JP6883838B2 - Method for modifying the object to be processed and device for modifying the object to be processed - Google Patents

Description

The present invention relates to a method for modifying an object to be processed and an apparatus for modifying an object to be processed.

Fluorine-based resin materials have higher heat resistance than other resin materials, and are also excellent in electrical insulation and chemical resistance, so they are applied to various products. However, the use of the fluororesin has been limited because the surface water repellency is high and the adhesion to other materials is inferior. Pretreatment with chemicals is known as a method for improving the adhesion between a fluororesin and a dissimilar material. In chemical pretreatment, dangling bonds are formed by the prohalogenity of the chemical. Molecules such as oxygen, hydrogen, and steam in the atmosphere chemically bond to this dangling bond. By this chemical bond, a functional group having wettability or adhesiveness, for example, a hydroxyl group (-OH) or a carboxyl group (-COOH) is formed, and the adhesiveness of the epoxy resin is improved. For example, as a technique for modifying the surface using a chemical wet method, a method for producing a fluororesin composition disclosed in Patent Document 1 is known.

Japanese Unexamined Patent Publication No. 2016-65217

According to the chemical wet method as in Patent Document 1, there are problems in terms of environment, cost, processing time, and the like. Therefore, a method for modifying the object to be treated and an apparatus for modifying the object to be treated, which are not based on a chemical wet method, have been desired.

One embodiment of the present invention is a method of modifying an object to be treated. The method of modifying the object to be processed is the first step of arranging the object to be processed in the processing space on the processing table set in the atmospheric pressure environment and the second step of generating the processing plasma of the processing gas provided in the processing space. The process, the third step of accelerating the ions in the processing plasma toward the processing table and colliding the accelerated ions with the processing surface of the processing object by supplying a voltage to the processing table, and the processing object. It comprises a fourth step of supplying a modified plasma of the modified gas for the functional group to be modified to the treatment space.

According to this method, in the second step, plasma supplied into the processing space, which is considered to be atmospheric pressure, is generated. Ions in atmospheric pressure plasma have a predetermined energy. Then, in the third step, the ions having the energy are accelerated and collided with the object to be processed. Then, the ions colliding with the object to be processed have kinetic energy due to acceleration in addition to the predetermined potential energy and internal energy. Such collisions of ions with sufficiently high energy make it possible to break the bonds between atoms on the surface of the object to be treated and form dangling bonds. Then, in the fourth step, a functional group is introduced into the formed dangling bond by a radical generated by the modified plasma. Therefore, the surface of the object to be treated can be modified regardless of the chemical wet method.

The fourth step may be performed after the second step and the third step are completed. According to these steps, the treatment for forming a dangling bond on the object to be treated is performed by the second and third steps, and then the functional group is introduced into the dangling bond by the fourth step. Therefore, since ion collision does not occur in the introduction of the functional group, the surface into which the functional group is introduced can be suitably protected.

The fourth step may be started before the second and third steps are completed. According to these steps, the process of forming a dangling bond and the process of introducing a functional group can be performed in parallel. Then, the functional group can be quickly introduced into the formed dangling bond. Therefore, the efficiency of the treatment for modifying the surface of the object to be treated can be increased.

The object to be treated may contain a fluororesin material. Even if the object to be treated is a fluororesin, it is possible to form a dangling bond. Therefore, the surface of the fluororesin having high surface water repellency can be suitably modified.

The processing gas is a gas containing helium, the modified gas is a gas containing ammonia, and in the third step, a DC voltage or a square wave voltage may be supplied to the processing table. According to this step, the surface of the object to be treated can be suitably modified with an amino group.

The processing gas is a gas containing helium, the modified gas is a gas containing oxygen, and in the third step, a DC voltage may be supplied to the processing table. According to this step, the surface of the object to be treated can be suitably modified with a carboxyl group.

Another embodiment of the present invention is an apparatus that modifies an object to be treated. The device for modifying the object to be processed is a processing plasma provided in an atmospheric pressure environment and a processing table in which the object to be processed is arranged, and a processing plasma that supplies a processing plasma of a processing gas provided in a processing space set on the processing table. The supply unit, the bias voltage supply unit that supplies voltage to the processing table in order to accelerate the ions in the plasma toward the processing table and collide the accelerated ions with the processing surface of the processing object, and the processing object. It is provided with a modified plasma supply unit that supplies a plasma of the modified gas for the functional group that modifies the processing space.

According to this device, in the processing plasma supply unit, plasma is supplied into the processing space which is considered to be atmospheric pressure. Ions in atmospheric pressure plasma have a predetermined energy. Then, the bias voltage supply unit accelerates the ions having the energy and causes them to collide with the object to be processed. Then, the ions colliding with the object to be processed have kinetic energy due to acceleration in addition to the predetermined potential energy and internal energy. Such collisions of ions with sufficiently high energy make it possible to break the bonds between atoms on the surface of the object to be treated and form dangling bonds. Then, the modified plasma supply unit introduces a functional group caused by radicals in the modified plasma into the dangling bond. Therefore, the surface of the object to be treated can be modified regardless of the chemical wet method.

According to the method for modifying the object to be treated and the apparatus for modifying the object to be processed according to one embodiment of the present invention, the surface of the object to be processed can be modified regardless of the chemical wet method.

FIG. 1 is a schematic view showing a configuration of an apparatus for modifying an object to be processed according to an embodiment of the present invention. FIG. 2 is a diagram showing a main step of a method for modifying an object to be processed according to the first embodiment. Part (a), part (b) and part (c) of FIG. 3 are diagrams for explaining phenomena occurring during the pretreatment and the modification treatment. FIG. 4 is a diagram showing a main step of the method for modifying the object to be processed according to the second embodiment. FIG. 5 is a fluorescence microscope image showing the result of Experimental Example 1. FIG. 6 is a fluorescence microscope image showing the results of Experimental Example 2. FIG. 7 is a fluorescence microscope image showing the result of Reference Example 1. Parts (a) to (f) in FIG. 8 are fluorescence microscope images showing the results of Experimental Example 3. Parts (a) to (f) in FIG. 9 are fluorescence microscope images showing the results of Experimental Example 4.

<First Embodiment>
Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same elements are designated by the same reference numerals, and duplicate description will be omitted.

First, an apparatus for modifying an object to be processed (hereinafter, also referred to as “atmospheric pressure plasma jet apparatus”) will be described. The atmospheric pressure plasma jet device modifies the surface of the object to be treated with a functional group. For example, examples of the object to be treated include a fluororesin. Moreover, the functional group includes an amino group, a carboxyl group, a hydroxyl group and the like. The object to be treated and the functional group are not limited to the above-mentioned substances.

As shown in FIG. 1, the atmospheric pressure plasma jet device 1 includes a processing table 2, a glass tube 3, a processing gas supply unit 4, a modified gas supply unit 6, a plasma voltage supply unit 7, and a bias voltage supply. It has a unit 8 and a control unit 9. When the processing gas supply unit 4 supplies the processing gas to the glass tube 3, the processing gas is turned into plasma by the voltage received from the plasma voltage supply unit 7. A bias voltage is supplied to the processing table 2 from the bias voltage supply unit 8. The ions in the plasma of the processing gas (hereinafter, also referred to as “processing plasma”) are accelerated toward the processing table 2 by the potential difference between the plasma voltage supply unit 7 and the bias voltage supply unit 8, and finally the object 100 to be processed. Collide with the surface. Further, when the modified gas is added to the processing gas and supplied from the modified gas supply unit 6 to the glass tube 3, the modified gas is turned into plasma by the voltage received from the plasma voltage supply unit 7. The plasma to which the modified gas is added (hereinafter, also referred to as “modified plasma”) is transported to the surface of the object to be treated 100. Then, the surface of the object to be treated 100 is modified with a desired functional group by the radical of the modified plasma. Hereinafter, the detailed configuration of the atmospheric pressure plasma jet device 1 will be described.

The processing table 2 supports the object to be processed 100. The processing table 2 has a movable mechanism controlled by an external computer and is arranged in atmospheric pressure. Therefore, the processing table 2 may be arranged inside a processing container (not shown) whose internal pressure is set to atmospheric pressure, or may be arranged indoors in an atmospheric pressure environment without being arranged in the processing container or the like. May be done. A processing space P is set on the processing table 2. Further, a bias voltage supply unit 8 is connected to the processing table 2.

The glass tube 3 forms a flow path for transporting the processed plasma and the modified plasma into the processing space P. The glass tube 3 is, for example, a cylindrical member made of quartz glass, and is arranged so that the lower end 3a is located in the processing space P. In the glass tube 3, various gases for plasma are provided from the upper end 3b, and the processed plasma and the modified plasma are discharged from the lower end 3a. When performing the modification process, the object to be processed 100 is arranged between the lower end 3a of the glass tube 3 and the processing table 2. The lower end 3a of the glass tube 3 may be brought into contact with the surface of the object to be processed 100, or may be provided at a predetermined interval.

The processing gas supply unit 4 supplies the processing gas for the processing plasma. Examples of the processing gas include helium and argon. The processing gas supply unit 4 is connected to the upper end 3b of the glass tube 3 and supplies the processing gas to the glass tube 3. The start and stop of the supply of the processing gas is in accordance with the command of the control unit 9.

The modified gas supply unit 6 supplies the modified gas for the modified plasma. Examples of the modified gas include ammonia, oxygen and water vapor. The modified gas supply unit 6 is connected to the upper end 3b of the glass tube 3 and supplies the modified gas to the glass tube 3. The start and stop of the supply of the modified gas are in accordance with the command of the control unit 9.

The plasma voltage supply unit 7 turns the processing gas and the processing gas into plasma by providing a voltage to the processing gas and the modified gas. Therefore, the plasma voltage supply unit 7 and the processing gas supply unit 4 constitute the processing plasma supply unit. The plasma voltage supply unit 7 has a plasma power supply 7a and a plasma electrode 7b. The plasma electrode 7b is arranged between the lower end 3a and the upper end 3b in the longitudinal direction of the glass tube 3 and provides a voltage to the processing gas and the modifying gas flowing from the upper end 3b to the lower end 3a inside the glass tube 3. To do. The plasma power supply 7a provides the plasma electrode 7b with the voltage required to generate each plasma in accordance with the instruction of the control unit 9.

The bias voltage supply unit 8 creates a potential difference with the plasma electrode 7b, and accelerates ions and / or radicals in the plasma by the potential difference. Therefore, the bias voltage supply unit 8 and the modified gas supply unit 6 constitute a modified plasma supply unit. The bias voltage supply unit 8 includes a bias power supply 8a and a bias electrode 8b. The bias electrode 8b is provided on the processing table 2. Further, the processing table 2 itself may be used as the bias electrode 8b. The operation of the bias voltage supply unit 8 follows the command of the control unit 9. In the processing space P on the processing table 2 where a predetermined potential difference is generated, ions and / or radicals in the plasma accelerate toward the processing table 2. Such a predetermined voltage includes a DC voltage and an AC voltage. The AC voltage includes a sinusoidal voltage having a predetermined frequency and amplitude, and a square wave voltage.

The control unit 9 controls the operation of each element such as the processing gas supply unit 4, the modified gas supply unit 6, the plasma voltage supply unit 7, and the bias voltage supply unit 8. That is, the control unit 9 controls the operation of these elements as a single unit, the operation timing between the elements, and the like. The control unit 9 is realized, for example, by executing a program on a personal computer.

Next, a method of modifying the surface of the object to be processed 100 using the atmospheric pressure plasma jet device 1 will be described in detail with reference to FIG.

First, the object to be processed 100 is arranged in the atmospheric pressure plasma jet device 1 (first step: step S1). The object to be treated 100 is, for example, a thin plate formed of a fluorine-based resin material. If necessary, a mask may be placed on the surface of the object to be treated 100. The mask is, for example, a copper plate. When a mask is used, it becomes possible to select a region to be modified on the surface of the object to be treated 100.

Next, the supply of the processed plasma is started (second step: step S2). Specifically, first, the control unit 9 gives a command to the processing gas supply unit 4 to start the supply of the processing gas (step S2a). Next, the control unit 9 gives a command to the plasma voltage supply unit 7 to supply a predetermined voltage to the processing gas (step S2b). By this control, the processing gas in the glass tube 3 is turned into plasma.

Next, the pretreatment is started (third step). The pretreatment refers to a treatment for forming a dangling bond on the surface of the object to be treated 100. Specifically, the control unit 9 gives a command to the bias power supply 8a of the bias voltage supply unit 8 to start providing the voltage to the bias electrode 8b (step S3). By providing this voltage, a desired potential difference is generated between the plasma electrode 7b and the bias electrode 8b. For example, in the case of this embodiment, a DC voltage is provided. By this control, the ions of the processed plasma generated in the glass tube 3 are accelerated and discharged from the lower end of the glass tube 3, and the object to be processed is arranged between the lower end of the glass tube 3 and the processing table 2. Collision with 100 surfaces.

Here, as shown in part (a) of FIG. 3, for example, when the object to be treated 100 is Teflon (registered trademark) as a fluorine-based resin, fluorine is bonded to carbon constituting the main chain as a side chain. ing. Ions, which are accelerated charged particles, have a predetermined energy in the original state. Then, the ions are further accelerated by the bias voltage and collide with the surface of the object to be processed 100. The collision of the ions breaks the bond between the main chain or side chain of the Teflon molecule. A dangling bond is formed at the cut portion.

This third step is continued for a predetermined time set in advance. After the elapse of the predetermined time, the control unit 9 stops providing the plasma voltage (step S4). The third step ends when the provision of the plasma voltage is stopped.

Next, the modification process is started (fourth step). The modification treatment refers to a treatment for introducing a functional group onto the surface of the object to be treated 100. Specifically, the control unit 9 gives a command to the modified gas supply unit 6 to start supplying the modified gas in addition to the already supplied processing gas (step S5). Here, the modified gas is turned into plasma inside the glass tube 3. Here, since the provision of the bias voltage supply unit 8 is stopped, the radical of the modified plasma is emitted from the lower end 3a of the glass tube 3. Then, the released radicals are introduced into the dangling bond formed on the surface of the object to be treated 100. Here, when a modified gas containing ammonia is supplied, the modified gas is turned into plasma to form NH and NH ₂ radicals. Then, as shown in part (b) of FIG. 3, the radical binds to the dangling bond formed in the third step. This bond modifies the amino group at the molecularly cleaved moiety on the Teflon surface, as shown in part (c) of FIG.

This fourth step is continued for a predetermined time set in advance. After the elapse of the predetermined time, the control unit 9 gives a command to the modified gas supply unit 6 to stop the supply of the modified gas (step S6). Then, the control unit 9 also gives a command to the plasma voltage supply unit 7 to stop the supply of the plasma voltage (step S8). The surface of the object to be treated 100 is modified by the above steps 1 to 4.

By the way, research on surface modification of fluororesins by plasma treatment has a long history, but there have been no reports of successful cases so far. Recently, there have been reports on improving the adhesiveness of Teflon-based resin rubber using plasma treatment and metal fine particles by an inkjet method. However, according to the reported contents, it is considered that the surface of the fluororesin is amorphized due to the annealing of the resin surface layer due to the thermal effect of the plasma treatment.

In the method for modifying the surface of the object to be treated 100 and the atmospheric pressure plasma jet device 1 according to the present embodiment, an important process in plasma modification of the fluororesin is to form a dangling bond on the resin surface. In the method of modifying the surface of the object to be processed 100 according to the present embodiment, ions in the plasma are made to collide with the resin surface by providing a high voltage negative bias voltage to the processing table 2 for forming a dangling bond. Then, after forming a dangling bond by ion collision, functional groups are introduced by various radicals contained in the discharge gas.

Specifically, according to the method of modifying the surface of the object to be treated 100 and the atmospheric pressure plasma jet device 1 according to the present embodiment, the treated plasma is generated in the second step. Ions in atmospheric pressure plasma have a predetermined energy. Then, in the third step, the ions having the energy are accelerated and collide with the object to be processed 100. Then, the ions colliding with the object to be processed 100 have kinetic energy due to acceleration in addition to the predetermined potential energy and internal energy. By the collision of ions having sufficiently high energy, it becomes possible to break the bond between atoms on the treated surface of the object to be treated 100 and form a dangling bond. Then, in the fourth step, a functional group is introduced into the formed dangling bond by radicals in the modified plasma. Therefore, the surface of the object to be treated 100 can be modified regardless of the chemical method.

That is, according to the modification method and the atmospheric pressure plasma jet device 1 according to the above embodiment, the molecular composition of only the resin surface layer is changed and the chemical modification is performed without causing the resin surface layer to be amorphized by thermal modification. It is possible to do. Therefore, it is possible to introduce functional groups by surface modification to the surface of fluorine-based ultrathin films and nanoparticles, and various industrial applications of these nanostructured fluorine-based resin materials are expected.

Further, the fourth step is performed after the third step is completed, and the period in which the third step is performed does not overlap with the period in which the fourth step is performed. According to these steps, the pretreatment of the object to be processed 100 is performed by the third step, and then the functional group is introduced by the fourth step. Therefore, since the introduction of the functional group does not cause the ion collision that occurs during the pretreatment, the treated surface into which the functional group has been introduced can be suitably protected.

In short, in the modification method and the atmospheric pressure plasma jet device 1 according to the present embodiment, one process without providing a time difference between the ion collision process for breaking the molecular bond of the fluororesin and the process for introducing the functional group. Dangling bonds of surface molecules are formed and functional groups are modified. The modification method and the atmospheric pressure plasma jet device 1 according to the present embodiment can also locally modify the surface of the fluororesin material. Therefore, it shows the possibility of micro applications that require microfabrication processing from macro applications that require large area processing, and is expected to be used in various industrial fields in the future.

<Second Embodiment>
In the first embodiment, after the processing of the second step and the third step is completed (after the step S4), the processing of the fourth step (step S5) is started. Therefore, there is no period during which the third step and the fourth step are performed in an overlapping manner. However, the method of modifying the surface of the object to be treated 100 is not limited to the order of this step. For example, as shown in FIG. 4, the second step and the third step and the fourth step may be carried out so as to have a period T in which they overlap each other. That is, a functional group may be introduced into the dangling bond while forming a dangling bond on the surface of the object 100 to be treated.

Hereinafter, the method of modifying the surface of the object to be treated 100 according to the second embodiment will be specifically described. The method according to the second embodiment differs only in the order of processing, and the apparatus used for the method according to the second embodiment is the same as the atmospheric pressure plasma jet apparatus 1 according to the first embodiment. Therefore, the description of the atmospheric pressure plasma jet device 1 will be omitted.

First, the object to be processed 100 is arranged in the atmospheric pressure plasma jet device 1 (step S1). Next, the control unit 9 gives a command to the processing gas supply unit 4 to start the supply of the processing gas (step S2a). Next, the control unit 9 gives a command to the modified gas supply unit 6 to start the supply of the processing gas (step S5). Next, the control unit 9 gives a command to the plasma voltage supply unit 7 to supply a predetermined voltage to the processing gas (step S2b). In this state, the processed plasma and the modified plasma are formed in the glass tube 3. Then, the control unit 9 gives a command to the bias power supply 8a of the bias voltage supply unit 8 to start providing the bias voltage (step S3). By carrying out this step S3, the ions of the treated plasma and the radicals of the modified plasma are provided on the surface of the object to be treated 100. The ions of the treated plasma and the radicals of the modified plasma are transported to the surface of the object to be processed 100 due to the potential difference caused by the bias voltage. Then, the formation of the dangling bond by ions and the introduction of the functional group into the dangling bond proceed in parallel.

Next, when the preset predetermined time elapses, the control unit 9 stops providing the bias voltage (step S7) and stops providing the plasma voltage (step S8). Next, the control unit 9 gives a command to the processing gas supply unit 4 to stop the supply of the processing gas (step S4), and at the same time, gives a command to the modified gas supply unit 6 to stop the supply of the modified gas. (Step S6). From the above steps, the surface of the object to be treated 100 is modified.

That is, according to the method according to the second embodiment, the fourth step is started before the second step and the third step are completed, and has a period T that overlaps with the period in which the fourth step is performed. .. The second step and the third step (step S20) referred to in the present embodiment may be from a step of starting the provision of the processing gas (step S2a) to a step of stopping the provision of the plasma voltage (step S8). Further, the fourth step (step S40) may be from a step of starting the provision of the modified gas (step S5) to a step of stopping the provision of the plasma voltage (step S8). According to this method, the process of forming a dangling bond by ion collision and the process of introducing a functional group can be performed in parallel. Then, the functional group can be quickly introduced into the formed dangling bond. Therefore, the efficiency of the treatment for modifying the surface of the object to be treated 100 can be increased.

The method according to the second embodiment is not limited to the above processing order. In short, it suffices that the processed plasma and the modified plasma have a period of being provided to the object 100 at the same time, and the timing of starting and stopping the supply of each gas, the timing of starting and stopping the supply of each voltage, and the like. May be modified in the manner in which the period T is formed.

An experiment was conducted in which various functional groups were modified in the object to be treated 100 by using the method and the apparatus according to the present embodiment. The results of Experimental Examples 1 to 3 will be described below.

<Experimental example 1>
In Experimental Example 1, a fluororesin plate having a Teflon surface as the object to be treated 100 was modified with an amino group as a functional group.

In the atmospheric pressure plasma jet device 1 used in Experimental Example 1, the inner diameter of the quartz glass tube 3 was 3 mm, and a copper tape was wound around the glass tube 3 as the plasma electrode 7b. In this atmospheric pressure plasma jet device 1, the upstream side is a ground electrode, and the downstream side is H.I. It has a two-electrode structure with V electrodes. A capillary having an inner diameter of 700 micrometers was attached to the tip of the glass tube 3. A mask, which is a copper film, was placed on the treated surface of the object to be treated 100. The mask was assumed to have a plurality of circular holes having a diameter of 100 micrometers. Detailed experimental conditions are shown below.
Pulse voltage (plasma voltage supply unit) ・ ・ ・ ・ ・ ± 8kV
Frequency (plasma voltage supply unit) ・ ・ ・ ・ ・ ・ ・ ・ 5kHz
Duty ratio (plasma voltage supply unit) ... 50%
Bias voltage (bias voltage supply unit) -500V (square wave)
Bias frequency (bias voltage supply unit) ・ ・ ・ 2.5Hz
Capillary inner diameter ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 700 μm
Processing gas type: Helium (He)
Processing gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 700sccm
Modified gas type: Ammonia (NH ₃ )
Modified gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 10sccm
Distance from the lower end of the capillary to the object to be processed: 600 μm
Processing time: 6 minutes

For confirmation of the functional group modification in the object to be treated 100 after the treatment, a chemical derivatization method using a fluorescent dye was used, and the surface after the treatment was observed using a fluorescence microscope. In Experimental Example 1, Alexa fluor 488 5-SD Pester was used as the fluorescent dye. FIG. 5 is a fluorescence microscope image of the treated surface. In the image of FIG. 5, the gray circular portion indicates the modified region. According to FIG. 5, the patterning treatment of amino groups was confirmed, and it was shown that the surface of the fluororesin can be modified with spatially controlled amino groups.

<Experimental example 2>
In Experimental Example 2, a fluororesin plate having a Teflon surface as the object to be treated 100 was modified with a carboxyl group as a functional group. The details of the atmospheric pressure plasma jet device 1 are the same as those of Experimental Example 1. Other detailed experimental conditions are shown below.
Pulse voltage (plasma voltage supply unit) ・ ・ ・ ± 8kV
Frequency (plasma voltage supply unit): 5 kHz
Duty ratio (plasma voltage supply unit) ... 50%
Bias voltage (bias voltage supply unit) ... Pre-processing: -500V (DC), Post-processing: 0V
Bias frequency (bias voltage supply unit) / DC capillary inner diameter: 700 μm
Processing gas type ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Helium (He)
Processing gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 700sccm
Modified gas type ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Oxygen (O ₂ )
Modified gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5sccm
Distance from the lower end of the capillary to the object to be processed ・ 0 μm (contact state)
Processing time ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Pre-processing: 3 minutes, post-processing: 3 minutes

For confirmation of the functional group modification in the object to be treated 100 after the treatment, a chemical derivatization method using a fluorescent dye was used, and the surface after the treatment was observed using a fluorescence microscope. In Experimental Example 2, Alexa fluor 594 cadaverince was used as the fluorescent dye. FIG. 6 is a fluorescence microscope image of the treated surface. In the image of FIG. 6, the gray portion indicates the modified region. According to FIG. 6, the patterning treatment of the carboxyl group was confirmed, and it was shown that the surface of the fluororesin can be modified by the spatially controlled carboxyl group.

<Reference example 1>
In order to compare with the result of Experimental Example 2, the experiment of Reference Example 1 was carried out. The details of the atmospheric pressure plasma jet device 1 are the same as those of Experimental Example 1. Other detailed experimental conditions are shown below.
Pulse voltage (plasma voltage supply unit) ・ ・ ・ ± 8kV
Frequency (plasma voltage supply unit): 5 kHz
Duty ratio (plasma voltage supply unit) 50%
Bias voltage (bias voltage supply unit) -500V (AC)
Bias frequency (bias voltage supply unit) 2.5Hz
Capillary inner diameter: 700 μm
Processing gas type ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Helium (He)
Processing gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 700sccm
Modified gas type ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Oxygen (O ₂ )
Modified gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5sccm
Distance from the lower end of the capillary to the object to be processed ・ 0 μm (contact state)
Processing time ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Pre-processing: 6 minutes, post-processing: 0 minutes (none)

FIG. 6 is a fluorescence microscope image of the treated surface. In the image of FIG. 7, the gray portion indicates the modified region. According to FIG. 7, the region where the patterning treatment of the carboxyl group confirmed in FIG. 6 was performed was not confirmed.

<Experimental example 3>
In Experimental Example 3, the relationship between the time of the pretreatment (third step) and the modification treatment (fourth step) and the state of modification was confirmed. The details of the atmospheric pressure plasma jet device 1 are the same as those of Experimental Example 1. Other detailed experimental conditions are shown below.
Pulse voltage (plasma voltage supply unit) ... ± 8 kV
Frequency (plasma voltage supply unit) ・ ・ ・ ・ ・ ・ 5kHz
Duty ratio (plasma voltage supply unit) ... 50%
Capillary inner diameter ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 700 μm
Distance from the lower end of the capillary to the object to be processed ・ 0 μm
Processing time ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3 minutes ・ Preprocessing Bias voltage ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ -500V
Bias frequency ································································
Processing gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 700sccm
・ Post-treatment Modified gas type ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Helium (He), oxygen (O ₂ ) mixed gas Modified gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ ・ Helium 700sccm, Oxygen 10 sccm

Part (a) of FIG. 8 is a fluorescence microscope image when the pretreatment is performed for 0.1 seconds and the modification treatment is performed for 179.9 seconds. Part (b) of FIG. 8 is a fluorescence microscope image when the pretreatment is performed for 1 second and the modification treatment is performed for 179 seconds. Part (c) of FIG. 8 is a fluorescence microscope image when the pretreatment is performed for 5 seconds and the modification treatment is performed for 175 seconds. Part (d) of FIG. 8 is a fluorescence microscope image when the pretreatment is performed for 10 seconds and the modification treatment is performed for 170 seconds. Part (e) of FIG. 8 is a fluorescence microscope image when the pretreatment is performed for 20 seconds and the modification treatment is performed for 160 seconds. Part (f) of FIG. 8 is a fluorescence microscope image when the pretreatment is performed for 30 seconds and the modification treatment is performed for 150 seconds. In the images of parts (a) to (f) of FIG. 8, the gray part indicates the modified region.

According to the parts (a) to (d) of FIG. 8, it was found that the modification state differs depending on the pretreatment time. Specifically, when the pretreatment time was short (for example, parts (a) to (c) of FIG. 8), sufficient modification could not be obtained. On the other hand, when the pretreatment time was long (for example, part (f) in FIG. 8), the modified region was smaller than the pore diameter of the mask. Therefore, it was suggested that the pretreatment time had an appropriate range, and it was found that under the conditions of Experimental Example 3, the pretreatment for 20 seconds was the best condition.

<Experimental Example 4>
In Experimental Example 4, the relationship between the bias voltage in the pretreatment (third step) and the modified state was confirmed. The details of the atmospheric pressure plasma jet device 1 are the same as those of Experimental Example 1. Other detailed experimental conditions are shown below.
Pulse voltage (plasma voltage supply unit) ... ± 8 kV
Frequency (plasma voltage supply unit) ・ ・ ・ ・ ・ ・ 5kHz
Duty ratio (plasma voltage supply unit) ... 50%
Capillary inner diameter ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 700 μm
Distance from the lower end of the capillary to the object to be processed ・ 0 μm
Processing time ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6 minutes ・ Preprocessing Bias voltage ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ -300V, -400V, -500V, -600V, -700V , -800V
Bias frequency ・ ・ ・ ・ ・ ・ ・ ・ DC processing gas type ・ ・ ・ ・ ・ ・ ・ ・ Helium (He)
Processing gas flow rate ・ ・ ・ ・ ・ ・ ・ ・ 700sccm
Pretreatment time ・ ・ ・ ・ ・ ・ ・ ・ 10 seconds ・ Posttreatment Modified gas type ・ ・ ・ ・ ・ ・ ・ ・ Mixed gas of _{helium (He) and ammonia (NH 3) Modified gas flow rate ・ ・ ・ ・ ・}・ ・ ・ ・ ・ Helium 700sccm, oxygen 10sccm
Post-processing time: 170 seconds

Part (a) of FIG. 9 is a fluorescence microscope image when the bias voltage is −300 V. Part (b) of FIG. 9 is a fluorescence microscope image when the bias voltage is −400 V. Part (c) of FIG. 9 is a fluorescence microscope image when the bias voltage is −500 V. Part (d) of FIG. 9 is a fluorescence microscope image when the bias voltage is −600 V. Part (e) of FIG. 9 is a fluorescence microscope image when the bias voltage is −700 V. Part (f) of FIG. 9 is a fluorescence microscope image when the bias voltage is −800 V. In the images of parts (a) to (f) of FIG. 9, the gray part indicates the modified region.

According to the parts (a) to (d) of FIG. 9, it was found that the modification state differs depending on the bias voltage in the pretreatment. Specifically, it was found that the effect of modification can be obtained when the bias voltage is −400 V or more (parts (b) to (f) in FIG. 9). In particular, when the bias voltage was −500 V, a uniform modification state could be confirmed. Therefore, it was suggested that the bias voltage in the pretreatment had an appropriate range, and it was found that the condition of the bias voltage of −500 V was the best condition under the condition of Experimental Example 4.

The present invention has been described in detail above based on the embodiment. However, the present invention is not limited to the above embodiment. The present invention can be modified in various ways without departing from the gist thereof.

In the above embodiment, the modification treatment (fourth step) is started after the pretreatment (third step) is started. However, the timing for starting these processes is not limited to the above order. For example, the timing of starting the pretreatment (third step) and the timing of starting the modification treatment (fourth step) may be the same.

1 ... atmospheric pressure plasma jet device, 2 ... processing table, 3 ... glass tube, 4 ... processing gas supply unit, 6 ... modified gas supply unit, 7 ... plasma voltage supply unit, 7a ... plasma power supply, 7b ... plasma electrode, 8 ... Bias voltage supply unit, 8a ... Bias power supply, 8b ... Bias electrode, 9 ... Control unit, 100 ... Object to be processed, P ... Processing space.

Claims (5)

The first step of arranging the object to be processed in the processing space on the processing table set in the atmospheric pressure environment, and
The second step of generating the processing plasma of the processing gas provided in the processing space, and
A third step of accelerating the ions in the processing plasma toward the processing table and causing the accelerated ions to collide with the processing surface of the object to be processed by supplying a voltage to the processing table.
Have a, a fourth step of supplying a modified plasma modification gas into the processing space for functional groups that modify the object to be processed,
The fourth step is a method of modifying an object to be processed, which is performed after the second step and the third step are completed. The method for modifying an object to be treated according to claim 1, wherein the object to be processed contains a fluororesin material. The processing gas is a gas containing helium.
The modified gas is a gas containing ammonia, and the modified gas is a gas containing ammonia.
The method for modifying an object to be processed according to claim 1 or 2 , wherein in the third step, a DC voltage or a square wave voltage is supplied to the processing table. The processing gas is a gas containing helium.
The modified gas is a gas containing oxygen and
The method for modifying an object to be processed according to any one of claims 1 to 3 , wherein in the third step, a DC voltage is supplied to the processing table. A processing table that is installed in an atmospheric pressure environment and where the object to be processed is placed,
A processing plasma supply unit that supplies the processing plasma of the processing gas provided in the processing space set on the processing table, and
A bias voltage supply unit that supplies a voltage to the processing table in order to accelerate the ions in the plasma toward the processing table and cause the accelerated ions to collide with the processing surface of the object to be processed.
A modified plasma supply unit that supplies a plasma of a modified gas for a functional group that modifies the object to be processed to the processing space is provided.
The modified plasma supply unit accelerates the operation of generating the processing plasma by the processing plasma supply unit and the ions in the processing plasma by the bias voltage supply unit toward the processing table, and accelerates the ions. After the operation of colliding with the treated surface of the object to be processed is completed, the operation of supplying the modified plasma of the modified gas for the functional group that modifies the object to be processed to the processing space is performed to modify the object to be processed. Equipment to do.

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