KR20190112835A - Film-formation device and film-formation method - Google Patents

Abstract

This invention provides the film-forming apparatus which forms a gas barrier laminated film which has sufficient gas barrier property and has bending resistance.
A gas supply device for supplying a film forming gas containing a vacuum chamber accommodating a substrate therein, an organometallic compound as a raw material of a thin film, and a reaction gas reacting with the organometallic compound, and disposed in the vacuum chamber A pair of electrodes, an alternating current power is applied to the pair of electrodes, and one or both of the gas supply device and the plasma generation power source are controlled, And a first reaction condition in which the organometallic compound and the reaction gas react to generate a compound including a metal element or a semimetal element that has formed the organometallic compound but not containing carbon, and the organometallic compound and the reaction Gas reacts to form carbon and metal elements or semimetal sources that have formed organometallic compounds For generating a carbon-containing compound that includes having a control unit for switching the second reaction conditions.

Description

FILM-FORMATION DEVICE AND FILM-FORMATION METHOD}

The present invention relates to a film forming apparatus and a film forming method.

This application claims priority based on Japanese Patent Application No. 2010-228917 for which it applied to Japan on October 8, 2010, and uses the content here.

The gas barrier film can be suitably used as a container suitable for packaging articles such as food and drink, cosmetics and detergents. In recent years, the gas-barrier film formed by forming the thin film of inorganic compounds, such as silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide, on one surface of base films, such as a plastic film, is proposed.

Thus, as a method of forming a thin film of an inorganic compound on the surface of a plastic substrate, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, etc., vacuum chemical vapor deposition, plasma chemical vapor deposition, etc. Chemical vapor deposition (CVD) is known.

Moreover, as a gas barrier film manufactured using such a film-forming method, for example, Unexamined-Japanese-Patent No. 4-89236 (patent document 1) has two or more layers formed by vapor deposition on the surface of a plastic base material. A gas barrier film provided with a laminated deposition film layer made of a silicon oxide film is disclosed.

Japanese Patent Laid-Open No. 4-89236

However, although the gas barrier film as described in the said patent document 1 can be used as a gas barrier film for packaging of the goods which can satisfy even if the gas barrier property of a packaging container is comparatively low, such as food-drinks, cosmetics, detergent, etc., it is organic Gas barrier films for packaging electronic devices such as EL devices and organic thin film solar cells were not necessarily sufficient in terms of gas barrier properties.

Moreover, the gas barrier film as described in the said patent document 1 has a problem that the gas barrier property with respect to oxygen gas or water vapor falls when this is bent, and it is necessary for the display apparatus which requires bend resistance like a flexible liquid crystal display. As a gas barrier film used, it was not necessarily sufficient in the gas barrier property at the time of bending a film.

This invention is made | formed in view of such a situation, and provides the film-forming apparatus which can manufacture the gas barrier laminated film which can not only have sufficient gas barrier property but also can fully suppress the gas barrier property fall even when the film is bent. For the purpose of In addition, another object of the present invention is to provide a film forming method that can efficiently produce such a gas barrier laminate film.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this invention is a film-forming apparatus which forms a thin film on a base material, The vacuum chamber which accommodates the said base material inside, The organometallic compound which is a raw material of the said thin film in the said vacuum chamber, and the said organic A gas supply device for supplying a deposition gas containing a reaction gas reacting with a metal compound, a pair of electrodes disposed in the vacuum chamber, and alternating current is applied to the pair of electrodes, and the plasma of the deposition gas is applied. A metal element which controls the plasma generating power source and the gas supply device or the plasma generating power source, wherein the organometallic compound and the reactive gas react to form the organometallic compound, or First reaction conditions for generating a compound including a semimetal element but not containing carbon, and the organic A first film forming apparatus having a control unit for switching a second reaction condition in which a compound of the compound reacts with the reaction gas to generate a carbon-containing compound containing carbon, which has formed the organometallic compound, and a metal element or a semimetal element; The "first embodiment" is provided.

In the present specification and claims, the "metal" of the "organic metal compound" shall contain a metal element and a semimetal element.

In addition, the definitions of some terms and expressions used herein are described below.

A "vacuum chamber" is a container for making the inside into a reduced pressure state, preferably a reduced pressure state close to vacuum. Typically, by operating a vacuum pump attached to the chamber, a reduced pressure environment, preferably a vacuum close to vacuum, is created in the chamber.

A "substrate" is an object which becomes a support body of the said film | membrane when forming a film | membrane.

"Film-forming gas" is a gas containing as an essential element the raw material gas which is a raw material of a film | membrane, reaction gas which reacts with raw material gas as needed, and forms a compound, although it is not contained in the formed film | membrane, plasma generation, film quality improvement, etc. It may contain the auxiliary gas which contributes further.

"Raw material gas" is gas which becomes a supply source of the material used as a main component of a film | membrane. For example, when forming a SiO _x film, a gas containing Si such as HMDSO, TEOS, silane, or the like is the source gas.

"Reactant gas" refers to a gas that is contained in the film formed by the reaction with the raw material gas, for instance if the SiOx film is formed is equivalent to the oxygen (O ₂₎ thereto.

In addition, the expression "does not contain carbon" used for a thin film in this specification means distance from the surface of the said thin film in the film thickness direction of the said thin film produced by performing XPS depth profile measurement with respect to this thin film, In the carbon distribution curve which shows the relationship with the ratio (atom ratio of carbon) to the quantity of carbon atoms with respect to the total amount of the atoms which comprise a thin film, it means that carbon content is 1 at% or less. Here, with respect to the said carbon distribution curve, "the total amount of the atoms which comprise a thin film" means the total number of the atoms which comprise a thin film, and "the amount of carbon atoms" means the number of carbon atoms. In addition, unit "at%" is abbreviation of "atomic%."

In the present invention, in the first reaction condition, the control unit is configured such that the film forming gas contains at least an equivalent of the reaction gas in a reaction in which the compound containing no carbon is generated from the organometallic compound and the reaction gas. In the second reaction condition, the gas supply device is preferably configured to control the gas supply device so that the reaction gas, which is less than the equivalent in the reaction in which the compound containing no carbon is generated, is included in the film forming gas.

In this invention, the said control part is comprised so that the said gas supply apparatus may continuously change the quantity of the said reaction gas contained in the said film-forming gas at the time of switching between the said 1st reaction condition and the said 2nd reaction condition. It is preferable.

In the present invention, in the second reaction condition, the control unit applies the alternating current power for generating the plasma having the intensity of generating the compound not containing carbon under the first reaction condition. The plasma generation power supply is preferably configured to apply an alternating current power for generating the plasma of the intensity for generating the plasma.

In this invention, it is preferable that the said control part is comprised so that the electric power of the said alternating current may change continuously with respect to the said plasma generation power supply at the time of switching of the said 1st reaction condition and the said 2nd reaction condition.

Moreover, this invention is a film-forming apparatus which continuously forms a film on the said substrate, conveying a long base material continuously, The vacuum chamber which accommodates the said base | substrate, and the conveyance which conveys the said base material continuously in the said vacuum chamber are carried out. Plasma generating means for generating a discharge plasma in a space overlapping with a part of the substrate to be conveyed, and generating a magnetic field in a plurality of places according to the conveying direction of the substrate in the space so as to spatially vary the plasma intensity. It has a magnetic field generating means, and the said conveying means provides the 2nd film-forming apparatus (it is called "2nd Embodiment") comprised so that it may convey, maintaining the said base material flat in the said space.

In addition, the present invention provides a film forming method for forming a thin film on a substrate, wherein the metal element or semimetal which has formed the organic metal compound from an organic metal compound that is a raw material of the thin film and a reaction gas reacted with the organic metal compound. The first step of performing plasma CVD using the reaction gas more than the equivalent in the reaction that the compound containing the element, but does not contain carbon, and the less than the equivalent in the reaction where the compound containing no carbon Provided is a first film forming method having a second step of performing plasma CVD to generate a carbon-containing compound containing carbon and a metal element or a semimetal element that has formed an organometallic compound using a reaction gas.

In addition, the present invention provides a film forming method for forming a thin film on a substrate, wherein the metal element or semimetal which has formed the organic metal compound from an organic metal compound that is a raw material of the thin film and a reaction gas reacted with the organic metal compound. A first step of performing plasma CVD by generating a discharge plasma having an intensity of occurrence of a compound containing an element but not containing carbon, and carbon containing a carbon, a metal element, or a semimetal element forming the organometallic compound; A second film forming method having a second step of generating plasma CVD by generating a discharge plasma having a strength for generating a compound is provided.

Moreover, this invention is the film-forming method which continuously forms a film on the said base material by the plasma CVD method, conveying a long base material continuously, The intensity | strength of discharge plasma is made spatially different according to the conveyance direction of the said base material, A third film forming method is provided, which has a step of conveying the substrate kept flat so as to overlap the space where the intensity of the discharge plasma changes.

According to the present invention, it is possible to provide a film forming apparatus and a film forming method capable of producing a gas barrier laminate film capable of not only having sufficient gas barrier property but also sufficiently suppressing a decrease in gas barrier property even when the film is bent.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the example of the laminated | multilayer film manufactured by the film-forming apparatus of one Embodiment of this invention.
2 is a diagram illustrating an example of a carbon distribution curve of a gas barrier laminate film.
3 is a schematic diagram illustrating a film forming apparatus according to a first embodiment of the present invention.
It is a schematic diagram explaining a control part.
It is a schematic diagram which shows the modification of the laminated | multilayer film manufactured by the film-forming apparatus of one Embodiment of this invention.
6 is a schematic diagram illustrating a film forming apparatus according to a second embodiment of the present invention.
FIG. 7 is a schematic diagram showing a state of film formation in the film forming apparatus of the second embodiment. FIG.

[First Embodiment]

Hereinafter, the film forming apparatus according to the first embodiment of the present invention will be described with reference to FIGS. 1 to 5. In addition, in all the following drawings, in order to make drawing clear, a dimension, a ratio, etc. of each component were changed suitably.

In the following description, the thin film having gas barrier property is formed on a base material using the film-forming apparatus 1000 of this embodiment, and a gas barrier laminated film is manufactured, First, it is made into the target gas barrier laminated film. After explaining, the film-forming apparatus of this embodiment used in order to manufacture a gas barrier laminated film is demonstrated.

<Gas barrier laminated film>

FIG. 1: is a schematic diagram which shows the gas barrier laminated film 1 manufactured by the film-forming apparatus of this embodiment. In the gas barrier laminated film 1 according to the present embodiment, the thin film 3 having gas barrier property is formed on the surface of the substrate 2, and the film has a gas barrier property as a whole.

(materials)

The gas barrier laminated film 1 manufactured by the film-forming apparatus of this embodiment is obtained by forming the thin film 3 in the one surface side of the base material 2.

As the base material 2 used for this embodiment, the film containing resin or the composite material containing resin is mentioned. Such a film may have light transmittance and may be opaque.

As resin used for such a base material (2), For example, Polyester-type resin, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); Polyolefin resins such as polyethylene (PE), polypropylene (PP), cyclic polyolefins, polyamide resins, polycarbonate resins, polystyrene resins, polyvinyl alcohol resins, saponified ethylene-vinyl acetate copolymers The copolymer etc. which combined 2 or more types of repeating units which comprise polyacrylonitrile resin, acetal resin, polyimide resin, aramid resin, or the polymer of these resin are mentioned. Moreover, as a composite material containing resin, silicone resins, such as polydimethylsiloxane and polysilsesquioxane, a glass composite substrate, a glass epoxy substrate, etc. are mentioned. Among these resins, polyester resins, polyolefin resins, glass composite substrates, and glass epoxy substrates are preferred from the viewpoint of high heat resistance and linear expansion coefficient. In addition, these resin can be used individually by 1 type or in combination of 2 or more type.

The base material 2 can also perform surface activation treatment for activating the surface from the viewpoint of adhesiveness with the thin film to be formed. Examples of such surface activation treatment include corona treatment, plasma treatment, and frame treatment.

(pellicle)

The thin film 3 manufactured by the film-forming apparatus of this embodiment is a layer which gives gas barrier property to the base material 2, and is formed in at least one surface of the base material 2. As shown in FIG. The thin film 3 contains the some layer from which a composition differs. In the figure, the thin film 3 is shown as having a three-layer structure in which the first layer 3a and the second layer 3b are alternately stacked.

The first layer 3a has a composition close to SiO ₂ represented by y ≒ 0 in SiO _x C _y (0 <x <2, 0 <y <2, x + y # 2). In contrast, the second layer 3b is y ≠ 0 in SiO _x C _y (0 <x <2, 0 <y <2, x + y ≒ 2), and has a composition represented by SiO _2-y C _y . Have The second layer 3b is not a uniform composition and is a ratio of the distance from the surface of the layer in the film thickness direction and the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of carbon In the carbon distribution curve showing the relationship with), all of the following conditions (i) and (ii) are satisfied.

First, (i) the second layer 3b has a carbon distribution curve having at least one extreme value.

In this specification, the maximum value of the element distribution curve of a thin film, such as a carbon distribution curve, is a point where the value of the atomic ratio of an element changes from increase to decrease, when the distance from the surface of the thin film 3 is changed, and the element of this point The value of the atomic ratio of the element at the position which changed the distance from the surface of the thin film 3 further 20 nm in the film thickness direction of the thin film 3 from the said point rather than the value of the atomic ratio of 1 at% or more decreases Say In addition, in this specification, the minimum value of the said element distribution curve is a point where the value of the atomic ratio of an element changes from decrease to increase, when the distance from the surface of the thin film 3 is changed, The value of the atomic ratio of the element of the position which changed the distance from the surface of the thin film 3 in the film thickness direction of the thin film 3 further 20 nm from the said point from the said point increases 1 at% or more.

(Ii) The second layer 3b has a difference between the maximum value and the minimum value of the atomic ratio of carbon in the second layer 3b of 5% or more (that is, the (maximum value of the atomic ratio of carbon)-(carbon The minimum value of the atomic ratio of?) Is 5%).

In this 2nd layer 3b, it is more preferable that the absolute value of the difference of the maximum value and minimum value of the atomic ratio of carbon is 6 at% or more, and it is especially preferable that it is 7 at% or more. When the said absolute value is less than 5 at%, when the gas barrier laminated film 1 obtained is bent, the thin film 3 will be easy to be damaged, and the gas barrier property at the time of bending the gas barrier laminated film 1 will be carried out. This becomes insufficient.

Here, the carbon distribution curve is used for the so-called XPS depth profile measurement, which performs surface composition analysis while exposing the inside of the sample by using X-ray photoelectron spectroscopy (XPS) and rare gas ion sputters such as argon in combination. Can be written by The distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of carbon (unit: at%) and the horizontal axis as the etching time (sputter time). In addition, in the distribution curve of the element whose horizontal axis is an etching time in this way, an etching time correlates generally with the distance from the surface of the thin film 3 in the film thickness direction of the thin film 3 in a film thickness direction. , "The distance from the surface of the thin film 3 in the film thickness direction of the thin film 3" from the surface of the thin film 3 calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance of can be adopted. As the sputtering method employed in the XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as the etching ion species is adopted, and the etching rate thereof is 0.05 nm / sec (SiO ₂ thermal oxide film conversion value). It is desirable to.

FIG. 2 is a diagram schematically showing a carbon distribution curve of the second layer 3b. In the horizontal axis which shows the distance from the surface of a layer, it represents using the code | symbol of the 1st layer 3a, the 2nd layer 3b, and the thin film 3 rather than a specific distance. In the 2nd layer 3b of the composition as shown in the figure, it has one maximum value, and the difference between the maximum value and minimum value of a carbon atom exceeds 5%.

Moreover, carbon content is 1 at% or less in the carbon distribution curve, and the 1st layer 3a is a layer which does not contain carbon.

In addition, in this embodiment, from the viewpoint of forming the thin film 3 which is uniform and excellent gas barrier property as a whole, the thin film 3 is substantially the same in the film surface direction (direction parallel to the surface of the thin film 3). It is preferable. In the present specification, the thin film 3 is substantially the same in the film surface direction when the carbon distribution curve is created for any two measurement points on the film surface of the thin film 3 by XPS depth profile measurement. The number of extreme values of the carbon distribution curve obtained at the measurement point at the point is the same, and the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve is the same or less than 5 at%. Say.

In addition, in this embodiment, it is preferable that the said carbon distribution curve is substantially continuous. Substantially continuous carbon distribution curve in this specification means that it does not contain the part which the atomic ratio of carbon in a carbon distribution curve changes discontinuously, Specifically, in the thin film 3 computed from an etching rate and an etching time. In the relationship between the distance (x, unit: nm) from the surface of the layer in the film thickness direction of at least one layer and the atomic ratio of carbon (C, unit: at%), the following formula (F1) is represented. To satisfy the condition.

| dC / dx | ≤1 ... (F1)

In addition, the thickness of the thin film 3 is preferably in the range of 5 nm to 3000 nm, more preferably in the range of 10 nm to 2000 nm, and particularly preferably in the range of 100 nm to 1000 nm. If the thickness of the thin film 3 is less than the lower limit, there is a tendency for gas barrier properties such as oxygen gas barrier property and water vapor barrier property to be inferior, whereas if the thin film 3 exceeds the upper limit, the thin film 3 tends to be damaged by bending. When it bends, there exists a tendency for gas barrier property to fall easily.

In the gas barrier laminated film 1 manufactured by the film-forming apparatus 1000 of this embodiment, the 1st layer 3a which does not contain a carbon atom expresses high gas barrier property, and contains a carbon atom. Since the second layer 3b can be bent more flexibly than the first layer 3a, it exhibits flex resistance. Therefore, the gas barrier laminated film 1 can exhibit the outstanding barrier property and bending resistance as a whole.

<Film forming device>

3 is a schematic diagram illustrating the film forming apparatus 1000 of the present embodiment. The film forming apparatus 1000 according to the present embodiment includes a chamber 11, a mounting table 12 arranged in the chamber 11 to mount the substrate 2, and a mounting table 12 above the mounting table 12. ), A pair of electrodes 13 disposed opposite to the electrode, a plasma generating power source 14 connected to the electrode 13, and a magnetic field disposed on the side of the electrode 13 that does not face the mounting table 12. The generation part 15 is provided.

Moreover, the gas supply pipe 16 which supplies various film-forming gas in the chamber 11 and the gas supply apparatus 17 connected to the gas supply pipe 16 through the piping 16a are provided. In the chamber 11, a vacuum pump 18 provided on the ceiling of the chamber 11 and an exhaust port (not shown) are appropriately provided.

In addition, the control part 100 which controls the drive of the plasma generation power supply 14 and the gas supply apparatus 17 is connected to the plasma generation power supply 14 and the gas supply apparatus 17.

In this apparatus, the plasma of the film forming gas supplied from the gas supply pipe 16 can be generated in the space between the electrode 13 and the mounting table 12 by the plasma generating power source 14. Plasma CVD film formation can be performed using plasma. Hereinafter, each structure is demonstrated in order.

The mounting table 12 loads the base material 2, and may include heating means for heating the base material 2 therein.

The pair of electrodes 13 has a plate shape and is disposed at a predetermined position in the height direction in the chamber 11 so that one surface side thereof faces the mounting table 12. By applying, for example, high frequency power to the pair of electrodes 13 from the plasma generation power supply 14 connected to the electrodes 13, to generate an electric field between and around the electrodes 13, The plasma of the film forming gas supplied from the gas supply pipe 16 is generated.

In the magnetic field generating unit 15, a plurality of magnets 15a in which the polarities on the mounting table 12 side are alternately inverted and arranged and a plurality of magnets 15a in the drawing are magnetically attached. It has a connecting member 15b. The magnetic field generating unit 15 forms a magnetic field in the space between the mounting table 12 and the electrode 13. In the figure, the magnetic field lines LM formed by the magnetic field generating unit 15 are schematically shown.

Since the intensity of the discharge plasma generated by applying to the electrode 13 is different depending on the intensity of the magnetic field formed by the magnetic field generating section 15, the plasma plasma region AR1 is a strong region and the plasma is weak. The weak plasma region AR2 is formed. The intensity of the magnetic field is determined by the number of magnets 15a of the magnetic field generating unit 15, the interval between the magnets 15a (shown by reference symbol L in the figure), and the height of the magnet 15a (shown by symbol H in the figure). By changing, the desired magnetic field can be formed.

For example, of the three magnets 15a shown in the drawing, the magnetic field generating unit 15 can be used in which the magnets 15a at both ends are made lower than the center one and separated from the electrode 13.

In addition, since the plasma is diffused until the generated plasma reaches the substrate 2, the plasma intensity is averaged, and the film is formed on the substrate 2 using a substantially uniform plasma.

The gas supply pipe 16 has a tubular shape extending from the lower side of the pair of electrodes 13 to cross the chamber 11, and supplies a film forming gas such as a raw material gas of plasma CVD from an opening provided in a plurality of places. do.

The gas supply apparatus 17 has a tank which stores film-forming gas (raw material gas, reaction gas, carrier gas), the valve which controls the supply amount of each gas which comprises film-forming gas, etc., and is suitable in the chamber 11, Positive deposition gas is supplied.

The source gas is an organometallic compound and can be appropriately selected and used depending on the material of the barrier film to be formed.

As the source gas, for example, an organosilicon compound containing silicon can be used.

Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, tetramethylsilane, hexamethyldisilane, methylsilane, dimethylsilane and trimethyl. Silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetra Siloxane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane and hexamethyldisilazane. Among these organosilicon compounds, HMDSO, 1,1,3,3-tetramethyldisiloxane is preferable from the viewpoints of the handleability of the compound and the gas barrier property of the barrier film to be obtained. In addition, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types. Moreover, it can also be used as a silicon source of the barrier film which forms the source gas which contained monosilane other than the organosilicon compound mentioned above.

As the film forming gas, a reaction gas is used in addition to the source gas. As such a reaction gas, a gas that reacts with the source gas and generates a metal element or semimetal element contained in the source gas and a compound containing no carbon such as an oxide or nitride can be appropriately selected and used. As a reaction gas for forming an oxide, oxygen and ozone can be used, for example. Moreover, as a reaction gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases may be used alone or in combination of two or more thereof. For example, in the case of forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride may be used in combination. Can be.

In order to supply source gas into a vacuum chamber, carrier gas may be used as a part of film-forming gas as needed. In addition, in order to generate plasma discharge, the gas for discharge may be used as a part of film-forming gas as needed. As the carrier gas and the gas for discharge, those which are appropriately known can be used, and examples thereof include rare gases such as helium, argon, neon, and xenon; Hydrogen may be used.

The vacuum pump 18 is used to control the pressure (vacuum degree) in the chamber 11. Although the pressure in the chamber 11 can be adjusted suitably according to the kind of source gas, etc., it is preferable that the pressure of the vicinity in which the base material 2 is mounted is 0.1 Pa-50 Pa. In order to suppress the gas phase reaction, the plasma CVD is usually 0.1 Pa to 10 Pa when the low pressure plasma CVD method is used. In addition, although the electric power of the electrode drum of a plasma generating apparatus can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable that it is 0.1-10 kW.

The control part 100 outputs the control signal which controls the drive of the plasma generation power supply 14 and the gas supply apparatus 17.

4 is a schematic diagram illustrating the control unit 100. As shown in the figure, the control unit 100 includes an input unit 101, an arithmetic unit 102 connected to the input unit 101, a signal output unit 103 and a storage unit (connected to the arithmetic unit 102). 104).

The input part 101 is an input device which inputs the operation conditions of the plasma generation power supply 14 and the gas supply apparatus 17 to the calculating part 102. FIG. The operating conditions of the plasma generating power supply 14 and the gas supply device 17 vary depending on the thickness of the thin film to be formed on the substrate X, the type of the substrate X to be used, the composition of the film forming gas, and the like. Specifies.

The calculating part 102 creates the control signal of the plasma generation power supply 14 and the gas supply apparatus 17 using the operation condition input from the input part 101, and supplies it to the signal output part 103. FIG.

The signal output unit 103 is an interface for outputting the control signals generated by the calculation unit 102 to the control signals of the plasma generation power supply 14 and the gas supply device 17, respectively.

In addition, although the operating condition itself of the plasma generation power supply 14 and the gas supply apparatus 17 can also be input from the input part 101, about the detailed operating condition, it is previously memorize | stored in the form of a lookup table etc. It is also possible to store the information in 104, and input designation information related to the stored operating condition. For example, if "Condition 1" is inputted, an operating condition corresponding to Condition 1 stored in the storage unit 104 is expressed. If "Condition 2" is inputted, the condition 2 stored in the storage unit 104 is entered. Substituting information may be input so that a corresponding operating condition is expressed. Thereby, the input work of an operating condition can be simplified.

(Film forming process)

Next, the reaction process at the time of manufacturing the gas barrier laminated film 1 shown in FIG. 1 using this film-forming apparatus is demonstrated. Here, it demonstrates as using the mixed gas of HMDSO and oxygen as film-forming gas.

First, the case of manufacturing the gas barrier laminated film 1 by controlling the gas supply apparatus 17 is shown. In this case, the control signal is output from the control part 100 to the plasma generation power supply 14 so that the electric power of the film forming gas can be made into plasma completely is supplied to the electrode 13 by a fixed amount of electric power. On the other hand, when manufacturing the 1st layer 3a and the 2nd layer 3b, the gas supply apparatus 17 outputs the control signal which controls so that the mixing ratio of HMDSO and oxygen may differ. The mixing ratio of the film forming gas is changed by, for example, controlling the opening degree of the valve that controls the supply amount of each gas.

First, in the film formation process of the first layer 3a, the control signal for controlling the mixing ratio of the film forming gas is controlled so that the gas supply device 17 from the controller 100 becomes the oxygen content rate at which the complete oxidation of HMDSO occurs stoichiometrically. Is output. For example, the mixing ratio of these gases is controlled so that oxygen is 12 times HMDSO, and these gases are supplied into the chamber 11. In the case of using such a gas mixture, the first layer 3a can be formed because SiO ₂ is generated by the reaction shown in Equation 1 during the plasma CVD process.

(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO _{2 ..} (1)

Subsequently, in the film forming step of the second layer 3b, the mixing ratio of the film forming gas is controlled such that the gas supply device 17 is not stoichiometrically produced from the control unit 100 without causing complete oxidation of HMDSO and the oxygen content rate is insufficient. A control signal is output. Specifically, the mixing ratio of these gases is controlled so that oxygen is less than 12 times HMDSO, and these gases are supplied into the chamber 11.

In addition, the mixing ratio of the film forming gas is continuously lowered after the oxygen content rate is lowered in the film forming step of the second layer 3b, and is changed until it is 12 times higher than HMDSO. When oxygen is 12 times HMDSO, film formation of the second layer 3b is completed.

In the case of using such a gas mixture, the second layer 3b can be formed because SiO _x C _y , which is a carbon-containing compound, is generated by the reaction as shown in Equation 2 in the process of plasma CVD. In Formula 2, for example, a reaction scheme when oxygen is 9 times HMDSO is shown.

_{(CH 3) 6 Si 2 O} + 9O 2 → 4CO 2 + 9H 2 O + 2SiOC and and and (2)

Second, the case where the gas barrier laminated film 1 is manufactured by controlling the power supply 14 for plasma generation is shown. In this case, a control signal is output to the gas supply device 17 so as to supply the film forming gas at a constant mixing ratio of the oxygen content rate at which the full oxidation of HMDSO occurs stoichiometrically.

On the other hand, when manufacturing the 1st layer 3a and the 2nd layer 3b, the control signal is output from the control part 100 to the plasma generation power supply 14 so that a plasma may be generated so that electric power may differ.

First, in the film formation process of the first layer 3a, a control signal is outputted from the control part 100 to supply the plasma generation power supply 14 with the complete oxidation of HMDSO. In this case, since complete oxidation occurs in the course of plasma CVD and SiO ₂ is generated by the reaction as shown in Equation 1, the first layer 3a can be formed.

Subsequently, in the film formation process of the second layer 3b, the electric power that does not completely generate HMDSO from the control unit 100 to the plasma generation power supply 14 (for example, when the first layer 3a is formed, is formed). The control signal is output to supply half of the power). In addition, the electric power supplied is continuously lowered in the film forming process of the second layer 3b, and subsequently increased, and changed until the electric power for the complete oxidation of HMDSO is supplied. When the supply power is increased up to the power at which complete oxidation of HMDSO occurs, film formation of the second layer 3b is terminated.

In this case, in the process of plasma CVD, for example, SiO _x C _y is generated by a reaction as shown in Equation 2, so that the second layer 3b can be formed.

In addition, it is also possible to manufacture the gas barrier laminated film 1 by controlling both the gas supply device 17 and the plasma generation power supply 14. Also in this case, the 1st layer 3a and the 2nd layer 3b can be formed by reaction as shown to said Formula 1, 2, respectively.

In the film forming apparatus 1000 as described above, since the control unit 100 controls the operating conditions to form the film, not only does it have sufficient gas barrier property but also sufficiently suppresses the decrease in gas barrier property even when the film is bent. It becomes possible to manufacture the possible gas barrier laminated film 1.

In addition, in this embodiment, although the 1st layer 3a and the 2nd layer 3b were laminated | stacked in 3 layers in total in the thin film 3, it is not limited to this. By repeating the above-mentioned film forming process, for example, as shown in FIG. 5, the gas barrier having the thin film 3 in which the first layer 3a and the second layer 3b are repeatedly stacked (total five layers in the drawing). The laminated film 1 can be manufactured.

In the case of such a thin film 3, the composition of the plurality of second layers 3b may be the same or different. In addition, when providing two or more layers of such thin films 3, these thin films 3 may be formed on one surface of the base material 2, or may be formed on both surfaces of the base material 2; It may be.

Second Embodiment

FIG. 6: is explanatory drawing of the film-forming apparatus 2000 which concerns on 2nd Embodiment of this invention. The film forming apparatus 2000 of the present embodiment has a structure which is partially in common with the film forming apparatus 1000 of the first embodiment. Therefore, in this embodiment, the same code | symbol is attached | subjected to the component which is common in 1st embodiment, and the detailed description of these components is abbreviate | omitted.

The film-forming apparatus 2000 shown in FIG. 6 can be formed into a film continuously in a conveyance process, conveying the elongate base material 2. Hereinafter, it demonstrates in order.

The film-forming apparatus 2000 is the delivery roll (conveying means) 21 which conveys the elongate base material 2 wound up in roll shape, and the conveyance rolls (conveying means) 22, 23 which convey the base material 2 ) And a winding roll (conveying means) 24 for winding the base material 2. The base material 2 is conveyed to the upper side of the mounting table 12 in a flat state without being bent, and is continuously plasma CVD deposited in the process of being conveyed to the upper side of the mounting table 12.

The electrode 13 is provided below the mounting table 12 so as to face the mounting table 12, and the magnetic field generating unit 15 is provided on the side of the electrode 13 that does not face the mounting table 12. . The gas supply pipe 16 extends so as to cross the chamber 11 above the mounting table 12. The electrode 13 and the plasma generation power supply 14 constitute the plasma generating means of the present invention.

For example, a plasma of the film forming gas supplied from the gas supply pipe 16 is generated by applying, for example, a high frequency electric power of a constant intensity to generate an electric field between the electrodes 13 and the space around the electrode 13. The deposition gas is controlled so that, for example, oxygen is from 9 mol times to 12 mol times of HMDSO.

At this time, discharge plasmas of different intensities are generated in accordance with the intensity of the magnetic field formed by the magnetic field generating unit 15, and the strong plasma region AR1, which is a region where the plasma is strong, on the upper side of the mounting table 12, and the plasma The weak plasma region AR2 is formed. In the steel plasma region (AR1), since the SiO ₂ by a reaction as shown in the formula (1) occurs, the first layer (3a) is formed. Further, in the weak plasma region AR2, since SiO _x C _y is generated by the reaction as shown in Equation 2, the second layer 3b is formed.

The base material 2 is conveyed by passing through the vicinity of the strong plasma area | region AR1 and the weak plasma area | region AR2 formed in this way. On the board | substrate 2, film-forming is performed continuously according to the reaction which generate | occur | produces in each plasma area | region AR1, AR2 in a conveyance process. That is, as shown in FIG. 7, when passing through the strong plasma area | region AR1 in the process of conveying the base material 2, the 1st layer 3a is formed, and when passing through the weak plasma area | region AR2, Two layer 3b is formed. In addition, since the strong plasma region AR1 and the weak plasma region AR2 are alternately passed through, the first layer 3a and the second layer 3b are alternately formed and laminated in accordance with the conveyance, and the gas barrier laminate is laminated. The film 1 is formed.

In the figure, four strong plasma regions AR1 are shown, and three weak plasma regions AR2 are shown. Therefore, when the film-forming apparatus 2000 of this embodiment is used, the gas barrier laminated | multilayer film 1 formed is a structure where the 1st layer 3a and the 2nd layer 3b alternately laminated | stacked seven layers in total. It becomes.

In the film forming apparatus 2000 as described above, a plurality of regions having different plasma intensities are passed through the long substrate 2 and formed in each of the plasma regions AR1 and AR2. Therefore, it becomes possible to manufacture the elongate gas barrier laminated film 1 which has sufficient gas barrier property and can fully suppress the fall of gas barrier property even when it is bent.

In addition, in the film-forming apparatus 2000, when forming the thin film 3 by roll-to-roll, the thin film 3 can be continuously formed in the state which kept the elongate base material 2 flat. When the thin film 3 is formed in the state in which the base material 2 is bent, since the gas barrier laminated film formed will have residual stress in the inside of a thin film when it extends flat, it will become easy to be damaged. However, there is no such concern in the gas barrier laminated film formed in the film-forming apparatus 2000 of this embodiment. Therefore, it becomes possible to easily manufacture a higher quality gas barrier laminated film in large quantities.

As mentioned above, although the preferred embodiment which concerns on this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. The various shapes, combinations, etc. of each structural member shown by the above-mentioned example are an example, and various changes are possible based on a design request etc. in the range which does not deviate from the main point of this invention.

INDUSTRIAL APPLICABILITY The present invention is very useful industrially because it provides a film forming apparatus and a film forming method capable of producing a gas barrier laminated film which can not only have sufficient gas barrier property but also sufficiently suppress the deterioration of gas barrier property even when the film is bent. Do.

2… Substrate, 3... Thin film, 11... Vacuum chamber, 13... Electrode, 14.. Power supply for plasma generation; Magnetic field generating portion (magnetic field generating means), 17. Gas supply unit, 21... Feed roll (conveying means), 22, 23... Conveying roll (conveying means), 24... Winding roll (conveying means), 100.. Control unit, 1000, 2000... Deposition device

Claims (3)

A first layer containing a metal element or a semimetal element which has reacted an organometallic compound with a reaction gas to form the organometallic compound, but does not contain carbon, on the elongated substrate, and the organometallic compound and the reaction gas Is a film forming apparatus for a gas barrier laminate film having a thin film in which a second layer containing carbon and a metal element or a semimetal element, which has formed the organometallic compound by reaction, is alternately laminated in the film thickness direction,
A vacuum chamber accommodating the substrate therein;
A gas supply device for supplying a film forming gas containing an organometallic compound, which is a raw material of the thin film, and a reaction gas reacting with the organometallic compound, into the vacuum chamber;
A conveying apparatus for continuously conveying the substrate in the vacuum chamber;
A plasma generator for generating a discharge plasma in a space overlapping with a part of the substrate to be conveyed;
A magnetic field generating device generating magnetic fields in a plurality of places in accordance with the conveyance direction of the base material in the space to make plasma intensity different in the space;
A control unit configured to control the first layer to be formed and to form the second layer on the first layer;
When a carbon distribution curve showing a relationship between the distance from the surface in the film thickness direction of the thin film and the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms is created, the carbon distribution curve is substantially The formation of the second layer is controlled by the control unit so as to have a maximum value and at least one extreme value in the carbon distribution curve, and that the difference between the maximum value and the minimum value of carbon is 5% or more;
When the distance x from the surface of the layer in the film thickness direction of the at least one layer constituting the thin film and the atomic ratio C of carbon are calculated from the etching rate and the etching time, these control parts are used. The relationship is controlled to satisfy the following formula (F1);
By the conveying apparatus, the substrate is continuously conveyed while being kept flat, and alternately passes through the vicinity of the strong plasma region, which is the region where the plasma is strong, and the vicinity of the weak plasma region, which is the region where the plasma is weak. And controlled to alternately stack the first layer formed when passing through the strong plasma region and the second layer formed when passing through the weak plasma region in a film thickness direction.
Deposition device.
| dC / dx | ≤1 ... (F1) On the elongate substrate, a plasma CVD method has a thin film in which a first layer formed when passing through a strong plasma region and a second layer formed when passing through a weak plasma region are alternately laminated in the film thickness direction. It is a manufacturing method of a gas barrier laminated film,
The manufacturing method,
In the state where the plasma discharge is performed so that the intensity of the discharge plasma is spatially different in accordance with the conveying direction of the substrate, the substrate is continuously conveyed while keeping the substrate flat, and the plasma is in the vicinity of the strong plasma region and the region where the plasma is weak. Alternately laminating the first layer and the second layer on the substrate in a film thickness direction by alternately passing the vicinity of the weak plasma region;
When the said 2nd layer created the carbon distribution curve which shows the relationship between the distance from the surface in the film thickness direction of the said thin film, and the ratio of the quantity of carbon atoms with respect to the total amount of a silicon atom, an oxygen atom, and a carbon atom, The carbon distribution curve is substantially continuous and has at least one extreme value in the carbon distribution curve, and the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5% or more; Also
When the distance (x) from the surface of the layer in the film thickness direction of at least one layer constituting the thin film and the atomic ratio (C) of carbon are calculated from the etching rate and the etching time, these relations are expressed by the following equation. Satisfying the condition indicated by (F1),
The manufacturing method of a gas barrier laminated film.
| dC / dx | ≤1 ... (F1) The method of claim 2,
The first layer is a layer formed from a reactant of the deposition gas generated in the strong plasma region,
The second layer is a layer formed from the reactant of the film forming gas generated in the weak plasma region,
The film forming gas includes an organometallic compound which is a raw material of the first layer and the second layer, and a reaction gas that reacts with the organometallic compound,
The manufacturing method of a gas barrier laminated film.

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