressure (vacuum degree) in the film forming chamber in the chamber. Then, film formation is performed while maintaining the vacuum degree between 0.1 Pa and 100 Pa.

  Power is supplied to the electrodes 230-3 and 230-4 from the power source 217-2, and plasma 216 is generated from the electrodes 230-3 and 230-4. At this time, the electrodes 230-3 and 230-4 rotate. Then, a thin film is formed on both surfaces of the base material 213. By-products during film formation are discharged from the vacuum exhaust pump 221.

  During film formation, the distance between the electrode units 215-1 and 215-2 and the distance between the electrode units 215-3 and 215-4 are adjusted so that the discharge impedance is constant.

  In the film forming apparatus 201, since one set of electrodes is provided on both sides of the base material 213, film formation on both surfaces of the base material 213 is possible, stress relaxation of the base material 213 is possible, and a high-quality thin film is formed. Can do.

Next, a film forming apparatus 301 according to a fourth embodiment of the present invention will be described.
FIG. 13 is a view showing a film forming apparatus 301. A partition wall 305 is provided in the chamber 303, and a film formation chamber 307 and an exhaust chamber 309 are formed in the chamber 303.

  Gas supply sections 313-1, 313-2, and 313-3 are provided in the chamber 303. The gas supply units 313-1, 313-2, and 313-3 are gas storage units 311-1, 311-2, and 311 via the flow rate controllers 314-1, 314-2, and 314-3 for each supply gas type. -3. The gas storage units 311-1, 311-2, and 311-3 store a film forming gas.

Electrode units 323-1 and 323-2 having electrodes 360-1 and 360-2 are provided in the chamber 303 as an electric floating level, and the electrodes 360-1 and 360-2 are connected to a power source 325.
The structures of the electrodes 360-1 and 360-2 are the same as those of the electrodes 35-1 and 35-2 in the first embodiment, and the electrode 360-1 can rotate in the directions A5 and B5 in FIG. 360-2 can rotate in directions C5 and D5 in FIG.
Similarly to the electrode units 15-1 and 15-2, the electrode units 323-1 and 323-2 can adjust the distance between the electrode units by moving on a rail (not shown).

  A rail 357 for running the tray 319 is provided in the chamber 303. A vacuum exhaust pump 331-1 is provided on the exhaust chamber 309 side via a pressure adjustment valve 329-1, and a vacuum exhaust pump 331-2 is provided on the film formation chamber 307 side via a pressure adjustment valve 329-2.

The vacuum exhaust pump 331-1 exhausts the exhaust chamber 309. The vacuum exhaust pump 331-2 exhausts the film formation chamber 307 side.
A load lock chamber (preliminary exhaust chamber) 351-1 is provided in the chamber 303 via a gate valve 341-1. A vacuum exhaust pump 355-1 is provided in the load lock chamber 351-1 via a pressure adjustment valve 353-1.

  In addition, a load lock chamber (preliminary exhaust chamber) 351-2 is provided in the chamber 303 via a gate valve 341-2. A vacuum exhaust pump 355-2 is provided in the load lock chamber 351-2 via a pressure adjustment valve 353-2.

  By providing these load lock chambers 351-1 and 351-2, the vacuum inside the chamber 303 having the film forming portion is continuously returned to the atmospheric pressure when the substrate is taken into and out of the atmosphere. A film forming process can be performed. As a result, an apparatus with high productivity can be obtained and a high degree of vacuum can be maintained, so that moisture adsorption can be prevented inside the chamber 303, and advantages such as a good quality film can be obtained.

The functions of the gas supply unit 313, the electrode 360, and the like in the chamber 303 are the same as those in the first embodiment.
The gate valve 341-1 opens and closes between the chamber 303 and the load lock chamber 351-1. The gate valve 341-2 opens and closes between the chamber 303 and the load lock chamber 351-2.

The load lock chamber 351-1 is provided with a tray transporting and moving mechanism so that a plurality of base materials can be stocked. A large number of trays 319 on which the base material 321 is placed are provided, and these trays 319 can be stored in a storage rack having an up / down function. The vacuum exhaust pump 351-1 exhausts the load lock chamber 351-1. The gate valve 341-1 can be opened and closed in a state where the degree of vacuum in the load lock chamber 351-1 is substantially equal to the degree of vacuum in the chamber 303 and there is no pressure difference.
A tray 319 runs on a rail 357 in the chamber 303.

  The gate valve 341-2 opens and closes between the chamber 303 and the load lock chamber 351-2. The load lock chamber 351-2 can store a large number of trays 319, and the trays 319 can move in the vertical direction. The vacuum exhaust pump 355-2 exhausts the load lock chamber 351-2.

Next, the schematic operation of the film forming apparatus 301 will be described.
The inside of the chamber 303 having the film formation chamber 307 and the exhaust chamber 309 is continuously exhausted by the vacuum exhaust pumps 331-1 and 331-2, and a desired degree of vacuum is achieved by the pressure adjustment valve 331-1 and the pressure adjustment valve 331-2. Set to

  In the atmosphere, the tray 319 on which the base material 321 is placed is set in the load lock chamber 351-1. Subsequently, the evacuation pump 355-1 is operated to open the pressure adjustment valve 353-1 to evacuate the load lock chamber 351-1.

  After the degree of vacuum of the load lock chamber 351-1 becomes the same as the degree of vacuum of the chamber 303 including the film formation chamber 307, the gate valve 341-1 can be opened. After the tray 319 travels on the rail 357 and the entire tray 319 passes through the gate valve 341-1 and is transported to the chamber 303, the gate valve 341-1 is closed.

  After the gate valve 341-1 is closed, the film forming gas stored in the gas storage units 311-1, 311-2, 311-3 are individually provided flow rate controllers 314-1, 314-2, A desired flow rate is supplied by 314-3, these gases are uniformly mixed in advance, and are ejected from the gas supply units 313-1, 313-2, and 313-3 toward the substrate 321 side. The film formation chamber 307 and the exhaust chamber 309 are set to pressures suitable for film formation by the vacuum exhaust pumps 331-1 and 331-2 and the pressure adjusting valves 329-1 and 329-2. In the exhaust chamber 309, film formation is performed at a higher degree of vacuum in the range of 10 times to 10000 times that of the film formation chamber 307.

  The tray 319 runs on the rail 357 in the chamber 303 and reaches a position below the electrodes 360-1 and 360-2. The tray 319 may stop at the electrodes 360-1 and 360-2, or may pass through while traveling at a constant speed. In addition, in order to obtain a required film thickness, the tray 319 may be repeatedly formed by bidirectional transfer.

  In order to stably form plasma and form a film having a desired sufficient density and adhesion, the film formation pressure (vacuum degree) in the film formation chamber in the chamber is the opening of the pressure adjustment valve 329-1. In order to perform film formation while maintaining the vacuum degree between 0.1 Pa and 100 Pa, and to efficiently exhaust the by-products generated on the substrate surface during the film formation, The pressure (degree of vacuum) is adjusted by adjusting the opening of the pressure adjustment valve 329-2, and the film is formed while being set and maintained at a degree of vacuum 10 to 10,000 times higher than the film forming chamber pressure.

At this time, power is supplied from the power source 325 to the electrodes 360-1 and 360-2, and plasma is generated from the electrodes 360-1 and 360-2. At this time, the electrodes 360-1 and 360-2 rotate simultaneously. Then, a thin film is formed on the base material 321.
During film formation, the distance between the electrode units 323-1 and 323-2 is adjusted so that the discharge impedance is constant.

  After the thin film is formed, the supply of power supplied to the electrodes 360-1 and 360-2 is stopped, and the plasma discharge is stopped. Further, the film forming gas supply is stopped, and the pressure adjusting valves 329-1 and 329-2 are fully opened to exhaust the residual gas in the chamber 303.

  Either the load lock chamber 351-1 or 351-2 can be used as a part for re-storing the film formation substrate. Here, the case of re-storing in the load lock chamber 351-2 will be described. In advance, a space for re-storing the film formation substrate is made in the load lock 351-2 chamber, the vacuum exhaust pump 355-2 is operated, the pressure adjustment valve 353-2 is fully opened, and the load lock chamber 351-. 2 Depressurize the inside.

  After the film formation process described above is completed and the residual gas is exhausted, the vacuum degree of the chamber 303 and the vacuum degree of the load lock chamber 351-2 are made the same, then the gate valve 341-2 is opened, and the substrate tray 319 and the deposition target substrate are transported on the rail 357 and moved to a predetermined position in the load lock chamber 351-2. After the substrate tray 319 passes through the gate valve 341-2 and the whole moves to the load lock chamber 351-2, the gate valve 341-2 is closed.

  It is also possible to continuously perform the above steps on a plurality of base materials 321. Further, after the film forming process is completed for all the base materials 321, the base material can be taken out by stopping the evacuation of the load lock chamber 351-2 and releasing it to the atmosphere.

  According to the fourth embodiment, since at least one load lock chamber 351-1 (or 351-2) is provided before and after the chamber 303, the evacuation process and the film formation process can be separated, and productivity is increased. Will improve.

In addition, since the tray 319 with wheels transports the base material 321 while traveling on the rail 357, productivity is improved, and uniform and stable continuous film formation on a large area portion of the base material 321 becomes possible.
In addition, as a base material transport mechanism, the tray 319 with wheels is transported on the rail 357, the end portion of the base material is held by a nail, the arm moving structure and the base material are loaded on the tray or the frame, and the whole is A mechanism that moves with an arm can also be used.

  Note that the surface of the tray 319 is preferably insulative, and the base member 321 is preferably at an electrically floating level. By making the tray 319 insulative, leakage of electric power can be prevented, the electric power used for film formation can be increased, the utilization efficiency for film formation is high, and stable film formation is possible.

Next, a film forming apparatus 501 according to the fifth embodiment of the present invention will be described. FIG. 14 is a view showing a film forming apparatus 501 according to the fifth embodiment.
Partition walls 405 and 407 are formed in the chamber 403. A base material transfer chamber 409 is formed above the partition wall 405, a film formation chamber 411 is formed in a space surrounded by the partition walls 405 and 407, and an exhaust chamber 413 is formed below the partition wall 407.

  An unwinding roller 415 and a winding roller 417 are provided in the base material transfer chamber 409. A drum 419 is provided so as to be sandwiched between the partition walls 405, and guide rollers 421-1, 421-2, 421-3 and a tension pickup roll 423-1 are provided between the unwinding roller 415 and the drum 419, and the drum 419 is provided. Guide rollers 421-4, 421-5, 421-6 and a tension pickup roll 423-2 are provided between the roller and the take-up roller 417.

  The unwinding roller 415 winds the base material 16, and the base material 16 is wound around the drum 419 via the guide rollers 421-1 and 421-2, the tension pickup roll 423-1, and the guide roller 421-3. Further, the film is taken up by the take-up roller 17 through the guide roller 421-4, the tension pickup roll 423-2, and the guide rollers 421-5 and 421-6. The tension of the base material 16 is adjusted by the tension pick-up rolls 423-1 and 423-2 and the base material is conveyed.

Further, in FIG. 14, the substrate transport direction is described so that the substrate proceeds from the unwinding roller 415 to the take-up roller 417, but film formation or substrate processing is performed while the substrate is transported in the reverse direction. It is also possible to repeat these steps. From the viewpoint of productivity and film quality, it is preferable to repeatedly form a film without returning the vacuum to atmospheric pressure.
The substrate 16 is a ceramic such as glass, a resin plate, a plastic film, a metal plate, a metal foil, paper, a nonwoven fabric, a fiber, or the like.

  A pre-processing device 425 and a post-processing device 427 are provided in the vicinity of the drum 419. As the pretreatment device 425, for example, a plasma discharge device is used. The post-processing device 427 is a device that removes the base material charge generated by film formation, and is, for example, a plasma discharge device.

Gas supply units 437-1, 437-2, and 437-3 are provided so as to be sandwiched between the partition walls 7, and the gas supply units 437-1, 437-2, and 437-3 are provided as flow controllers 435-1 and 435-, respectively. 2 and 435-3 to be connected to gas reservoirs 433-1, 433-2 and 433-3.
The gas storage units 433-1, 433-2, and 433-3 store a film forming gas.

  The gas supply ports 437-1, 437-2, and 437-3 have their outlets directed toward the base material 16 on the drum 419. For this reason, the film forming gas can be uniformly diffused and supplied to the surface of the base material 16, and uniform film formation can be performed on a large area portion of the base material 16.

  An electrode unit 439-1 including an electrode 455-1 is provided between the gas supply units 437-1 and 437-2, and an electrode 455-2 is provided between the gas supply units 437-2 and 437-3. A unit 439-2 is provided, and the electrodes 455-1 and 455-2 are connected to a power source 441, and power is supplied from the power source 441. The electrodes 455-1 and 455-2 are electrically set to a floating level.

The structures of the electrodes 455-1 and 455-2 are the same as those of the electrodes 35-1 and 35-2 in the first embodiment, and the electrode 455-1 can rotate in the directions A6 and B6 in FIG. 455-2 can rotate in the C6 and D6 directions of FIG.
Similarly to the electrode units 15-1 and 15-2, the electrode units 439-1 and 439-2 can move on a rail (not shown) to adjust the distance between the electrode units.

The substrate transfer chamber 409 is provided with a vacuum exhaust pump 431-1 through a pressure adjustment valve 429-1, and the film formation chamber 411 is provided with a vacuum exhaust pump 431-2 through a pressure adjustment valve 429-2. The exhaust chamber 13 is provided with a vacuum exhaust pump 431-3 via a pressure adjustment valve 429-3.
By adjusting the exhaust capability of these vacuum exhaust pumps and the opening of the pressure adjusting valve, it is possible to set an arbitrary degree of vacuum.

  The drum 419 has a cylindrical shape and includes rotating shafts at both ends, and the rotating shaft is fixed to the apparatus main body via a bearing or the like. In order to control the drum temperature, piping for circulating a temperature control medium such as a refrigerant or a heat medium is installed inside the drum and the rotary shaft.

  The drum can be adjusted to a constant temperature between −20 ° C. and + 200 ° C. by adjusting the temperature of the temperature adjusting medium circulating in the drum, and its temperature controllability is set at a set temperature ± 2 ° C. Preferably there is. Electrical insulation portions are provided on both sides of the drum, which is a non-film formation region, and on the surface of the rotating shaft so as not to generate discharge at portions where power is not required, and the base material 16 is conveyed at the center of the drum.

  The drum 419 may be installed at an electrical ground level. When the drum 419 is installed at the ground level, the charged charges accumulated on the surface of the substrate 16 are released to the ground level, and as a result, stable film formation is possible. In this case, it can be realized by using a metal conductive material for the drum body, the rotating shaft, the bearing, and the drum support.

Further, the drum 419 may be placed at an electrically floating level, that is, an insulation potential. By setting the potential of the drum 419 to a floating level, leakage of electric power can be prevented, the electric power used for film formation can be increased, and the use efficiency for film formation can be increased.
In this case, it can be realized by using any one or more of the drum rotation shaft, the bearing, and the drum support member as an insulating component.

  When the drum 419 is at an electrically floating level, it is possible to install a mechanism that applies a DC potential to the drum 419 to enhance or weaken the effect of implanting the ionized film forming material onto the substrate 16.

  In order to enhance the ionization implantation effect, it is preferable to apply a minus potential of minus 10 V to minus 3000 V to the base material 16, and in order to weaken the ionization implantation effect, a plus potential of plus 10 V to plus 3000 V is preferably applied to the substrate 16. . Moreover, although it is expensive in terms of equipment, AC power having a frequency of 10 Hz to 27.12 MHz may be applied to the base material 16.

  The substrate transfer chamber 409 is partitioned by a partition wall (zone seal) 405 and has a different pressure from the film formation chamber 411 where the electrodes 455-1 and 455-2 exist. By making the base material transfer chamber 409 and the film formation chamber 411 different in pressure, the plasma 443 in the film formation chamber 411 leaks into the base material transfer chamber 409, so that the plasma discharge state of the film formation chamber 411 becomes unstable. No damage to the members of the substrate transfer chamber 409, electrical damage to the electric circuit for controlling the substrate transfer mechanism, causing control failure, and stable film formation and substrate transfer It becomes possible.

  Specifically, the film formation pressure in the film formation chamber 411 is between 0.1 Pa and 100 Pa. By performing film formation at such a film formation pressure, stable plasma 443 can be formed.

  Then, the pressure (degree of vacuum) of the base material transfer chamber 409 is made 10 to 10,000 times higher than the pressure (degree of vacuum) at the time of film formation in the film formation chamber 411. In this manner, by setting the pressure in the substrate transfer chamber 409, the plasma 443 in the film formation chamber 411 does not leak into the substrate transfer chamber 409, and plasma CVD film formation in the film formation chamber 411 is stably performed. It can be carried out.

  The exhaust chamber 413 is partitioned from the film formation chamber 411 by a partition wall (zone seal) 407 and has a different pressure. The exhaust chamber 413 has a pressure (degree of vacuum) that is 410 times or more and 10,000 times or less than the pressure at the time of film formation in the film formation chamber 411. By partitioning the film formation chamber 411 and the exhaust chamber 413 and providing a pressure difference between the film formation chamber 411 and the exhaust chamber 413, the by-product generated during the film formation can be efficiently exhausted from the vicinity of the surface of the substrate 16. it can.

  A post-processing device 427 as a base material charge removing unit for removing base material charge generated by film formation is provided in the base material transfer chamber 409 downstream of the film formation chamber 411.

  The post-processing apparatus 427 is installed in the base material transfer chamber 409 downstream of the film formation chamber 411, and by removing the base material charge, the base material 16 can be quickly separated from the drum 419 at a predetermined position and transferred. It becomes possible to convey the material, prevent damage to the base material 16 due to electrification and quality deterioration, and improve post-processing suitability by improving the wettability of the front and back surfaces of the base material 16.

  As the post-processing device 427 serving as a charge removing unit, for example, an arbitrary processing device such as a plasma discharge device, an electron beam irradiation device, an ultraviolet irradiation device, a charge removal bar, a glow discharge device, or a corona treatment device can be used.

  When a discharge is formed using a plasma processing apparatus or a glow discharge apparatus, a discharge gas such as argon, oxygen, nitrogen, helium or the like is supplied in the vicinity of the substrate 16 as a single substance or a mixture, and alternating current (AC) plasma, direct current ( Any discharge method such as DC) plasma, arc discharge, microwave, surface wave plasma, etc. can be used. In a reduced pressure environment, a charging method using a plasma discharge device is most preferable.

  A pretreatment apparatus 425 is provided in the base material transfer chamber 409 upstream of the film formation chamber 411. The pretreatment device 425 is a plasma discharge treatment device, and this plasma discharge treatment device can physically etch the surface of the base material 16 by subjecting the base material 16 to plasma discharge treatment before film formation. In addition to being able to form a concavo-convex shape on the surface of the base material 16, it is possible to improve the adhesion of the film during subsequent film formation by changing the chemical bonding state or functional group.

  The drum 419 is formed of a material containing at least one of stainless steel, iron, copper, and chromium. The surface of the drum 419 may be subjected to a hard chrome hard coat treatment or the like to prevent damage. Since these materials are easy to process and the thermal conductivity of the drum itself is good, the temperature controllability is excellent when performing temperature control.

  The drum 419 has a surface average roughness Ra of 10 nm or less, preferably 5 nm or less, and more preferably 2 nm or less. Usually, the average surface roughness Ra of the base material 16 such as a plastic film or a metal plate (steel plate) is usually 10 to 50 nm, 5 to 10 nm for the base material 16 processed with special surface flatness, and surface coating. When flattening is performed by processing, the drum 419 preferably has the above range in order to efficiently adjust the temperature such as cooling and heating with respect to the base material 16 because the surface flatness is 5 nm or less.

The surface of the drum 419 is preferably as flat as possible, but the measurement limit of the surface average roughness Ra is 0.1 nm at present, and this value is set as the lower limit for convenience.
The drum 419 has a temperature adjustment mechanism that can set a constant temperature between −20 ° C. and + 200 ° C. by using a cooling medium and / or a heat source medium or a heater.

  The temperature adjustment mechanism can suppress fluctuations in the temperature of the base material 16 due to heat generated during film formation. Specifically, an ethylene glycol aqueous solution is used as a cooling medium (refrigerant), silicon oil is used as a heat source medium (heating medium), the temperature is adjusted by circulating in the drum 419, or a heater is placed at a position facing the drum 419. It is possible to install.

  In particular, in the film forming apparatus 501, it is preferable that the set temperature can be set to a constant temperature between −20 ° C. and + 200 ° C. from the viewpoint of heat resistance restrictions of related mechanical parts and versatility. In the process using, it is preferable to control the temperature within a range of set temperature ± 2 ° C.

  The drum 419 has an insulating region in the both ends that are not covered with the base material 16, the side surface of the drum, the rotation shaft, and the like in the width direction of the base material 16. By forming the insulating portion, there is no region where the conductive metal portion is exposed in the film formation chamber 411, so that the plasma formed for film formation does not electrically fall on the drum 419, and stable plasma 443 Formation is possible.

  The insulating portion is formed of one or more oxide films, nitride films, or oxynitride films of Al, Si, Cr, Ta, Ti, Nb, V, Bi, Y, W, Mo, Zr, and Hf. . Alternatively, the insulating portion is covered with a molded body or coating film of any one of polyimide resin, fluororesin, and mica. Since these methods and materials have reliable insulation, heat resistance, plasma resistance, and excellent durability, they can be used stably over a long period of time.

  Next, a schematic operation of the film forming apparatus 501 will be described. The gas for forming a film is supplied from the gas storage units 433-1, 433-2, 433-3 to the gas supply units 437-1, 437-2, 437-3, and the gas supply units 437-1, 437-2, 437 are supplied. The film-forming gas is ejected from −3 toward the substrate 16.

In addition, power is supplied from the power source 441 to the electrodes 489-1 and 489-2, plasma 443 is emitted from the electrodes 489-1 and 489-2 toward the base material 16, and a thin film is formed on the base material 16. . At this time, the electrodes 489-1 and 489-2 rotate simultaneously.
During film formation, the distance between the electrode units 439-1 and 439-2 is adjusted so that the discharge impedance is constant.

Next, a sixth embodiment of the present invention will be described.
FIG. 15 is a diagram showing a film forming apparatus 601. The film forming apparatus 601 includes a chamber 503 for performing a film forming process on the base material 516, a first base material transport chamber 515 for transporting the base material 516, a second base material transport chamber 519, and the like. A partition 505 and a partition 507 are formed in the chamber 503. A film formation chamber 508 is formed in a space surrounded by the partition walls 505 and 507, and an exhaust chamber is formed above the partition walls 505 and below the partition walls 507. A lower side of the partition wall 507 is a first exhaust chamber 509, and an upper side of the partition wall 505 is a second exhaust chamber 511.

The first base material transfer chamber 515 feeds out the base material 516 before film formation, and the second base material transfer chamber 519 performs winding up of the base material 516 after film formation.
In the first base material transfer chamber 515, an unwinding roller 541, a guide roller 543-1, and a pretreatment device 545 are provided. The second base material transfer chamber 519 is provided with a winding roller 547, guide rollers 543-2, 543-3, 543-4, a tension pickup roll 544, and a post-processing device 549.

  The unwinding roller 541 winds the base material 516. The base material 516 is a base that is a slit-like horizontal gap through which the base material 516 provided on the wall separating the first base material transfer chamber 515 and the chamber 503 passes from the unwinding roller 541 through the guide roller 543-1. It is fed into the film forming chamber 508 through the material carry-in port 535.

  On the other hand, a similar gap is provided as a substrate carry-out port 537 on the wall that separates the chamber 503 and the second substrate transfer chamber 519, and the substrate 516 that has completed the film formation process in the film formation chamber 508 has a base. The material is delivered to the second base material conveyance chamber 519 via the material carry-out port 537 and is taken up by the take-up roller 547 via the guide roller 543-2, the tension pickup roll 544, and the guide rollers 543-3 and 543-4. The tension pickup roll 544 adjusts the tension of the base material 516 and transports the base material 516.

In FIG. 15, the base material conveyance direction is described so that the base material 516 advances from the unwinding roller 541 to the take-up roller 517, but film formation may be performed while the base material is conveyed in the reverse direction. It is also possible to perform processing and to repeat these. From the viewpoint of productivity and film quality, it is preferable to repeatedly form a film without returning the vacuum to atmospheric pressure.
The base material 516 is a ceramic such as glass, a resin plate, a plastic film, a metal plate, a metal foil, paper, a nonwoven fabric, a fiber, or the like.

In the first base material transfer chamber 515, a pretreatment device 545 is provided between the guide roller 543-1 and the base material carry-in port 535, and in the second base material transfer chamber 519, the base material carry-out port 537 and the guide are provided. A post-processing device 549 is provided between the rollers 543-2.
The pretreatment device 545 and the posttreatment device 549 are provided so as to sandwich the base material 516 on both sides of the base material 516. The pretreatment device 545 is a plasma discharge device, for example, and the posttreatment device 549 is a device that removes the base material charge generated by film formation, and is, for example, a plasma discharge device.

  The chamber 503 is provided so as to be sandwiched between the first base material transport chamber 515 and the second base material transport chamber 519, and the base material 516 is transported horizontally between the base material carry-in port 535 and the base material carry-out port 537. The free span part is configured. The base material 516 is moved up in the film forming chamber 508 by being taken up by the take-up roller 547, and during this time, the film forming process is performed.

In the chamber 503, a gas supply unit 521 and an electrode unit 527 are provided on both the upper surface side and the lower surface side of the base material 516.
On the upper surface side of the base material 516, gas supply units 521-1, 521-2, and 521-3 are provided so as to be sandwiched between the partition walls 505, and the gas supply units 521-1, 521-2, and 521-3 are The gas reservoirs 525-1, 525-2, and 525-3 are connected to each other through the flow rate controllers 523-1, 523-2, and 523-3.

  In addition, on the lower surface side of the base material 516, gas supply units 521-4, 521-5, and 521-6 are provided so as to be sandwiched between the partition walls 507, and the gas supply units 521-4, 521-5, and 521-6 are provided. Is connected to the gas reservoirs 525-4, 525-5, 525-6 via the flow rate controllers 523-4, 523-5, 523-6.

The gas storage units 525-1 to 525-6 store the film forming gas.
The flow rate controllers 523-1 to 523-6 respectively measure the flow rates of the gases sent from the gas storage units 533-1 to 533-6 to the gas supply units 521-1 to 521-6.

  The gas supply parts 521-1 to 521-6 have their jet ports directed to the base material 516.

  In the upper part of the base material 516, an electrode unit 527-1 including an electrode 555-1 is provided between the gas supply units 521-1 and 521-2, and an electrode is provided between the gas supply units 521-2 and 521-3. An electrode unit 527-2 including 555-2 is provided, and the electrodes 555-1 and 555-2 are connected to the power source 529-1 and power is supplied from the power source 529-1. The electrodes 555-1 and 555-2 are electrically set at a floating level.

  On the other hand, the lower surface of the base 516 is similarly provided with an electrode unit 527-3 including an electrode 555-3 between the gas supply units 521-4 and 521-5, and the gas supply units 521-5 and 521-6. Is provided with an electrode unit 527-4 including an electrode 555-4, and the electrodes 555-3 and 555-4 are connected to a power source 529-2 and supplied with power from the power source 529-2. The electrodes 555-3 and 555-4 are electrically set at a floating level.

The structures of the electrodes 555-1, 555-2, 555-3, and 555-4 are the same as those of the electrodes 35-1 and 35-2 in the first embodiment, and the electrodes 555-1 are A7 and B7 in FIG. The electrode 555-2 can rotate in the C7 and D7 directions of FIG.
Similarly, the electrode 555-3 can rotate in the directions A8 and B8 in FIG. 15, and the electrode 555-4 can rotate in the directions C8 and D8 in FIG.

  Similarly to the electrode units 15-1 and 15-2, the electrode units 527-1, 527-2, 527-3, and 527-4 adjust the distance between the electrode units by moving on a rail (not shown). Is possible.

  Each of the first substrate transfer chamber 515, the second substrate transfer chamber 519, the first exhaust chamber 509 below the chamber 503, the second exhaust chamber 511 above the chamber 503, and the film forming chamber 508 in the chamber 3 , An evacuation pump 533 is provided via a pressure control valve 531.

  That is, the first base material transfer chamber 515 is evacuated via a pressure adjustment valve 531-4, and the second base material transfer chamber 519 is evacuated via a pressure adjustment valve 531-5. A pump 533-5 is evacuated to the first exhaust chamber 509 via a pressure adjustment valve 531-3, and a vacuum exhaust pump 533-3 to the second exhaust chamber 11 via a pressure adjustment valve 531-1. In the film formation chamber 508, a vacuum exhaust pump 533-2 is provided in the film formation chamber 508 via a pressure adjustment valve 531-2.

  The pressures of the first and second base material transfer chambers 515 and 519 and the film forming chamber 508 and the first and second exhaust chambers 509 and 511 are set differently by the pressure adjusting valve 531 and the vacuum exhaust pump 533. Is possible.

  That is, by forming the film formation chamber 511 and the first and second base material transfer chambers 515 and 519 into pressure different spaces, the plasma 528 in the film formation chamber 508 is changed into the first and second base material transfer chambers 515, The plasma discharge state of the film forming chamber 508 becomes unstable due to leakage to the 519, the members of the first and second base material transfer chambers 515 and 519 are damaged, and an electric circuit for controlling the base material transfer mechanism is used. Electrical damage is not caused to cause poor control, and stable film formation and substrate transport are possible.

  Specifically, the film formation pressure in the film formation chamber 508 is between 0.1 Pa and 100 Pa. By performing film formation at such a film formation pressure, a stable plasma 28 can be formed.

  The pressure (degree of vacuum) in the first and second base material transfer chambers 515 and 519 is set to be 10 to 10,000 times higher than the pressure (degree of vacuum) in the film formation chamber 508. In this manner, by setting the pressures in the first and second base material transfer chambers 515 and 519, the plasma 528 in the film formation chamber 508 does not leak into the first and second base material transfer chambers, and film formation is performed. Plasma CVD film formation in the chamber 508 can be performed stably.

  On the other hand, the first exhaust chamber 509 and the second exhaust chamber 511 are partitioned from the film formation chamber 508 by a partition wall (zone seal) 507 and a partition wall (zone seal) 505, respectively, and have different pressures. The first and second exhaust chambers 509 and 511 have a degree of vacuum that is 10 to 10,000 times higher than the pressure at the time of film formation in the film formation chamber 508. By providing such a pressure difference, a by-product generated during film formation can be efficiently exhausted from the vicinity of the surface of the substrate 516.

  Next, a schematic operation of the film forming apparatus 601 will be described. A film-forming gas is supplied from the gas storage units 525-1, 525-2, and 525-3 to the gas supply units 521-1, 521-2, and 437-3, and the gas supply units 521-1, 521-2, and 521 are supplied. The gas for film formation is ejected from −3 toward the upper surface of the base material 516.

Further, the film forming gas is supplied from the gas storage units 525-4, 525-5, and 525-6 to the gas supply units 523-4, 523-5, and 523-6, and the gas supply units 521-4 and 521-5 are supplied. , 521-6 toward the upper surface of the base material 516.

  In addition, power is supplied from the power source 529-1 to the electrodes 555-1 and 555-2, plasma 528 is emitted from the electrodes 489-1 and 489-2 toward the base material 16, and a thin film is formed on the upper surface of the base material 16. Is formed. At this time, the electrodes 489-1 and 489-2 rotate simultaneously.

Further, power is supplied from the power source 529-2 to the electrodes 555-3 and 555-4, and plasma 528 is emitted from the electrodes 489-1 and 489-2 toward the base material 516, and a thin film is formed on the upper surface of the base material 516. Is formed. At this time, the electrodes 555-3 and 555-4 rotate simultaneously.
During film formation, the distance between the electrode units 527-1 and 527-2 and the distance between 527-3 and 527-4 are adjusted so that the discharge impedance is constant.

  The embodiments according to the present invention have been described above. In the second to fifth embodiments, the functions of the gas storage unit, the gas supply unit, the power source, the electrodes, and the like are the same as those in the first embodiment. It is the same as the form. The power supply voltage, the power supply control method, the potential of the base material, the potential of the gas supply unit, etc. may be the same as in the first embodiment. Further, the electrodes shown in FIGS. 3 and 4 and those shown in FIGS. 5, 6, 7, 8, 8, and 10 may be used as appropriate.

Next, an experimental result when actually forming a film using the film forming apparatus 101 shown in FIG. 11 will be described.
In the film forming apparatus 101 shown in FIG. 11, the electrodes 149-1 and 149-2 are set to an electrically floating level, the magnetron structure magnet shown in FIG. 7 is set, and the average horizontal magnetic flux density on the substrate surface is 1000 gauss. Was set to be.

  The film formation chamber was at the ground level, the substrate holder was made of Teflon (registered trademark) resin, the coupling portion was not provided, and the substrate was at an electrically floating level. A coolant using an ethylene glycol aqueous solution having a concentration of 30% as a coolant was separately circulated and supplied to the substrate holder, electrode 149-1 and electrode 149-2, and the substrate holder was cooled to 0 ° C. At this time, the resistance between the electrode 149-1 and the substrate holder, between the electrode 149-2 and the substrate holder, and between the electrode 149-1 and the electrode 149-2 was 1 MΩ.

A silicon wafer was prepared as a substrate and set on a substrate holder. Both the exhaust chamber and the film formation chamber were evacuated to 1 × 10 ⁻⁴ Pa by a vacuum exhaust pump. TEOS (tetraethoxysilane Si (OC ₂ H ₅ ) ₄ was vaporized and supplied at a heating temperature of 120 ° C. as a film forming gas, and oxygen (O ₂ ) and argon (Ar) were prepared as film forming gases. did.

TEOS, oxygen, and argon were supplied at 20 sccm, 500 sccm, and 200 sccm, respectively, and mixed uniformly. Then, the gas was supplied onto the substrate in the deposition chamber in a shower shape through the deposition gas supply unit.
Next, the pressure adjusting valve attached to the vacuum exhaust pump was adjusted to adjust the pressure so that the film forming chamber pressure was a constant pressure of 10 Pa and the exhaust chamber pressure was a constant pressure of 0.5 Pa.

  Using a power source for film formation with a frequency of 40 kHz (manufactured by Advanced Energy Industries Inc., PEII 10 kW) and rotating the electrodes 149-1 and 149-2 in the A2 and C2 directions at 5 revolutions per minute, A power of 5 kW was applied by a power control method, and film formation was performed with a film formation time of 5 minutes. During this time, the average discharge voltage was 520V. Also, as a result of counting the number of occurrences of arcing (abnormal discharge) of discharge visually, it was found that the occurrence was zero and stable film formation was possible without abnormal discharge.

After film formation, the residual gas in the chamber was evacuated, the substrate was taken out, and the film thickness and refractive index of the SiO2 film formed on the wafer substrate were measured using spectroscopic ellipsometry (manufactured by JOBIN YVON, UVISEL). The refractive indexes at 478 nm and 633 nm were 1.47 and a dense film.
Further, when this film formation was carried out five times in succession, as shown in FIG. 16, it was found that a reproducible result was obtained and a stable film formation was possible.

  On the other hand, as a comparative example, the same film forming apparatus as in the example was prepared, and the film was formed in the same manner as in the example except that the film was not formed while controlling the distance between the electrodes by controlling the discharge impedance. went. At this time, the average discharge voltage and the number of arcing were as shown in FIG.

Further, after the film formation, the film thickness and refractive index of the SiO2 film formed on the wafer substrate were measured. The film thickness was 304 nm and the refractive index at 633 nm was 1.45, indicating that the film thickness was thin and the film formation rate was slow. It became a good film. FIG. 17 shows the result of continuously performing this film formation five times.
It can be seen that the thickness of the formed film is smaller than that of the example, the refractive index is slightly low and the film is sparse, the average discharge voltage is high, and arcing is often generated.

  A film forming apparatus shown in FIG. 14 was prepared. Magnets having a magnetron structure shown in FIG. 7 were set on the electrodes 455-1 and 455-2, and the average horizontal magnetic flux density on the substrate surface was set to 1000 gauss.

  The film forming chamber was set to the ground level, and the film forming drum 419 and the electrodes were set to the electrically floating level. A refrigerant using an ethylene glycol aqueous solution having a concentration of 30% as a refrigerant was separately circulated and supplied to the film formation drum 419, the electrode 455-1, and the electrode 455-2, and the film formation drum 419 was cooled to 0 ° C. At this time, the resistance between the electrode 455-1 and the film formation drum 419, between the electrode 455-2 and the film formation drum 419, and between the electrode 455-1 and the electrode 455-2 was 1 MΩ.

A 0.6 m wide PET film (Toyobo Co., Ltd., A4100, thickness 100 μm) was prepared as a substrate and set in a substrate transport system. Both the exhaust chamber and the film formation chamber were evacuated to 1 × 10 ⁻⁴ Pa by a vacuum exhaust pump. TEOS (tetraethoxysilane Si (OC ₂ H ₅ ) ₄ was vaporized and supplied at a heating temperature of 120 ° C. as a film forming gas, and oxygen (O ₂ ) and argon (Ar) were prepared as film forming gases. did.

TEOS, oxygen, and argon were supplied at 20 sccm, 500 sccm, and 200 sccm, respectively, and mixed uniformly. Then, the gas was supplied onto the substrate in the deposition chamber in a shower shape through the deposition gas supply unit.
Next, the pressure adjustment valve attached to the vacuum exhaust pump was adjusted, and the pressure was adjusted so that the film forming chamber pressure was a constant pressure of 10 Pa, and the base material transfer chamber and the exhaust chamber pressure were a constant pressure of 0.5 Pa.

The frequency of 40 kHz (Advanced
Using a power supply of PEII 10 kW manufactured by Energy Industries Inc., while rotating the electrodes 455-1 and 455-2 in the directions of B6 and C6, respectively, 5 kW of power was applied by the power control method, and the line speed was 5 m / The film was formed 1200 m by min. In addition, after the start of film formation, the number of discharge arcing (abnormal discharge) that occurred during film formation at a film formation distance of 200 m was counted.

  After film formation, the residual gas in the chamber was evacuated, the substrate was taken out, the substrate surface was visually observed and sampled every 200 m, and the film thickness measurement, film density measurement, and gas barrier property measurement of these samples were performed. .

  The film thickness was determined by performing cross-sectional measurement using a scanning electron microscope (SEM; manufactured by Hitachi, Ltd., S-5000H). The film density was calculated using an X-ray reflectivity measuring apparatus (manufactured by Rigaku Corporation, ATX-E) and attached software. The gas barrier property is determined by oxygen permeability measuring device (MOCON, OX-TRAN 2/20 type, measurement conditions: temperature 23 ° C., humidity 90% Rh, with independent measurement) and water vapor permeability measuring device (MOCON, PERMATRAN W3 / 31 type, measurement conditions: temperature 40 ° C., humidity 90% Rh). The above results are summarized in FIG.

In addition, as a comparative example, a film forming apparatus similar to that of the example was prepared, and film formation and evaluation were performed in the same manner as in the example, except that the film was not formed while controlling the distance between the electrodes by controlling the discharge impedance. went. The results are shown in FIG.
From the comparison between the example and the comparative example, in the example, arcing during discharge hardly occurs and a high-quality and uniform film can be formed. In addition, since the electric power to be input is effectively used for film formation, it can be seen that the film formation rate is improved and a high-quality film with high film density, that is, high density can be formed.
Further, when evaluated as a gas barrier film, it can be seen that a film having a small oxygen permeability and water vapor permeability and having a gas barrier property can be stably formed.

  A film forming apparatus shown in FIG. 15 was prepared. Magnets having a magnetron structure shown in FIG. 7 were set on the electrodes 555-1, 555-2, 555-3, and 555-4, and the average horizontal magnetic flux density on the substrate surface was set to 1000 gauss.

The film formation chamber was set to the ground level, and the electrodes 555-1, 555-2, 555-3, and 555-4 and the first roll that first contacted after film formation were set to the electrically floating level. A refrigerant using a 30% concentration ethylene glycol aqueous solution as a refrigerant was individually circulated and supplied to the electrodes 555-1, 555-2, 555-3, and 555-4, and the electrodes were cooled to 0 ° C. At this time, the resistance between the electrode 555-1 and the chamber, the electrode 555-2 and the chamber, the electrode 555-3 and the chamber, the electrode 555-4 and the chamber, and the resistance between the electrodes were 1 MΩ.

A 0.6 m wide PET film (Toyobo Co., Ltd., A4100, thickness 100 μm) was prepared as a substrate and set in a substrate transport system. Both the exhaust chamber and the film formation chamber were evacuated to 1 × 10 ⁻⁴ Pa by a vacuum exhaust pump. TEOS (tetraethoxysilane Si (OC ₂ H ₅ ) ₄ was vaporized at a heating temperature of 120 ° C. and supplied as a film forming gas, and oxygen (O ₂ ) and argon (Ar) were prepared as film forming gases. did.

TEOS, oxygen, and argon are supplied at 20 sccm, 500 sccm, and 200 sccm, respectively, and mixed uniformly, and then the gas is showered onto the substrate in the deposition chamber through the deposition gas supply unit that is electrically placed at the floating level. Were supplied in the form of
Next, the pressure adjustment valve attached to the vacuum exhaust pump was adjusted, and the pressure was adjusted so that the film forming chamber pressure was a constant pressure of 10 Pa, and the base material transfer chamber and the exhaust chamber pressure were a constant pressure of 0.5 Pa.

The frequency of 40 kHz (Advanced
Using the power source of Energy Industries, Inc., PEII, 10kW), the electrode 555-1 and the electrode 555-2 were rotated at 20 revolutions per minute in the A7 and D7 directions, respectively, and 4 kW of power was applied to the electrode 555-3. 4 kW was applied while rotating the electrode 555-4 at 20 revolutions per minute in the B8 and C8 directions, respectively. These electric powers were controlled by impedance control. A 1200 m film was formed at a substrate line speed of 5 m / min. After the start of film formation, the number of occurrences of arcing (abnormal discharge) of discharge that occurred during each film formation distance of 200 m was counted.

  After film formation, the residual gas in the chamber was evacuated, the substrate was taken out, the substrate surface was visually observed and sampled every 200 m, and the film thickness and film density of these samples were measured. Sampling of the center part of the base-material width direction was performed every 200 m, and the film thickness measurement, film density measurement, gas barrier property measurement, and base-material curvature measurement of these samples were performed.

  The film thickness, film density measurement, and gas barrier property measurement were measured and evaluated in the same manner as in Example 2. The substrate warpage measurement is performed by cutting a sample into a size of 20 mm × 20 mm, placing the upper side on an upper (plus side) flat reference surface at the time of film formation, and by warping from the flat reference surface due to the substrate warpage. The highest substrate height was measured with a laser displacement meter. The above results are shown in FIG.

  Further, as a comparative example, the film formation apparatus shown in FIG. 15 was prepared, and the film formation was performed in the same manner as in the example except that the film was formed without controlling the distance between the electrodes so that the discharge impedance was constant during the film formation. . The results are shown in FIG.

  From the comparison between the example and the comparative example, in the example, arcing during discharge hardly occurs and a high-quality and uniform film can be formed. In addition, since the electric power to be input is effectively used for film formation, it can be seen that the film formation rate is improved and a high-quality film with high film density, that is, high density can be formed. In addition, the film formation according to the present invention can form a film on both sides uniformly and can form a film free from substrate warpage (curl).

  The preferred embodiments of the film forming apparatus and the like according to the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It will be apparent to those skilled in the art that various changes or modifications can be conceived within the scope of the technical idea disclosed in the present application, and these naturally belong to the technical scope of the present invention. Understood.

The figure which shows the film-forming apparatus 1 1 is a perspective view of FIG. Top view of FIG. Enlarged view of the electrode unit 15-1 in FIG. Modified example of FIG. Modified example of FIG. Cross section of electrode unit 15-1 Modified example of FIG. Modification of electrode unit 15-1 Modification of electrode unit 15-1 Modification of electrode unit 15-1 The figure which shows the film-forming apparatus 101 The figure which shows the film-forming apparatus 201 The figure which shows the film-forming apparatus 301 The figure which shows the film-forming apparatus 501 The figure which shows the film-forming apparatus 601 The figure which shows the film-forming result by the film-forming apparatus 101 The figure which shows the film-forming result by the film-forming apparatus 101 The figure which shows the film-forming result by the film-forming apparatus 501 The figure which shows the film-forming result by the film-forming apparatus 501 The figure which shows the film-forming result by the film-forming apparatus 601 The figure which shows the film-forming result by the film-forming apparatus 601

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,101,201,301,501,601 ......... Film formation apparatus 3,103,203,303,403,503 ......... Chamber 5,111,205,311,433,525 ......... Gas storage part 7 , 113, 207, 313, 437, 521... Gas supply unit 8, 114, 240, 314, 435, 523... Flow rate controller 13, 121, 213, 321, 16, 516. , 123, 215, 323, 439, 527 ......... Electrode unit 17, 125, 217, 325, 441, 529 ......... Power source 35, 149, 230, 360, 455, 555 ......... Electrode

Claims (31)

A film forming apparatus for forming a thin film on a substrate under reduced pressure by a plasma CVD method,
A chamber;
A gas supply unit for supplying gas into the chamber;
In the chamber, a set of electrodes that are movably disposed on the same surface side of the base material and are installed at an electrically floating level;
An AC power source connected to the two electrodes;
Adjusting means for adjusting the distance between the two electrodes;
Measuring means for measuring plasma discharge impedance;
Comprising
The electrode is provided with an auxiliary wing formed of an insulating material on the surface,
The film forming apparatus characterized in that the adjusting means adjusts the distance between the electrodes so that the discharge impedance measured using the measuring means is constant. A film forming apparatus for forming a thin film on a substrate under reduced pressure by a plasma CVD method,
A chamber;
A gas supply unit for supplying gas into the chamber;
In the chamber, a set of electrodes that are movably disposed on the same surface side of the base material and are installed at an electrically floating level;
An AC power source connected to the two electrodes;
Adjusting means for adjusting the distance between the two electrodes;
Measuring means for measuring plasma discharge impedance;
A drum that is provided in the chamber and winds the base material; a transport mechanism that transports the base material;
Comprising
The chamber has a film formation chamber and an exhaust chamber, and the electrode is provided in the exhaust chamber,
The film forming apparatus characterized in that the adjusting means adjusts the distance between the electrodes so that the discharge impedance measured using the measuring means is constant. A film forming apparatus for forming a thin film on a substrate under reduced pressure by a plasma CVD method,
A chamber;
A gas supply unit for supplying gas into the chamber;
In the chamber, a set of electrodes that are movably disposed on the same surface side of the base material and are installed at an electrically floating level;
An AC power source connected to the two electrodes;
Adjusting means for adjusting the distance between the two electrodes;
Measuring means for measuring plasma discharge impedance;
A drum that is provided in the chamber and winds the base material; a transport mechanism that transports the base material;
Comprising
The chamber has a film formation chamber and a substrate transfer chamber, and a substrate charge removal unit is provided in the substrate transfer chamber upstream of the film formation chamber,
The film forming apparatus characterized in that the adjusting means adjusts the distance between the electrodes so that the discharge impedance measured using the measuring means is constant. A drum provided in the chamber and around which the substrate is wound;
A transport mechanism for transporting the substrate;
The film forming apparatus according to claim 1, further comprising: The substrate is held in the chamber to have a straight free span,
The film forming apparatus according to claim 1, wherein film formation is performed in the free span portion of the base material. The film forming apparatus according to claim 1 , wherein the gas supply unit is attached to the electrode side of the base material and supplies gas toward the surface of the base material. The film forming apparatus according to claim 1, wherein the electrode has a cylindrical shape. The film forming apparatus according to claim 1, wherein the pair of electrodes have the same rotation direction. 4. The film forming apparatus according to claim 1, wherein each of the pair of electrodes has a different rotation direction. 5. The film deposition apparatus according to claim 2 , wherein an auxiliary wing is provided on a surface of the electrode. The ailerons, film forming apparatus according to claim 1 0, wherein the is formed of an insulating material. The electrode includes a magnet that concentrates and forms plasma near the substrate,
The film formation apparatus according to any one of claims 1 to 3, wherein the magnet does not rotate simultaneously with the electrode and is fixed to face the surface of the base material. The magnets are film forming apparatus according to claim 1 2, wherein the horizontal magnetic flux density at the substrate surface is 10000 Gauss from 10 gauss. The magnets are film forming apparatus according to claim 1 2, wherein the having the magnetron structure.   The film forming apparatus according to claim 1, wherein a plurality of sets of electrodes including the one set of electrodes are provided on both surfaces of the base material. The chamber deposition apparatus according to claim 1 or claim 3, characterized in that it has a the deposition chamber and the exhaust chamber.   The film forming apparatus according to claim 1, further comprising a base material transport mechanism.   The film forming apparatus according to claim 1, further comprising a load lock chamber adjacent to the chamber. The chamber deposition apparatus according to claim 1 or claim 2, characterized in that it has a film forming chamber and the substrate transfer chamber. 20. The film forming apparatus according to claim 3, further comprising: a base material charge removing unit that removes base material charge generated by film formation in the base material transfer chamber downstream of the film forming chamber. . 5. The film forming apparatus according to claim 2, further comprising a temperature adjusting unit configured to maintain the drum at a constant temperature between −20 ° C. and 200 ° C. 6. The film formation apparatus according to claim 2, wherein the drum has electrically insulating regions at both ends. The insulating region is formed of one or more oxide films, nitride films, or oxynitride films of Al, Si, Cr, Ta, Ti, Nb, V, Bi, Y, W, Mo, Zr, and Hf. The film forming apparatus according to claim 22 . 23. The film forming apparatus according to claim 22 , wherein the insulating region is covered with a molded body or coating film of any one of polyimide resin, fluororesin, and mica. The film forming apparatus according to claim 1 , further comprising a roll provided in the chamber and in contact with the substrate after film formation. 26. The film forming apparatus according to claim 25, wherein the roll has a cooling mechanism. 26. The film forming apparatus according to claim 25 , wherein the roll includes a base material charge removing unit that removes base material charge generated by film formation. 26. The film forming apparatus according to claim 25 , further comprising a base material charge removing portion before the roll. A film forming method for forming a thin film on a substrate under reduced pressure by a plasma CVD method,
Supplying gas into the chamber,
In the chamber, a plasma is generated by supplying electric power from an AC power source to a set of electrodes that are movably disposed on the same surface side of the base material and are electrically installed at a floating level, and impedance of plasma discharge And adjusting the distance between the electrodes so that the discharge impedance is constant,
Forming a thin film on the substrate;
The electrode is deposited and wherein the Rukoto aileron made of an insulating material on the surface is provided. A film forming method for forming a thin film on a substrate under reduced pressure by a plasma CVD method,
Wrap the substrate around the drum provided in the chamber,
Supplying gas into the chamber;
In the chamber, it is arranged so as to be movable on the same surface side of the base material, and power is supplied from an alternating current power source to a pair of electrically floating level electrodes, plasma is generated, and impedance of plasma discharge is measured. , While adjusting the distance between the electrodes so that the discharge impedance is constant, forming a thin film on the substrate ,
The chamber has a the film forming chamber and the exhaust chamber, wherein the electrode film forming method according to claim Rukoto provided in the exhaust chamber. A film forming method for forming a thin film on a substrate under reduced pressure by a plasma CVD method,
Wrap the substrate around the drum provided in the chamber,
Supplying gas into the chamber;
In the chamber, it is arranged so as to be movable on the same surface side of the base material, and power is supplied from an alternating current power source to a pair of electrically floating level electrodes, plasma is generated, and impedance of plasma discharge is measured. , While adjusting the distance between the electrodes so that the discharge impedance is constant, forming a thin film on the substrate ,
The chamber has a film forming chamber and the substrate transfer chamber, a film forming method according to claim Rukoto base charge removing portion is provided on the substrate transfer chamber stage preceding the deposition chamber.

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