JP3972393B2 - Surface treatment method and apparatus, piezoelectric element manufacturing method, inkjet printhead manufacturing method, liquid crystal panel manufacturing method, and microsampling method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a surface treatment technique for etching, ashing, modifying, or forming a thin film on the surface of a material to be treated, and in particular, surface treatment is performed using excited active species generated in plasma under atmospheric pressure or a pressure in the vicinity thereof. The present invention relates to a method and an apparatus. In addition, the present invention uses a surface treatment technology using plasma under a pressure near atmospheric pressure, and a piezoelectric vibrator, SAW (surface acoustic wave) formed of a piezoelectric crystal or a piezoelectric ceramic material such as quartz. The present invention relates to a method for manufacturing a piezoelectric element such as a device, a method for manufacturing an ink jet printer head, and a method for manufacturing a liquid crystal panel. Furthermore, the present invention relates to a microsampling technique for collecting foreign substances attached to or immersed in the surfaces of various materials.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, there are known techniques for variously treating the surface of a material to be processed using excited active species generated by plasma discharge. The conventional surface treatment method for discharging so as to generate plasma in a vacuum or under a reduced pressure environment has a problem that a special apparatus / equipment such as a vacuum chamber is required and the manufacturing cost increases. Therefore, recently, as described in, for example, Japanese Patent Laid-Open No. 6-2149, plasma discharge is performed under a pressure near atmospheric pressure, so that vacuum equipment is not required and the apparatus can be easily and miniaturized at low cost. Surface treatment techniques that can do this have been proposed.
[0003]
In the surface treatment with plasma under atmospheric pressure, a direct method in which gas discharge is directly generated between the electrode and the material to be processed, and excited active species are generated by discharge between the power supply electrode and the ground electrode. There is an indirect method in which a gas flow containing gas is ejected to the surface of the material to be treated. While the direct method can achieve a high processing rate, it may not be able to handle the case where the material to be processed is damaged by charge-up, the shape of the material to be processed is complex or uneven, or the processing range is limited. There is. On the other hand, the indirect method requires a higher output because the processing rate is lower than the direct method, but there is no risk of damage to the material to be processed due to charge-up, and the shape of the nozzle that ejects the gas flow By changing the flow rate or adjusting the gas flow rate, local surface treatment corresponding to the shape of the material to be processed and the limitation of the processing range is possible.
[0004]
[Problems to be solved by the invention]
Conventionally, when the surface of a material to be processed is washed by etching, ashing, or the like, wet processing using an organic solvent or an etching solution is performed. However, in such a processing solution, when it is desired to process only a limited narrow region or part or when there is a part that does not want to be processed around, it is necessary to mask the periphery with a resist material or the like in advance. There is a problem that the process is cumbersome and time-consuming, and productivity is lowered. Also, if you want to treat the inside of narrow gaps, pipes and recesses that cannot be easily accessed from the outside, it is difficult to enter the treatment liquid, and if bubbles enter, it is difficult to remove it. There was a problem that I could not.
[0005]
In the case of the above-described plasma processing in a vacuum, since the discharge spreads over a wide range, if only a limited narrow region / part is to be processed, a mask processing is necessary as in the wet processing. However, there is a problem in that a desired surface treatment cannot be performed because no discharge occurs in a narrow space.
[0006]
However, the conventional surface treatment apparatus using atmospheric pressure plasma is generally premised on efficiently treating a relatively large area of the surface of the material to be treated. For this reason, when it is desired to process only a very narrow region or part, there is a limit in selecting only that part and processing it locally. Even in the indirect method, it is very difficult to create an active plasma in the discharge gas at a pressure close to atmospheric pressure and to concentrate the excited active species at a high density to selectively apply to an extremely narrow part of the material to be processed. there were. In addition, when it is desired to surface-treat the inside of a narrow gap or pipe line that cannot be easily accessed from the outside, a power supply electrode is placed in the surface to cause direct gas discharge, or a gas flow containing high-density excited active species. It is extremely difficult to send in from the outside.
[0007]
Therefore, the present invention has been made in view of the above-described conventional problems, and its purpose is to use a very limited microscopically active species of plasma generated under a pressure near atmospheric pressure. To provide a surface treatment method and apparatus having a novel configuration capable of easily and satisfactorily surface-treating a narrow internal structure such as a gap or a pipe line that cannot be easily approached from any part or region or from the outside. .
[0008]
Another object of the present invention is a method for manufacturing a piezoelectric element such as a piezoelectric vibrator or a SAW device by using surface treatment with excited active species of plasma generated under a pressure near atmospheric pressure, and for inkjet. The object is to improve a method for producing a print head, a method for producing a liquid crystal panel, or a microsampling method for collecting foreign matter from a sample.
[0009]
More specifically, in the case of a piezoelectric element manufactured by soldering a lead terminal of a plug to an electrode land formed on the surface of an element piece made of a piezoelectric body and vacuum-sealing the inside of the case, In order not to corrode the electrode, soldering by a reflow method using hot air or the like is generally performed without using a flux. However, since the soldering surface is very small and is easily oxidized by ambient air or the like, there is a problem that soldering failure is likely to occur and the yield is reduced.
[0010]
Further, in the case of a SAW device including a SAW (surface acoustic wave) piece in which a comb-shaped electrode is formed on the surface of a piezoelectric body, frequency adjustment is usually performed after the SAW piece is mounted in the base. The frequency adjustment is generally performed by directly etching the electrode formed of Al or the like and etching the piezoelectric body. In the case of etching a fine Al electrode, dry etching using a chlorine-based gas is appropriate, but the chlorine-based gas has problems in handling and safety. Therefore, conventionally, the etching process of the piezoelectric body has been performed in a vacuum, but there is a problem that the apparatus is expensive and large, the operation is complicated and troublesome, the productivity is low, and the cost is high.
[0011]
Further, in the manufacturing process of the liquid crystal panel, the liquid crystal material is injected into a narrow gap inside the cell container after the two glass substrates are integrally bonded with the shield material, and thus the liquid crystal material is injected therein. There is a problem that air bubbles easily enter. Conventionally, since the surfaces of both glass substrates were washed before they were superposed, the stains in the cell container that occurred during bonding could not be washed sufficiently. Therefore, it is advantageous if the inner surface of the cell container can be treated to promote the wettability with respect to the liquid crystal material. However, since the gap is about 4, 5 μm to about several tens of μm, wet processing using an etching solution or the like is substantially impossible. Further, in the case of dry etching using plasma in vacuum, the gap is too narrow, so that no discharge occurs inside the cell container. Furthermore, since a rubbing-treated alignment film is formed on the glass substrate surface in the cell container, it is necessary to perform a surface treatment so as not to break the alignment.
[0012]
In particular, in the case of an ink jet print head having a structure in which an ink flow path leading from the ink supply port to the nozzle opening is provided, if the wettability of the ink flow path with respect to ink is low, bubbles enter the ink flow path when ink is injected. For this reason, there is a problem in that the ink is not sufficiently ejected and printing is unclear or printing defects such as missing dots occur. Also in this case, since the ink flow path is very narrow, wet processing using an etching solution or the like is impossible, and surface treatment with plasma in vacuum hardly causes discharge in the ink flow path. Therefore, effective processing cannot be expected.
[0013]
[Means for Solving the Problems]
The surface treatment method of the present invention is for achieving the above-described object, and a predetermined discharge gas is allowed to flow inside a workpiece made of a dielectric material under atmospheric pressure or a pressure near the atmospheric pressure. It is characterized in that a gas discharge is generated inside the workpiece by energizing an electrode disposed outside the workpiece, and the surface inside the workpiece is exposed to the excited active species of the discharge gas generated by this gas discharge. To do.
[0014]
According to the method of the present invention, even if the inside of the object to be processed is a narrow space such as a gap or a pipe that cannot be easily accessed from the outside, the discharge gas is externally used as a gas channel. Since the gas discharge can be generated inside the object to be processed and maintained in a good state, the surface treatment can be performed directly by the excited active species of the discharge gas generated inside the object to be processed. Actually, even if the inside of the object to be processed is a narrow space in which the length is a and the narrower width is b and b ≦ 1 mm and b / a ≦ 1/10, A gas can be circulated and a gas discharge can be generated, whereby a good surface treatment can be achieved. Here, the narrower width b is the inner diameter when the inside of the workpiece is circular in cross section, the shorter diameter when it is elliptical, and the width in the short side direction when it is an elongated slit. Shall point to.
[0015]
Using the surface treatment method of the present invention, when manufacturing an ink jet print head having an ink flow path leading from an ink supply port to a nozzle opening, while flowing a discharge gas from the ink supply port toward the nozzle opening, An electrode disposed outside the print head is energized to generate a gas discharge in the ink flow path, and the inner surface of the ink flow path is exposed to the excited active species of the discharge gas generated thereby. It is advantageous to select a gas containing helium as the discharge gas. As a result, the inner surface of the ink flow path is exposed to the helium excited active species and cleaned, and the wettability is improved and the ink can easily flow. Can be made possible.
[0016]
When a liquid crystal panel is manufactured using the surface treatment method of the present invention, two glass substrates on which an alignment film is formed are integrated with a shielding material so as to have a certain narrow gap therebetween. After forming the cell container by adhering to the electrode, before enclosing the liquid crystal material in the cell container, energize the electrodes arranged along the cell container while flowing a predetermined discharge gas from the liquid crystal inlet into the cell container. Then, a gas discharge is generated in the cell container, and the surface inside the cell container is exposed to the excited active species of the discharge gas generated thereby. According to the invention, it is advantageous if the discharge gas comprises helium. As a result, the inner surface of the cell container can be cleaned and its wettability can be improved, so that even a relatively viscous liquid crystal material can be injected smoothly and reliably.
[0017]
The surface treatment apparatus according to the present invention includes a means for supplying a discharge gas so as to flow inside the object to be processed, the object made of a dielectric material having an internal space with a narrow cross section, and the object to be processed. And an electrode for causing gas discharge to the discharge gas under atmospheric pressure or a pressure in the vicinity thereof. When the discharge gas supplied from the gas supply means flows through the inside of the object to be processed, the electrode is energized, whereby a gas discharge is generated along the flow of the discharge gas in the internal space of the object to be processed. Since the surface inside the object to be treated is directly exposed to the excited active species of the discharge gas generated by this discharge, the desired surface treatment can be satisfactorily and easily performed.
[0018]
Further, the surface treatment apparatus of the present invention is a dielectric that defines a gas flow path having a narrow cross section between a proximal end connected to a discharge gas supply source and a distal end that opens toward an object to be processed. It has a discharge tube made of a material, and a power supply electrode and a ground electrode arranged so as to face each other with the discharge tube interposed therebetween. It is characterized in that gas discharge is generated in the discharge gas under the pressure of.
[0019]
With this configuration, a gas discharge is generated in the discharge tube along the flow of the discharge gas, and the excited active species of the generated discharge gas has a very thin gas flow corresponding to a narrow cross section of the gas flow path. As described above, since it is sprayed from the tip of the discharge tube, a very narrow portion or region of the surface of the object to be processed can be limitedly processed, or the inside of the narrow recess can be sufficiently processed.
[0020]
According to the present invention, the discharge tube has a narrow gas flow path when the length a of the gas flow path and the narrow width b thereof are in the relationship of b ≦ 1 mm and b / a ≦ 1/10. A discharge can be generated. For example, the discharge tube can be formed of a circular tube such as an elongated glass whose length a and inner diameter b are in the above relationship, whereby the surface of the object to be processed can be processed in a spot shape. A plurality of circular tubes may be provided, and by arranging them in parallel or in a predetermined direction, a large number of portions can be spot-processed simultaneously. In another embodiment, a discharge tube having a gas flow path having a slit-like cross section in which the length a and the narrow width b are in the above relationship can be used, and the surface of the object to be processed is very thin. It can be processed linearly.
[0021]
Further, according to the present invention, a discharge tube made of a dielectric material that defines a gas flow path between a proximal end connected to a discharge gas supply source and a distal end opening toward the object to be processed; There is provided a surface treatment apparatus comprising: a power supply electrode disposed along the discharge tube; and a casing made of a conductive material that accommodates the discharge tube and an object to be processed and is grounded. The power electrode can be composed of a coil wound around the discharge tube.
[0022]
By using the casing itself as the ground electrode in this way, an electric field is formed in the radial direction between the power supply electrode and the casing, so that gas discharge occurs along the gas flow path inside the discharge tube. In particular, when the discharge tube is configured to have an elongated circular tube or a slit-like narrow gas flow path, the discharge can be generated and maintained satisfactorily. The discharge tube generates a discharge even in a narrow gas flow path such that the dimension is a length and the narrow width is b, and b ≦ 1 mm and b / a ≦ 1/10. This is advantageous because a narrow portion can be processed in the form of spots or straight lines.
[0023]
Furthermore, according to the present invention, a discharge tube made of a dielectric material that defines a gas flow path between a proximal end connected to a discharge gas supply source and a distal end that opens toward the object to be processed; A power supply electrode and a ground electrode arranged on the upstream side and downstream side of the gas flow path along the tube, respectively, and when the power supply electrode is energized, the discharge gas is converted into a discharge gas under atmospheric pressure or a pressure in the vicinity thereof. There is provided a surface treatment apparatus characterized by causing gas discharge. At least one of the power electrode and the ground electrode can be constituted by a coil wound around the discharge tube.
[0024]
The gas discharge is generally generated between the power supply electrode and the ground electrode along the flow of the discharge gas in the discharge tube, and the excited active species of the discharge gas generated thereby corresponds to a narrow cross section of the gas flow path. A very thin gas flow is sprayed from the tip of the discharge tube to the surface of the workpiece. Therefore, a very narrow portion or region on the surface of the object to be processed can be limitedly processed, or the inside of the narrow recess can be sufficiently processed. In this case, the discharge tube generates a discharge in the narrow gas flow path when the length a of the gas flow path and the narrow width b are in the relationship of b ≦ 1 mm and b / a ≦ 1/10. It is advantageous because a very narrow portion can be processed in a spot shape or a straight line shape.
[0025]
According to another aspect of the present invention, there is provided a method of manufacturing a piezoelectric element by soldering a lead terminal of a plug to an electrode formed on a surface of an element piece made of a piezoelectric body and attaching a vacuum case to the plug. Before the soldering, the discharge tube is made of a dielectric material that defines a gas flow path having a narrow cross section, and the discharge gas is allowed to flow from the base end portion toward the nozzle opening at the tip end portion. By energizing the electrodes arranged along the line, a gas discharge is generated in the discharge tube at or near the atmospheric pressure, and a gas flow containing excited active species of the discharge gas generated thereby is generated from the nozzle opening. In addition, a novel method for manufacturing a piezoelectric element is provided, which includes a step of performing a surface treatment by spraying at least one of the bonding surface of the electrode of the element piece and the surface of the plug terminal.
[0026]
As described above, gas discharge is favorably generated in the discharge tube along the flow of the discharge gas, and a thin gas flow corresponding to the cross section of the gas flow path is injected from the nozzle opening at the tip of the discharge tube. Only the bonding surface of the electrode of the element piece or the surface of the plug terminal can be exposed to the excited active species of the discharge gas. Therefore, we can improve the wettability by effectively surface-treating only the part to be soldered without affecting the frequency of the excited active species acting on the piezoelectric material of the element piece and the electrode part other than the joint surface. It is possible to achieve good connection with a smaller amount of solder.
[0027]
Furthermore, according to the present invention, a SAW (surface acoustic wave) piece in which an electrode is formed on the surface of a piezoelectric body is mounted in a package, the electrode is electrically connected to a package terminal, and the package is vacuum-sealed. A discharge element containing a fluorine compound from a base end portion toward a nozzle opening at a tip end portion of a discharge tube made of a dielectric material that defines a gas flow path having a narrow cross section. By energizing the electrodes arranged along the discharge tube while flowing, a gas discharge is generated in the discharge tube under atmospheric pressure or a pressure in the vicinity thereof, and an excited active species of the discharge gas generated thereby is included. It includes a process of adjusting the frequency of the SAW piece by injecting a gas flow from the nozzle opening at the tip of the discharge tube to the portion of the piezoelectric material exposed on the electrode forming surface of the piezoelectric body and performing etching. That the method for manufacturing a piezoelectric element is provided.
[0028]
Also in this case, as described above, gas discharge is favorably generated along the flow of the discharge gas in the discharge tube, and a thin gas flow corresponding to the cross section of the gas flow path is injected from the nozzle opening at the tip of the discharge tube. Therefore, the frequency of the SAW piece can be cut while controlling the piezoelectric portion by a small amount while monitoring the frequency of the SAW piece, so that the frequency can be adjusted more precisely. In particular, when the piezoelectric body is made of quartz, it can be easily etched by using a discharge gas containing a fluorine compound. As a result, a more accurate piezoelectric element can be manufactured more easily and at low cost by an etching process under atmospheric pressure.
[0029]
This etching process can be performed after the SAW piece is mounted on the package and the electrode is electrically connected to the package terminal. In addition, etching can be performed before mounting the SAW piece on the package. In this case, after dicing the piezoelectric wafer on which the electrodes are formed, before connecting the cut-out SAW piece electrodes to the package terminals, the individual chips are diced on the individual chips or on the piezoelectric wafer on which the electrodes are formed. Etching can be performed in the state of the wafer before it is cut out.
[0030]
According to the present invention, a method of manufacturing an ink jet print head of a type that selectively ejects ink injected into a plurality of cavities defined by a partition member between a nozzle member and a diaphragm, After the partition member is bonded to the diaphragm, discharge is performed while flowing a predetermined discharge gas from the base end portion toward the opening of the tip end portion in the discharge tube made of a dielectric material that defines a gas passage having a narrow cross section. By energizing the electrodes arranged along the tube, a gas discharge is generated in the discharge tube at atmospheric pressure or a pressure in the vicinity thereof, and a gas flow containing excited active species of the discharge gas generated thereby is discharged into the discharge tube. There is provided a method for manufacturing an ink jet print head, which includes a step of ashing by spraying from the opening of a tip portion to the vicinity of an adhesive portion between a diaphragm and a partition member.
[0031]
In the case of an ink jet print head, if adhesive remains on the surface of the diaphragm or partition member, bubbles are likely to be generated in the ink injected into the cavity. There is a possibility that the ink is dissolved in the ink to change its composition, adheres to the vicinity of the nozzle opening, obstructs the ejection of the ink, and causes printing failure. However, since the cavity defined between the adjacent partition members is very narrow, the conventional wet process or plasma process easily removes excess adhesive protruding from the vicinity of the bonding portion between the diaphragm and the partition member. I couldn't. Therefore, as described above, by ejecting a very thin gas flow containing the excited active species of the discharge gas, it is possible to easily remove the excess adhesive adhering to the diaphragm and the partition member by ashing, It is possible to more easily manufacture a print head that does not cause a print defect.
[0032]
Furthermore, according to the present invention, there is provided a microsampling method for collecting minute foreign matters from the surface of a sample by attaching them to the tip of the probe, and before the probe tip is brought close to the foreign matter, a gas passage having a narrow cross section is provided. A predetermined discharge gas is allowed to flow from the base end portion toward the opening at the tip end portion of the discharge tube made of the dielectric material to be demarcated, and an electrode disposed along the discharge tube is energized to greatly increase the discharge tube. A gas discharge is generated under atmospheric pressure or a pressure near it, and a gas flow containing excited active species of the discharge gas generated thereby is ejected from the opening at the tip of the discharge tube to the sample surface, so that the sample is taken from around the foreign material. There is provided a microsampling method characterized in that it includes a step of partially removing.
[0033]
When foreign matter is partially or completely immersed on the surface of the sample, it is difficult for the conventional microsampling method to bring the probe tip close to the foreign matter. According to this method, by appropriately selecting the discharge gas according to the properties of the sample or the foreign material, the gas flow containing the excited active species can be injected only to the necessary portion. The sample can be partially etched or ashed from around the foreign material without affecting the foreign material, and the space necessary for approaching the probe tip can be secured, making it easier to collect the foreign material. And it can be done reliably.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
1 and 2 schematically show a first embodiment of a surface treatment apparatus having a first configuration according to the present invention. This surface treatment apparatus includes a discharge tube 1 made of an elongated circular tube made of a dielectric material such as glass, which defines a gas flow path having a narrow cross section inside, and a pair of electrodes disposed opposite to each other with the discharge tube interposed therebetween. A flat power supply electrode 2 and a ground electrode 3 are provided. The power electrode 2 is connected to a high frequency power source 5 through a high voltage transformer 4. The discharge tube 1 has a base end 6 connected to a gas supply source 7, and a nozzle portion 8 that opens toward the workpiece 9 at the tip.
[0035]
When it is desired to surface-treat the narrow region 10 of the workpiece 9, a predetermined discharge gas corresponding to the surface treatment is introduced from the gas supply source 7 into the discharge tube 1 and ejected from the nozzle portion 8, while being supplied from the power source 5. A predetermined voltage is applied to the power supply electrode 2. Inside the discharge tube 1, gas discharge occurs in a region 11 sandwiched between both electrodes as shown in FIG. 2. In the discharge region 11, active species such as excited species and ions of the discharge gas are generated by dissociation, ionization, excitation, and the like of the discharge gas by plasma. These excited active species are ejected from the nozzle portion 8 toward the region 10 as a thin gas flow and perform a desired surface treatment.
[0036]
The discharge tube 1 may be an extremely thin capillary tube having a relationship of 1 μm ≦ b1 ≦ 1 mm and b1 / a1 ≦ 1/10, where the length is a1 and the inner diameter is b1. For example, a rare gas such as helium or argon, or a fluorine compound such as oxygen, nitrogen, or CF4 as the discharge gas is 1 kgf / cm at the base end. ² When a high frequency power source of 20 kHz was used as a power source, the pressure was supplied at a moderate pressure, and a stable and good discharge state was maintained in the discharge tube in any case. In addition, when 13.56 MHz is used for the power source, a good discharge state can be obtained similarly by using a mixed gas of a rare gas such as helium and a fluorine compound such as oxygen, nitrogen or CF4 as the discharge gas. It was. It was confirmed that the processing rate was higher when the power supply frequency was 13.56 MHz.
[0037]
In general, when the discharge gas is a single rare gas, the wettability is improved. When the discharge gas is a gas containing oxygen, ashing is performed. When the discharge gas is a gas containing CF4, surface treatment for etching is performed. According to the present invention, it is possible to satisfactorily surface-treat only the region 10 of the object to be processed without substantially affecting the surrounding portion by the thin gas flow corresponding to the inner diameter b1 of the discharge tube 1. It was. Further, according to the present invention, when a narrow groove or hole is formed on the surface of the workpiece 9 as in a plastic molding die, the nozzle portion 8 of the discharge tube 1 is inserted into the narrow groove or hole so that the gas flow The inner surface can be surface-treated more effectively by spraying directly.
[0038]
Further, the dirt adhering to the inside of the discharge tube 1 is not sufficiently cleaned by a wet process using a conventional cleaning liquid or the like because the gas flow path is very narrow. However, according to the present invention, it is confirmed that the plasma active species can easily perform self-cleaning by appropriately selecting a discharge gas for performing a cleaning process such as etching and ashing and causing discharge inside the discharge tube 1. It was. Therefore, after the surface treatment of the object to be treated is completed or during the period, the discharge is performed by changing the gas type as appropriate, so that the inside of the discharge tube is always kept clean and the gas flow path is secured to stabilize the discharge state. And surface treatment can be performed satisfactorily.
[0039]
FIG. 3 shows a second embodiment of the surface treatment apparatus having the first configuration. In the surface treatment apparatus of the second embodiment, the discharge tube 13 has two rectangular thin plates made of dielectric material such as glass plates 14 and 15 facing each other with a slight gap as shown in FIG. In addition, both side portions thereof are bonded with an adhesive tape 16 or the like. Inside the discharge tube 13, a narrow slit-shaped gas passage having a rectangular cross section is defined from a proximal end portion 17 connected to the gas supply source 7 toward a nozzle portion 18 opening at the distal end. A flat power supply electrode 2 and a ground electrode 3 are disposed on both sides of the discharge tube 13 so as to sandwich the discharge tube 13.
[0040]
A predetermined discharge gas is introduced into the discharge tube 13 from the gas supply source 7, and a predetermined voltage is applied from the power supply 5 to the power supply electrode 2 while being ejected from the nozzle portion 18. Inside the discharge tube 13, gas discharge occurs in a region 19 sandwiched between the two electrodes. In the present embodiment, the gas flow is jetted from the slit-shaped nozzle portion 18 into a thin linear shape, and the thin linear region 20 of the workpiece 9 is surface-treated by the excited active species of the discharge gas contained therein. The
[0041]
The dimensions of the discharge tube 13 are set to 1 μm ≦ b2 ≦ 1 mm and b2 / a2 ≦ 1/10, similarly to the discharge tube 1 of the first embodiment, where the length is a2 and the gap between both glass plates is b2. be able to. As in the first embodiment, a rare gas such as helium or argon or a fluorine compound such as oxygen, nitrogen or CF4 is used as the discharge gas at the base end 6 at 1 kgf / cm. ² When a high frequency power source of 20 kHz was used as a power source, the pressure was supplied at a moderate pressure, and a stable and good discharge state was maintained in the discharge tube in any case. In addition, when 13.56 MHz is used for the power source, a good discharge state can be obtained similarly by using a mixed gas of a rare gas such as helium and a fluorine compound such as oxygen, nitrogen or CF4 as the discharge gas. It was.
[0042]
The length of the processing region 20 is adjusted by changing the width of the gas flow path according to the dimensions of the discharge tube 13. In another embodiment, the width or gap of the gas flow path can be gradually narrowed from the base end portion 17 toward the nozzle portion 18. Thereby, the density of the excited active species contained in the gas flow can be increased. In yet another embodiment, a plurality of gas flow paths can be arranged in parallel by partitioning the inside of the discharge tube 13 along the flow direction of the discharge gas.
[0043]
FIG. 5 shows another modification of the first embodiment shown in FIG. In this modification, a plurality of discharge tubes 1 each made of an elongated circular tube of dielectric material are arranged in parallel in a row adjacent to each other between a pair of opposed power supply electrodes 2 and ground electrodes 3. . The base end portion 6 of each discharge tube 1 is connected to a common gas supply source 7. When a predetermined voltage is applied from the power source 5 to the power supply electrode 2 while simultaneously supplying a predetermined discharge gas from the gas supply source into each discharge tube 1 and spraying from the nozzle portions 8 toward the workpiece 9, Gas discharge occurs simultaneously in each of the discharge tubes. The nozzle portion 8 of each discharge tube injects a gas flow toward a narrow region of the corresponding workpiece 9 so that the linear region 22 can be surface-treated at the same time.
[0044]
Further, in this embodiment, only a part of the region 22 of the workpiece 9 is selectively surfaced by supplying a discharge gas from the gas supply source 7 to only a part of the discharge tubes 1 and generating a gas discharge. It can also be processed. Further, in the present embodiment, the discharge tube and the discharge tube can be appropriately separated according to the position of each region to be processed of the workpiece 9. Further, if each discharge tube can be moved in the lateral direction between the electrodes 2 and 3, it is possible to easily cope with a change in the position of the region to be processed of the workpiece. In another embodiment, the discharge tubes 1 can be arranged between the electrodes 2 and 3 in two or more rows. In yet another embodiment, a plurality of regions on the curved surface of the workpiece 9 can be simultaneously surface-treated by arranging the discharge tubes in different directions, for example, in a radial direction instead of in parallel. it can.
[0045]
FIG. 6 shows still another modification of FIG. A nozzle member 23 whose tip opening is tapered narrowly is fitted to the nozzle portions 8 of the plurality of discharge tubes 1 arranged in parallel in one horizontal row. Similarly, in the embodiment shown in FIG. 7, a nozzle member 23 is attached to the nozzle portion 18 of the discharge tube 13 of FIG. By restricting the gas flow from each nozzle part 8 and 18 with the nozzle member 23, the speed of the gas flow injected to the surface of the workpiece 9 is increased, and the plasma density is increased to further increase the processing rate. Can do.
[0046]
Next, FIG. 8 schematically shows the configuration of a surface treatment apparatus having a second configuration according to the present invention. This surface treatment apparatus has a box-shaped casing 24 formed of a conductive material and grounded. At the center of the casing 24, a discharge tube 25 is suspended vertically with its nozzle portion 26 facing downward. A table 27 on which the workpiece 9 is placed is disposed immediately below the discharge tube 25.
[0047]
As shown well in FIG. 9, the discharge tube 25 has an elongated circular tubular portion 28 that defines a gas passage having a narrow cross section, as in the embodiment of FIG. And is integrally formed of a dielectric material such as glass. The circular tube portion 28 is disposed with the nozzle portion 26 at the tip facing the surface of the workpiece 9. The enlarged diameter portion 29 has a double structure and defines an annular vacant space 31 between the inner diameter tube 30 and the inner tube 30 arranged concentrically. The empty space 31 is connected to the gas supply source 7 and communicates with the gas flow path of the circular pipe portion 28. A rod-shaped power supply electrode 32 connected to the power supply 5 via the high-voltage transformer 4 is inserted into the inner tube 30.
[0048]
The predetermined discharge gas introduced from the gas supply source 7 into the annular vacant chamber 31 is ejected from the nozzle portion 26 toward the surface of the workpiece 9 through the circular tube portion 28. At the same time, a predetermined voltage is applied from the power supply 5 to the power supply electrode 32. In this embodiment, the casing 24 is used as a ground electrode, and an electric field is formed in the radial direction from the power supply electrode 32 located at the center thereof. Therefore, the gas discharge is generated in a relatively wide region 33 inside the enlarged diameter portion 29 and the circular tube portion 28 as shown in FIG. The excited active species of the discharge gas due to this discharge is ejected from the nozzle portion 26 as a thin gas flow, and the narrow region 10 of the object 9 to be exposed can be surface-treated.
[0049]
The dimensions of the circular tube portion 28 are set to have a relationship of 1 μm ≦ b1 ≦ 1 mm and b1 / a1 ≦ 1/10, where the length is a1 and the inner diameter is b1, as in the discharge tube 1 of FIG. . When a rare gas such as helium or argon or a gas mixed with a fluorine compound such as oxygen, nitrogen or CF4 is used as the discharge gas, and a 20 kHz high frequency power source is used as the power source, a stable and good discharge state is obtained. Obtained. In particular, when the discharge gas was a single rare gas such as helium, it was observed that the discharge region 33 extended out of the nozzle portion 26 and directly exposed the surface of the workpiece 9. Further, when the mixed gas was used as the discharge gas, the discharge region 33 was reduced as the flow rate of oxygen, nitrogen or CF4 contained therein was increased. When the surface treatment for improving the wettability of the polyimide coating to water was performed using the surface treatment apparatus of this example, the treatment time which conventionally required several tens of seconds could be reduced to 10 seconds or less.
[0050]
According to the present invention, a discharge tube and electrode structure different from the embodiment of FIG. 9 can be used. For example, in the embodiment of FIG. 10, a circular discharge tube 1 is used as in the embodiment of FIG. 1, and a cylindrical power supply electrode 34 is fitted on the outer periphery thereof. In the embodiment of FIG. 11, a coil electrode 35 is provided on the outer periphery of the circular discharge tube 1. In the embodiment of FIG. 12, as in the embodiment of FIG. 3, a flat plate-like power source is provided on one side surface of a plate-like discharge tube 13 having a slit-like gas flow channel in which two glass plates are stacked. An electrode 2 is provided. In any of these cases, as in the case of FIG. 9, a gas discharge can be generated in the discharge tube, and surface treatment can be performed using the gas flow.
[0051]
Next, a surface treatment apparatus having a third configuration according to the present invention will be described. FIG. 13 schematically shows the configuration of the surface treatment apparatus according to the first embodiment. As in the embodiment of FIG. 1, the surface treatment apparatus has a discharge tube 1 made of an elongated circular tube made of a dielectric material such as glass. A cylindrical power supply electrode 34 and a ground electrode 36 are fitted on the outer periphery of the discharge tube 1, and are separated from each other by an appropriate distance between the upstream side close to the base end portion 6 and the downstream side close to the nozzle portion 8. Yes.
[0052]
A predetermined discharge gas is introduced into the discharge tube 1 from the gas supply source 7, and a predetermined voltage is applied from the power supply 5 to the power supply electrode 34 while being ejected from the nozzle portion 8. In the discharge tube 1, a gas discharge is generated in a region 37 between the electrodes. The excited active species of the discharge gas by the plasma generated in the discharge region 37 is jetted from the nozzle portion 8 toward the object 9 as a thin gas flow. Thereby, only the narrow area | region 10 of the to-be-processed object 9 can be favorably surface-treated without affecting the surrounding part at all.
[0053]
The dimensions of the discharge tube 1 were set in the range of 1 μm ≦ b1 ≦ 1 mm and b1 / a1 ≦ 1/10, where the length is a1 and the inner diameter is b1, as in the embodiment of FIG. As a discharge gas, for example, a rare gas such as helium or argon, or a mixed gas of these and a fluorine compound such as oxygen, nitrogen or CF4 and a high frequency power source of 20 kHz is used. A smooth discharge state was maintained. Further, it was confirmed that the power supply electrode 34 and the ground electrode 36 discharge well even if they are separated to a distance of several tens of centimeters.
[0054]
When the discharge region extends out from the nozzle portion 8 of the discharge tube as in the embodiment of FIG. 10, the surface of the workpiece 9 is directly exposed to the discharge, and the treatment rate is increased, but the surface of the workpiece is damaged. There is a risk of adverse effects such as. In the case of the present embodiment, the discharge region 37 can be limited within the discharge tube 1 to some extent by appropriately selecting each of the above gases as the discharge gas and the presence of the ground electrode 36.
[0055]
FIG. 14 is a modification of the first embodiment shown in FIG. 13, and the power supply electrode 35 and the ground electrode 38 are each composed of a coil electrode wound around the outer periphery of the discharge tube 1. When a rare gas such as helium or argon or a mixed gas of these with a fluorine compound such as oxygen, nitrogen or CF4 is used as a discharge gas and a high frequency power source of 20 kHz is used, the power supply electrode 35 to the vicinity of the nozzle section 8 is used. Gas discharge occurred in a wide area. In particular, when a rare gas is used as the discharge gas and a high frequency power source of 20 kHz is used, the discharge region is formed along the gas flow ejected from the nozzle portion 8 as in the embodiment of FIG. It extended to the outside.
[0056]
In another embodiment, either the power electrode or the ground electrode can be the coil electrode of FIG. 14 and the other can be the cylindrical electrode of FIG. In any of these cases, a gas discharge can be generated in the discharge tube 1 as in the embodiment of FIG. 13 to satisfactorily surface-treat the workpiece.
[0057]
FIG. 15 shows a second embodiment of the surface treatment apparatus having the third configuration. As in the embodiment of FIG. 3, this surface treatment apparatus is a discharge tube in which two thin sheets of dielectric material are opposed to each other with a slight gap and a narrow slit-like gas flow path is defined in the inside. 13 A power supply electrode 39 and a ground electrode 40 each consisting of two flat plates are arranged on both sides of the discharge tube 13 so as to sandwich the discharge tube 13 with an appropriate distance between the upstream side and the downstream side of the discharge tube 13. .
[0058]
The discharge tube 13 was set in the range of 1 μm ≦ b2 ≦ 1 mm and b2 / a2 ≦ 1/10, where the length was a2 and the gap between both glass plates was b2, as in the embodiment of FIG. As in the embodiment of FIG. 13, while introducing a rare gas such as helium or argon or a mixed gas of these with a fluorine compound such as oxygen, nitrogen or CF4 as a discharge gas from the gas supply source 7 into the discharge tube 13. When a predetermined voltage was applied to the power source electrode 39 from a 20 kHz high frequency power source as the power source 5, a stable gas discharge was obtained in the region 37 between the two electrodes. A thin linear gas flow containing the excited active species of the discharge gas was ejected from the slit-shaped nozzle portion 18, and the narrow linear region 20 of the workpiece 9 could be surface-treated.
[0059]
FIG. 16 shows a third embodiment of the surface treatment apparatus having the third configuration. The discharge tube 25 of the third embodiment has the same configuration as that of the embodiment of FIG. 9, and is continuous with an elongated circular tube portion 28 that defines a gas passage having a narrow cross section inside, and a base end side thereof. It consists of an enlarged diameter portion 29. The circular tube portion 28 is disposed with the nozzle portion 26 at the tip facing the surface of the workpiece 9. In the enlarged diameter portion 29 having a double structure, a rod-shaped power supply electrode 32 is inserted into the inner tube 30, and a cylindrical ground electrode 41 is fitted near the nozzle portion 26 on the outer periphery of the circular tube portion 28. Has been.
[0060]
At the same time as a predetermined discharge gas is introduced from the gas supply source 7 into the annular vacant space 31 defined in the enlarged diameter portion 29 and is ejected from the nozzle portion 26 toward the object 9 through the circular tube portion 28. A predetermined voltage is applied from the power source 5 to the power electrode 32. As a result, gas discharge occurs in a region 33 between the vicinity of the tip of the power supply electrode 32 and the ground electrode 41 in the enlarged diameter portion 29 and the circular tube portion 28. The excited active species of the discharge gas due to this discharge is jetted from the nozzle portion 26 toward the object 9 as a thin gas flow, and the narrow region 10 is surface-treated.
[0061]
The dimensions of the circular tube portion 28 have a relationship of 1 μm ≦ b1 ≦ 1 mm and b1 / a1 ≦ 1/10, where the length is a1 and the inner diameter is b1, similarly to the discharge tube 1 of FIGS. Set to. As a discharge gas, a rare gas such as helium or argon or a gas mixed with a fluorine compound such as oxygen, nitrogen or CF4 is used as in the other embodiments described above, and a high frequency power source of 20 kHz is used as a power source. However, a stable and good discharge state was obtained. According to this example, only the region 10 of the object to be processed could be satisfactorily surface-treated without affecting the surrounding portions.
[0062]
The surface treatment method of the present invention described above can be applied to various fields as described below. FIG. 17 shows a method of manufacturing a so-called bar AT type piezoelectric vibrator using the surface treatment method of the present invention. In general, the bar AT type piezoelectric vibrator includes a piezoelectric vibrating piece 42 and a plug 43 for supporting the piezoelectric vibrating piece 42 and connecting to an external circuit.
[0063]
The piezoelectric vibrating piece 42 has the same rectangular pattern on both sides of a piezoelectric material having a small rectangular shape with a length of about 4.5 to 7 mm and a width of about 1.5 to 2 mm, for example, a piezoelectric chip made of a thin quartz substrate. Each of the excitation electrodes 44 is formed to a thickness of 1000 to 4000 mm by vapor-depositing or sputtering Ag on the Cr underlayer. At the lower end of the piezoelectric chip, connection lands 45 drawn from the excitation electrode 44 are provided on both the left and right sides. The excitation electrode can be formed of a thin film of Au instead of Ag.
[0064]
The plug 43 is a so-called hermetic terminal, and has two lead wires penetrating an insulator 46 made of glass with a metal ring fitted on the outer periphery thereof. The lead wire includes a short flat inner lead 47 projecting upward from the insulator 46 and an elongated pin-shaped outer lead 48 extending downward from the insulator. The inner lead 47 of the plug is connected to the land 45 of the piezoelectric vibrating piece 42 by soldering. For this reason, the surface of the inner lead is pre-soldered before connecting the piezoelectric vibrating piece. The inner lead has a very small size of about 1 mm in length and a width of about 0.6 mm, and the size of the land is also very small.
[0065]
The piezoelectric vibrating piece 42 is soldered by aligning the plug 43 so that the inner lead 47 is placed on the land 45 and heating the solder plating by reflow using hot air such as nitrogen gas. The In this way, the piezoelectric vibrating piece is cantilevered by the plug 43, and the excitation electrode 44 is electrically connected to the lead wire. Further, the piezoelectric vibrating piece is housed in a case (not shown) in a vacuum, and is hermetically sealed by press-fitting the metal ring, the outer surface of which is pre-soldered, into the opening of the case. .
[0066]
According to the present invention, as the pretreatment for soldering the piezoelectric vibrating piece 42 and the plug 43, the surfaces of the land 45 and the inner lead 47 are treated. The surface treatment apparatus of the present embodiment is similar to the embodiment shown in FIGS. 13 and 14, for example, the discharge tube 1 made of a long and thin circular tube made of a dielectric material such as glass, and the nozzle portion 8 of the piezoelectric vibrating piece. It is arranged toward the land surface of the plug or the inner lead surface of the plug. On the outer periphery of the discharge tube 1, a coil-shaped power supply electrode 35 and a cylindrical ground electrode 36 are fitted and separated from each other along the flow direction of the discharge gas. While a discharge gas is introduced into the discharge tube 1 from the gas supply source 7 and ejected from the nozzle portion 8, a predetermined voltage is applied from the power supply 5 to the power supply electrode 35, and a gas is introduced into the discharge tube 1 between the two electrodes. Causes a discharge.
[0067]
The excited active species of the discharge gas generated by the gas discharge is jetted from the nozzle portion 8 toward the land surface of the piezoelectric vibrating piece or the inner lead surface of the plug in a thin gas flow. In this embodiment, a mixed gas of helium and CF4 is selected as the discharge gas. As a result, stable discharge is obtained with helium, and the oxide film is first etched on the surface of the land 45 and the surface of the solder plating previously applied to the inner lead 47 by the thin gas flow containing the excited active species of CF4. Are removed and then modified to improve wettability.
[0068]
Thus, by improving the wettability of the soldered portion, as described above, the very small piezoelectric vibrating piece 42 and the plug 43 can be connected well, and the amount of solder to be used can be reduced as compared with the prior art. According to the present invention, particularly when the land 45 having a very small area is surface-treated, the diameter of the nozzle portion of the surface treatment apparatus is set to a size corresponding to the land 45, and the surface to be treated is not directly exposed to the discharge. It is convenient that there is no possibility that the excited active species may affect the surrounding piezoelectric vibrating piece 42 and the frequency may be fluctuated.
[0069]
In the above embodiment, both the land and the inner lead are surface-treated, but the same effect can be obtained by treating only one of them. In another embodiment, a stable discharge and improved wettability can be achieved using a mixed gas of a rare gas other than helium and a fluorine compound other than CF4 (for example, Freon (trade name)). . Further, the surface treatment apparatus of FIG. 17 is merely an example, and the piezoelectric element can be similarly manufactured using the surface treatment apparatus of the present invention having the various discharge tubes or electrode structures described above. Furthermore, by incorporating this into a soldering apparatus as a pre-processing apparatus and making it inline, continuous processing becomes possible, and quality and yield can be further improved. Needless to say, the piezoelectric element manufacturing method of the present invention also connects other piezoelectric vibrators such as tuning fork type and other piezoelectric elements such as SAW devices by soldering the piezoelectric vibrating piece or SAW piece to the lead terminal. It can be applied in the same way.
[0070]
FIG. 18 shows a method of adjusting the frequency in the manufacturing process of the SAW device by using the surface treatment method according to the present invention. The SAW device of this embodiment includes a SAW piece 49 made of a quartz (SiO2) chip cut into a small rectangular thin plate having a size of about 3 mm in width, about 4 mm in length, and about 0.5 mm in thickness. The SAW piece 49 has an interdigitated electrode (IDT) formed by combining a pair of comb-shaped electrodes in the approximate center of one surface (main surface) of the crystal chip, and a lattice-like reflector on both sides thereof. Is provided.
[0071]
These electrodes and reflectors are formed by patterning an Al thin film formed on the surface of the quartz chip by vapor deposition or sputtering using a photolithography technique. The natural frequency of the SAW piece, that is, the frequency of the SAW device is basically determined by the width, pitch and film thickness of the Al electrode pattern. The SAW piece 49 in which the electrodes and the like are formed in this way is fixed to the inside of the base 50 formed of a ceramic material or the like with a conductive paste such as a silver paste or an adhesive 51, and the electrodes are fixed to the base by the bonding wires 52. It is electrically connected to 50 electrodes.
[0072]
According to the present invention, in this state, the frequency of the SAW device is finely adjusted by etching the crystal portion of the SAW piece and cutting it off by a small amount. In the surface treatment apparatus of this embodiment, as shown in FIG. 1, the discharge tube 1 made of an elongated circular tube of dielectric material such as glass is directed toward the surface of the SAW piece 49 where the crystal of the SAW piece 49 is exposed. Arrange. On both sides of the discharge tube 1, a pair of flat plate electrodes 2 and 3 are arranged to face each other. A discharge gas is introduced into the discharge tube 1 from the gas supply source 7, and a predetermined voltage is applied from the power supply 5 to the power supply electrode 2 while being ejected from the nozzle portion 8, thereby generating a gas discharge in the discharge tube 1.
[0073]
The excited active species of the discharge gas generated by this gas discharge is jetted from the nozzle portion 8 toward the quartz exposed surface of the SAW piece as a thin gas flow. Also in the surface treatment apparatus of the present embodiment, the diameter of the nozzle portion 8 is set to a size corresponding to the size of the quartz exposed surface. Moreover, since the surface to be processed is not directly exposed to the discharge, the discharge does not affect the Al electrode and the reflector of the SAW piece 49.
[0074]
In this embodiment, a mixed gas of helium and CF4 is used as the discharge gas. As a result, not only a stable discharge is obtained with helium, but also only the quartz exposed surface of the very small SAW piece 49 is formed of Al as described above by the thin gas flow containing the excited active species of CF4. Etching can be done in small amounts without affecting the electrode or reflector. This etching is performed while monitoring the frequency of the SAW piece and finely adjusted to a desired frequency. When the frequency adjustment is finished, the cap member is attached in a nitrogen atmosphere to hermetically seal the inside of the base 50.
[0075]
Conventionally, the frequency of the SAW device is adjusted by dry etching in a vacuum, so the equipment is large and expensive, and the work is troublesome and time consuming. This is a cause of low productivity and increased cost. It was. On the other hand, according to the present invention, as described above, work can be performed at atmospheric pressure, so that the equipment can be reduced in size and cost, and continuous processing by in-line processing is possible, improving productivity and reducing cost. Can be achieved.
[0076]
The frequency adjustment of the SAW device according to the present invention can be performed before the SAW piece is mounted in the base. That is, after forming an electrode pattern on the surface of the quartz wafer using photolithography technology and dicing and cutting into individual chips, before fixing this inside the base and connecting it to the electrodes, as described above While monitoring the frequency of this chip, the exposed quartz surface is etched. Further, before the crystal wafer on which the electrode pattern is formed is diced and cut into individual chips, the exposed crystal surface can be etched while monitoring the frequency of each electrode pattern in the wafer state.
[0077]
In another embodiment, similarly stable discharge and fluorination treatment can be realized by using a mixed gas of a rare gas other than helium and a fluorine compound other than CF4 (for example, Freon (trade name)). . Further, when chlorine or a compound containing chlorine is used as the discharge gas, the frequency can be adjusted by directly etching the Al electrode, but the handling and safety of the chlorine-based gas is difficult.
[0078]
In yet another embodiment, a conductive material such as Au or Al—Cu alloy is used as an electrode material in addition to Al, and a piezoelectric material such as lithium tantalate or lithium niobate is used as a chip material for the SAW piece 49 other than quartz. Even in the case of using the frequency adjustment, the frequency adjustment according to the present invention can be similarly performed.
[0079]
Moreover, liquid crystal panels of various LCDs such as STN type, TFT type, MIM type and the like can be manufactured by using the surface treatment method according to the present invention. In general, as shown in FIGS. 19A and 19B, a liquid crystal panel uniformly coats and fires a polyimide resin on the surface of the glass substrate 53 on which the drive electrodes are formed, and rubs this in a certain direction to form the alignment film 54. Form. For example, a UV (ultraviolet) curable sealing material 55 is printed along the outer periphery of the surface on which the alignment film is formed, and another glass substrate 57 on which the alignment film 56 is also formed is overlapped thereon via a spacer. The cell container 58 is formed by integrally bonding the sealing material by curing. A liquid crystal material is injected into the cell container 58 as described later.
[0080]
According to the present invention, before injecting the liquid crystal material, the inner surface of the cell container is surface-treated to improve the wettability. In this embodiment, the sealing material 55 exhausts the discharge gas at the approximate center of the other short side in addition to the liquid crystal injection port 59 to the cell container provided at the approximate center of one short side of the glass substrate 57. In order to provide the mouth 60, it is applied to leave each of these portions. Further, the cell gap of the cell container 58, that is, the gap between the two glass substrates is very narrow, from about 7 μm of the STN type panel to about 1.5 μm when the ferroelectric liquid crystal is used, and usually about 5 μm. .
[0081]
As well shown in FIG. 19A, the liquid crystal injection port 59 is connected to the gas supply source 7 via the communication pipe 61. On both the upper and lower sides of the cell container 58, the flat power supply electrode 2 and the ground electrode 3 are disposed so as to sandwich the cell container 58 therebetween. The discharge gas supplied from the gas supply source 7 is introduced into the cell container 58 from the liquid crystal injection port 59, passes through the discharge gas, and flows out from the opposite exhaust port 60 to the outside. In this way, when the power supply electrode 2 is energized from the power supply 5 while flowing the discharge gas into the cell container 58, gas discharge occurs in the cell container. By matching the size of both electrodes to the size of the smaller glass substrate 57, the discharge region can be expanded to the entire inside of the cell container 58.
[0082]
In this embodiment, helium is selected as the discharge gas. Thereby, the inner surface of the cell container is directly exposed to the excited active species, and wettability is improved. As can be seen from the description given above with reference to FIGS. 3 and 4, according to the present invention, a good discharge state can be obtained even in a cell container having a cell gap of about 1.5 μm, and a good surface treatment is possible. It is. On the other hand, plasma discharge in a conventional vacuum does not occur in such a narrow gap cell container.
[0083]
Thereafter, the exhaust port is closed, and the inside of the cell container is brought into a certain vacuum state by being placed in a vacuum chamber. Next, a liquid crystal material is attached to the liquid crystal injection port 59, the inside of the vacuum chamber is returned to atmospheric pressure, and liquid crystal is injected into the cell container 58. The liquid crystal injection port is closed using a UV curable adhesive like the sealing material.
[0084]
According to the present invention, as described above, the wettability of the inner surface of the cell container is greatly improved as compared with the prior art, so even if it is a highly viscous liquid crystal material, bubbles do not remain inside the cell container 58. Can be injected smoothly and reliably. Moreover, since it is not necessary to wash | clean before and after each overlapping a glass substrate like the past, it can complete | finish by one process, Therefore Work efficiency is good and productivity improves.
[0085]
In addition, an inkjet printhead can be manufactured using the surface treatment method according to the present invention. The print head 62 shown in FIG. 20A divides the gap between the nozzle plate 64 having a large number of nozzles 63 having a diameter of about 30 μm and the diaphragm 65 into a large number of cavities 67 by partition members 66 in accordance with the positions of the nozzles. The piezoelectric transducer 68 is disposed behind the diaphragm 65 in correspondence with the cavities. By applying an electrical signal to the piezoelectric transducer to mechanically vibrate the diaphragm 65, the corresponding ink 69 in the cavity is ejected from the nozzle 63.
[0086]
Each partition member 66 is attached to a predetermined position of the diaphragm 65 by an ordinary adhesive. As shown in FIG. 20B, excess adhesive 70 that protrudes may remain in the vicinity of the bonding portion between the partition member and the diaphragm. However, since the size of the cavity 67 is very small, for example, about 100 μm in width and about 220 μm in height, it is relatively difficult to remove the adhesive 70.
[0087]
According to the present embodiment, the surface treatment apparatus having various configurations having the discharge tube 1 made of an elongated circular tube made of a dielectric material, for example, as shown in FIG. A gas discharge is generated in a discharge gas flowing inside the discharge tube 1 disposed above the diaphragm 65 to which the member 66 is bonded. In another embodiment, a surface treatment apparatus having a discharge tube 25 composed of an elongated circular tube portion and an enlarged diameter portion as shown in FIG. 9 or FIG. 16 of the present invention can be used.
[0088]
As a discharge gas, a mixed gas of a rare gas such as helium and oxygen is used, and a gas flow containing the excited active species is injected from the nozzle portion 8 toward a narrow gap between the partition members of the diaphragm 65. By using, for example, a capillary tube having a diameter of 50 μm for the circular tube portion of the discharge tube 1 or the discharge tube 25, the adhesive 70, which is usually an organic resin, can be removed by ashing from the very narrow cavity 67 as described above. . In this way, a high-quality print head that eliminates defective printing due to the generation of bubbles in the cavity and the deterioration of the ink by assembling the diaphragm 65 from which the excess adhesive adhered inside the cavity has been removed in advance can be obtained. Can be manufactured.
[0089]
FIG. 21 shows an inkjet print head 71 having a structure different from that of the print head of FIG. The print head 71 includes a thick first substrate 72 formed of an insulating material such as glass or resin, and a thin second substrate 73 integrally bonded thereto. On one surface of the first substrate 72, four grooves 74 extending from the wider base end portion toward the tapered tip end portion are provided by wet etching using a photolithography technique. Yes. Each groove 74 is provided with a wide portion serving as an ink reservoir, which will be described later, at a position close to the base end portion. The number of the grooves 74 can be appropriately set as required.
[0090]
A second substrate 73 made of a flat plate having the same shape is attached to the one surface of the first substrate 72 so as to close the groove. As a result, a print head 71 is formed in which four ink flow paths 78 communicating with the nozzle 77 opened at the tip end from the ink supply port 75 opened at the base end through the ink reservoir 76 are provided. The On the outer surface of the second substrate, ink in the ink reservoir is ejected from the nozzle 77 by mechanically vibrating the second substrate at positions corresponding to the ink reservoir 76, as in the embodiment of FIG. A known piezo transducer for mounting is attached.
[0091]
The inner dimension of the ink flow path 78 is very small considering that the size of the print head 71 is, for example, about 10 mm in both length and width. For example, the maximum portion of the ink reservoir 76 shown in FIG. 21B has a width of about 400 μm and a depth of about 80 μm, and the other portions have a width and a depth of about 50 μm near the nozzle shown in FIG. 21C. Therefore, it is important to improve the wettability of the inner surface of the ink flow path in order to always ensure a clear and good printing state.
[0092]
According to the present invention, before the piezo converter is attached, the inner surface of the ink flow path of the print head is surface-treated to improve the wettability. In this embodiment, a connecting tube 79 is connected to the base end as shown in FIG. 22 under atmospheric pressure, and a discharge gas is supplied from the gas supply source 7. The discharge gas passes through the ink flow path 78 from the ink supply port 75 and is discharged from the nozzle 77 to the outside. On both the upper and lower sides of the print head 71, flat power supply electrodes 2 and ground electrodes 3 are disposed so as to sandwich the print head 71 therebetween. When a predetermined voltage is applied from the power supply 5 to the power supply electrode 2, gas discharge occurs in the ink flow path 78.
[0093]
In this embodiment, a rare gas such as helium is selected as the discharge gas so that a good discharge state can be obtained. Thereby, the inner surface of the ink flow path is directly exposed to the excited active species of the discharge gas, and the wettability with respect to the ink is improved. Therefore, the flow of ink in the ink flow path 78 and the removal of bubbles generated in the ink in the flow path are improved, so that a high-quality print head that eliminates the possibility of printing defects can be obtained. As can be seen from the description given above with reference to FIGS. 1 and 5, according to the present invention, even within the narrow ink flow path 78 of the print head, a good surface treatment is possible by stable discharge. On the other hand, in the conventional plasma discharge in a vacuum, since a discharge is not easily generated in the ink flow path 78, a sufficient surface treatment effect cannot be expected.
[0094]
FIG. 23 shows a modification of the embodiment shown in FIG. In this modification, instead of the pair of flat plate electrodes 2 and 3, a coil electrode 35 similar to the embodiment shown in FIG. Also in this case, the surface treatment is performed by supplying the discharge gas from the gas supply source 7 into the ink flow path 78 through the communication tube 79 and directly exposing to the gas discharge generated in the discharge gas flowing therethrough. In addition, the wettability of the ink flow path 78 with respect to ink can be improved.
[0095]
FIG. 24 shows a modification of the embodiment shown in FIG. In this modification, the connecting tube 80 attached to the base end portion of the print head 71 is formed of a dielectric material, and the coil electrode 35 is wound around the outer periphery thereof. Accordingly, the gas discharge is generated inside the connecting tube 80, and the surface treatment is indirectly performed when the excited active species of the discharge gas supplied from the gas supply source 7 flows as a gas flow through the ink flow path 78. . In this case as well, the wettability of the ink flow path 78 with respect to ink can be improved.
[0096]
In addition, by using the surface treatment method of the present invention, it is possible to easily perform microsampling for collecting and analyzing tens to hundreds of μm of minute inorganic or organic foreign matter immersed in the surface of the sample. . First, a case where the sample is an organic material such as a polyimide film used for a flexible substrate and the foreign matter is an inorganic material will be described. As shown in FIG. 25A, the discharge tube 1 made of, for example, an elongated circular tube made of a dielectric material as shown in FIG. 1 is disposed above the sample 81 with the nozzle portion 8 facing the position where the foreign material 82 is immersed. .
[0097]
A mixed gas of a rare gas such as helium and oxygen is used as a discharge gas, a gas discharge is generated in the discharge tube 1, and a gas flow containing the excited active species of the discharge gas is injected onto the surface of the sample 81. In the present embodiment, for example, by using a capillary tube having a diameter of 50 μm for the discharge tube 1, only a small sample 81 existing around the foreign material 82 can be partially ashed and removed. Therefore, as shown in FIG. 25B, a small dent 83 is formed around the foreign material 82, and the foreign material is exposed therein. The probe 84 is inserted into the recess 83 using a sampling device such as a conventional manipulator. Since the tip of the probe 84 usually has a radius of about 1 μm, the probe 84 can be easily approached to the foreign material 82 and can be easily collected by engaging the foreign material.
[0098]
When the sample is an inorganic material such as ceramic or silicon and the foreign matter is an organic material, a mixed gas of a rare gas such as helium and a fluorine compound such as CF4 is used as the discharge gas, and surface treatment is performed in the same manner as in FIG. 25A. . In this case, the surface of the sample 81 is removed by partially etching the periphery of the foreign material 82, and similarly, a recess 83 is formed and the foreign material 82 is exposed therein, so that it is easy to use a conventional manipulator. Can be collected.
[0099]
In the case where both the sample and the foreign material are organic or inorganic, the surface treatment method shown in FIG. 25 described above cannot be collected by ashing or etching even the foreign material. In such a case, as shown in FIG. 26A, the nozzle portion 8 of the discharge tube 1 is arranged toward the surface of the sample 81 around the foreign material 82, and surface treatment is performed. A gas flow containing excited active species of the discharge gas is jetted from the discharge tube 1 toward the surface of the sample 81 so as not to directly hit the foreign material 82 while moving the discharge tube 1 around the foreign material 82. As a result, an annular recess 85 is formed around the foreign material 82 on the surface of the sample 81. Therefore, also in this case, using a conventional manipulator, the probe 84 can be inserted into the recess 85 to approach the foreign material 82, and can be easily collected by engaging with the tip.
[0100]
Although the preferred embodiments of the present invention have been described above, the present invention can be implemented by adding various modifications and changes to the above embodiments within the technical scope thereof. For example, a mesh-like thing can be used for the ground electrode 3 arranged opposite to the flat power supply electrode 2. In addition to the above-described embodiments, various discharge tubes described with reference to FIGS. 1 to 16 are used for manufacturing piezoelectric elements, liquid crystal panels, inkjet pudding heads, and microsampling. In addition, a surface treatment apparatus having an electrode structure can be used.
[0101]
【The invention's effect】
Since this invention is comprised as mentioned above, there exists an effect as described below.
According to the surface treatment method of the present invention, the inside of the object to be processed cannot be easily accessed from the outside by applying an electric field from the outside while flowing the discharge gas from the outside with the inside of the object to be processed as a gas flow path. Even in a narrow space such as a road, a gas discharge is generated inside the object to be processed and maintained in a good state, and the inside of the object to be processed is directly exposed to the excited active species of the discharge gas, and is stable and good. Can be surface treated. Therefore, surface treatment with plasma under atmospheric pressure is possible in a wider range of fields, and high versatility can be obtained.
[0102]
If this surface treatment method is applied to the manufacture of an ink jet print head, the wettability of the ink flow path built in the head can be improved, so that the ink flow is improved and there is a risk of print defects during use. This eliminates the problem and enables clearer printing. In addition, in the manufacture of the liquid crystal panel, by appropriately selecting the discharge gas, the wettability inside the cell container is improved in one step before injecting the liquid crystal material, so that the liquid crystal material injection operation is smooth. In addition, the liquid crystal panel can be manufactured with higher quality by improving the yield.
[0103]
According to the surface treatment apparatus of the present invention, it is possible to generate a gas discharge along the flow of the discharge gas within the narrow internal space of the object to be processed, and to directly expose the excited active species of the generated discharge gas. By doing so, it is possible to sufficiently treat the very narrow inner surface of the workpiece. Therefore, surface treatment with plasma under atmospheric pressure can be used for a wider range of applications.
[0104]
Further, the surface treatment apparatus of the present invention is arranged such that the power supply electrode and the ground electrode are arranged at positions facing each other with the discharge tube interposed therebetween, or upstream and downstream of the gas flow path along the discharge tube, respectively. A stable gas discharge can be generated in a narrow space of the flow path. Furthermore, according to the present invention, the casing disposed around the discharge tube and the power supply electrode is used as a ground electrode, and an electric field is formed in the radial direction centered on the power supply electrode. A stable gas discharge can be generated.
[0105]
According to the piezoelectric element manufacturing method of the present invention, gas discharge is generated using a discharge tube having a gas passage with a narrow cross section, and only the electrodes and plug terminals of the element pieces soldered to each other by the gas flow. , Or only one of them can be effectively surface-treated by exposure to the excited active species of the discharge gas to improve the wettability of the solder. A good connection state can be obtained, and the yield and productivity can be improved and the cost can be reduced. Further, since there is no possibility that the excited active species act on the piezoelectric material and affect the frequency, stable performance can be obtained.
[0106]
Further, according to the present invention, in the SAW device manufacturing process, before or after mounting the SAW piece in the package, gas discharge is performed on the discharge gas containing the fluorine compound using the discharge tube having the gas passage with a narrow cross section. By injecting the gas flow, the etching process can be performed by slightly controlling only the exposed portion of the piezoelectric material, and the frequency can be easily fine-tuned while monitoring the frequency. Therefore, continuous processing by in-line processing is possible, productivity is improved, and higher-quality and high-performance SAW devices can be manufactured at low cost.
[0107]
According to the method for manufacturing an ink jet print head of the present invention, a gas discharge is generated in a discharge gas using a discharge tube having a gas flow path having a narrow cross section, and the gas flow is jetted to thereby partition the diaphragm and the diaphragm. Excess adhesive that protrudes from the joint with the member to the surface of the narrow cavity can be removed by ashing relatively easily, so that a high-quality print head that does not cause printing defects can be manufactured at low cost. .
[0108]
According to the microsampling method of the present invention, it is possible to inject excited active species generated by plasma generated under a pressure close to atmospheric pressure onto the sample surface as a very thin gas flow by a discharge tube having a gas passage with a narrow cross section. The sample surface can be partially removed from the periphery of a foreign object that is partially or completely immersed in the surface of the sample, so that the sample surface can be removed by a small amount sufficient to approach the probe. It can be done easily and reliably. In addition, there is no possibility that the influence of the surface treatment may affect other parts of the sample or the foreign matter itself.
[Brief description of the drawings]
FIG. 1 is a perspective view schematically showing a first embodiment of a surface treatment apparatus having a first configuration according to the present invention;
FIG. 2 is a longitudinal sectional view of FIG.
FIG. 3 is a longitudinal sectional view schematically showing a second embodiment of a surface treatment apparatus having a discharge tube different from that in FIG. 1;
4 is a perspective view showing the discharge tube of FIG. 3. FIG.
FIG. 5 is a perspective view showing still another modification of FIG. 1;
6 is a plan view showing a modification of FIG.
7 is a plan view showing a modification of the second embodiment of FIG. 3. FIG.
FIG. 8 is a diagram schematically showing an embodiment of a surface treatment apparatus having a second configuration according to the present invention.
FIG. 9 is an enlarged longitudinal sectional view showing the discharge tube of FIG.
FIG. 10 is a longitudinal sectional view showing a modified example of the discharge tube and electrode structure different from FIG.
11 is a longitudinal sectional view showing a modification of the electrode structure different from FIG.
12 is a longitudinal sectional view showing a modified example of the discharge tube and electrode structure further different from FIG. 9; FIG.
FIG. 13 is a longitudinal sectional view schematically showing a first embodiment of a surface treatment apparatus having a third configuration according to the present invention;
14 is a longitudinal sectional view showing a modification of FIG.
15 is a longitudinal sectional view schematically showing a second embodiment of a surface treatment apparatus having a discharge tube different from that shown in FIG.
16 is a longitudinal sectional view schematically showing a third embodiment of a surface treatment apparatus having a discharge tube further different from that in FIG. 13; FIG.
FIG. 17 is a perspective view showing a process of surface-treating an electrode of a piezoelectric element by the method of the present invention.
FIG. 18 is a diagram showing a process of adjusting the frequency of the piezoelectric element by the method of the present invention.
FIG. 19A is a sectional view schematically showing a process of surface-treating the inside of a cell of a liquid crystal panel by the method of the present invention, and FIG. 19B is a plan view thereof.
20A is an enlarged cross-sectional view showing a nozzle portion of an inkjet print head, and FIG. 20B is a diagram showing a process of surface-treating a diaphragm.
21A is a plan view in which a part of an inkjet print head having another structure is crushed, FIG. 21B is a sectional view taken along line BB, and FIG. 21C is a sectional view taken along line CC.
22 is a schematic cross-sectional view showing a process of surface-treating the ink flow path of the print head shown in FIG.
23 is a plan view showing a process of surface treatment with an electrode structure different from FIG.
24 is a plan view showing a modification of FIG. 23. FIG.
FIG. 25 is a cross-sectional view showing a process of collecting foreign matter immersed in the sample surface by the method of the present invention in the order of FIG. A and FIG.
26 is a cross-sectional view showing the process according to the modification of FIG. 25 in the same order as FIG. A and FIG.
[Explanation of symbols]
1 Discharge tube
2 Power supply electrode
3 Ground electrode
4 High voltage transformer
5 High frequency power supply
6 Base end
7 Gas supply source
8 Nozzle
9 Workpiece
10 Processing area
11 Discharge area
13 Discharge tube
14, 15 Rectangular plate
16 Spacer
17 Base end
18 Nozzle
19 Discharge area
20 processing area
22 Processing area
23 Nozzle member
24 casing
25 discharge tube
26 Nozzle
27 tables
28 Pipe part
29 Expanded part
30 Inner pipe
31 annular vacancy
32 Power supply electrode
33 Discharge area
34, 35 Power supply electrode
36 Ground electrode
37 Discharge area
38 Ground electrode
39 Power supply electrode
40, 41 Ground electrode
42 Piezoelectric vibrating piece
43 plug
44 Excitation electrode
45 rand
46 Insulator
47 Innerlead
48 Outerlead
49 SAW pieces
50 base
51 Adhesive
52 Bonding wire
53 Glass substrate
54 Alignment film
55 Sealing material
56 Alignment film
57 Glass substrate
58 cell container
59 Liquid crystal inlet
60 exhaust port
61 Connecting pipe
62 Printhead
63 nozzles
64 nozzle plate
65 Diaphragm
66 Partition member
67 cavities
68 Piezo transducer
69 ink
70 Adhesive
71 print head
72 First substrate
73 Second substrate
74 Groove
75 Ink supply port
76 Ink reservoir
77 nozzles
78 Ink channel
79, 80 Connecting pipe
81 samples
82 Foreign matter
83 dent
84 Probe
85 dent

Claims (23)

  While a predetermined discharge gas is allowed to flow inside a workpiece made of a dielectric material under atmospheric pressure or a pressure in the vicinity thereof, a gas is discharged inside the workpiece by energizing an electrode disposed outside the workpiece. The surface of the object to be processed is exposed to the excited active species of the discharge gas generated by the gas discharge, and the object to be processed is processed. A surface treatment method characterized in that the internal dimensions have a relationship of b ≦ 1 mm and b / a ≦ 1/10, where a is the length and b is the narrower width.   Means for supplying a discharge gas so as to flow inside the object to be processed in order to process an inner surface of a narrow cross section of the object to be processed made of a dielectric material, and disposed along the object to be processed; An electrode for generating a gas discharge in the discharge gas under atmospheric pressure or a pressure in the vicinity of the inside of the object to be processed, and the dimension inside the object to be processed has a length a and a narrower width. A surface treatment apparatus characterized by having a relationship of b ≦ 1 mm and b / a ≦ 1/10 as b.   A discharge tube made of a dielectric material that defines a gas flow path having a narrow cross section between a proximal end connected to a discharge gas supply source and a distal end opening toward the workpiece; A power electrode and a ground electrode disposed opposite to each other across the discharge tube so as to cause a gas discharge in the discharge gas under atmospheric pressure or a pressure in the vicinity thereof, and the length a of the gas flow path And a narrower width b is in a relationship of b ≦ 1 mm and b / a ≦ 1/10.   4. The surface treatment apparatus according to claim 3, wherein the discharge tube comprises at least one elongated circular tube having a length a and an inner diameter b.   The surface treatment apparatus according to claim 3, wherein the discharge tube has a gas flow path having a slit-like cross section having a length of a and a width of b.   A discharge tube made of a dielectric material that defines a gas flow path between a proximal end connected to a discharge gas supply source and a distal end that opens toward the object to be processed, and is disposed along the discharge tube And a casing made of a conductive material that contains the discharge tube and the object to be processed and is grounded, and the length a of the gas flow path and the narrower width b are b ≦ 1 mm, A surface treatment apparatus having a relationship of b / a ≦ 1/10.   7. The surface treatment apparatus according to claim 6, wherein the discharge tube comprises at least one elongated circular tube having a length a and an inner diameter b.   The surface treatment apparatus according to claim 6, wherein the discharge tube has a gas flow path having a slit-like cross section having a length a and a width b.   The surface treatment apparatus according to claim 6, wherein the power supply electrode is a coil wound around the discharge tube.   A discharge tube made of a dielectric material defining a gas flow path between a proximal end connected to a supply source of the discharge gas and a distal end opening toward the object to be processed; and the gas along the discharge tube A power supply electrode and a ground electrode, which are disposed on the upstream side and the downstream side of the flow path, respectively, and cause a gas discharge in the discharge gas under atmospheric pressure or a pressure in the vicinity thereof in the discharge tube; A surface treatment apparatus, wherein the length a and the narrower width b are in a relationship of b ≦ 1 mm and b / a ≦ 1/10.   11. The surface treatment apparatus according to claim 10, wherein the discharge tube comprises at least one elongated circular tube having a length a and an inner diameter b.   The surface treatment apparatus according to claim 10, wherein the discharge tube has a gas flow path having a slit-like cross section having a length of a and a width of b.   The surface treatment apparatus according to claim 10, wherein at least one of the power supply electrode and the ground electrode is a coil wound around the discharge tube. A method of manufacturing a piezoelectric element by soldering a lead terminal of a plug to an electrode formed on a surface of an element piece made of a piezoelectric body, and attaching a vacuum case to the plug,
Prior to the soldering, a predetermined discharge gas flows from the base end portion toward the opening of the tip end portion of the discharge tube made of a dielectric material that defines a gas flow path having a narrow cross section. By energizing the electrodes disposed along the discharge tube, a gas discharge is generated in the discharge tube under atmospheric pressure or a pressure in the vicinity thereof, and a gas flow containing excited active species of the discharge gas generated thereby is discharged into the discharge tube. It comprises a process of surface treatment by spraying at least one of the junction surface of the electrode of the element piece or the surface of the plug terminal from the opening of the tip of the tube, and the length a of the gas flow path and the narrower width b Is a relationship of b ≦ 1 mm and b / a ≦ 1/10. A SAW (surface acoustic wave) piece in which an electrode is formed on the surface of a piezoelectric body is mounted in a package, the electrode is electrically connected to a terminal of the package, and the package is hermetically sealed to thereby provide a piezoelectric element. A method of manufacturing comprising:
In a discharge tube made of a dielectric material that defines a gas passage having a narrow cross section, a discharge gas containing a fluorine compound flows from the base end portion toward the opening of the tip portion, and is arranged along the discharge tube. By energizing the electrodes, a gas discharge is generated in the discharge tube under atmospheric pressure or a pressure near the atmospheric pressure, and a gas flow containing excited active species of the discharge gas generated thereby is opened at the tip of the discharge tube. From the process of adjusting the frequency of the SAW piece by spraying and etching the portion of the piezoelectric material exposed on the electrode forming surface of the piezoelectric body, and the length a and the narrower width of the gas flow path. b is a relation of b ≦ 1 mm and b / a ≦ 1/10.   16. The method of manufacturing a piezoelectric element according to claim 15, wherein the etching process using the excited active species of the discharge gas is performed after the electrode of the SAW piece is electrically connected to the package terminal.   The method for manufacturing a piezoelectric element according to claim 15 or 16, wherein the piezoelectric body is quartz. A cell container is formed by integrally bonding two glass substrates on which an alignment film is formed with a shielding material so as to have a certain narrow gap therebetween, and a liquid crystal material is sealed in the cell container. A method of manufacturing a liquid crystal panel,
Before enclosing the liquid crystal material, a predetermined discharge gas is allowed to flow from the liquid crystal injection port into the cell container, and an electrode disposed along the cell container is energized to generate a gas discharge inside the cell container. The surface of the cell container is exposed to the active species of the discharge gas generated by the gas discharge to expose the surface of the cell container, and the dimension of the cell container A manufacturing method of a liquid crystal panel, wherein a has a relationship of b ≦ 1 mm and b / a ≦ 1/10, where a is a narrow width and b is b ≦ a mm.   The method of manufacturing a liquid crystal panel according to claim 18, wherein the predetermined discharge gas includes helium. A method of manufacturing an ink jet print head of a type that selectively ejects ink injected into a plurality of cavities defined by a partition member between a nozzle member and a diaphragm,
After adhering the partition member to the diaphragm, a predetermined discharge gas is allowed to flow from the base end portion toward the opening of the tip end portion in the discharge tube made of a dielectric material that defines a gas passage having a narrow cross section. And energizing an electrode disposed along the discharge tube, thereby causing a gas discharge in the discharge tube at atmospheric pressure or a pressure near the atmospheric pressure, and including an excited active species of the discharge gas generated thereby. The gas flow consists of a process of ashing by injecting a gas flow from the opening at the front end of the discharge tube to the vicinity of the bonding portion between the diaphragm and the partition member, and the length a of the gas flow path and the narrower width b are b. ≦ 1 mm, b / a ≦ 1/10. A method for manufacturing an ink jet print head. A method of manufacturing an ink jet print head having an ink flow path leading from an ink supply port to a nozzle opening,
While flowing a predetermined discharge gas from the ink supply port to the nozzle opening, an electrode disposed outside the print head is energized to generate a gas discharge in the ink flow path, and the gas generated by the gas discharge The process comprises exposing the inner surface of the ink flow path to the excited active species of the discharge gas. The dimension of the ink flow path is b ≦ 1 mm, b / a ≦ 1, where the length is a and the narrow width is b. A method of manufacturing an ink jet print head, characterized by having a relationship of / 10.   The method of manufacturing an ink jet print head according to claim 21, wherein the predetermined discharge gas contains helium. A micro-sampling method in which a minute foreign substance is attached to the tip of a probe and collected from the surface of the sample,
Before allowing the probe tip to approach the foreign substance, a predetermined discharge gas is allowed to flow from the base end portion toward the opening of the tip portion in the discharge tube made of a dielectric material that defines a gas flow path having a narrow cross section. A gas containing excited active species of the discharge gas generated by energizing an electrode arranged along the discharge tube to cause a gas discharge in the discharge tube under atmospheric pressure or a pressure in the vicinity thereof by injecting the sample surface flow from the tip opening of the discharge tube, it consists process of removing the sample partially from the periphery of the foreign matter, the length a and the narrower the width b of the gas flow path Is a relationship of b ≦ 1 mm and b / a ≦ 1/10 .

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