JP2018062713A - Plasma CVD apparatus and plasma CVD method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma CVD apparatus and a method for forming an oxide film and a nitride film on a large area substrate of 3 m x 3 m class or more with a uniformity of ±1% or less in a low-E glass field and an organic EL filed, where conventionally, in the plasma CVD apparatus and the method targeting a substrate of 3 m x 3 m class or more, a uniformity of a thin film is limited to about ±5-10% and a uniformity of ±1% or less could not be realized.SOLUTION: Multiple large electrode plates are arranged in parallel with one edge of the electrode plate faced a film deposition surface of a substrate, an exhaust nozzle of a raw material gas for ejecting the raw material gas including at least an organic compound raw material is arranged adjacent to the other edge of the electrode plate, a plasma is generated by the multiple large electrodes, and an oxide film, a nitride film, and a carbide film are deposited on a large area substrate of 3 m x 3 m class or more.SELECTED DRAWING: Figure 7

Description

  The present invention relates to a plasma CVD apparatus and a plasma CVD method for a large area substrate. In particular, the present invention relates to a plasma CVD apparatus and a plasma CVD method for forming a light reflecting film, an infrared reflecting film, or a barrier film in the fields of low-E glass, organic EL, and the like for a 3 mx 3 m class super large area substrate.

  In recent years, in fields such as low-E glass and organic EL, a plasma CVD apparatus and a plasma CVD method targeting a 3 mx 3 m class super large area substrate for forming a light reflecting film, an infrared reflecting film or a barrier film have improved the quality of products. In addition, it is attracting attention from the viewpoint of reducing the film forming cost.

Regarding the low-E glass, for example, Patent Document 1 describes the following. That is, a conductive film having transparency in the visible region is formed on the surface of the glass substrate, and a high heat shielding (or high heat insulation) / low radiation glass (generally Low--) utilizing free carrier absorption of electrons in the infrared region. E glass) has been proposed and has already been put to practical use. By using Low-E glass for building window glass, etc., it is possible not only to reduce the cooling load in the summer, but also to reduce the heating load in the winter, and not only can reduce the cost for adjusting the temperature in the room, It can also contribute to the prevention of global warming, which is a global problem.
Patent Document 1 describes the following. Low-E glass is glass with a silica coating in which a tin oxide layer, a silica coating, and a tin oxide layer are laminated in order from the glass substrate. A glass product (Low-E glass) in which an alloy oxide layer made of zinc and tin, a metal layer made of gold, silver or copper, and an alloy oxide layer made of zinc and tin are provided on a glass substrate in this order. )

  In the field of low-E glass, it is known that the uniformity of film thickness needs to be ± 1% or less in the formation of a thin film relating to low-E glass. However, the uniformity of the film thickness is defined as 100 × (maximum thickness−minimum thickness) / (maximum thickness + minimum thickness).

Regarding the barrier film for organic EL, for example, Patent Document 2 describes the following. That is, when forming a film on an organic EL substrate, a sealing film (passivation film) is often formed by a CVD method or the like. In this organic EL device, since oxidation at the organic layer and the electrode interface in contact with the organic layer causes a serious deterioration in display performance, a high barrier property of 10 ⁻⁵ g / m ² / d level is required as the water vapor transmission rate. ing. Moreover, since the glass transition temperature of the organic layer to be used is as low as 100 ° C. or lower, a thin film having a high barrier property at a low temperature is desired.
Patent Document 2 describes the following technique. That is, the first layer silicon nitride film formed on the surface of the organic EL substrate on which the sealing film is formed and the surface of the first layer silicon nitride film are formed on the surface after passivating. An organic EL sealing film comprising a second layer silicon nitride film.

  In the field of organic EL, it is known that the uniformity of film thickness needs to be ± 1% or less in the formation of a thin film related to organic EL. However, the uniformity of the film thickness is defined as 100 × (maximum thickness−minimum thickness) / (maximum thickness + minimum thickness).

  It is known that there are Patent Documents 3 to 8 as representative techniques of a plasma CVD apparatus and a plasma CVD method for a large area substrate.

  Patent Document 3 describes the following. That is, a reaction vessel containing a substrate on which an amorphous thin film is formed, and a first discharge in which a plurality of electrode plates are arranged in parallel in the reaction vessel so that an edge faces one surface of the substrate. A plurality of electrode plates in the reaction container, a second discharge electrode arranged in parallel with an edge facing one surface of the substrate, and the first and second discharge electrodes A power source for supplying a discharge voltage between the electrodes, a coil and an AC power source that surrounds the reaction vessel and generates a magnetic field in a direction orthogonal to the electric field generated between the pair of discharge electrode plates, and the pressure in the reaction vessel is reduced. An amorphous thin film forming apparatus comprising a gas supply facility for supplying a reactive gas.

  Patent Document 4 describes the following. That is, a substrate to be processed held by a single holding electrode and a single discharge electrode are arranged in a discharge container so as to face each other, and a substantially uniform discharge is provided between the discharge electrode and the substrate to be processed. A method for supplying power to a discharge electrode that generates a state in a wide range, and when supplying power to the discharge electrode through a plurality of power supply points, the phase of the voltage waveform of the high-frequency power supplied to one power supply point; The voltage distribution generated in the discharge electrode is changed by temporally changing the difference from the phase of the voltage waveform of the high-frequency power supplied to at least one other feeding point, thereby changing the unit of the voltage distribution. A method for supplying power to a discharge electrode, characterized in that an average value per time or an integral value per unit time is made substantially uniform, and generation of standing waves in the voltage distribution of the discharge electrode is suppressed.

Patent Document 5 describes the following. That is, a vacuum chamber, a substrate holder disposed inside the vacuum chamber, a hollow shower head disposed at a position facing the substrate holder, and a power supply device that applies a voltage to the shower head, The shower head includes a container-shaped head main body and a single shower plate that covers the opening of the head main body and forms the hollow, the shower plate being directed to the substrate holder, Is provided with a plurality of discharge ports. When a film forming gas is supplied into the shower head and a voltage is applied to the shower head while discharging the film forming gas from the discharge port, the film forming gas is plasma. The plasma CVD apparatus is configured such that the film-forming gas that has been converted to plasma is sprayed onto the substrate holder, wherein the power supply apparatus is duplicated. A number, a phase controller is connected to each of the power supply, the phase control device is configured the phase of high frequency voltage each said power supply device outputs to control each respective said power supply, said The high frequency voltages respectively connected to the feeding points arranged at different positions at equal distances from the center on the bottom surface of the head main body and respectively supplied from the power supply devices to the feeding points are respectively sent to the shower plate, and the shower A plasma CVD apparatus configured to generate discharge using a plate as a cathode.

Patent Document 6 describes the following. That is, a plasma CVD apparatus in which an inductively coupled electrode is disposed in a film forming chamber, wherein the inductively coupled electrode has a folded portion and is folded with a constant center-to-center distance. A high-frequency power feeding section and a grounding section are provided, and a plurality of the inductively coupled electrodes are arranged in parallel in the same plane with the feeding section and the grounding section on the same side, and the plurality of inductive couplings In each of the mold electrodes, high-frequency power is supplied so that a standing wave of a half wavelength or a natural number multiple thereof is generated between the power feeding unit and the folded unit and between the ground unit and the folded unit, and in the feeding portion adjacent Ri suit electrodes of a plurality of inductively coupled electrodes, a plasma CVD apparatus characterized by being configured such that the high frequency phase are opposite phases to each other.

  Patent Document 7 describes the following. That is, in an inductively coupled plasma apparatus using high frequency discharge, each antenna is supplied with high frequency power, each of which is coated with an insulator and terminated without going around the vacuum vessel, and has a quarter wavelength of the high frequency. A plurality of antennas made of linear or plate-like conductors shorter than the length are provided in a vacuum vessel, and each of the one or more antennas is provided with a plate shape provided outside the vacuum vessel from a high frequency power source. A high-frequency power is supplied in parallel by a conductor, and the distance between the high-frequency feeding point and each of the one or more antennas in a straight line is shorter than the length of 1/4 wavelength of the high-frequency. It is provided so that it may become. The plasma apparatus characterized by the above-mentioned.

  Patent Document 8 describes the following. That is, a waveguide connected to a microwave source and having a plurality of slot antennas formed on the magnetic field surface of the waveguide; and a microwave radiated from the plurality of slot antennas is introduced into the plasma processing chamber to generate a surface wave plasma. A dielectric plate for generating a film, an insulating shield member formed so as to surround the film forming region where the surface wave plasma is generated, and formed of a plate-like insulator, and a material for the film forming region A surface wave plasma CVD apparatus comprising: a gas ejection portion that ejects a reactive process gas; and a support member that is disposed at an end of the film formation region and has the insulating shield member attached to the film formation region.

JP 2006-143525 A JP2013-145668 JP 05-076549 Patent 3316490 Patent 4404303 Patent 5287944 Patent 3751909 Patent 543463

Conventionally, the light reflecting film and the infrared reflecting film in the field of low-E glass are mainly formed using a reactive sputtering apparatus, so that the initial investment of the manufacturing apparatus is large, and the film forming speed is low. There is a problem of low productivity. In the application of plasma CVD to the organic EL field, the organic EL element is a thin film with a thickness of several tens to several hundreds of nm. Therefore, if the film thickness is not uniform, a short circuit is likely to occur inside the organic EL element. , It becomes a problem
In the field of low-E glass and organic EL, in order to improve the productivity of thin film formation by plasma CVD, improve the quality, and reduce the cost, the substrate size should be 3mx3m class and the film thickness uniformity should be ± 1% or less. Although demanded, there is a problem that the conventional technology cannot meet the needs. The film thickness uniformity is defined as 100 × (maximum thickness−minimum thickness) / (maximum thickness + minimum thickness).
Accordingly, an object of the present invention is to provide a plasma CVD apparatus and a plasma CVD method which can realize a film thickness uniformity of ± 1% or less with a substrate size of 3 mx 3 m.

The first invention of the present invention for solving the above-mentioned problems is a method of storing a substrate holding means on which a substrate to be deposited is placed, supplying a reaction vessel provided with an exhaust means, and supplying a raw material gas to the reaction vessel A raw material gas supply means, a plurality of electrode plates arranged in parallel in the reaction vessel and having an edge facing the film forming surface of the substrate to be deposited, and an alternating current between the plurality of electrode plates A power supply means for supplying power to generate plasma between the plurality of electrode plates, and a plasma CVD apparatus comprising:
The source gas supply means includes a source gas containing at least one selected from an organic compound source, oxygen, nitrogen, ammonia, hydrogen and a carrier gas, and includes a plurality of source gas ejection holes for ejecting the source gas. The electrode plate is arranged at a position adjacent to an edge not facing the film forming surface of the film forming substrate.

According to a second aspect of the present invention, there is provided a reaction vessel having a substrate holding means on which a film-formed substrate is placed and provided with an exhaust means, a raw material gas supply means for supplying a raw material gas to the reaction vessel, and an inside of the reaction vessel A plurality of electrode plates arranged in parallel to each other and having an edge facing the film-forming surface of the film-forming substrate, and supplying AC power to the plurality of electrode plates, A power supply means for generating plasma, and a plasma CVD apparatus comprising:
The raw material gas supply means includes a raw material gas containing at least one selected from organic compound raw materials, oxygen, nitrogen, ammonia, hydrogen, and a carrier gas, and is selected from oxygen, nitrogen, hydrogen, and a rare gas. Discharge gas ejection holes including at least one kind of discharge gas are disposed, and discharge gas ejection holes for ejecting the discharge gas are arranged at positions adjacent to edges of the plurality of electrode plates that do not face the film formation surface of the film formation substrate. The raw material gas ejection holes for ejecting the raw material gas are arranged at positions adjacent to the edge of the plurality of electrode plates facing the film forming surface of the film forming substrate.

  In a third aspect based on the first aspect, the source gas supply means includes a source gas supply passage through which the source gas passes between the plurality of electrode plates, and the exhaust means includes the plurality of electrodes. It has an exhaust passage through which exhaust gas passes between the plates.

  In a fourth aspect based on the second aspect, the source gas supply means includes a discharge gas supply passage through which the discharge gas passes between the plurality of electrode plates, and the exhaust means includes the plurality of discharge gas passages. And an exhaust passage through which exhaust gas passes between the electrode plates.

  According to a fifth invention, in any one of the first to fourth inventions, the power supply means has a power frequency of 50 Hz or 60 Hz as a commercial frequency.

  According to a sixth invention, in any one of the first to fourth inventions, the frequency of the power of the power supply means is a frequency selected from a range of several KHz to 1 MHz or less.

  According to a seventh invention, in any one of the first to sixth inventions, the source gas is tetraethoxysilane (TEOS), hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDS), titanium. It contains at least one selected from organic compounds such as tetraisopropoxide (TTIP), trimethylzinc and trimethylaluminum.

According to an eighth aspect of the present invention, there is provided a reaction vessel having a substrate holding means on which a substrate to be deposited is placed and provided with an exhaust means, a raw material gas supply means for supplying a raw material gas to the reaction vessel, and an inside of the reaction vessel A plurality of electrode plates arranged in parallel to each other and having an edge facing the film-forming surface of the film-forming substrate, and supplying AC power to the plurality of electrode plates, A plasma CVD method using a plasma CVD apparatus provided with power supply means for generating plasma,
A source gas containing at least one selected from an organic compound source, oxygen, nitrogen, ammonia, and hydrogen is used as the source gas, and source gas ejection holes for ejecting the source gas are formed as the films on the electrode plates. It is arranged at a position adjacent to the edge that does not face the film-forming surface of the substrate, and the length of the plurality of electrode plates is increased in accordance with the increase in the area size of the film-forming substrate, and the plurality of the plurality of electrode plates The number of electrode plates is increased.

According to a ninth aspect of the present invention, there is provided a reaction vessel having a substrate holding means on which a film-formed substrate is placed and having an exhaust means, a raw material gas supply means for supplying a raw material gas to the reaction vessel, and an inside of the reaction vessel A plurality of electrode plates arranged in parallel to each other and having an edge facing the film-forming surface of the film-forming substrate, and supplying AC power to the plurality of electrode plates, A plasma CVD method using a plasma CVD apparatus provided with power supply means for generating plasma,
As the plasma discharge gas generated by the plurality of electrode plates, at least one selected from oxygen, nitrogen, argon, hydrogen, and a rare gas,
As the source gas, at least one selected from an organic compound source, oxygen, nitrogen, ammonia, hydrogen, and a rare gas of carrier gas is selected.
Disposing the discharge gas ejection holes for ejecting the discharge gas at positions adjacent to the edge of the plurality of electrode plates that do not face the film-forming surface of the film-forming substrate;
A source gas ejection hole for ejecting the source gas is disposed at an edge of the plurality of electrode plates facing the film forming surface of the substrate to be deposited, and the discharge gas is supplied to the plurality of electrode plates. Plasma is generated by the electric power supplied from the means, and the raw material gas is converted into plasma by bringing the plasmaized discharge gas and the raw material gas ejected from the raw material gas ejection hole into contact with each other and mixing them. It is characterized by.

According to the present invention, a transparent conductive film or a barrier film such as a silicon oxide film, a silicon nitride film, tin oxide and zinc oxide necessary for the low-E glass field and the organic EL field is formed by plasma CVD with a substrate size of 3 mx 3 m and a film thickness. It can be formed with a uniformity of ± 1% or less, so that it can contribute to high quality and low cost in the production of transparent conductive film or barrier film in the field of low-E glass and organic EL. Play.
In particular, in the field of low-E glass, since the film forming speed is remarkably faster than that of a conventional reactive sputtering apparatus, there is an effect that the contribution to the reduction of the manufacturing cost is remarkably large.

FIG. 1 is a schematic external view seen from the substrate side for explaining the concept of the configuration of the plasma CVD apparatus according to the first embodiment of the present invention. FIG. 2 is a schematic explanatory view for explaining an electrode plate and power supply means which are constituent members of the plasma CVD apparatus according to the first embodiment of the present invention. FIG. 3 is a schematic external view for explaining a source gas supply box which is a constituent member of the plasma CVD apparatus according to the first embodiment of the present invention. FIG. 4 is a schematic configuration diagram showing the configuration of the plasma CVD apparatus according to the first embodiment of the present invention. FIG. 5 is a schematic external view seen from the substrate side for explaining the concept of the configuration of the plasma CVD apparatus according to the second embodiment of the present invention. FIG. 6 is a schematic external view for explaining a source gas supply box and a discharge gas supply box which are constituent members of a plasma CVD apparatus according to the second embodiment of the present invention. FIG. 7 is a schematic configuration diagram showing a configuration of a plasma CVD apparatus according to the second embodiment of the present invention. FIG. 8 is a schematic external view seen from the substrate side for explaining the concept of the structure of the plasma CVD apparatus according to the third embodiment of the present invention. FIG. 9 is a schematic external view for explaining a source gas supply box which is a constituent member of a plasma CVD apparatus according to the third embodiment of the present invention. FIG. 10 is a schematic configuration diagram showing a configuration of a plasma CVD apparatus according to the third embodiment of the present invention.

Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. In each figure, the same code | symbol is attached | subjected to the same member and the overlapping description is abbreviate | omitted.
In addition, this invention is not limited to the following description, In the range which does not deviate from the summary of this invention, it can change suitably.
In the drawings shown below, the scale of each member may be different from the actual one for convenience of explanation. In addition, the scale may be different between the drawings.

(First embodiment)
A plasma CVD apparatus and a plasma CVD method according to the first embodiment of the present invention will be described. First, the configuration of the plasma CVD apparatus will be described.
FIG. 1 is a schematic external view seen from the substrate side for explaining the concept of the configuration of the plasma CVD apparatus according to the first embodiment of the present invention. FIG. 2 is a schematic explanatory view for explaining an electrode plate and power supply means which are constituent members of the plasma CVD apparatus according to the first embodiment of the present invention. FIG. 3 is a schematic external view for explaining a source gas supply box which is a constituent member of the plasma CVD apparatus according to the first embodiment of the present invention. FIG. 4 is a schematic configuration diagram showing the configuration of the plasma CVD apparatus according to the first embodiment of the present invention.

1 to 4, reference numeral 1 denotes a reaction vessel. The reaction vessel 1 has airtightness, and the degree of vacuum reached is 2.66 to 3.99 × 10 ⁻ by exhausting through the first exhaust port 2a and the second exhaust port 2b with a vacuum pump (not shown). It becomes about ⁵ Pa (2-3 × 10 ⁻⁷ Torr). Moreover, the inner wall of the reaction vessel 1 has no adhesion of impurities and satisfies the specifications applicable to plasma CVD.
The first and second exhaust ports 2a and 2b are exhausted so as to maintain the pressure inside the reaction vessel 1 at a predetermined value in cooperation with a vacuum pump (not shown) and a pressure gauge (not shown). Here, if the flow rate of the source gas is about 100 sccm to 5,000 sccm, an arbitrary pressure can be controlled in the range of about 1.33 Pa to 666.6 Pa (0.01 Torr to 5 Torr).
Reference numeral 3 denotes a film formation substrate. The film formation substrate 3 is a substrate made of a material such as glass, plastic, or silicon, and can be arbitrarily selected. Here, for example, a blue plate glass having a size: length 3 mx width 10 cm x thickness 5 mm is used as the film formation substrate 3.
As will be described later, the substrate size can be arbitrarily selected as long as it is in the range of about 0.1 mx 0.1 m to about 5 mx 5 m.
Reference numeral 3a denotes a substrate support shelf on which the film-formed substrate 3 is placed. The film formation substrate 3 is placed on the substrate support shelf 3a by a substrate carry-in / out device (not shown) and is carried out.

Reference numeral 5 denotes a plurality of electrode plates. The plurality of electrode plates 5 are arranged so that adjacent electrodes have a relationship between the non-ground electrode 5a and the ground electrode 5b. The power of the AC power supply 6 is supplied to the non-ground electrode 5a and the ground electrode 5b via the power supply conductors 8 and 9.
The frequency of the AC power source 6 is selected within a commercial frequency or a range of several KHz to 1 MHz. The reason is that the condition that the wavelength λ of the standing wave of power generated between the electrodes is sufficiently longer than the substrate size is satisfied. This eliminates the problems of plasma instability and plasma density non-uniformity due to standing waves. Here, the frequency of the output of the AC power supply 6 is a commercial frequency (for example, 60 Hz).
Reference numeral 7 denotes a variable resistor, which can adjust the output current of the AC power supply 6.
The length L of the plurality of electrode plates 5 is selected according to the size of the substrate. Further, the number of the plurality of electrode plates 5 can be increased or decreased according to the size of the substrate. That is, as the substrate size increases, it is possible to cope by increasing the length L and the number of the plurality of electrode plates 5 so as to be approximately equal to the size.
Reference numerals 10a and 10b are current introduction terminals for a vacuum vessel. The current introduction terminals 10a and 10b connect the air side and the vacuum side of the power supply conductors 8 and 9 so that there is no vacuum leakage.
Reference numeral 11 a is a connection point between the non-ground electrode 5 a and the power supply conductor 8. Reference numeral 11 b is a connection point between the ground electrode 5 b and the power supply conductor 9.

Reference numeral 12 denotes an electrode plate support member that fixes the plurality of electrode plates 5. The electrode plate support member 12 is made of an insulator. The electrode plate support member 12 fixes the electrode plate 5 and a later-described source gas supply box 15a. The electrode plate support member 12 and the source gas supply box 15a are hermetically sealed so that source gas described later does not leak. The electrode plate support member 12 is fixed to the reaction vessel 1.
Reference numeral 13 denotes a feed line laying hole for laying the power supply conductors 8 and 9. The feed line laying hole 13 is a through hole provided in the electrode plate support member 12, and is used to connect the connection point 11a between the power supply lead 8 and the non-ground electrode 5a. The electric wire laying hole 13 is used for connection of the connection point 11b between the power supply lead 9 and the ground electrode 5b.

Reference numeral 15a denotes a source gas supply box. The raw material gas supply box 15a has a large number of raw material gas ejection holes 16a through which a raw material gas supplied from a later-described raw material gas supply pipe 17a is ejected between the plurality of electrode plates 5.
The source gas ejection holes 16a have a hole diameter of about 0.3 mm to 1.2 mm and are arranged at intervals of about 2 mm to 10 mm. If it is the said hole diameter and the range of the said space | interval, the source gas injected between the electrode plates 5 will be injected substantially uniformly. Here, the diameter of the source gas ejection holes 16a is 0.6 mm, and the interval is 5 mm.
Reference numeral 17a denotes a source gas supply pipe. The raw material gas supply pipe 17a supplies an organic compound raw material, which will be described later, and a mixed gas of argon gas and oxygen to the raw material gas supply box 15a. Here, the number of source gas supply pipes 17a is described as one, but a plurality of source gas supply pipes 17a may be installed.

Reference numeral 20 denotes an organic compound raw material supply apparatus. The organic compound raw material supply device 20 stores an organic compound raw material that is liquid at room temperature and transports it to the liquid flow meter 21. The liquid flow meter 21 can set the flow rate of the organic compound raw material transported from the organic compound raw material supply device 20 to an arbitrary value within a range of about 0.1 sccm to 200 sccm, for example.
Reference numeral 22 denotes a carrier gas cylinder. The carrier gas is used to convey the organic compound raw material to the raw material gas supply pipe 17a. As the carrier gas, inert gas Ar or He which is an inert gas is used. Here, for example, Ar gas is used.
Reference numeral 23 denotes a carrier gas flow meter. The carrier gas flow meter 23 can set the carrier gas flow rate to an arbitrary value within a range of about 100 sccm to 5,000 sccm.
Reference numeral 25 denotes a vaporizer. The vaporizer 25 vaporizes the organic compound raw material transported to the vaporizer 25, mixes it with the carrier gas, and transports the mixed gas to the raw material gas supply pipe 17a.
Reference numeral 26 denotes an oxygen cylinder. The oxygen cylinder 26 stores oxygen and transports it to an oxygen flow meter 27 described later.
The oxygen flow meter 27 adjusts the flow rate of oxygen and transports it to the source gas supply pipe 17a. The flow rate of oxygen can be set to an arbitrary value in the range of about 100 sccm to 5,000 sccm.

  Note that when the substrate 3 to be deposited is carried into or out of the reaction vessel 1, a substrate loading / unloading door (not shown) is opened and closed. When film formation is completed and the substrate 3 is unloaded from the reaction vessel 1, a leak valve (not shown) attached to the outer wall of the reaction vessel 1 is opened to return the pressure in the reaction vessel 1 to atmospheric pressure. . Then, the substrate loading / unloading door (not shown) is opened and closed.

Next, using the plasma CVD apparatus shown in FIG. 1 to FIG. 4, a film forming method will be described by taking an organic EL barrier film and a SiO ₂ film, which is a low refractive index film of low-E glass, as an example.
As the source gas for the SiO ₂ film, a source gas containing at least one of an organic compound source containing silicon, oxygen, nitrogen, hydrogen, and a rare gas is used. Here, an organic compound material containing silicon and oxygen are selected, and Ar gas is used as a carrier gas for the organic compound material.
As an organic compound raw material, tetraethoxysilane (TEOS): “S _i (OC ₂ H ₅ ) ₄ ” or HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ” is selected. . Here, for example, HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ”. Ar gas is used as a carrier gas for transporting the organic compound raw material to the raw material gas supply pipe 17a.
When forming a silicon nitride (SiNx) film, as an organic compound material, for example, aminosilane: “(CH ₇ NS _i N ₂ )” or hexamethyldisilazane (HMDS): “(CH ₃ ) ₃ It is preferable to select “SiNHS _i (CH ₃ ) ₃ ”. Then, it is preferable to select at least one of N ₂ and NH ₃ as the nitriding auxiliary gas and use Ar gas as the carrier gas.
When forming a titanium oxide (T _i O _x ) film, for example, titanium tetraisopropoxide (TTIP): “T _i {OCH (CH ₃ ) ₂ } ₄ ” is selected as the organic compound raw material. good. Then, it is preferable to use O ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.
When forming a zinc oxide (Z _n O) film, as an organic compound raw material, for example, trimethyl zinc: “(CH ₃ ) ₃ Z _n ” or triethyl zinc: “(C ₂ H ₅ ) ₃ Z _n ”is better. Then, it is preferable to use O ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.
When an aluminum oxide (Al ₂ O _x ) film is formed, for example, trimethylaluminum: “(CH ₃ ) ₂ Al” is preferably selected as the organic compound material. Then, it is preferable to use H ₂ and CO ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.

In the following method for forming a SiO ₂ film, the film forming conditions are not required, and known film forming conditions are used.
In addition, in advance, the conditions of the power supply means such as the output of the AC power source 6, the size of the plurality of electrode plates 5 and the spacing between the electrodes, the conditions of the source gas, the deposition rate of the SiO ₂ film, the film quality, It is preferable to grasp the relationship with the film thickness distribution and select optimum conditions from the data.
Here, for example, the film formation substrate is a blue plate glass of size: length 3 mx width 10 cm x thickness 5 mm.
The size of the plurality of electrode plates 5 is length 3.2 mx width 5 cm x thickness 5 mm. The number of the electrode plates 5 is six. The distance between the electrodes is 2.5 cm. In addition, when the board | substrate size of the direction orthogonal to the width direction of the electrode plate 5 is long, the number of the some electrode plates 5 is increased so that it may correspond.
The frequency of the AC power supply 6 is a commercial frequency (here, 60 Hz), and the output can be arbitrarily selected within a range of 100 W to 10 KW. Here, for example, 2 kW is assumed. Note that the current density between the electrode plates can be increased or decreased by adjusting the variable resistor 7. Current density, good about 10μA ^/ cm ² ~100μA ^/ cm 2 is.

A substrate loading / unloading door (not shown) is opened, and the film-forming substrate 3 is placed on the substrate support shelf 3a. Then, a substrate loading / unloading door (not shown) is closed.
Next, a vacuum pump (not shown) is operated to lower the pressure inside the reaction vessel 1 to a vacuum level, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr).
The liquid flow meter 21 of the organic compound raw material supply apparatus 20 sets the HMDSO (hexamethyldisiloxane) to about 1 sccm to 8 sccm, for example, 5 sccm. The flow rate of the Ar gas as the carrier gas is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the carrier gas flow meter 23.
The oxygen flow rate is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the oxygen gas flow meter 27.
Then, the internal pressure of the reaction vessel 1 is set to about 1.33 Pa to 133.3 Pa (0.01 Torr to 1.0 Torr), for example, 13.3 Pa (0. 1 Torr).
Under this condition, a mixed gas of HMDSO (hexamethyldisiloxane), Ar gas, and oxygen gas is ejected between the plurality of electrode plates 5 from the source gas ejection hole 16a through the source gas supply pipe 17a.
Next, it is confirmed that the internal pressure of the reaction vessel 1 is kept constant under a predetermined condition, and is maintained at a required pressure, for example, 13.3 Pa (0.1 Torr).
Note that the temperature of the film formation substrate 3 is set to room temperature, and is not particularly set to a high temperature using the substrate temperature adjusting device.

Next, power is supplied from the AC power supply 6 to the plurality of power supply plates 5, that is, the non-ground electrode 5a and the ground electrode 5b. When electric power is supplied from the AC power supply 6 to the plurality of power supply plates 5, an electric field is generated between the electrode plates 5, and plasma is generated.
That is, in FIG. 4, the mixed gas supplied between the non-ground electrode 5a and the ground electrode 5b is turned into plasma. The plasma generation region is indicated by reference numeral 28 in FIG.

When the mixed gas is turned into plasma, the mixed gas is dissociated and radicals such as Si, C, O, and H that are electrically neutral are generated in addition to ions and electrons. Electrically neutral radicals move from the plurality of electrode plates 5 in the plasma generation region toward the film formation substrate 3 due to the diffusion phenomenon, and are deposited. As a result, a SiO ₂ film is formed on the deposition substrate 3.
In plasma at 60 Hz, ions in the plasma move following the electric field, collide with the electrode, and there are electrons generated by the γ effect, so the electron temperature becomes high and the dissociation action of the mixed gas by the plasma is strong. Therefore, radicals such as Si, C, O, and H that are electrically neutral are easily generated. As a result, the SiO ₂ film is effectively formed.

That is, the mixed gas of HMDSO (hexamethyldisiloxane), Ar gas, and oxygen gas introduced between the plurality of electrode plates 5 is intermolecularly interacted with high-energy electrons in the plasma 28 of FIG. Bonds dissociate.
The dissociated radicals of various molecules exist mainly in the plasma as radicals having a relatively small mass number. Specifically, Si, SiO, SiH, H, H ₂ , H ₂ O, C, O, CO, CO ₂ are generated. Then, as shown by a dotted arrow 29 in FIG. 4, the plasma moves from the plasma 28 toward the substrate 3 due to the diffusion phenomenon, and deposits on the surface of the substrate 3.
On the surface of the substrate 3, various radicals generated by the plasma cause a reaction represented by the following formula. CO ₂ and H ₂ O ride on the flow of exhaust gas and are discharged from the first and second exhaust holes 2a and 2b.
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
However, when dissociation of the mixed gas by plasma is insufficient or when the supply amount of oxygen is insufficient, for example, the following reaction occurs.
(CH ₃ ) ₆ Si ₂ O + 9O ₂ → 4CO ₂ + 9H ₂ O + 2SiOC
Therefore, the best film forming conditions in actual application are the conditions of the power supply means such as the output of the AC power supply 6, the size of the plurality of electrode plates 5 and the spacing between the electrodes, and the conditions of the source gas in advance. It is preferable to grasp the relationship between the film forming speed, the film quality, and the film thickness distribution of the SiO ₂ film and select the optimum conditions from the data.

Next, when a predetermined film forming time elapses in the film forming, the output of the AC power source 6 is reduced to zero. Then, the source gas supply device 20, the carrier gas cylinder 22 and the oxygen cylinder 26 (not shown) are closed to stop the supply of the source gas.
Thereafter, the pressure inside the reaction vessel 1 is once lowered to a degree of vacuum, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr). Then, a leak valve (not shown) is opened, and the atmosphere is introduced into the reaction vessel 1.
When the inside of the reaction vessel 1 reaches atmospheric pressure, a substrate loading / unloading door (not shown) is opened, and the film formation substrate 3 is taken out.

A substantially uniform SiO ₂ film is formed on the substrate 3 of the extracted long size (blue plate glass of length 3 mx width 10 cm x thickness 5 mm).
The projected area of the plasma 28 region viewed from the substrate side is as follows. In the above embodiment, the length of the plurality of electrode plates 5 is 3.2 m, the thickness is 5 mm, the electrode spacing is 2.5 cm, and the number of electrodes. Since there are 6 sheets, it is about 3.2 mx 15 cm.

As can be seen from the above description, the plasma CVD apparatus and plasma CVD method according to the first embodiment of the present invention have a function of forming a thin film corresponding to a 3 mx 3 m class substrate.
That is, in the plasma CVD apparatus having the configuration shown in FIGS. 1 to 4, the length of the plurality of electrode plates is set to about 3.2 m, the thickness is set to about 5 mm, and the number thereof is set to about 100, thereby reducing the substrate size. : A SiO ₂ film can be formed on a 3 mx 3 m class super large area substrate.
When the substrate size is 4mx4m to 5mx5m, the length of the plurality of electrodes 5 is set to 4m to 5m, and the number of the plates can be adapted to that, for example, 134 to 167 for easy application. Is possible.
In addition, the plasma CVD apparatus and plasma CVD method according to the first embodiment of the present invention do not apply an electric field for plasma generation to the substrate 3 and are not damaged by ion bombardment and are electrically neutral radicals. Since film formation by diffusion is utilized, high quality film formation is possible.
Therefore, in the application to the production of the organic EL barrier film and the SiO ₂ film which is the low refractive index film of low-E glass, there is an effect that it is possible to contribute to the improvement of the quality of the product and the improvement of the productivity.

The plasma CVD apparatus and the plasma CVD method according to the first embodiment of the present invention using the above-described SiO ₂ film as a representative example, of course, as an organic compound material, for example, aminosilane: “(CH ₇ NS _i N ₂ ”” Or hexamethyldisilazane (HMDS): “(CH ₃ ) ₃ SiNHS _i (CH ₃ ) ₃ ” can also be used to form a silicon nitride (SiNx) film.
Further, as an organic compound raw material, for example, titanium tetraisopropoxide (TTIP): “T _i {OCH (CH ₃ ) ₂ } ₄ ” can be used for forming a titanium oxide (T _i O _x ) film. .
Further, as an organic compound raw material, for example, a zinc oxide (Z _n O) film using trimethyl zinc: “(CH ₃ ) ₃ Z _n ” or triethyl zinc: “(C ₂ H ₅ ) ₃ Z _n ” is formed. It can also be used.
Further, as an organic compound raw material, for example, it can be used to form an aluminum oxide (Al ₂ O _x ) film using trimethylaluminum: “(CH ₃ ) ₂ Al”.
Similarly, it can be used to form various oxide films, nitride films, and carbonized films using various organic compound raw materials.

(Second Embodiment)
Next, a plasma CVD apparatus and a plasma CVD method according to the second embodiment of the present invention will be described with reference to FIGS.
In addition, in each figure, the same code | symbol is attached | subjected to the same member shown to FIG. 1 thru | or FIG. 4, and the overlapping description is abbreviate | omitted.
In the drawings shown below, the scale of each member may be different from the actual one for convenience of explanation. In addition, the scale may be different between the drawings.

  FIG. 5 is a schematic external view seen from the substrate side for explaining the concept of the configuration of the plasma CVD apparatus according to the second embodiment of the present invention. FIG. 6 is a schematic external view for explaining a source gas supply box and a discharge gas supply box which are constituent members of a plasma CVD apparatus according to the second embodiment of the present invention. FIG. 7 is a schematic configuration diagram showing a configuration of a plasma CVD apparatus according to the second embodiment of the present invention.

First, the configuration of the plasma CVD apparatus according to the second embodiment of the present invention will be described with reference to FIGS.
Reference numeral 15b denotes a discharge gas supply box. The discharge gas supply box 15b includes a discharge gas injection hole 16aa for discharging a discharge gas, which will be described later, between the plurality of electrode plates 5, and is supplied from a discharge gas supply pipe 17b, which will be described later. Gas is discharged from the discharge gas ejection hole 16aa,
It is ejected between the non-ground electrode 5a and the ground electrode 5b of the plurality of electrode plates 5.
Reference numeral 15c denotes a source gas supply box. The source gas supply box 15c includes a source gas ejection hole 16b that ejects source gas supplied from a source gas supply pipe 17c, which will be described later, in the vicinity of an edge portion facing the substrate 3 of a plurality of electrode plates 5, which will be described later. A source gas supplied from a source gas supply pipe 15c described later is supplied to the source gas ejection hole 16b.
However, the region where the source gas ejection holes 16b are arranged is the edge portion (depth W) of the electrode 5 indicated by the symbol W in FIG. Here, W = 5 mm. That is, the source gas ejection hole 16
b ejects the source gas in the vicinity of the edge of the plurality of electrode plates 5 facing the substrate 3.
Reference numeral 17b denotes a discharge gas supply pipe. The discharge gas supply pipe 17b supplies oxygen gas supplied from the oxygen cylinder 26 via the oxygen flow meter 27 to the discharge gas supply box 15b.
Reference numeral 17c is a raw material gas supply pipe. The source gas supply pipe 17c supplies a mixed gas of the organic compound source and carrier gas supplied from the vaporizer 25 to the source gas supply box 15c.

Next, using the plasma CVD apparatus shown in FIG. 5 to FIG. 7, a film forming method will be described by taking an organic EL barrier film and a SiO ₂ film, which is a low refractive index film of low-E glass, as an example.
As the source gas for the SiO ₂ film, a source gas containing at least one of an organic compound source containing silicon, oxygen, nitrogen, hydrogen, and a rare gas is used. Here, an organic compound raw material containing silicon, oxygen, and Ar gas are selected.
Tetraethoxysilane (TEOS): “S _i (OC ₂ H ₅ ) ₄ ” or HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ” is selected as the organic compound raw material. Here, for example, HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ”. Select oxygen as the auxiliary oxygen gas. Ar gas is used as a carrier gas for transporting the organic compound raw material to the raw material gas supply pipe 17c.
When forming a silicon nitride (SiNx) film, as an organic compound material, for example, aminosilane: “(CH ₇ NS _i N ₂ )” or hexamethyldisilazane (HMDS): “(CH ₃ ) ₃ It is preferable to select “SiNHS _i (CH ₃ ) ₃ ”. Then, it is preferable to select at least one of N ₂ and NH ₃ as the nitriding auxiliary gas and use Ar gas as the carrier gas.
When forming a titanium oxide (T _i O _x ) film, for example, titanium tetraisopropoxide (TTIP): “T _i {OCH (CH ₃ ) ₂ } ₄ ” is selected as the organic compound raw material. good. Then, it is preferable to use O ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.
When forming a zinc oxide (Z _n O) film, as an organic compound raw material, for example, trimethyl zinc: “(CH ₃ ) ₃ Z _n ” or triethyl zinc: “(C ₂ H ₅ ) ₃ Z _n ”is better. Then, it is preferable to use O ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.
When an aluminum oxide (Al ₂ O _x ) film is formed, for example, trimethylaluminum: “(CH ₃ ) ₂ Al” is preferably selected as the organic compound material. Then, it is preferable to use H ₂ and CO ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.

In the following method for forming a SiO ₂ film, the film forming conditions are not required, and known film forming conditions are used.
In addition, in advance, the conditions of the power supply means such as the output of the AC power source 6, the size of the plurality of electrode plates 5 and the spacing between the electrodes, the conditions of the source gas, the deposition rate of the SiO ₂ film, the film quality, It is preferable to grasp the relationship with the film thickness distribution and select optimum conditions from the data.
Here, for example, the film formation substrate is a blue plate glass of size: length 3 mx width 10 cm x thickness 5 mm.
The size of the plurality of electrode plates 5 is length 3.2 mx width 5 cm x thickness 5 mm. The number of the electrode plates 5 is six. The distance between the electrodes is 2.5 cm.
The frequency of the AC power source 6 is a commercial number (here, 60 Hz), and the output can be arbitrarily selected within a range of 300 W to 10 KW. Here, for example, 3 kW is assumed.
Note that the current density between the electrode plates can be increased or decreased by adjusting the variable resistor 7. The current density between the electrode plates can be increased or decreased by adjusting the variable resistor 7. Current density, good about 10μA ^/ cm ² ~100μA ^/ cm 2 is.

A substrate loading / unloading door (not shown) is opened, and the film-forming substrate 3 is placed on the substrate support shelf 3a. Then, a substrate loading / unloading door (not shown) is closed.
Next, a vacuum pump (not shown) is operated to lower the pressure inside the reaction vessel 1 to a vacuum level, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr).
The liquid flow meter 21 of the organic compound raw material supply device 20 is set to about 1 sccm to 8 sccm of HMDSO (hexamethyldisiloxane), for example, 3 sccm.
The flow rate of the Ar gas as the carrier gas is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the carrier gas flow meter 23. The mixed gas of the organic compound raw material and the carrier gas is transported from the vaporizer 25 to the raw material gas supply pipe 17c.
Then, the source gas is ejected from the vicinity of the edge facing the film forming surface of the substrate 3 of the plurality of electrode plates 5 from the source gas supply pipe 15c through the source gas ejection hole 16b.
The flow rate of oxygen in the oxygen cylinder 26 is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the oxygen gas flow meter 27. The oxygen gas supplied from the oxygen cylinder 26 via the oxygen gas flow meter 27 is supplied to the discharge gas supply pipe 17b. And it is made to eject between the some electrode plates 5 from the discharge gas ejection hole 16aa with which the discharge gas supply box 15b is equipped from the discharge gas supply pipe | tube 17b.

Then, the internal pressure of the reaction vessel 1 is set to about 1.33 Pa to 133.3 Pa (0.01 Torr to 1.0 Torr), for example, 13.3 Pa (0. 1 Torr).
Under these conditions, a mixed gas of HMDSO (hexamethyldisiloxane) and Ar gas is supplied from the source gas injection hole 16b through the source gas supply box 15c and in the vicinity of the edge facing the film forming surface of the substrate 3 of the plurality of electrode plates 5. The raw material gas is spouted from.
On the other hand, oxygen gas is ejected between the plurality of electrode plates 5 from the discharge gas ejection holes 16aa through the discharge gas supply box 17b.
Next, it is confirmed that the internal pressure of the reaction vessel 1 is kept constant under a predetermined condition, and is maintained at a required pressure, for example, 13.3 Pa (0.1 Torr).
Note that the temperature of the film formation substrate 3 is set to room temperature, and is not particularly set to a high temperature using the substrate temperature adjusting device.

Next, power is supplied from the AC power supply 6 to the plurality of power supply plates 5, that is, the non-ground electrode 5a and the ground electrode 5b. When electric power is supplied from the AC power supply 6 to the plurality of power supply plates 5, an electric field is generated between the electrode plates 5, and oxygen gas plasma is generated.
That is, in FIG. 7, the discharge gas, that is, oxygen gas supplied between the non-ground electrode 5a and the ground electrode 5b is turned into plasma.
The oxygen plasma generation region is a region indicated by reference numeral 30 in FIG. The oxygen plasma in the oxygen generation region plasma 30 is pushed out by the oxygen gas supplied from the discharge gas ejection holes 16aa to form an oxygen plasma flow 31 from between the plurality of electrode plates 5 toward the substrate 3. Move while spreading.

  Part of the source gas ejected from the source gas ejection hole 16 b is converted into plasma by the electric field of the electrode plate 5 generated by the electric power supplied from the AC power source 6. Most of the plasma is converted into plasma by contact with the oxygen plasma flow 31. The source gas plasma region is indicated by reference numeral 32 in FIG.

In general, an organic compound is easily dissociated by electron collision in plasma. Therefore, if the plasma electron energy and plasma density are too high, it becomes difficult to form a thin film having a target composition.
For example, when forming a SiO ₂ film using HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ” as a raw material organic compound,
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
Not obeying the following equation:
(CH ₃ ) ₆ Si ₂ O + 9O ₂ → 4CO ₂ + 9H ₂ O + 2SiOC
As a result.

In contrast, when the source gas HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ” is exposed to oxygen plasma, the dissociation of the methyl group and the oxidation reaction proceed appropriately. In the plasma, radicals having a relatively small mass number are generated. Specifically, C, O, H, H ₂ , Si, SiO, SiH, H ₂ O, CO, CO _{2 and the} like are generated.
Then, various radicals move from the plasma 32 toward the substrate 3 due to the diffusion phenomenon and are deposited on the surface of the substrate 3 from the plasma region 32 of the source gas, as indicated by a dotted arrow 33 in FIG.
Various radicals generated by the plasma on the surface of the substrate 3 or in the vicinity thereof cause a reaction represented by the following formula.
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
Note that CO ₂ and H ₂ O ride on the flow of exhaust gas and are discharged from the first and second exhaust holes 2a and 2b.

Next, when a predetermined film forming time elapses in the film forming, the output of the AC power source 6 is reduced to zero. Then, the supply gas supply is stopped by closing the valve of the raw material gas supply device 20, the valve of the carrier gas cylinder 22 and the valve of the oxygen cylinder 26 (not shown).
Thereafter, the pressure inside the reaction vessel 1 is once lowered to a degree of vacuum, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr). Then, a leak valve (not shown) is opened to bring the atmosphere into the reaction vessel 1.
When the inside of the reaction vessel 1 reaches atmospheric pressure, a substrate loading / unloading door (not shown) is opened, and the film formation substrate 3 is taken out.

A substantially uniform SiO ₂ film is formed on the substrate 3 of the extracted long size (blue plate glass of length 3 mx width 10 cm x thickness 5 mm).
The total area of the plasma 28 viewed from the substrate side is as follows. In the above embodiment, the length of the plurality of electrode plates 5 is 3.2 m, the thickness is 5 mm, the electrode spacing is 2.5 cm, Since the number of sheets is 6, it is about 3.2 mx 15 cm.

As can be seen from the above description, the plasma CVD apparatus and plasma CVD method according to the first embodiment of the present invention have a function of forming a thin film corresponding to a 3 mx 3 m class substrate.
That is, in the plasma CVD apparatus having the configuration shown in FIGS. 5 to 7, the length of the plurality of electrode plates is set to about 3.2 m, the thickness is set to about 5 mm, and the number thereof is set to about 100, thereby reducing the substrate size. : A SiO ₂ film can be formed on a 3 mx 3 m class super large area substrate.
When the substrate size is 4mx4m to 5mx5m, the length of the plurality of electrodes 5 is set to 4m to 5m, and the number of the plates can be adapted to that, for example, 134 to 167 for easy application. Is possible.
In addition, the plasma CVD apparatus and the plasma CVD method according to the second embodiment of the present invention utilize movement caused by diffusion of various electrically neutral radicals without applying an electric field for plasma generation to the substrate 3. Therefore, high quality film formation is possible.

In the plasma CVD apparatus and the plasma CVD method according to the second embodiment of the present invention, compared with the plasma CVD apparatus and the plasma CVD method according to the first embodiment of the present invention, HMDSO ( Hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ” can be brought into contact with oxygen plasma to form a film without ion bombardment. As a result, a high-quality SiO ₂ film can be formed. It is.

The plasma CVD apparatus and the plasma CVD method according to the second embodiment of the present invention convert the source gas into plasma by bringing oxygen plasma into contact with the source gas of the organic compound in a region close to the surface of the substrate 3. Therefore, it is possible to easily form a high-quality SiO ₂ film, and the film forming speed is high.
Therefore, in the application to the production of the organic EL barrier film and the SiO ₂ film which is the low refractive index film of low-E glass, there is an effect that it is possible to contribute to the improvement of the quality of the product and the improvement of the productivity.

The plasma CVD apparatus and the plasma CVD method according to the second embodiment of the present invention using the above-described SiO ₂ film as a representative example, as a matter of course, as an organic compound material, for example, aminosilane: “(CH ₇ NS _i N ₂ ”” Or hexamethyldisilazane (HMDS): “(CH ₃ ) ₃ SiNHS _i (CH ₃ ) ₃ ” can also be used to form a silicon nitride (SiNx) film.
Further, as an organic compound raw material, for example, titanium tetraisopropoxide (TTIP): “T _i {OCH (CH ₃ ) ₂ } ₄ ” can be used to form a titanium oxide (T _i O _x ) film. .
In addition, formation of a zinc oxide (Z _n O) film using, for example, trimethyl zinc: “(CH ₃ ) ₃ Z _n ” or triethyl zinc: “(C ₂ H ₅ ) ₃ Z _n ” as an organic compound raw material It can also be used.
Further, as an organic compound raw material, for example, it can be used to form an aluminum oxide (Al ₂ O _x ) film using trimethylaluminum: “(CH ₃ ) ₂ Al”.
Similarly, it can be used to form various oxide films, nitride films, and carbonized films using various organic compound raw materials.

(Third embodiment)
Next, a plasma CVD apparatus and a plasma CVD method according to the third embodiment of the present invention will be described with reference to FIGS.
In addition, in each figure, the same code | symbol is attached | subjected to the same member shown to FIG. 1 thru | or FIG. 7, and the overlapping description is abbreviate | omitted.
In the drawings shown below, the scale of each member may be different from the actual one for convenience of explanation. In addition, the scale may be different between the drawings.
FIG. 8 is a schematic external view seen from the substrate side for explaining the concept of the structure of the plasma CVD apparatus according to the third embodiment of the present invention. FIG. 9 is a schematic external view for explaining a source gas supply box which is a constituent member of a plasma CVD apparatus according to the third embodiment of the present invention.
FIG. 10 is a schematic configuration diagram showing a configuration of a plasma CVD apparatus according to the third embodiment of the present invention.

First, the configuration of a plasma CVD apparatus according to the third embodiment of the present invention will be described.
8 to 10, reference numeral 50 denotes an insulating material frame made of an insulating material. The insulating material frame 50 electrically insulates the plurality of electrode plates 5 and the source gas supply box 15c and prevents the source gas from leaking.
The source gas supply box 15 c has a large number of source gas ejection holes 16 a through which the source gas supplied from the source gas supply pipe 17 a is ejected between the plurality of electrode plates 5.
In FIG. 8, a plurality of electrode plates 5 are alternately arranged with a ground electrode 5b, a non-ground electrode 5a, a ground electrode 5b, and a non-ground electrode 5a in order from the left end as shown in FIG. Then, as shown in FIG. 8, the space formed by the adjacent electrodes in order from the left end is alternately formed into an exhaust passage 52 through which the exhaust gas passes and a source gas supply passage 51 through which the source gas passes.

As shown in FIGS. 8 to 10, the plasma CVD apparatus according to the third embodiment of the present invention is characterized in that a source gas supply passage 51 through which source gas passes between a plurality of electrode plates and a space between a plurality of electrode plates are exhausted. It has an exhaust passage 52 through which gas passes.

Next, using the plasma CVD apparatus shown in FIG. 8 to FIG. 10, the film forming method will be described by taking an organic EL barrier film and a SiO ₂ film as a low refractive index film of low-E glass as an example.
As the source gas for the SiO ₂ film, a source gas containing at least one of an organic compound source containing silicon, oxygen, nitrogen, hydrogen, and a rare gas is used. Here, an organic compound raw material containing silicon, oxygen, and Ar gas are selected.
Tetraethoxysilane (TEOS): “S _i (OC ₂ H ₅ ) ₄ ” or HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ” is selected as the organic compound raw material. Here, for example, HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ”. Ar gas is used as a carrier gas for transporting the organic compound raw material to the raw material gas supply pipe 17a.

When forming a silicon nitride (SiNx) film, as an organic compound material, for example, aminosilane: “(CH ₇ NS _i N ₂ )” or hexamethyldisilazane (HMDS): “(CH ₃ ) ₃ It is preferable to select “SiNHS _i (CH ₃ ) ₃ ”. Then, it is preferable to select at least one of N ₂ and NH ₃ as an auxiliary gas for nitriding and use Ar gas as a carrier gas.
When forming a titanium oxide (T _i O _x ) film, for example, titanium tetraisopropoxide (TTIP): “T _i {OCH (CH ₃ ) ₂ } ₄ ” is selected as the organic compound raw material. good. Then, it is preferable to use O ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.
When forming a zinc oxide (Z _n O) film, as an organic compound raw material, for example, trimethyl zinc: “(CH ₃ ) ₃ Z _n ” or triethyl zinc: “(C ₂ H ₅ ) ₃ Z _n ”is better. Then, it is preferable to use O ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.
When an aluminum oxide (Al ₂ O _x ) film is formed, for example, trimethylaluminum: “(CH ₃ ) ₂ Al” is preferably selected as the organic compound material. Then, it is preferable to use H ₂ and CO ₂ as the oxidation auxiliary gas and Ar gas as the carrier gas.

In the following method for forming a SiO ₂ film, the film forming conditions are not required, and known film forming conditions are used.
In addition, in advance, the conditions of the power supply means such as the output of the AC power source 6, the size of the plurality of electrode plates 5 and the spacing between the electrodes, the conditions of the source gas, the deposition rate of the SiO ₂ film, the film quality, It is preferable to grasp the relationship with the film thickness distribution and select optimum conditions from the data.
Here, for example, the film formation substrate is a blue plate glass of size: length 3 mx width 10 cm x thickness 5 mm.
The size of the plurality of electrode plates 5 is length 3.2 mx width 5 cm x thickness 5 mm. The number of the electrode plates 5 is 10. The distance between the electrodes is 2.5 cm.
The frequency of the AC power source 6 is a commercial frequency (here, 60 Hz), and the output can be arbitrarily selected within a range of 300 W to 10 KW. Here, for example, 2 kW is assumed. Note that the current density between the electrode plates can be increased or decreased by adjusting the variable resistor 7. Current density, good about 10μA ^/ cm ² ~100μA ^/ cm 2 is.

A substrate loading / unloading door (not shown) is opened, and the film-forming substrate 3 is placed on the substrate support shelf 3a. Then, a substrate loading / unloading door (not shown) is closed.
Next, a vacuum pump (not shown) is operated to lower the pressure inside the reaction vessel 1 to a vacuum level, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr).
The liquid flow meter 21 of the organic compound raw material supply apparatus 20 sets the HMDSO (hexamethyldisiloxane) to about 1 sccm to 8 sccm, for example, 5 sccm. The flow rate of the Ar gas as the carrier gas is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the carrier gas flow meter 23. The oxygen flow rate is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the oxygen gas flow meter 27.
Then, the internal pressure of the reaction vessel 1 is set to about 1.33 Pa to 133.3 Pa (0.01 Torr to 1.0 Torr), for example, 13.3 Pa (0. 1 Torr).
Under this condition, a mixed gas of HMDSO (hexamethyldisiloxane), Ar gas, and oxygen gas is ejected between the plurality of electrode plates 5 from the source gas ejection hole 16a through the source gas supply pipe 17a.
Next, it is confirmed that the internal pressure of the reaction vessel 1 is kept constant under a predetermined condition, and is maintained at a required pressure, for example, 13.3 Pa (0.1 Torr).
Note that the temperature of the film formation substrate 3 is set to room temperature, and is not particularly set to a high temperature using the substrate temperature adjusting device.

Next, power is supplied from the AC power supply 6 to the plurality of power supply plates 5, that is, the non-ground electrode 5a and the ground electrode 5b. When electric power is supplied from the AC power supply 6 to the plurality of power supply plates 5, an electric field is generated between the electrode plates 5, and plasma is generated.
That is, in FIG. 10, the mixed gas supplied between the non-grounded electrode 5a and the grounded electrode 5b is turned into plasma.

When the mixed gas is turned into plasma, the mixed gas is dissociated and radicals such as Si, C, O, and H that are electrically neutral are generated in addition to ions and electrons.
Electrically neutral radicals move from the plurality of electrode plates 5 in the plasma generation region toward the film-forming substrate 3 due to a diffusion phenomenon, and are deposited. As a result, a SiO ₂ film is formed on the deposition substrate 3.
In plasma at 60 Hz, ions in the plasma move following the electric field, collide with the electrode, and there are electrons generated by the γ effect, so the electron temperature becomes high and the dissociation action of the mixed gas by the plasma is strong. Therefore, radicals such as Si, C, O, and H that are electrically neutral are easily generated. As a result, the SiO ₂ film is effectively formed.

That is, the mixed gas of HMDSO (hexamethyldisiloxane), Ar gas, and oxygen gas introduced between the plurality of electrode plates 5 interacts with high energy electrons in the plasma generated between the electrodes in FIG. Causes dissociation of intramolecular bonds.
The dissociated radicals of various molecules exist mainly in the plasma as radicals having a relatively small mass number. Specifically, Si, SiO, SiH, H, H ₂ , H ₂ O, C, O, CO, CO ₂ are generated. Then, various electrically neutral radicals move from the plasma generated between the electrode plates toward the substrate 3 due to a diffusion phenomenon as shown by a dotted arrow 53 in FIG. 10 and are deposited on the surface of the substrate 3. To do.

On the surface of the substrate 3, various radicals generated by the plasma cause a reaction represented by the following formula.
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
If powder or particles not shown in the reaction formula are generated, they are discharged along with the CO ₂ and H ₂ O along with the air flow in the exhaust passage 52 formed by the ground electrode 5b and the non-ground electrode 5a.
In the plasma CVD apparatus shown in FIGS. 8 to 10, since the plurality of electrode plates 5 alternately form the source gas supply passages 51 and the exhaust passages 52, the gas discharge near the film forming surface of the substrate 3 is performed. Evenly and easily done.
Note that since the gas is discharged well, secondary reactions and tertiary reactions of radicals with high reactivity in plasma can be suppressed, and as a result, mixing of powder and particles into the film can be suppressed.
Further, the supply of the source gas supplied from the source gas supply passage 51 is performed substantially uniformly in the vicinity of the film forming surface of the substrate 3. Similarly, the gas exhausted from the exhaust passage 52 is discharged uniformly.
In general, when a large area substrate is targeted, the uniform supply amount of the source gas and the uniform distribution of the exhaust gas flow are important conditions for uniform film formation on the surface of the substrate 3. It is.

Next, when a predetermined film forming time elapses in the film forming, the output of the AC power source 6 is reduced to zero. Then, the source gas supply device 20, the carrier gas cylinder 22 and the oxygen cylinder 26 (not shown) are closed to stop the supply of the source gas.
Thereafter, the pressure inside the reaction vessel 1 is once lowered to a degree of vacuum, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr). Then, a leak valve (not shown) is opened to bring the atmosphere into the reaction vessel 1.
When the inside of the reaction vessel 1 reaches atmospheric pressure, a substrate loading / unloading door (not shown) is opened, and the film formation substrate 3 is taken out.

A substantially uniform SiO ₂ film is formed on the substrate 3 of the extracted long size (blue plate glass of length 3 mx width 10 cm x thickness 5 mm).

As can be seen from the above description, the plasma CVD apparatus and plasma CVD method according to the third embodiment of the present invention have a function of forming a thin film corresponding to a 3 mx 3 m class substrate.
That is, in the plasma CVD apparatus configured as shown in FIGS. 8 to 10, the length of the plurality of electrode plates is set to about 3.2 m, the thickness is set to about 5 mm, and the number thereof is set to about 100, thereby reducing the substrate size. : A SiO ₂ film can be formed on a 3 mx 3 m class super large area substrate.
In addition, the plasma CVD apparatus and the plasma CVD method according to the third embodiment of the present invention have an apparatus configuration that utilizes movement by diffusion of various electrically neutral radicals that are important in film formation by plasma CVD. High quality film formation is possible.
Therefore, in the application to the production of the organic EL barrier film and the SiO ₂ film which is the low refractive index film of low-E glass, there is an effect that it is possible to contribute to the improvement of the quality of the product and the improvement of the productivity.

The plasma CVD apparatus and the plasma CVD method according to the first embodiment of the present invention using the above-described SiO ₂ film as a representative example, of course, as an organic compound material, for example, aminosilane: “(CH ₇ NS _i N ₂ ”” Or hexamethyldisilazane (HMDS): “(CH ₃ ) ₃ SiNHS _i (CH ₃ ) ₃ ” can also be used to form a silicon nitride (SiNx) film.
Further, as an organic compound raw material, for example, titanium tetraisopropoxide (TTIP): “T _i {OCH (CH ₃ ) ₂ } ₄ ” can be used to form a titanium oxide (T _i O _x ) film. .
In addition, formation of a zinc oxide (Z _n O) film using, for example, trimethyl zinc: “(CH ₃ ) ₃ Z _n ” or triethyl zinc: “(C ₂ H ₅ ) ₃ Z _n ” as an organic compound raw material It can also be used.
Further, as an organic compound raw material, for example, it can be used to form an aluminum oxide (Al ₂ O _x ) film using trimethylaluminum: “(CH ₃ ) ₂ Al”.
Similarly, it can be used to form various oxide films, nitride films, and carbonized films using various organic compound raw materials.

(Fourth embodiment)
Next, a plasma CVD apparatus and a plasma CVD method according to the fourth embodiment of the present invention will be described.
First, the configuration of a plasma CVD apparatus according to the fourth embodiment of the present invention will be described. In the plasma CVD apparatus and the plasma CVD method in the first to third embodiments described above, the substrate 3 is placed on the substrate support shelf 3a by a substrate carry-in / out device (not shown) and is kept stationary during film formation. Was. Unlike this, the plasma CVD apparatus and the plasma CVD method according to the fourth embodiment of the present invention are characterized in that the substrate is moved during film formation using a substrate transfer conveyor 60 (not shown).
The configuration of the plasma CVD apparatus according to the fourth embodiment of the present invention is replaced with a substrate transfer conveyor 60 (not shown) that uses the substrate support shelf 3a for moving the substrate in FIG. The rest is the same as FIG. 7 of the plasma CVD apparatus in the second embodiment described above.

A substrate loading / unloading door (not shown) is opened, and the film-forming substrate 3 is placed on the substrate moving conveyor 60. Then, a substrate loading / unloading door (not shown) is closed.
Next, a vacuum pump (not shown) is operated to lower the pressure inside the reaction vessel 1 to a vacuum level, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr).
The liquid flow meter 21 of the organic compound raw material supply device 20 is set to about 1 sccm to 8 sccm of HMDSO (hexamethyldisiloxane), for example, 3 sccm.
The flow rate of the Ar gas as the carrier gas is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the carrier gas flow meter 23. The mixed gas of the organic compound raw material and the carrier gas is transported from the vaporizer 25 to the raw material gas supply pipe 17c.
Then, the source gas is ejected from the vicinity of the edge facing the film forming surface of the substrate 3 of the plurality of electrode plates 5 from the source gas supply pipe 15c through the source gas ejection hole 16b.
The flow rate of oxygen in the oxygen cylinder 26 is set to about 400 sccm to 1600 sccm, for example, 800 sccm by the oxygen gas flow meter 27. The oxygen gas supplied from the oxygen cylinder 26 via the oxygen gas flow meter 27 is supplied to the discharge gas supply pipe 17b. And it is made to eject between the some electrode plates 5 from the discharge gas ejection hole 16aa with which the discharge gas supply box 15b is equipped from the discharge gas supply pipe | tube 17b.

Then, the internal pressure of the reaction vessel 1 is set to about 1.33 Pa to 133.3 Pa (0.01 Torr to 1.0 Torr), for example, 13.3 Pa (0. 1 Torr).
Under these conditions, a mixed gas of HMDSO (hexamethyldisiloxane) and Ar gas is supplied from the source gas injection hole 16b through the source gas supply box 15c and in the vicinity of the edge facing the film forming surface of the substrate 3 of the plurality of electrode plates 5. The raw material gas is spouted from.
On the other hand, oxygen gas is ejected between the plurality of electrode plates 5 from the discharge gas ejection holes 16aa through the discharge gas supply box 15b.
Next, it is confirmed that the internal pressure of the reaction vessel 1 is kept constant under a predetermined condition, and is maintained at a required pressure, for example, 13.3 Pa (0.1 Torr).
Note that the temperature of the film formation substrate 3 is set to room temperature, and is not particularly set to a high temperature using the substrate temperature adjusting device.

Next, power is supplied from the AC power supply 6 to the plurality of power supply plates 5, that is, the non-ground electrode 5a and the ground electrode 5b. When electric power is supplied from the AC power supply 6 to the plurality of power supply plates 5, an electric field is generated between the electrode plates 5, and oxygen gas plasma is generated.
That is, in FIG. 7, the discharge gas, that is, oxygen gas supplied between the non-ground electrode 5a and the ground electrode 5b is turned into plasma.
The oxygen plasma generation region is a region indicated by reference numeral 30 in FIG. The oxygen plasma in the oxygen generation region plasma 30 is pushed out by the oxygen gas supplied from the discharge gas ejection holes 16aa to form an oxygen plasma flow 31 from between the plurality of electrode plates 5 toward the substrate 3. Move while spreading.

  Part of the source gas ejected from the source gas ejection hole 16 b is converted into plasma by the electric field of the electrode plate 5 generated by the electric power supplied from the AC power source 6. Most of the plasma is converted into plasma by contact with the oxygen plasma flow 31. The source gas plasma region is indicated by reference numeral 32 in FIG.

Next, the substrate moving conveyor 60 is operated. The conveyance speed of the board | substrate movement conveyor 60 which mounted the board | substrate 3 is arbitrarily selected in the range of 1 cm / min-2 m / min. Here, for example, the conveyance speed is 30 cm / min.
When the substrate is placed on the substrate moving conveyor 60, the substrate monitoring control device 61 is installed at the substrate moving conveyor (not shown), and the position of the substrate 3 and the plasma generation region 32 is set by the device. The relationship is monitored. The timing at which the substrate 3 enters the plasma generation region 32 and the timing at which the substrate finishes passing through the plasma generation region 32 can be controlled.

In FIG. 7, in the source gas plasma generation region 32, the source gas HMDSO (hexamethyldisiloxane): “O [S _i (CH ₃ ) ₃ ] ₂ ” and the oxygen plasma flow are in contact with each other, and the source gas is moderately When converted into plasma, the source gas is dissociated, and radicals such as SiO, _Si , C, O, and H that are electrically neutral are generated in addition to ions and electrons.
Electrically neutral radicals move from the plasma generation region 32 of the source gas to the deposition target substrate 3 by the diffusion phenomenon as shown by reference numeral 33 in FIG. As a result, a SiO ₂ film is formed on the deposition substrate 3.
_Si radicals and O radicals in various electrically neutral radicals form SiO ₂ on the substrate 3, and radicals such as C, O, and H form CO ₂ and H ₂ O, and exhaust gas. It is discharged in the gas stream.

Next, when a predetermined film forming time elapses in the above film formation, that is, when the substrate monitoring control device 61 senses the timing when the substrate has finished passing through the plasma generation region 32, the output of the AC power source 6 is reduced to zero. To.
Then, the supply gas supply is stopped by closing the valve of the raw material gas supply device 20, the valve of the carrier gas cylinder 22 and the valve of the oxygen cylinder 26 (not shown).
Thereafter, the pressure inside the reaction vessel 1 is once lowered to a degree of vacuum, for example, about 2.66 Pa (2 × 10 ⁻⁷ Torr). Then, a leak valve (not shown) is opened to bring the atmosphere into the reaction vessel 1.
When the inside of the reaction vessel 1 reaches atmospheric pressure, a substrate loading / unloading door (not shown) is opened, and the film formation substrate 3 is taken out.

A substantially uniform SiO ₂ film is formed on the substrate 3 of the extracted long size (blue plate glass of length 3 mx width 10 cm x thickness 5 mm).
Since the length of the electrode in the plasma CVD apparatus according to the fourth embodiment of the present invention is 3.2 m, the size of the substrate on which the film is formed is 3.2 m and the length of the electrode. It can be selected by adjusting the length of the moving conveyor 60 in the substrate conveyance direction.
Further, the size of the source gas plasma generation region 32 in the conveyance direction of the substrate moving conveyor 60 can be increased to an arbitrary value by increasing the number of the plurality of electrode plates 5.

As can be seen from the above description, the plasma CVD apparatus and plasma CVD method according to the fourth embodiment of the present invention have a function of forming a thin film corresponding to a 3 mx 3 m class substrate.
That is, it can be easily realized by appropriately selecting the length of the substrate transfer conveyor 60 in the substrate transfer direction and the transfer speed.
In addition, the size of the plasma generation region 32 of the source gas is set such that the length of the plurality of electrode plates is about 3.2 m, the thickness is about 5 mm, and the number is about about the number in the plasma CVD apparatus configured as shown in FIG. By setting the number to 100, it is possible to easily cope with a super large area substrate having a substrate size of 3 mx 3 m.
When the substrate size is 4 mx 4 m to 5 mx 5 m, the length of the plurality of electrodes 5 is set to 4 m to 5 m, and the number of the materials is set to be, for example, 134 to 167, so that the source gas By further increasing the plasma generation region 32, it is possible to easily cope with a substrate with a substrate size of 4mx4m class.

By moving the substrate 3 using a substrate moving conveyor 60 (not shown), the uniformity of the film thickness can be significantly improved.
Therefore, in the application to the production of the organic EL barrier film and the SiO ₂ film which is the low refractive index film of low-E glass, there is an effect that it is possible to contribute to the improvement of the quality of the product and the improvement of the productivity.

Of course, in the plasma CVD apparatus and plasma CVD method according to the fourth embodiment of the present invention using the SiO ₂ film as a representative example, as an organic compound material, for example, aminosilane: “(CH ₇ NS _i N _2). ”” Or hexamethyldisilazane (HMDS): “(CH ₃ ) ₃ SiNHS _i (CH ₃ ) ₃ ” can also be used to form a silicon nitride (SiNx) film.
Further, as an organic compound raw material, for example, titanium tetraisopropoxide (TTIP): “T _i {OCH (CH ₃ ) ₂ } ₄ ” can be used to form a titanium oxide (T _i O _x ) film. .
In addition, formation of a zinc oxide (Z _n O) film using, for example, trimethyl zinc: “(CH ₃ ) ₃ Z _n ” or triethyl zinc: “(C ₂ H ₅ ) ₃ Z _n ” as an organic compound raw material It can also be used.
Further, as an organic compound raw material, for example, it can be used to form an aluminum oxide (Al ₂ O _x ) film using trimethylaluminum: “(CH ₃ ) ₂ Al”.
Similarly, it can be used to form various oxide films, nitride films, and carbonized films using various organic compound raw materials.

1 ... reaction vessel,
2a, 2b ... 1st and 2nd exhaust port 2a, 2b,
3 ... Film-forming substrate,
5 ... a plurality of electrode plates,
5a, 5b ... non-grounded electrode and grounded electrode,
6 ... AC power supply,
8, 9 ... power supply lead,
12 ... Electrode plate support member,
15a ... Raw material gas supply box,
16a, 16b ... Raw material gas ejection holes,
16aa ... oxygen gas ejection hole,
17a, 17b ... Raw material gas supply pipes,
20 ... Organic compound raw material supply device,
21 ... Liquid flow meter,
22 ... Carrier gas cylinder,
23 ... Carrier gas flow meter,
25 ... Vaporizer,
26... Oxygen cylinder 60...

Claims (9)

A substrate holding means on which a substrate to be deposited is placed is housed, a reaction vessel provided with an exhaust means, a raw material gas supply means for supplying a raw material gas to the reaction vessel, and parallel to the reaction vessel, and A plurality of electrode plates arranged with their edges facing the film-forming surface of the substrate to be deposited, and a power supply for generating plasma between the plurality of electrode plates by supplying AC power to the plurality of electrode plates A plasma CVD apparatus comprising:
The source gas supply means includes a source gas containing at least one selected from an organic compound source, oxygen, nitrogen, ammonia, hydrogen and a carrier gas, and includes a plurality of source gas ejection holes for ejecting the source gas. A plasma CVD apparatus having a structure in which the electrode plate is disposed at a position adjacent to an edge not facing the film forming surface of the film forming substrate. A substrate holding means on which a substrate to be deposited is placed is housed, a reaction vessel provided with an exhaust means, a raw material gas supply means for supplying a raw material gas to the reaction vessel, and parallel to the reaction vessel, and A plurality of electrode plates arranged with their edges facing the film-forming surface of the substrate to be deposited, and a power supply for generating plasma between the plurality of electrode plates by supplying AC power to the plurality of electrode plates A plasma CVD apparatus comprising:
The raw material gas supply means includes a raw material gas containing at least one selected from organic compound raw materials, oxygen, nitrogen, ammonia, hydrogen, and a carrier gas, and is selected from oxygen, nitrogen, hydrogen, and a rare gas. Discharge gas ejection holes including at least one kind of discharge gas are disposed, and discharge gas ejection holes for ejecting the discharge gas are arranged at positions adjacent to edges of the plurality of electrode plates that do not face the film formation surface of the film formation substrate. And a source gas ejection hole for ejecting the source gas is disposed at a position adjacent to an edge of the plurality of electrode plates facing the film forming surface of the film forming substrate. CVD equipment. The source gas supply means has a source gas supply passage through which the source gas passes between the plurality of electrode plates, and the exhaust means has an exhaust passage through which exhaust gas passes between the plurality of electrode plates. The plasma CVD apparatus according to claim 1. The source gas supply means has a discharge gas supply passage through which the discharge gas passes between the plurality of electrode plates, and the exhaust means has an exhaust passage through which the exhaust gas passes between the plurality of electrode plates. The plasma CVD apparatus according to claim 2, wherein the plasma CVD apparatus is provided. 5. The plasma CVD apparatus according to claim 1, wherein a frequency of power of the power supply unit is a commercial frequency of 50 Hz or 60 Hz. 5. The plasma CVD apparatus according to claim 1, wherein a frequency of power of the power supply unit is a frequency selected from a range of several KHz to 1 MHz or less. The source gas is at least selected from organic compounds such as tetraethoxysilane (TEOS), hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDS), titanium tetraisopropoxide (TTIP), trimethylzinc and trimethylaluminum. The plasma CVD apparatus according to claim 1, wherein the plasma CVD apparatus includes one type. A substrate holding means on which a substrate to be deposited is placed is housed, a reaction vessel provided with an exhaust means, a raw material gas supply means for supplying a raw material gas to the reaction vessel, parallel to the reaction vessel, and A plurality of electrode plates arranged with their edges facing the film-forming surface of the substrate to be deposited, and a power supply for generating plasma between the plurality of electrode plates by supplying AC power to the plurality of electrode plates A plasma CVD method using a plasma CVD apparatus comprising:
A source gas containing at least one selected from an organic compound source, oxygen, nitrogen, ammonia, and hydrogen is used as the source gas, and source gas ejection holes for ejecting the source gas are formed as the films on the electrode plates. It is arranged at a position adjacent to the edge that does not face the film-forming surface of the substrate, and the length of the plurality of electrode plates is increased in accordance with the increase in the area size of the film-forming substrate, and the plurality of the plurality of electrode plates A plasma CVD method characterized in that the number of electrode plates is increased. A substrate holding means on which a substrate to be deposited is placed is housed, a reaction vessel provided with an exhaust means, a raw material gas supply means for supplying a raw material gas to the reaction vessel, parallel to the reaction vessel, and A plurality of electrode plates arranged with their edges facing the film-forming surface of the substrate to be deposited, and a power supply for generating plasma between the plurality of electrode plates by supplying AC power to the plurality of electrode plates A plasma CVD method using a plasma CVD apparatus comprising:
As the plasma discharge gas generated by the plurality of electrode plates, at least one selected from oxygen, nitrogen, argon, hydrogen, and a rare gas,
As the source gas, at least one selected from an organic compound source, oxygen, nitrogen, ammonia, hydrogen, and a rare gas of carrier gas is selected.
Disposing the discharge gas ejection holes for ejecting the discharge gas at positions adjacent to the edge of the plurality of electrode plates that do not face the film-forming surface of the film-forming substrate;
A source gas ejection hole for ejecting the source gas is disposed at an edge of the plurality of electrode plates facing the film forming surface of the substrate to be deposited, and the discharge gas is supplied to the plurality of electrode plates. Plasma is generated by the electric power supplied from the means, and the raw material gas is converted into plasma by bringing the plasmaized discharge gas and the raw material gas ejected from the raw material gas ejection hole into contact with each other and mixing them. A plasma CVD method characterized by the above.

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