JP5865617B2 - Plasma generation method and apparatus therefor - Google Patents

Description

  The present invention relates to a plasma generation method used for film formation or surface modification by a plasma CVD method and an apparatus therefor, and particularly, a substrate to be processed is an insulating material such as plastic or rubber and has low heat resistance. Even if it exists, it is related with the plasma generation method and apparatus for it which can perform film-forming or surface modification efficiently in a short time.

For example, an amorphous carbon film such as a diamond-like carbon film (hereinafter sometimes referred to as “DLC film”) is a film having wear resistance, adhesion resistance, and the like and having a low friction coefficient. Therefore, various conventional metal base material modifications such as cutting tools, tooling tools such as molds, protective films for various devices, and base material modifications that add excellent physical, chemical and mechanical functions. Used in various fields.
In recent years, jigs and devices based on resin or rubber have been developed in consideration of weight reduction of the base material itself, mass productivity such as press and injection molding, and workability. There has been a demand for the formation of an amorphous carbon film as in the case of a metal-based substrate.
Amorphous carbon film also has the property of preventing the permeation of water vapor and oxygen, and by forming a thin film of several tens of nanometers on the surface of various resin films and three-dimensional containers made of organic polymers, the gas barrier It becomes possible to give high added value such as property.

This amorphous carbon film can be formed by a plasma CVD method, an ion plating method, a sputtering method, etc. Among them, the plasma CVD method utilizing a plasma process is formed by a reactive gas, and is formed by a process. Since the structure of the membrane device is relatively simple and inexpensive, it is preferably used, and various methods have been developed for the device.
In addition to the film formation on the object to be processed (hereinafter, also referred to as “non-processed substrate” or “work”), the apparatus using the plasma can remove foreign substances existing on the surface of the substrate to be processed. It is also frequently used for surface modification of a substrate to be treated, such as cleaning with plasma, peeling of another film formed on the surface of the substrate to be treated, and improving the adhesion of the surface of the substrate to be treated.

In film formation or surface modification using a plasma generator, uniform film formation or surface modification is required regardless of the surface shape of the substrate to be treated.
For example, Patent Document 1 proposes an apparatus using an electrode having a specific shape as an apparatus capable of forming a thin film with a uniform film thickness regardless of the shape of an object to be processed.
In the plasma CVD apparatus described in Patent Document 1, a first electrode made of a helical wire that forms a plasma generation region having a size capable of accommodating a substrate to be processed in a reaction container, and the first electrode A second electrode that is not at the same potential as one electrode; and a support member that supports the object to be processed in the plasma generation region and is electrically connected to the second electrode, and applies a high-frequency voltage to the first electrode. This is a device that can be configured.
And according to the said apparatus, the conventional subject that a uniform film | membrane will not be formed if the relative position adjustment of a cathode electrode and a to-be-processed object goes wrong is solved, and a uniform film thickness irrespective of the shape of a to-be-processed base material Although it is said that a thin film can be formed, the thing which has to-be-processed base-material conductivity is a premise.

However, in the case where the workpiece is usually electrically insulating, such as a resin part or rubber product, the device described in Patent Document 1 on the assumption that the workpiece is conductive cannot be used.
In other words, when the work is insulative, it is not possible to apply a method in which the work itself is used as one electrode, and thus a plasma generation source, and plasma is generated uniformly around the work. A plasma CVD apparatus specifically designed for the workpiece, which is designed to have a mechanism for supplying a raw material gas between the workpiece and the another electrode, is required.

For example, Patent Document 2 describes an apparatus in which an outer peripheral electrode is disposed so as to surround an outer surface of a container, and a film is formed on the outer surface of the container by a plasma CVD method while supplying a starting material to the outer surface of the container. Has been.
Further, in Patent Document 3, in a device in which a plasma source is arranged in a specific direction and place in the device, a rotation mechanism for revolving the workpiece with respect to the plasma source is provided in the vacuum device, and a substrate to be processed is provided. There has also been proposed a mechanism in which a material is mounted, the surface to be processed of the substrate to be processed is exposed while being uniformly rotated with respect to the plasma source, and processing is performed.

JP 2000-80478 A JP 2006-176865 A JP-A-11-131241

However, when the work is made of a base material having low heat resistance such as a resin, the following measures are also required as a measure against heat deformation of the base material due to heat generation.
(1) In order to prevent the workpiece itself from being deformed or damaged by the heat generated by the plasma or current flowing through the workpiece support, a cooling mechanism is introduced for cooling the workpiece in contact with the workpiece.
(2) During processing of the workpiece, the power source of the plasma CVD apparatus is stopped at regular time intervals to prevent the workpiece from being rapidly heated.
(3) A plasma generation source is installed at a location far away from the workpiece, and film formation is performed at a lower temperature on the premise of film formation using deactivated plasma.

In particular, in the apparatuses described in Patent Documents 2 and 3, a CVD method (high frequency plasma CVD method) using a high frequency (RF) power source is adopted as a method for generating plasma around the workpiece. In addition, in the direct current plasma CVD method, since the current flows without interruption, the plasma temperature rises quickly, and at least the film formation temperature becomes about 200 ° C. or more in a short time after the film formation is started.
Therefore, in the conventional high-frequency plasma CVD method, in order to prevent the workpiece temperature from rising, a method of intermittently repeating film formation is employed. For example, after film formation is performed by inputting a high frequency for a predetermined time. The DLC film having a required film thickness is formed by repeating the complicated operation such as stopping the output for a predetermined time and manually repeating this for the required number of times.

  Further, when the work is a thin plate made of a base material that is insulating and deforms at a low temperature (hereinafter sometimes referred to as “insulating low temperature deformation base material”), the work is cooled to a thin plate-like work. Although it is not impossible to form a film while cooling it by bringing the device into surface contact, an expensive and complicated cooling mechanism is required. Furthermore, in the case of a three-dimensional workpiece, the entire three-dimensional surface is reduced. It is extremely difficult to form a film while cooling.

Therefore, the present inventors tried to apply to an insulating low-temperature deformable substrate using a plasma CVD apparatus using a DC pulse power supply that has been put into practical use in recent years. Compared with the plasma CVD method, when the plasma CVD method using a pulsed direct current (pulse DC) power source is adopted, the duty ratio of energization can be suppressed to about 1 to 2%, and the temperature rise curve can be controlled. It has been found.
However, even in this apparatus, it is impossible to generate plasma around an insulating base material that does not conduct electricity as in the case of other apparatuses. A dedicated plasma generating electrode adapted to the above is created and placed around the workpiece, and a source gas is supplied between the workpiece and the electrode, or an electrode for plasma generation is placed at a location away from the workpiece, It is necessary to introduce a mechanism that revolves the workpiece.

Further, in the conventional practice, even in a plasma CVD apparatus using a pulsed DC power supply, the following measures (1) and (2) are required when processing an insulating low-temperature deformable substrate such as a resin. Come.
(1) For example, when the thin plate-like insulating low-temperature deformable base material is a workpiece, the workpiece is placed on a metal substrate that can be energized, and the metal substrate is energized to form an electric field around the workpiece. It is possible to perform plasma treatment by generating plasma on the surface of the workpiece. In this case, however, the applied (energization) voltage is lowered, and a large current flows through the metal substrate to raise the temperature of the metal substrate. Need to prevent.
(2) It is necessary to shorten the energization time in one pulse input and lower the duty ratio of the power source.

However, when the method of (1) is used, a resin that is an insulating low-temperature deformable substrate having a deformation temperature of around 100 ° C., whereas a voltage of −4 kV or higher is usually applied in the formation of a metal substrate. In order to form a substrate, the applied voltage must be reduced to about -2 kV.
An applied voltage of −4 kV or higher, which is usually used for film formation on a metal substrate, means that adhesion between the substrate and the amorphous carbon film is increased by increasing the ion implantation acceleration to the film formation substrate. This voltage is necessary for controlling the hardness of the steel.
However, at an applied voltage of about −2 kV, the formed amorphous carbon film has poor adhesion to the resin base material, and in the worst case, when a commercially available cellophane tape or the like is applied and peeled off, the amorphous carbon film However, there are cases where the film is peeled off from the resin substrate.
When the method (2) is used, for example, when the pulse frequency is 10 kHz and the pulse width is normally 10 μs, the pulse width is reduced to about 1 μs or 2 μs, and the energization time is short. Therefore, the time required for the film formation is 3 to 4 times or more (a remarkable decrease in the film formation rate) compared to 10 μs.
As described above, in any of the above methods (1) and (2), the film formation on the insulating low-temperature deformable base material such as resin is inefficient, and the quality of the finished product is the required level. The comparison was insufficient.

As described above, without using a rotation mechanism such as self-revolution, and a substrate cooling device, insulators (including substrates that are difficult to energize), in particular, the entire surface of a substrate such as resin or rubber that deforms at a lower temperature, In addition, there is currently no apparatus that enables plasma processing of any selected surface.
The present invention solves such a problem in the prior art, and does not use a rotation mechanism such as self-revolution and a substrate cooling device, and is used for an insulator of various shapes, particularly an insulator with low heat resistance, An object of the present invention is to provide a method and an apparatus therefor that can efficiently perform plasma film formation and reforming treatment in a short time.

As a result of intensive studies to achieve the above object, the present inventors have found that the combination of the following plasma processing methods (1) to (4) is effectively established when the object to be processed is an insulator. I found.
(1) The reaction vessel of the plasma CVD apparatus is used as the other electrode. An object to be processed is placed in the reaction vessel.
(2) A fixed distance at which the plasma generated toward the treatment-needed surface of the object to be treated is not deactivated with respect to the treatment-needed surface of the object to be treated disposed in the reaction vessel also serving as the other electrode Place one electrode.
(3) The one electrode has a shape such as a metal mesh, a metal slit, or a metal coil.
(4) A high-voltage micropulse DC power supply is used for applying the plasma generation voltage.
This high-voltage micropulse DC power supply is capable of (a) controlling the energization interval and continuous energization time in units of microseconds.
(Power supply duty ratio can be controlled)
(B) Therefore, the temperature increase of the one-side electrode or the substrate processing required surface that is the object to be processed is performed.
Easy to control.
(C) A high voltage can be applied to the one electrode in the form of instantaneous pulses,
High activity even from a certain distance away from the treatment required surface
Plasma can be generated and supplied.
It has the characteristics.

The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] Introducing the raw material gas into the evacuated reaction vessel,
In the method of causing a reaction on the substrate to be treated installed in the reaction vessel, while applying the voltage to the one electrode installed in the reaction vessel to convert the source gas into plasma,
At least a part of the one electrode is an electrode through which a raw material gas can pass, and the one electrode is disposed so as not to be in direct contact with the substrate to be processed, and a pulsed DC voltage is applied to the one electrode. A method for generating plasma.
[2] The plasma generation method according to [1], wherein the electrode through which the source gas is permeable has a mesh shape, a spiral shape, a slit shape, or a perforated shape.
[3] The plasma generation method according to [1] or [2], wherein the substrate to be treated is a semiconductor substrate or an insulating substrate.
[4] The plasma generation method of [1] or [2], wherein the substrate to be treated is a substrate that deforms at a low temperature.
[5] The above-mentioned [1], wherein the substrate to be treated has a three-dimensional shape, and the electrode through which the raw material gas can pass is disposed so as to surround the substrate to be treated. The plasma generation method according to any one of [4].
[6] A film forming method using the plasma generation method according to any one of [1] to [5].
[7] The film forming method of [6], wherein an amorphous carbon film is formed on a substrate to be processed.
[8] A surface modification method using the plasma generation method according to any one of [1] to [5].
[9] a reaction vessel that can be evacuated and can accommodate a substrate to be treated;
Means for introducing a source gas serving as a plasma generation source into the reaction vessel;
One electrode installed in the reaction vessel;
The other electrode facing the one electrode;
Means for applying a voltage between the one electrode and the other electrode;
The raw material gas after being introduced into the reaction vessel is turned into plasma by the electric field generated by the voltage application means, and between the surface of the substrate to be treated installed in the reaction vessel and the plasma In a device that causes a reaction in
At least a part of the one electrode is an electrode through which the source gas can pass, and the one electrode and the other electrode are separated from each other by a predetermined distance so as not to directly contact the substrate to be processed. Has been placed,
The plasma generator is characterized in that the applied voltage is a pulsed DC voltage.
[10] The plasma generator according to [9], wherein the shape of the electrode through which the source gas can pass is a mesh shape, a spiral shape, a slit shape, or a perforated shape.
[11] The plasma generator according to [9] or [10], wherein the substrate to be treated is a semiconductor substrate or an insulating substrate.
[12] The plasma generator according to [9] or [10], wherein the substrate to be treated is a substrate that deforms at a low temperature.
[13] The above-mentioned [9], wherein the substrate to be treated has a three-dimensional shape, and an electrode through which the raw material gas can pass is disposed so as to surround the substrate to be treated. -The plasma generator in any one of [12].
[14] A film forming apparatus using the plasma generator of any one of [9] to [13].
[15] The film forming apparatus of [14], which is an apparatus for forming an amorphous carbon film on a substrate to be processed.
[16] A surface modification apparatus using the plasma generator of any one of [9] to [13].

According to the present invention, the following effects (a) to (c) are exhibited.
(A) A rotating mechanism in a vacuum device for processing an insulating material or a substrate that has low electrical conductivity and does not easily form plasma around the substrate itself, and that requires film formation at a particularly low temperature. This can be realized without a cooling mechanism.
(B) Insulating properties that require a low-temperature treatment, especially when the conditions such as applied voltage and pulse duty ratio are the same as those for conventional metal substrates, and the temperature of the substrate to be treated does not increase. It is possible to speed up the processing of the substrate, and it is possible to increase the operating rate of the apparatus.
(C) By arranging the auxiliary electrode in an arbitrary portion, selective partial film formation and modification by plasma can be performed.

The figure which shows typically 1st Embodiment of the film-forming apparatus of an amorphous carbon film The figure which shows typically 2nd Embodiment of the film-forming apparatus of an amorphous carbon film The figure which shows typically 3rd Embodiment of the film-forming apparatus of an amorphous carbon film The figure which shows arrangement | positioning of this work and a mesh electrode in the film-forming to the solid-shaped work which consists of an insulating low-temperature deformation base material The upper left photograph is a photograph before the PET bottom outer peripheral part and the PP cap part are formed, the upper right photograph is the PET bottom outer peripheral part after the amorphous carbon film is formed, and the lower photograph is the amorphous carbon film formed. It is an enlarged image of the photograph which image | photographed the later PP cap part. The figure which shows the result of the Raman spectrum analysis of the amorphous carbon film formed on the glass piece for evaluation arrange | positioned at the PET bottom outer peripheral part of a workpiece | work The figure which shows the result of the Raman spectrum analysis of the amorphous carbon film formed on the glass piece for evaluation arrange | positioned at the PP cap part of a workpiece | work The figure which shows arrangement of a work and a mesh electrode in plasma surface modification of a solid thing which consists of an insulating substrate

  In the method of the present invention, the raw material gas is introduced into a vacuum evacuated reaction vessel, and a voltage is applied to one electrode installed in the reaction vessel, thereby converting the raw material gas into plasma, and the reaction vessel In the method of causing a reaction to occur on the substrate to be treated installed therein, at least a part of the one electrode is an electrode through which a raw material gas can pass, and the one electrode is not in direct contact with the substrate to be treated. And a pulsed DC voltage is applied to the one electrode.

Further, the apparatus of the present invention includes a reaction vessel that can be evacuated and can accommodate a substrate to be processed therein, means for introducing a raw material gas serving as a plasma generation source into the reaction vessel, and the reaction vessel A first electrode disposed in the first electrode, a second electrode facing the first electrode, and a means for applying a voltage to the first electrode, and the source gas after being introduced into the reaction vessel by the voltage applying means. In the apparatus for generating plasma by the generated electric field and causing a reaction between the surface of the substrate to be processed and the plasma installed in the reaction vessel, at least a part of the one electrode is the source gas. , And the first electrode and the second electrode are spaced apart from each other by a predetermined distance so as not to directly contact the substrate to be treated. There, characterized in that the pulse-like DC voltage.
In one embodiment of the present invention, at least a part of the one electrode is an electrode with a “space” such as a mesh shape through which the source gas can permeate. Therefore, it is possible to efficiently discharge surplus electrons generated by the electron avalanche of the plasma, and to prevent the plasma from being densified due to the clogging of the surplus electrons, and the locally concentrated state of plasma (generation of the holocathode).
When the workpiece in one embodiment of the present invention is a low-temperature deformable insulator, since a heating material such as an electrode is not in direct contact with the workpiece, the heat from the heating electrode or the like is in the vacuum apparatus and is transferred to the workpiece by convection. Since it is difficult to propagate, it is not necessary to use a substrate cooling mechanism or the like.
Further, in one embodiment of the present invention, when the substrate to be processed has a three-dimensional shape, by disposing the electrode through which the raw material gas can pass so as to surround the substrate to be processed, It can be applied to a substrate to be processed having various three-dimensional shapes without using a complicated and expensive rotating / revolving mechanism with a high maintenance cost, and a dedicated electrode for specific workpieces with poor compatibility with workpiece shapes. A possible plasma generation method and apparatus can be realized.

  The plasma generation method and the plasma generation apparatus of the present invention described above are directed to the surface of the substrate to be processed, with respect to the substrate to be processed installed in the reaction vessel, the reaction product from the plasma, particularly plasma ions and radicals. It is used for a film forming method or a film forming apparatus to be deposited thereon, or a surface modifying method and a surface modifying apparatus for purifying or modifying the surface of the substrate to be treated by irradiation with the plasma ions or the radicals.

Hereinafter, a plasma generation method and a plasma generation apparatus of the present invention will be described with reference to the drawings.
FIG. 1 is a diagram schematically showing one embodiment of an apparatus in which the method and apparatus of the present invention are used in an amorphous carbon film forming method.
In the figure, 1 is a reaction vessel, 2 is a substrate to be treated (sometimes referred to as “work”), 3 is one electrode, and 4 is a raw material gas permeable electrode (“ 5 is a high-voltage DC pulse power source, and 6 is an insulating support means provided on the bottom surface of the reaction vessel for supporting or placing the substrate to be processed. Yes.
In the apparatus shown in FIG. 1, the high-voltage DC pulse power supply 5 is electrically connected to one electrode 3 (cathode electrode), and the auxiliary electrode 4 is electrically connected to the tip of the one electrode 3. . On the other hand, the reaction vessel 1 is grounded (grounded) and serves as a counter electrode (anode electrode) of the one electrode 3. The auxiliary electrode 4 is disposed so as to cover the substrate 2 to be treated and is disposed so as not to contact the substrate to be treated, and the reaction vessel 1 which is the other counter electrode is also provided with insulating support means. 6 is arranged so as not to contact the substrate 2 to be processed.

FIG. 2 shows another embodiment of the apparatus of the present invention, wherein the support means 6 is provided at the end of one electrode 3 so that the substrate 2 to be treated is suspended by the support means 6. The auxiliary electrode 4 is changed so as to cover the substrate 2 to be processed, and the two electrodes are arranged so as not to contact the substrate 2 to be processed.
The auxiliary electrode 4 is disposed so as to be energized from the one electrode 3.

  FIG. 3 shows another embodiment of the apparatus of the present invention, in which the auxiliary electrode 4 is changed so as to cover only a part of the substrate 2 to be processed. According to the apparatus, a film can be formed only on a predetermined portion covered with the auxiliary electrode.

  In the embodiment shown in FIGS. 1 to 3, the auxiliary electrode 4 disposed so as to surround the substrate 2 to be treated is connected to one electrode 3, and the inner wall of the reaction vessel 1 is electrically used as the other electrode. The pulsed DC voltage is applied to the one electrode 3, but the other electrode is not limited to these embodiments. For example, the position and shape of the reactor can be adjusted as required. Needless to say, the material may be additionally provided.

In the present invention, specific examples of the shape of the auxiliary electrode through which the source gas can permeate include a mesh shape, a spiral shape, a slit shape, and a perforated shape. Since it can deform | transform, it is used suitably.
The material is not particularly limited as long as it has electrical conductivity, not only iron, alloys such as tungsten steel and stainless steel, other conductive materials subjected to thin film surface treatment such as plating, sputtering, and vapor deposition, Conductive materials such as carbon can also be used.
In the case of a mesh electrode, the mesh opening ratio is 40% to 90%, preferably 60% to 90%. In addition, the diameter of the wire constituting the mesh is 10 μm to 5 mm in diameter and the opening width is 10 μm to 5 cm. If the aperture ratio is smaller than this, depending on the shape of the auxiliary electrode, Abnormal discharge is induced and the supply efficiency of the raw material gas is reduced. On the other hand, if it is too large, the plasma generation density is lowered, and it becomes difficult to ensure a continuous surface treatment and a sufficient film formation rate on the workpiece.

  In the embodiment shown in FIG. 1, the auxiliary electrode through which the source gas can pass is disposed so as not to contact the substrate to be processed and to cover at least a part of the substrate to be processed. For example, if the shape of the substrate to be treated is a cylinder, it is preferable to use a cylindrical auxiliary electrode, but the shape of the auxiliary electrode is not limited to this embodiment.

  The distance to the insulating low temperature deformable substrate depends on the size and shape of the substrate to be processed, but it reaches the deposition rate, the supply efficiency of the source gas, and the plasma work generated by the auxiliary electrode. From the standpoints of preventing deactivation and cluster generation until aging, radiation of the heat from the auxiliary electrode to the workpiece in vacuum, and prevention of uneven film thickness due to the shadow of the auxiliary electrode when the distance is too close 0.5 cm to 10 cm is preferable.

  Although the pulsed DC voltage applied in the present invention depends on the purpose of film formation and the purpose of surface modification, the frequency is 1 kHz to 10 kHz, the pulse interval is 1 μs to 10 μs, and the applied voltage is −2 kV to −20 kV, preferably Is -3 kV to -15 kV.

  Examples of the substrate to be processed formed by the method and apparatus of the present invention include insulators (including substrates that are difficult to energize), particularly organic materials such as resins, rubbers such as polyethylene, polypropylene, and polystyrene that are deformed at lower temperatures, and cellulose. In addition, any material such as glass, silicon, ceramics and other inorganic materials can be used depending on the application.

  When an amorphous carbon film is formed on these substrates using the method and apparatus of the present invention, an inert gas such as argon is used as a cleaning gas for the substrate, and methane, ethylene is used as a reactive gas. Various gases serving as plasma generation sources can be used, such as hydrocarbon gases such as acetylene and benzene, and hydrocarbon gases containing silicon such as trimethylsilane and tetramethylsilane. Moreover, argon gas, hydrogen gas, etc. can be used as carrier gas.

Various conditions such as gas concentration, base material temperature, pressure, and film formation time during film formation are as follows: base material for plasma treatment, film composition of amorphous carbonaceous film to be formed, surface roughness, film thickness It sets suitably according to etc.
The source gas for other plasma film formation and reforming treatment can be appropriately selected depending on the application as long as it can be converted into plasma.

  EXAMPLES Hereinafter, although demonstrated using the Example and reference example of this invention, this invention is not limited to these Examples.

Example 1
In this example, the entire surface was formed on a three-dimensional workpiece made of an insulating low-temperature deformable substrate (however, the workpiece holding portion was excluded).
A part of a PET bottle (Nichirei Foods Acerola Sea Life 280ml, main body PET, cap part PP) distributed in the market is cut out, and this cut piece is used as a workpiece, and the workpiece in this three-dimensional shape is specified. Surrounded by a mesh electrode separated from the workpiece by a distance of a range, placed in the reaction vessel of the high-pressure pulse plasma CVD apparatus by the method shown in FIG. 2, and the mesh electrode is energized to form an amorphous carbon film on the workpiece surface. A film was formed.

<Film formation method conditions>
(1) Mesh electrode: Stainless steel (SUS304) mesh container Wire mesh wire diameter: about 230 μm, opening width: about 1.2 mm
An outline of the arrangement is shown in FIG.
The distance from the workpiece processing surface to the mesh electrode is 10 mm for the short part and 32 mm for the long part.
Although omitted in FIG. 4, the mesh electrode including the workpiece is accommodated in a cylindrical reaction vessel of a high-pressure pulse plasma CVD apparatus, and this reaction vessel serves as the ground and serves as the other electrode.
The distance between the side surface of the mesh electrode and the side wall (also serving as the ground) of the cylindrical reaction vessel of the high-pressure pulse plasma CVD apparatus is approximately 20 cm in a concentric radial shape, and the bottom of the mesh electrode and the high-pressure pulse plasma. The distance from the bottom of the cylindrical reaction vessel of the CVD apparatus was approximately 32 cm.
(2) Plasma film formation method (i) High-pressure pulse plasma CVD apparatus Ultimate pressure after evacuation: 1 × 10 ⁻³ Pa
(Ii) Applied voltage: step-up from −2.5 kV to −4, 5 kV, pulse frequency 10 kHz, pulse width 10 μs
Normally, when depositing a workpiece that deforms at a low temperature using a high-pressure pulse plasma CVD system, the pulse width is shortened and deposition is performed while suppressing rapid temperature rise over time (duty ratio of power supply: 1% In this example, a pulse width of 10 μs (duty ratio of power supply: 10%) in the case where a film was formed at a relatively high temperature (such as metal) was used.
(Iii) Source gas: C ₂ H ₂ 30SCCM Gas pressure: 2Pa
(3) Deposition time 3 minutes

<sample>
The outer peripheral part of the PET bottom part of the workpiece (distance of 10 mm between the mesh electrode and the film forming surface) and the PP cap part (the surface part having the cylindrical body curved surface of the cylindrical cap body). A small piece of glass as an insulator was attached to a distance of 25 mm) and used as an evaluation sample of the formed amorphous carbon film. The reason why the glass piece is used for the evaluation sample is that it is an insulating material like the workpiece, and a sample having a smooth surface is required for measuring the thickness of the thin film.
The glass piece of the evaluation sample has a size of 5 mm × 5 mm and a thickness of 1 mm. Two pieces for film thickness measurement and for Raman spectrum analysis are used, a PET bottom outer peripheral part of the workpiece, and a PP cap part (not shown). Two pieces of each were attached with double-sided tape. Refer to FIG. 4 for the position where the thermolabel for temperature measurement is attached to the outer peripheral portion of the PET bottom, the arrangement of the mesh electrode, and the like.

<result>
(1) The upper left photograph in FIG. 5 is a photograph of the outer peripheral portion of the PET bottom and the PP cap portion before the amorphous carbon film is formed, and the upper right photograph in FIG. 5 is the amorphous carbon film formed. FIG. 6 is a partially enlarged photograph of the molding pattern of the bottom of the rear PET bottle (distance from the mesh electrode of 13 mm to 32 mm), and the lower photograph in FIG. 5 shows the cap part (PP of the PET bottle after the amorphous carbon film formation) It is a partially enlarged photograph of manufactured.
In this embodiment, an abnormal discharge is not generated up to a predetermined applied voltage of −4, 5 kV, and an amorphous carbon film having a clean continuity is formed on a curved surface including fine three-dimensional irregularities on the surface of the workpiece. did it.
Furthermore, it was also confirmed that the metal mesh pattern of the mesh electrode was not transferred.
If the mesh electrode is in contact with the workpiece, the amorphous carbon film becomes discontinuous, and the desired effects such as gas barrier properties cannot be expressed. May be damaged by heat deformation.
(2) An amorphous carbon film formed under the above conditions is an evaluation sample using a glass piece attached to the vicinity of the outer periphery of the bottom of the PET bottle as a work, and an evaluation sample using a glass piece placed on the PP cap portion of the work. evaluated.

(I) Thickness of the deposited carbon film As a result of measurement using a stylus-type surface shape measuring instrument “DEKTAK150 stylus profiler” manufactured by VEECO as a measuring instrument, a glass sample for evaluation attached to the outer periphery of the bottom of the PET bottle The average amorphous carbon film thickness at any three points of 32 nm is 32 nm (deposition rate: 10.6 nm / min), and the average amorphous carbon value at any three points of the glass sample for evaluation placed on the PP cap portion of the workpiece The carbon film thickness was 46 nm (film formation rate: 15.4 nm / min).
The rate of the PP cap part of the work is a film formation rate approaching approximately 18 nm / min when a voltage is applied to the conductive work itself to generate plasma and the film is formed. Thus, it was confirmed that an amorphous carbon film can be formed without significantly deteriorating the film formation rate.
(Ii) Raman spectrum analysis FIG. 6 and FIG. 7 show the results of Raman spectrum analysis. The analyzer used was NRS-3300 manufactured by JASCO. FIG. 6 shows the Raman spectrum of the amorphous carbon film formed on the glass sample placed on the outer periphery of the PET bottom of the workpiece, and FIG. 7 shows the non-crystal formed on the glass sample placed on the PP cap portion of the workpiece. It is a Raman spectrum of a crystalline carbon film.
From FIG. 6 and FIG. 7, it was confirmed that an amorphous carbon film was formed on both.
Raman spectrum of a typical amorphous carbon film is having a shoulder band around the main peak and 1390 cm ^-1 in the vicinity of 1540 cm ^-1, 6, two peaks with 7 both have been identified in the fitting, The formed film is considered to have an amorphous carbon film structure.
(Iii) Heat resistance It was confirmed that the thermolabel attached to the vicinity of the outer periphery of the bottom of the PET bottle did not change to a color indicating that the temperature reached 60 ° C. Therefore, it is judged that the amorphous carbon film could be formed on the PET surface at a temperature sufficiently lower than the heat resistant deformation temperature of PET.
A thermolabel is attached to the outside of the cylindrical metal mesh electrode (outside of the housing portion) at a position facing the glass sample for evaluation attached near the outer periphery of the bottom of the PET bottle, and the temperature after film formation is adjusted. Also confirmed.
Since this position is located outside the accommodating portion made of the mesh electrode as described above, it does not affect the formation of the amorphous carbon film on the glass sample for evaluation.
As a result, it was confirmed that the thermolabel attached directly on the metal mesh electrode showed a color change indicating that the temperature reached 160 ° C. far exceeding the heat-resistant deformation temperature of PET or PP.

  According to this embodiment, when an insulator is arranged in the space formed by the mesh electrode, the temperature of the work to be deposited is not increased, the supply of the source gas is ensured, and abnormal discharge such as a holo cathode is performed. Generation | occurrence | production was suppressed and the high voltage required for film-forming of an amorphous carbon film was able to be applied, and as a result, it has confirmed that film-forming of a quality amorphous carbon film was possible.

(Reference Example) Film Formation on Conductive Workpiece The same mesh electrode as in Example 1 was used, the contents were made of the same shape work made of aluminum foil, and the amorphous carbon film was placed in the same manner as in Example 1 A film was formed. In order to energize the contents of the conductive material, the holding insulator of the cap portion was fixed so that the workpiece could be placed at the same position.
<Plasma deposition method>
(1) High-pressure pulse plasma CVD apparatus Ultimate pressure after evacuation: 1 × 10 ⁻³ Pa
Pulse frequency 10 kHz, pulse width: 10 μs
(2) Source gas: Acetylene Gas flow rate: 30 SCCM
When film formation was started at an applied voltage of −2 kV at a gas pressure of 2 Pa, severe abnormal discharge occurred at the bottom of the mesh electrode (near the cap), and the continuation of film formation immediately became impossible, and the applied voltage was reduced to −1.5 kV. However, the abnormal discharge did not end and the film formation was stopped.

(Example 2)
In this example, plasma surface modification to a three-dimensional object made of an insulating base material was performed.
A cylindrical insulator having a diameter of about 5 cm with an amorphous carbon film attached was placed in the mesh electrode below, and surface modification was performed by sputtering with argon plasma under the following conditions (previously attached to the insulator surface) Stripping of the amorphous carbon film was performed.
1. Mesh electrode Stainless steel (SUS304) mesh container Wire mesh wire diameter: about 230 μm, opening width: about 1.2 mm was used. An outline of the work and electrode arrangement is shown in FIG.
In addition, since the insulator has heat resistance, the same stainless steel (SUS304) wire mesh was also used at the bottom where the insulator was placed.
2. Argon plasma sputtering conditions (1) High-pressure pulse plasma CVD apparatus Ultimate pressure after evacuation: 1 × 10 ⁻³ Pa
(2) Applied voltage: -4 kV (10 minutes), -4, 5 kV (15 minutes), -4 kV (10
Repeat for 3 minutes) for a total of 35 minutes Pulse frequency 10 kHz, Pulse width 10 μs
(3) Source gas: Argon gas Gas flow rate: 30 SCCM Gas pressure: 2 Pa

<Measuring method>
The thickness of the amorphous carbon film from which the carbon film is peeled off by sputtering is the same as that of the Si (100) sample piece that has been deposited on the top of the charged insulator and has been measured. A part of the surface layer of the amorphous carbon film is partially coated with a commercially available oily marker (“Magic Ink” (registered trademark)), irradiated with argon gas plasma, the oily marker coated part and the part exposed to the argon gas plasma The method was performed by measuring the step.
As the level difference measuring device, a stylus type surface shape measuring device “DEKTAK150 stylus profiler” manufactured by VEECO was used.

<result>
As a result of measuring the step, a step of 326 nm was confirmed, and it was confirmed that the amorphous carbon film was etched with argon gas plasma.

1: Reaction vessel 2: Substrate to be treated (workpiece)
3: One electrode 4: Raw material gas permeable electrode (mesh electrode, auxiliary electrode)
5: High voltage DC pulse power supply 6: Insulating support means

Claims (16)

Introducing the raw material gas into the evacuated reaction vessel,
By applying a voltage to the one electrode installed in the reaction vessel, the raw material gas is turned into plasma and reacted on a substrate to be treated made of an insulating organic material installed in the reaction vessel. In the method of causing
At least a portion of the one electrode, the aperture ratio is 40% to 90%, opening width as a raw material gas capable transmissive electrode having an opening 10Myuemu～5cm, the one electrode is not the direct and the object to be treated substrate And arranging the electrode through which the source gas is permeable so as to cover at least a part of the substrate to be treated with a distance of 0.5 to 10 cm from the substrate to be treated ,
The reaction vessel is used as the other electrode, and the substrate to be treated is supported by an insulating support means or placed on an insulating support means so as not to be in direct contact with the reaction container, and
A plasma generation method, wherein a pulsed DC voltage is applied to the one electrode. The plasma generation method according to claim 1, wherein the other electrode facing the one electrode is provided so that the other electrode does not directly contact the substrate to be processed. The plasma generation method according to claim 1 or 2 , wherein the shape of the electrode through which the source gas can pass is a mesh shape, a spiral shape, a slit shape, or a perforated shape. 4. The plasma according to claim 1, wherein the pulsed DC voltage has a frequency of 1 kHz to 10 kHz, a pulse interval of 1 μs to 10 μs, and an applied voltage of −2 kV to −20 kV. 5. How it occurs. The treated substrate be one having a three-dimensional shape, the material gas is permeable electrode, any of claim 1 to 5, characterized in that it is arranged to surround the該被treated substrate The plasma generation method according to claim 1.   A film forming method using the plasma generation method according to claim 1.   The film forming method according to claim 6, wherein an amorphous carbon film is formed on the substrate to be processed.   A surface modification method using the plasma generation method according to claim 1. A reaction vessel that can be evacuated;
A substrate to be treated made of an insulating organic material, housed in the reaction vessel;
Means for introducing a source gas serving as a plasma generation source into the reaction vessel;
One electrode installed in the reaction vessel;
It means for applying a voltage to the one electrode,
The raw material gas after being introduced into the reaction vessel is turned into plasma by the electric field generated by the voltage application means, and between the surface of the substrate to be treated installed in the reaction vessel and the plasma In a device that causes a reaction in
At least a part of the one electrode is an electrode through which a raw material gas having an opening ratio of 40% to 90% and an opening width of 10 μm to 5 cm is permeable , and the one electrode does not directly contact the processing substrate. Rutotomoni is placed as the raw material gas is permeable electrode, wherein disposed to cover at least a portion of the treated substrate and 0.5~10cm the treated substrate at a distance of And
The reaction vessel is used as the other electrode, and an insulating support means for supporting or placing the substrate to be treated is provided, and the substrate to be treated is arranged so as not to come into direct contact with the reaction vessel,
The plasma generator is characterized in that the applied voltage is a pulsed DC voltage. 10. The plasma generation according to claim 9, further comprising: the other electrode facing the one electrode, wherein the other electrode and the one electrode are disposed so as not to be in direct contact with the substrate to be processed. apparatus. The plasma generating apparatus according to claim 9 or 10, wherein the shape of the electrode through which the source gas is permeable is a mesh shape, a spiral shape, a slit shape, or a perforated shape. 12. The plasma according to claim 9, wherein the pulsed DC voltage has a frequency of 1 kHz to 10 kHz, a pulse interval of 1 μs to 10 μs, and an applied voltage of −2 kV to −20 kV. Generator.   The said to-be-processed base material has a three-dimensional shape, Comprising: The electrode which can permeate | transmit the said source gas is arrange | positioned so that this to-be-processed base material may be enclosed. 2. The plasma generator according to claim 1.   A film forming apparatus using the plasma generator according to any one of claims 9 to 13.   The film forming apparatus according to claim 14, which is an apparatus for forming an amorphous carbon film on a substrate to be processed.   A surface modification apparatus using the plasma generator according to any one of claims 9 to 13.