CN1700953A - Plasma processing apparatus, method for producing reaction vessel for plasma generation, and plasma processing method - Google Patents

Plasma processing apparatus, method for producing reaction vessel for plasma generation, and plasma processing method Download PDF

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CN1700953A
CN1700953A CN 200480001115 CN200480001115A CN1700953A CN 1700953 A CN1700953 A CN 1700953A CN 200480001115 CN200480001115 CN 200480001115 CN 200480001115 A CN200480001115 A CN 200480001115A CN 1700953 A CN1700953 A CN 1700953A
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electrode
hole
gas
processing apparatus
plasma
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CN1323751C (en
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柴田哲司
山崎圭一
田口典幸
泽田康志
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Panasonic Electric Works Co Ltd
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Matsushita Electric Works Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a plasma processing apparatus capable of expanding a processing area and of carrying out uniform processing, and allowing design to be easily changed in response to an object of processing.

Description

The manufacture method and the method for plasma processing of plasma processing apparatus, generation reaction vessel for plasma
Technical field
The present invention relates to be used for effectively carrying out plasma processing apparatus and the method that large area plasma is handled.
Background technology
In the past, plasma surface treatment has been widely used for following purposes: remove impurity on the pending object such as organic materials, etching or peel off resist, improve the adhesivity of organic membrane, reducing metal oxide, form film, the pre-treatment of electroplating and applying, and the surface of various material and part is revised.
For example, Japanese Patent Laid Open Publication [kokai] number 11-335868 discloses and has utilized plasma body to carry out surface treatment, wherein plasma body is providing plasma body to generate gas to discharge space when, by generating in the electric discharge between electrodes space applying voltage between the pair of electrodes.In this plasma surface treatment, because the activation particle (species) of plasma body or plasma body is penetrated from single-nozzle, and object is being carried out plasma treatment when transporting object on the orthogonal direction of direction with penetrating, therefore have such problem, promptly the treatment effect to object changes easily.
In addition, Japanese Patent Laid Open Publication [kokai] number 4-358076 discloses: increase processing area by the activation particle that utilizes plasma body or plasma body, wherein, plasma body is to have the reaction vessel that applies the dielectric medium electrode by utilization to generate, and described coating dielectric medium electrode is to obtain by on a plurality of electrode surfaces of parallel placement the solid dielectric material being set.According to this technology, can be once object be carried out surface treatment than big area.Yet considering by uniform air flow provides the activation particle of plasma body or plasma body to the entire treatment zone, also has the very big space of improving.In addition, this large area plasma is handled has another problem, and promptly the mass consumption of gas causes the increase of operating cost.
In addition, for the object as the glass that is used for liquid crystal panel, be desirably in the following processing area that further increases.In order to handle various objects, need to increase degree of freedom in the device design.
Summary of the invention
Consider the problems referred to above, main consideration of the present invention provides a kind of plasma processing apparatus, it has higher degree of freedom according to pending object on Design of device, and has the processing area of increasing and consume the promptly low ability of carrying out even processing originally that operates as of less gas.
That is to say, (be used for coming activate plasma to generate gas G at a kind of like this plasma processing apparatus by discharge, and to object 5 injection activatory plasma bodys generation gases) in, plasma treatment appts of the present invention is characterised in that: have the reaction vessel R that is formed by insulating element 1, and this reaction vessel comprises: a plurality of through holes 2, each through hole has the inlet opening that is used for plasma body generation gas G at the one end, and has the outflow opening that is used for activatory plasma body generation gas G in its opposite end; And electrode 3,4, be used for discharging at each through hole 2.
According to plasma treatment appts of the present invention, by under atmospheric pressure or under near the air pressure the normal atmosphere in each through hole 2, carrying out geseous discharge, and air-flow (it contains the activation particle that generates by geseous discharge) by providing the activatory plasma body to generate gas G to object 5 from through hole 2, can on big area, generate uniform plasma body expeditiously, and big area object 5 be carried out surface treatment equably with less airshed.In addition, by using the appropriate combination of a plurality of insulating elements 1, can design suitable plasma processing apparatus with higher degree of freedom according to the shape and the size of object 5.
In above-mentioned plasma processing apparatus, preferably, electrode 3,4 is formed in the layer in the insulating element 1, and has hole (aperture) 8 in the position corresponding to through hole, and does not wherein have vacancy (deficit) part 30 between the adjacent pores in electrode 8.In this case, owing to can reduce the appearance of insulating element 1 upper surface discharge 31, be difficult to carry out arc-over 5 from surface-discharge 31 to object.Therefore, can reduce because the damage that arc-over causes object 5.
In addition, preferably, electrode 3,4 is formed in the layer, and with towards insulating element 1, and it is outwards outstanding with respect to the peripheral portion of another electrode that is positioned at the air flow line upstream side to be positioned at the peripheral portion of an electrode in air flow line downstream side.In this case, can prevent on the insulating material 1 between the peripheral portion of electrode 3,4 and surface-discharge 31 appears in the position outside hole 8.Thus, can further reduce the damage of the object 5 that causes by arc-over.
In addition, preferably, above-mentioned plasma processing apparatus also comprises thermoswitch, and it is configured to the temperature of insulating element 1 is controlled at the temperature that is easy to launch secondary electron.In this case, by the secondary electron that discharges from insulating element 1, increased plasma body and generated density.Therefore, can improve Cement Composite Treated by Plasma efficient, for example, remove or revise the efficient of object 5.
Plasma processing apparatus according to the preferred embodiment of the present invention comprises:
The pair of electrodes plate has a plurality of through holes;
Insulcrete has a plurality of through holes, and it is arranged between the battery lead plate, makes the lead to the hole site of battery lead plate corresponding to the lead to the hole site of insulcrete;
Gas supply unit is configured to that plasma body is generated gas and is fed to a plurality of discharge spaces that the through hole by the through hole of battery lead plate and insulcrete forms; And
Voltage applying unit is configured to apply voltage between battery lead plate, to generate the plasma body that plasma body generates gas simultaneously in discharge space.
In addition, comprise according to the plasma processing apparatus of the another preferred embodiment of the present invention: tubular vessel, it has pair of electrodes and is arranged at insulcrete between the electrode; Gas supply unit is configured to generate gas from an end supplying plasma of tubular vessel; And voltage applying unit, be configured between electrode, apply voltage, in tubular vessel, to generate the plasma body that plasma body generates gas, utilize the plasma body that penetrates from the other end of tubular vessel that object is carried out surface treatment thus.This device is characterised in that: provide electrode by the battery lead plate with a plurality of through holes, insulcrete has a plurality of through holes, tubular vessel has a plurality of discharge spaces that the through hole by the through hole of battery lead plate and insulcrete forms, and the plasma body plasma body that generates gas is by applying between the battery lead plate that voltage produces simultaneously and penetrating from the other end of tubular vessel in discharge space.
Another consideration of the present invention provides the manufacture method of a kind of reaction vessel R, and this reaction vessel is used for being created on the plasma body that above-mentioned plasma processing apparatus uses.That is, this method comprises the steps:
Between the plate that has a plurality of openings and form (sheet), place the conducting film that forms by electro-conductive material, thereby the opening of these plates is corresponded to each other by insulating material; And
The synthetic lamination is carried out global formation, thereby provide insulating element 1, electrode (3,4) and through hole 2 by the opening of these plates, conducting film and these plates respectively.According to the method, can easily make the reaction vessel R that is applicable to above-mentioned plasma processing apparatus.In addition, can accurately form through hole 2 and electrode (3,4).
Another consideration of the present invention provides the method for plasma processing that uses above-mentioned plasma processing apparatus.That is, this plasma body treatment process comprises the steps:
Discharge in through hole 2 by applying voltage, make plasma generation gas G flow to the other end simultaneously, thus, in through hole 2, generate plasma body and generate gas G with the activatory plasma body from an end of through hole 2 to electrode (3,4); And
Spray activatory plasma body generation gas G on the surface of object 5 from the other end of through hole 2.According to the method, can on big area, generate plasma body expeditiously, and carry out surface treatment equably to having this larger area object 5 with less airshed.
Describedly be used to realize that optimal mode of the present invention will be expressly understood other features of the present invention and the advantage of bringing thus from following.
Description of drawings
Figure 1A and 1B are according to the top schematic view of the plasma processing apparatus of the preferred embodiment of the present invention and viewgraph of cross-section;
Fig. 2 A and 2B are according to the top schematic view of the plasma processing apparatus of another preferred embodiment of the present invention and viewgraph of cross-section;
Fig. 3 A is the viewgraph of cross-section according to the plasma treatment appts of the another preferred embodiment of the present invention, and Fig. 3 B is the viewgraph of cross-section along the A-A line intercepting of Fig. 3 A;
Fig. 4 A be generate under the situation of arranging electrode on the parallel direction of the air flow line of gas with plasma body, the viewgraph of cross-section of explanation line of electric flux direction, and Fig. 4 B be generate under the situation of arranging electrode on the direction that the air flow line of gas intersects with plasma body, the viewgraph of cross-section of explanation line of electric flux direction;
Fig. 5 A and 5B are the top views according to the electrode of the preferred embodiment of the present invention;
Fig. 6 A and 6B are respectively along the viewgraph of cross-section of the A-A ' line of Fig. 5 A and 5B intercepting;
Fig. 7 A to 7C is according to the top schematic view of the plasma processing apparatus of the another preferred embodiment of the present invention and viewgraph of cross-section;
Fig. 8 is the schematic cross-sectional view according to the plasma processing apparatus of the another preferred embodiment of the present invention;
Fig. 9 is the schematic cross-sectional view according to the plasma processing apparatus of the another preferred embodiment of the present invention;
Figure 10 is the schematic cross-sectional view according to the plasma processing apparatus of the another preferred embodiment of the present invention;
Figure 11 is an instance graph that is illustrated in the voltage waveform that applies between the electrode;
Figure 12 is another instance graph that is illustrated in the voltage waveform that applies between the electrode;
Figure 13 is the another instance graph that is illustrated in the voltage waveform that applies between the electrode;
Figure 14 A and 14B are the partial cross-sectional view according to the plasma processing apparatus of the preferred embodiment of the present invention;
Figure 15 A to 15D is plane and the side-view by the reaction vessel that forms of a plurality of insulating elements of combination;
Figure 16 A is the schematic circuit diagram according to the plasma processing apparatus of the preferred embodiment of the present invention, and Figure 16 B is the voltage oscillogram that expression puts on unit A and B;
Figure 17 is the schematic circuit diagram according to the plasma processing apparatus of the another preferred embodiment of the present invention; And
Figure 18 is the synoptic diagram of plasma processing apparatus used in comparative example 1.
Be used to realize optimal mode of the present invention
According to the preferred embodiment, describe in detail below plasma processing apparatus of the present invention, be used to generate the manufacture method and the method for plasma processing of the reaction vessel of plasma body.
The preferred embodiment of plasma processing apparatus of the present invention is shown in Figure 1A, 1B, 2A and 2B.These plasma processing apparatus have reaction vessel R, this reaction vessel comprise the through hole that is formed in the tabular insulating element 12 and embed in the insulating element 1 a plurality of (to) electrode 3,4.
Preferably, insulating element 1 is made by having dystectic insulation (dielectric) material.For example, can use to have high heat impedance and high-intensity pottery or glass material, such as silica glass, aluminum oxide, zirconium white, mullite and aluminium nitride.Insulating element is not limited to these materials.Consider the ratio of performance to price and high strength, especially preferably use aluminum oxide.Alternatively, can use high dielectric material, such as titanium oxide and barium titanium oxide.Electrode 3,4 can be made such as copper, tungsten, aluminium, brass and stainless steel by conductive metallic material.Especially, preferably use tungsten or copper.The material of insulating element 1 and electrode 3,4 is preferably selected like this, make the difference of the coefficient of linear expansion between them minimize, to prevent because when making reaction vessel R or when in Cement Composite Treated by Plasma, applying thermal load, the deflection difference between insulating element and the electrode and the destruction that reaction vessel causes is occurred.
The shape of insulating element 1 and through hole 2 can suitably be designed.For example, insulating element 1 is configured to plate shape.In the drawings, insulating element 1 is orthogonal plate shape in its plan view.In plan view, be circular through hole 2 and on the thickness direction of insulating element 1, penetrate.The opposite end of each through hole 2 provides opening in the apparent surface of insulating element 1.An opening is as gas stream inbound port 2a, and another opening is as gas stream outbound port 2b.
Through hole 2 can form suitable shape.For example, being circular through hole 2 in plan view can arrange by two-dimensional pattern.Alternatively, the through hole 2 that is rectangular shape (slit (slit) shape shape) can be arranged parallel to each other.Especially, when the through hole 2 that is circle is arranged with two-dimensional pattern, under the condition that the diameter and the pitch of through hole 2 are suitably selected, can on than big area, spray activatory plasma body generation gas G equably, control the flow (flow velocity) that plasma body generates the time per unit of gas G simultaneously.
In addition, form electrode 3,4, in through hole 2, produce discharge when between the two, applying voltage.For example, between electrode 3,4, connect electric power source 6, and between electrode 3,4, apply the pulse-like voltage that has resting stage (rest period).An electrode can be used as ground-electrode.Space in each through hole 2 between the electrode is defined as discharge space.As mentioned above, the shape of electrode 3,4 can suitably be disposed, to produce discharge in discharge space.For example, preferably, electrode 3,4 embeds in the insulating element 1, and vicinity through hole 2 is separately placed.The accurate formation of through hole 2 and electrode 3,4 also helps the surface-treated homogeneity.
In Figure 1A, 1B, 2A and 2B, the apparent surface of insulating element 1 places upside and downside, and being circular through hole 2 is penetrating on the direction up and down, thereby the opening by forming in the upper surface of insulating element 1 and lower surface provides gas stream inbound port 2a and gas outflow port 2b respectively.The opening of through hole 2 is arranged with two-dimensional pattern at the upper surface and the lower surface of insulating element 1.In the drawings, through hole 2 is arranged with cubic grid pattern, thereby makes the fixed interval between the adjacent through-holes 2.
The arrangement of through hole 2 is unrestricted, and can be with optional arranged in patterns.For example, when through hole 2 in plan view during with sexangle solid matter (interlocking) arranged in patterns, they can closely and equably be arranged.As a result, can further improve object 5 surface-treated homogeneities.
Interval between the size of through hole 2 and the adjacent through-holes 2 is suitably determined, thereby the effective activate plasmas of discharge that pass through in the through hole 2 generate gas, and activatory plasma body generation gas is evenly penetrated from through hole 2.Especially, the diameter (internal diameter) of preferred through hole 2 is in 0.01 to 15mm scope.In this case, can provide wide area surface to handle by the controlled flow that plasma body generates gas.In addition, preferably, the interval between the adjacent through-holes 2 is in 0.03 to 60mm scope.For example, carrying out under the situation of Cement Composite Treated by Plasma having relative object 5 than small area, through hole 2 is preferably designed for has less relatively diameter.
In the embodiment shown in Fig. 3 A and the 3B, the apparent surface of insulating element 1 places upside and downside, and the through hole 2 that is rectangle (slit-shaped) shape in plan view is penetrating on the direction up and down, thereby the opening that forms in upper surface by insulating element 1 and the lower surface provides gas stream inbound port 2a and gas outflow port 2b respectively.The opening of through hole 2 is arranged with pattern parallel at the upper surface and the lower surface of insulating element 1, thus the fixed distance between the adjacent through-holes 2.
The size of suitable definite through hole 2 and the interval between the adjacent through-holes 2, thus gas generated by the effective activate plasmas of discharge in each through hole 2, and activatory plasma body generation gas G is evenly penetrated from through hole 2.Especially, the width (minor face) of preferred rectangular through-hole 2 size is in 0.01 to 15mm scope.In this case, can further improve the surface-treated homogeneity by to carrying out Cement Composite Treated by Plasma along the object 5 that transports on the short side direction of through hole 2.
In addition, preferably, the interval between the adjacent through-holes 2 is in 0.01 to 30mm scope.In this case, the activatory plasma body generates gas G and can penetrate continuously by the longitudinal direction from the gas stream outbound port 2b of through hole 2 along through hole.Therefore, to carrying out under the situation of Cement Composite Treated by Plasma, can further improve the surface-treated homogeneity along the object 5 that transports on the short side direction of through hole 2.
In the embodiment shown in Figure 1A, 1B, 2A and the 2B, two electrodes 3,4 all embed in the insulating element 1.Electrode 4 places upper surface one side (that is, having surface one side of gas stream inbound port 2a) of insulating element 1, and electrode 3 places lower surface one side (that is surface one side that, has gas stream outbound port 2b) of insulating element 1.With through hole 2 in plasma body generate on the direction that the flow direction of gas G parallels, electrode 3 separates with electrode 4.Insulation (dielectric) material that constitutes insulating element 1 is between electrode 3,4.
In this case, electrode 3,4 be formed at insulating element 1 the layer in, thereby the position of a plurality of holes 8 of electrode 3,4 corresponding to the position of the through hole 2 of insulating element 1, and each through hole 2 by the corresponding hole 8 of electrode 3,4 around.The situation that forms electrode 3,4 with each through hole 2 is separately compared, and hole 8 is formed in each plate electrode 3,4, thereby the internal surface of the hole 8 of electrode 3,4 is used as discharging surface, is used for discharging at through hole 2.
In the embodiment shown in Figure 1B, because the diameter of the hole 8 of electrode 3,4 equals the diameter of through hole 2, the internal surface of each through hole of insulating element 1 flushes with the internal surface of the through hole 8 of electrode 3,4.Therefore, the internal surface of the hole 8 of electrode 3,4 is exposed to the inside of each through hole 2.In this case, can easily discharge by between electrode, applying voltage, and the activation Particle Density among the increase plasma body generation gas G, to improve processing efficiency.When plasma body generation gas G does not comprise reactant gases, preferred exposed electrode 3,4, because the damage of the exposed electrode 3,4 that is caused by discharging is less relatively, and discharge is carried out easily.
In the embodiment shown in Fig. 2 A and the 2B, hole 8 diameters of electrode 3,4 are greater than the diameter of through hole 2, and internal surface is insulated parts 1 covering in the hole 8 of electrode 3,4.That is to say that electrode 3,4 is not exposed to the inside of through hole 2.In this case, when applying voltage between the electrode 3,4, in each through hole 2, carry out dielectrically impeded discharge.Therefore, electrode 3,4 directly is not exposed to the plasma body or the discharge of generation.In other words, because the discharging surface of electrode 3,4 is subjected to constituting the protection of insulation (dielectric) material of insulating element 1, thereby can prevent the damage of electrode 3,4.This generates under the situation of gas G effective especially at the plasma body that use contains reactant gases.
In addition, also there is another advantage that can make discharge stability and increase plasma body generation density.When electrode 3,4 is exposed, there is such possibility: become unstable when applying high-voltage owing to the arc-over that occurs causes discharge.On the other hand, when electrode 3,4 is coated with insulation (dielectric) material, can effectively prevent the appearance of arc-over, thereby stably keep discharge.The thickness of insulation (dielectric) material that forms on the internal surface of electrode 3,4 is appropriately determin.For adequately protect electrode surface and make the discharge be easy to carry out, preferably, this thickness is in 0.01 to 3mm scope.In addition, preferably, the distance between the electrode 3,4 (being the interval between the discharging surface) in 0.01 to 5mm scope, thereby stably generate geseous discharge (plasma body).
As mentioned above, when electrode 3,4 in each through hole 2 is generating when being spaced from each other on the parallel direction of the flow direction of gas G with plasma body, the direction of the line of electric flux that produces in through hole 2 by the potential difference between the electrode 3,4 is parallel to the flow direction of plasma body generation gas G.At this moment, can produce the hyperpycnal flow discharge in the discharge space on the direction parallel, in through hole 2 with the flow direction of plasma generation gas G.This discharge has increased plasma body and has generated among the gas G and activate Particle Density, and therefore further improves the efficient of plasma surface treatment.In the embodiment shown in the figures, because the discharging surface of electrode 3,4 extends, then around through hole 2, produce line of electric flux (electric flux line) around through hole 2.As a result, can obtain plasma body expeditiously.
In addition, when the electrode 3 that places gas stream outbound port 2b one side is formed by ground-electrode (this means that placing the electrode of pending object one side is ground-electrode), can prevent that by the potential difference between control electrode 3 and the object 5 arc-over between them from occurring.As a result, the situation of effectively having avoided object 5 to be damaged by discharge.
Preferably, the above-mentioned electrode 3,4 that forms in layer does not have vacancy (penetrating) part except hole 8.That is, Fig. 5 A and 5B are illustrated respectively in the embodiment of the electrode 3,4 that forms in the insulating element 1 shown in Fig. 2 B.In this case, preferably use the electrode 3,4 (wherein around hole 8, not having vacancy part 30 to exist) of Fig. 5 B, rather than the electrode 3,4 of Fig. 5 A (wherein around hole 8, forming a plurality of vacancy parts 30).
Applying under the voltage condition by utilizing between the electrode 3,4 of electric power source 6 in insulating element 1, at Fig. 5 A, on the lower surface of insulating element 1, corresponding to the position of hole 8 with corresponding to the position of vacancy part 30 surface-discharge 31 is appearring, as shown in Figure 6A.On the other hand, when by utilizing when applying voltage between the electrode 3,4 of electric power source 6 in insulating element 1, at Fig. 5 B, only surface-discharge 31 appears in the position corresponding to hole 8 on the lower surface of insulating element 1, shown in Fig. 6 B.Therefore, compare the situation of Fig. 6 A, can reduce surface-discharge 31.
Surface-discharge 31 is the discharges that produce in the position of approaching object (work) 5.Therefore, when surface-discharge increases, occur easily from the arc-over of surface-discharge 31 to object 5.In the insulating element 1 of Fig. 6 B, can reduce surface-discharge owing to compare the situation of Fig. 6 A, then be difficult to occur arc-over.As a result, the damage minimum that object 5 is discharged.
About the electrode 3,4 that in layer, forms, preferably, be positioned near the peripheral portion of the electrode 3 of object 5 one sides outwards outstanding with respect to the peripheral portion that is positioned at away from the electrode 4 of object 5 one sides.That is to say, have therein among the rectangular projection figure of insulating element 1 of pair of electrodes 3,4, shown in Fig. 7 A to 7C, top electrode 4 has the lower electrode 3 basic similar shape shown in the dotted line with Fig. 7 A, and electrode 3,4 preferably forms with such size, makes top electrode 4 can be overlapped in the zone of lower electrode 3.Thus, when the area of lower electrode 3 during greater than the area of top electrode 4, the peripheral portion of lower electrode 3 is outwards outstanding with respect to the peripheral portion of top electrode 4, shown in Fig. 7 A and 7B.In this case, voltage between the peripheral portion of electrode 3,4 allows less than the voltage between the electrode in the through hole 23,4, prevents thus on the lower surface of insulating element 1, surface-discharge 31 occurs corresponding to the position of the peripheral portion of electrode 3,4.In other words, can prevent from surface-discharge 31 except position, occurring, and further reduce the damage that object 5 is brought by arc-over corresponding to hole 8.In Fig. 7 B, some through holes are not drawn.Electrode 3,4 can form with the suitable shape except that above-mentioned shape.In addition, a plurality of electrodes 3,4 can with through hole 2 in plasma body generate on the direction that the flow direction of gas G intersects (for example vertical direction) and arrange.
In the embodiment shown in Fig. 3 A and the 3B, electrode 3,4 places insulating element 1 with such pattern, makes an electrode separate on identical horizontal plane with another electrode.That is to say that electrode 4 is positioned at a side of each through hole 2, and electrode 3 is positioned at the opposite side of each through hole 2.In the embodiment shown in the figures, two electrodes 3,4 embed in the insulating element 1, and are positioned on the identical horizontal plane in insulating element 1. Electrode 3,4 is spaced from each other intersecting on the direction of (vertical) with flow direction that plasma body generates gas G.Insulation (dielectric) material that constitutes insulating element 1 is between electrode 3,4.
In an embodiment, electrode 3,4 is formed in the insulating element 1.That is to say that each electrode 3,4 forms with the pectination shape, its have the feed-in (feed) of extending along the arrangement of through hole 2 partly (3a, 4a), and have a plurality of electrodes parts of on the longitudinal direction of each through hole 2, extending (3b, 4b).(3b 4b) alternately places between the adjacent through hole 2 the electrode part of electrode 3,4.Therefore, electrode part 4b is positioned at a side of through hole 2, and electrode part 3b is positioned at the opposite side of through hole 2.Thus, electrode part 3b, 4b are integrally formed at respectively in the plate electrode 3, rather than each through hole 24 forms electrode 3,4 separately.Therefore, the side surface of electrode 3b, 4b is used as discharging surface, is used for discharging at through hole 2.
In order stably to carry out geseous discharge (plasma body), preferably, the distance between the electrode 3,4 is in 0.01 to 5mm scope.In this case, the line of electric flux that produces in through hole 2 by the potential difference between the electrode 3,4 has the crossing direction of flow direction that generates gas G with plasma body, shown in the arrow of Fig. 4 B.At this moment, discharge, generate gas G with activate plasma along intersecting direction.
In the embodiment shown in Fig. 3 A and the 3B, (3b, 4b) distance between is greater than the width edge (width side) of through hole 2 for the adjacent electrode of electrode 3,4 part.Therefore, the electrode part embeds in the insulating element 1 fully.In other words, electrode part 3b, 4b are not exposed to the inside of through hole 2.In this case, the same because the discharging surface of electrode 3,4 is subjected to constituting the protection of insulation (dielectric) material of insulating element 1 as the situation of Fig. 2 A and 2B, can prevent effectively that the damage of electrode 3,4 from occurring.In addition, preferably, the coating thickness of insulation (dielectric) material on the electrode 3,4 is in 0.01 to 3mm scope.
Although attached not shown in the figures, (3b, 4b) distance between can equal the width edge of through hole 2 to the adjacent electrode part of electrode 3,4.In this case, the surface of electrode part 3b, 4b flushes with the internal surface of the through hole 2 of insulating element 1, thereby electrode part 3b, 4b are exposed to the inside of each through hole 2.As a result, as the situation of Figure 1B, can increase plasma body and generate among the gas G and activate Particle Density, and improve processing efficiency.
Under the situation of using the slit-shaped through hole 2 shown in Fig. 3 A and the 3B, although it is attached not shown in the figures, but upper surface one side that electrode 4 can place insulating element 1 (promptly, near near the side the gas stream inbound port 2a), and lower surface one side that electrode 3 can place insulating element 1 (promptly, side near gas stream outbound port 2b), the same as the situation of Figure 1A, 1B, 2A and 2B.In addition, can with through hole 2 in plasma body generate on the parallel direction of the flow direction of gas G, through constituting insulation (dielectric) material of insulating element 1, electrode 3 and electrode 4 are separated.
For example, electrode 3,4 can be formed in the layer in the insulating element 1 continuously, thereby is forming hole corresponding to the position of through hole 2, and through hole 2 is arranged in the corresponding hole of electrode 3,4.In this case, the line of electric flux that produces in through hole 2 by the potential difference between the electrode has the parallel direction of flow direction that generates gas G with plasma body, shown in Fig. 4 A.In the discharge space of each through hole 2, can produce the hyperpycnal flow discharge.As a result, can increase the activation Particle Density of discharge generation, and improve the efficient of plasma surface treatment.
In the reaction vessel R that is made of insulating element 1 and the electrode 3,4 that wherein forms, electrode 3,4 and through hole 2 can be easy to intensive formation.In addition, by the electrode 3,4 that forms micro through-hole 2 and be used for discharging in micro through-hole, the activatory plasma body generates gas G and can penetrate from the through hole of arranging with two-dimensional pattern 2.As a result, can realize the inhomogeneity raising of processing area and treatment effect.
Reaction vessel R with insulating element 1 and electrode 3,4 can mix with tackiness agent by the powder with insulating material, be plate (sheet) with the synthetic mixture forming, and stacked onboard conducting film obtains.This plate can by with ceramic powder such as silica glass, aluminum oxide, zirconium white, mullite and aluminium nitride with tackiness agent and mix with various types of additives if desired, and the synthetic mixture forming is prepared for plate shape.Plate thickness can be determined according to the thickness of insulating element 1 and the distance between the electrode 3,4.For example, preferably, thickness of slab is in 0.05 to 5mm scope.
On the other hand, can be by conductive metallic material be formed conducting film such as the mode that copper, tungsten, aluminium, brass and stainless steel are printed on the insulating element.For example, form onboard after the conducting film, plate and other plate with conducting film are stacked, thereby conducting film places between the described plate.Thus obtained lamination is sintered to obtain insulating element 1.In addition, through hole 2 can form by lamination is holed.Alternatively, thus preferably by utilizing the plate that before is formed with through hole 2 and stacked sheet metal forming being made that the position of through hole 2 of plate is corresponding mutually, carry out stacked simultaneously and formation through hole 2.
Shown in Figure 1B and 2B, when (promptly in a face side of insulating element 1, upside with gas stream inbound port 2a) provides electrode 4 and in apparent surface's a side (downside that promptly has gas stream outbound port 2b) when electrode 3 is provided, by be formed for the conducting film of electrode 4 (or 3) on the surface that is printed on first plate with the expection pattern, second plate is placed on the conducting film then.Then, by be formed for the conducting film of electrode 3 (or 4) on the surface that is printed on second plate with the expection pattern.In addition, the 3rd plate is placed on this conducting film to obtain a lamination.
Alternatively, form this lamination by following processing.That is to say, have the conducting film of printing with the expection pattern that is used for electrode 4 plate, have the plate of printing with the expection pattern that is used for electrode 3 and the plate that does not all have conducting film superposes like this, make each conducting film place between the panel material, and two outermost layers of this lamination are formed by panel material.The lamination of gained is sintered, to obtain reaction vessel R.
Shown in Fig. 3 A and 3B, when same horizontal plane that two electrodes 3,4 are formed in the insulating element 1, by be formed for the conducting film of electrode 3,4 on the surface that is printed on first plate with the expection pattern, second plate is placed on this conducting film to obtain lamination then.Then, the lamination that is obtained is sintered, to obtain reaction vessel R.Reaction vessel R is placed in plasma body and generates in the flow passage of gas G, thereby plasma body generates gas from gas stream inbound port 2a, through through hole 2, mobile towards gas stream outbound port 2b.
In Fig. 8, use the reaction vessel R shown in Fig. 2 A and the 2B, and on the upper surface (having gas stream inbound port 2a) of insulating element 1, provide gas reservoir 11.Through hole 2 communicates with the inside of gas reservoir 11.Gas reservoir 11 is formed with: gas inlet 10 is used for generating gas G from one end (its top) to this gas reservoir supplying plasma; And pneumatic outlet 9, be used for the plasma body that (its bottom) forms in its opposite end and generate gas.Insulating element 1 places under the pneumatic outlet 9 of gas reservoir 11.In the present embodiment, the pneumatic outlet 9 of gas reservoir 11 is made up of a plurality of pneumatic outlets 9 corresponding to the position of the through hole 2 of insulating element 1.As a result, the inside of gas reservoir 11 communicates with through hole 2 via pneumatic outlet 9.
Preferably, gas reservoir 11 has the even unit of gas, is used for generating gas G with even flow basically to through hole 2 supplying plasmas.When plasma body generates gas G via gas inlet 10 inflow gas storeies 11, owing to increasing, volumetrical reduced air pressure, thereby generating gas G, plasma body can flow into all through holes 2 with even velocity of flow.As a result, can supply the activatory plasma body equably from all through holes 2 of insulating element 1 and generate gas G, and under the velocity flow profile of improved plasma body generation gas G, can carry out uniform Cement Composite Treated by Plasma.
In addition, preferably, plasma processing apparatus has the scatterer 7 that is used to cool off insulating element 1.In this case, can prevent by the destruction that thermal distortion caused of insulating element 1 such as crackle etc., and the ununiformity that prevents when insulating element 1 local superheating the plasma body that penetrates from through hole 2, uniform surface treatment stably kept thus.
For example, gas reservoir 11 also is allowed to have the function of scatterer 7.In this case, insulating element 1 is formed with scatterer 7 and contacts.In the embodiment shown in the figures, scatterer 7 is made of the end of the pneumatic outlet 9 with gas reservoir 11 and the part integrally formed with described end (sidepiece), and it extends between the top of gas reservoir 11 and bottom.Radiator element 7b is formed on the outside surface of sidepiece, thereby outwards outstanding.On the other hand, heat absorbing sheet 7a is formed on the end not and pneumatic outlet 9 corresponding positions, thereby inner outstanding at gas reservoir 11.
By the formation of this scatterer 7, heat is generated gas G by heat absorbing sheet 7a from plasma body and absorbs, and is transferred to radiator element 7b via end and sidepiece, and finally is dispersed into the outside of device from radiator element 7b.As a result, can prevent that plasma body from generating the increase of the temperature of gas G and insulating element 1.
Above-mentioned scatterer 7 is to use the air cooling type of radiator element 7b.Alternatively, can use the scatterer 7 of water cooling type.In the embodiment shown in Fig. 9 and 10, water coolant is allowed to flow into coolant passage 7c, and each passage is formed on the position between the adjacent pneumatic outlet 9 in the end, with cooling insulating element 1.Fig. 9 represents that scatterer 7 is formed on the situation on the reaction vessel R shown in Fig. 2 A and the 2B.Figure 10 represents that scatterer 7 is formed on another situation on the reaction vessel R shown in Figure 1A and the 1B.In these cases, owing to the end of placing that contacts with insulating element 1 is cooled, thereby can effectively cools off insulating element 1 and prevent that the temperature of insulating element 1 from increasing.
Water coolant also can be used as thermoswitch, is used for the temperature of insulating element 1 is controlled to be the temperature of easy release secondary electron.That is to say,, can discharge secondary electron from insulating element 1 by generate electronics contained among the gas G and ionic influence at the activatory plasma body.The temperature of insulating element 1 is high more, easy more release secondary electron.Yet, consider the damage of the insulating element 1 that causes by thermal expansion, the temperature of insulating element 1 is suitable for until near 100 ℃.
Therefore, preferably by using water coolant the temperature of insulating element 1 to be controlled within 40 to 100 ℃ the scope.Thus, the water coolant that is higher than room temperature by use temperature, the surface temperature of insulating element 1 can increase with the temperature that is higher than room temperature when bringing into use this device, thereby compares with the situation of at room temperature bringing into use this device, can easily discharge secondary electron from insulating element 1.As a result, can increase plasma body by the secondary electron that discharges from insulating element 1 and generate density, to improve the Cement Composite Treated by Plasma effect, such as the effect of correction and cleaning of objects 5.Consider and handle convenience and energy expenditure, the temperature of further preferred water coolant is within 50 to 80 ℃ scope.
Preferably, gas reservoir 11 and scatterer 7 are made by the material with high thermal conductivity.For example, can use copper, stainless steel, aluminium or aluminium nitride (AlN).When gas reservoir 11 and scatterer 7 when making such as the insulating material of aluminium nitride, can be minimized in the influence of the radio-frequency voltage that applies between the electrode, therefore discharge effectively, prevented the loss of the electric power that between electrode, applies simultaneously basically.In addition, realize high cooling efficiency by high thermal conductivity.
In addition, when the temperature by scatterer 7 control insulating elements 1 increases, can prevent that insulating element 1 is subjected to the damage of thermal distortion.In addition, when insulating element 1 local superheating, exist along with plasma body generation density uprises at superheat section, through hole 2 ionic medium bodies generate the uneven trend that becomes.Increase by the temperature that prevents insulating element 1, can prevent the ununiformity that plasma body generates in the through hole 2, thereby can evenly carry out surface treatment.
In addition, when electric heater is set when being used for the thermoswitch of insulating element 1 in scatterer 7, can obtain and above-mentioned similar effect.In this case, preferably, the laying temperature measuring unit is such as thermopair, with the temperature of monitoring scatterer 7 in scatterer 7.Alternatively, amber ear card (Peltier) equipment can be used as scatterer 7.
Preferably, insulating element 1 is connected to scatterer 7, thereby prevents that plasma body from generating the leakage of gas G, and thermal conductivity can not worsen.For example, they can engage by using heat conduction lubricating grease, heat conduction double-sided adhesive tape or containing the material that engages resin.Alternatively, joint can be pushed then each other by mirror polish in the surface of insulating element 1 and scatterer 7.
In addition, preferably, insulating element 1 and scatterer 7 are integrally formed.In this case, can absorb heat effectively from discharge space by scatterer 7.In addition, generate the leakage of gas G owing to prevented plasma body, the uniform temperature that can obtain insulating element 1 distributes, and makes discharge stability.
In order to utilize above-mentioned plasma processing apparatus that object 5 is carried out surface treatment, plasma body process gas G is supplied to gas reservoir 11 via gas inlet 10, flows into the through hole 2 that port 2a is sent to insulating element 1 via pneumatic outlet 9 and gas then.Next, plasma body generates gas G and activates by the discharge that the discharge space between the electrode (3,4) carries out in through hole 2, and penetrates from gas stream outbound port 2b.
In order to generate gas G to through hole 2 supplying plasmas of reaction vessel R via gas reservoir 11, can form the gas supply unit (not shown), it for example is made of gas cylinder, tracheae, mixing tank and pressure valve.In this case, gas cylinder (respectively storing the gaseous constituent that plasma body generates gas G) is connected to gas reservoir 11 by tracheae.At this moment, mixed by mixing tank with required ratio of mixture from the gaseous constituent of gas cylinder supply, the synthetic mixture is pressed valve and sends to pneumatic outlet 9 under required air pressure then.
Preferably, the gas supply unit supply contains rare gas, nitrogen, oxygen and airborne at least a gas, perhaps contains the mixed gas of its two or more gases, is used as plasma body and generates gas G.
Under the situation of using air, can realize the surface correction of object 5 and remove organic materialss from object 5 by Cement Composite Treated by Plasma.Preferably use and contain wetly dry air hardly as air.As rare gas, can use helium, argon, neon or krypton.Consider the ratio of performance to price and discharge stability, preferably use argon.Use the Cement Composite Treated by Plasma of rare gas or nitrogen to provide the surface of object 5 to revise.In addition, use the Cement Composite Treated by Plasma of oxygen that the removal of organic materials from object 5 is provided.In addition, the Cement Composite Treated by Plasma of the mixed gas of use rare gas and oxygen provides the removal of surface correction and organic materials.Reactant gases can add rare gas or nitrogen to such as oxygen and air.The kind of reactant gases can be determined according to the purposes of handling.
Under the situation of adherent organic materials, removal resist, etching organic membrane or surface cleaning LCD or sheet glass on the cleaning of objects 5, preferably use oxidizing gas such as oxygen, air, CO 2And N 2O.In addition, fluoro-gas is such as CF 4, SF 6And NF 3Can be used as reactant gases.Under the situation of the etching of carrying out silicon or resist or ashing, it is effective using fluoro-gas.Under the situation of reducing metal oxide, can use reducing gas such as hydrogen or ammonia.
Plasma body generates gas G and activates by the discharge that the discharge space between the electrode 3,4 carries out in through hole 2.When between electrode 3,4, applying high-voltage, produce electric field at discharge space by electrification source 6.By the generation of electric field, in discharge space, obtain geseous discharge with near the air pressure normal atmosphere or the normal atmosphere.Plasma body generates gas G and activates by geseous discharge, and allows to become plasma body in such as atomic group and ionic discharge space producing the activation particle.
At this moment, preferably, generate gas G to through hole 2 supplying plasmas under such air pressure, this air pressure is enough to provide required flow at time per unit, and the loss influence that is not stressed.In other words, preferably supplying plasma generates gas G like this, makes that the air pressure in the gas reservoir 11 is atmospheric gas pressure or near the air pressure (being preferably 100 to 300kpa) of atmospheric gas pressure.
The voltage (in order to activate the plasma body generation gas G that is fed to through hole 2 from gas stream inbound port 2a) that applies between electrode 3,4 by power supply 6 can be confirmed as having suitable waveform, such as AC wave shape, pulse waveform or its overlaid waveforms.Especially, preferably use power supply 6, it can apply the voltage of the pulse type waveform with resting stage between electrode 3,4.In this case, can in each through hole 2, stably evenly discharge expeditiously, therefore improve processing efficiency.In addition, owing to effectively prevented the appearance of the non-discharge area in the through hole 2, can in each through hole, keep uniform discharge.As keeping the inhomogeneity reason of discharge,, recover by applying voltage once more betwixt in the past in resting stage then even be sure of that the discharge condition in each through hole was cancelled once in resting stage when discharge in the part of through hole 2 disappears accidentally.
Each Figure 11,12 and 13 expressions have the waveform of the pulse-like voltage of resting stage.That is, Figure 11 represents the square wave pulse, wherein alternately repeats square topped pulse and resting stage.Figure 12 represents wave of oscillation pulse, wherein repeats with required circulation one group of positive rise, damping period and resting stage.Figure 13 represents symmetrical pulse, and wherein one group of positive pulse voltage output in a wavelength, resting stage, negative pulse voltage output and resting stage repeat as a circulation, as the situation of square wave pulse.According to the symmetrical pulse waveform of Figure 13, discharge condition approaches by utilizing the discharge condition of square wave pulse gained.In addition, under low relatively voltage, can switch, and can use transformer to be used for pressurization.Therefore, compare, can simplify the structure of power supply 6 with the situation of utilizing the square wave pulse.According to the internal diameter of through hole 2 and the distance between the electrode 3,4, determine between electrode 3,4, to apply, in order to carry out the voltage of geseous discharge continuously at discharge space.For example, this voltage can be confirmed as 0.05 to 30kV scope.
In addition, preferably use pulse type waveform power supply, be used between electrode 3,4, applying voltage with 1H to 200kHz frequency.When the repetition rate of the voltage waveform that applies between electrode 3,4 is lower than 1Hz, exists owing to the reduction of the discharge stability in the discharge space and can not effectively carry out the surface-treated worry.On the other hand, when frequency surpassed 200kHz, will become was difficult to discharge equably in through hole 2, because the temperature of geseous discharge (plasma body) rolls up in discharge space, and discharge concentrates on the part of through hole 2 easily.In the said frequencies scope, the discharge of carrying out between the electrode 3,4 is stabilized, thereby further improves processing efficiency.In addition, generate this excessive increase of temperature of gas G by preventing plasma body, and can avoid the appearance of the cause thermal damage of object 5.And the part place that concentrates on through hole 2 by preventing to discharge can carry out uniform surface treatment.
In addition,, preferably use pulse type waveform power supply, be used between electrode 3,4, applying the pulse-like voltage of voltage waveform with 0.01 to 80% dutycycle as power supply 6.In this case, owing to, can further improve processing efficiency to obtain stable discharge expeditiously.Square wave duty of ratio as shown in figure 11 can be by determining like this: with the positive rise of a pulse and the width between the negative edge divided by at the positive rise of this pulse with through the width between the positive rise of next pulse of resting stage.In addition, under the situation of using the wave of oscillation pulse shown in Figure 12 and 13, dutycycle can be by determining like this: with the width between the waveform of the negative edge of the positive rise of first pulse and second pulse divided by the cycle that comprises from the positive rise of first pulse to oscillation damping phase and resting stage.
In the present invention, also be preferably electrode 3,4 and be mid point (neutral) ground connection.In this case, can reduce the electromotive force between activatory plasma body generation gas G and the object 5, and can prevent to generate the appearance of gas G to the arc-over of object 5 from the activatory plasma body.In other words, owing to applying voltage under the condition that all is in quick condition at two electrodes 3,4, therefore can reduce the electromotive force between activatory plasma body generation gas G (plasma jet) and the object 5 with respect to ground.As a result, can prevent to cause the arc-over of the cause thermal damage of object 5 to occur.
For example, shown in Figure 14 A, be applied in the top electrode 4 that is connected to power supply 6 as 13kV and during lower electrode 3 ground connection (0kV), between two electrodes, can obtain the potential difference of 13kV.In this case, generate the potential difference that occurs several at least kV between gas G and the object 5 at the activatory plasma body, thereby can produce arc-over Ar.In use put under the situation of ground connection, when the electromotive force of top electrode 4 is+6.5kV, and the electromotive force of lower electrode 3 be-situation of 6.5kV under, as shown in Figure 14B, between two electrodes, can obtain the potential difference of 13kV.In this case, the potential difference that generates between gas G and the object 5 at the activatory plasma body approaches 0.That is to say, when using neutral earthing, can reduce the potential difference between activatory plasma body generation gas G and the object 5, and and irrelevant as the same electrical potential difference between electrode 3,4 under the situation of not using neutral earthing.As a result, can prevent to generate the appearance of gas G to the arc-over of object 5 from the activatory plasma body.
Subsequently, containing the plasma body generation gas G that activates particle penetrates continuously from gas stream outbound port 2b.Therefore, can generate gas G, carry out surface treatment by spraying the activatory plasma body at least a portion object 5 below placing gas stream outbound port 2b.
When below object 5 is placed in gas stream outbound port 2b, can transport object such as cylinder and rotary conveyor by delivery unit.In this case, a plurality of objects 5 can be handled by continuous surfaces, these a plurality of objects just are being transported to the position below the gas stream outbound port 2b successively by delivery unit.
In addition, the distance between gas stream outbound port 2b and the object 5 can generate the kind of gas G according to the flow velocity, plasma body that plasma body generates gas G, the kind and the surface-treated purposes of object 5 suitably determined.For example, this distance can be determined to be in 1 to 30mm scope.
In above-mentioned surface treatment, produce geseous discharge at each through hole 2, and on object 5, spray by geseous discharge activatory plasma body generation gas G through through hole 2.Therefore, obtain big area and uniform plasma body expeditiously, handle thereby can carry out wide area surface equably to object 5 with the airshed that reduces.
Thus, according to the present invention, can increase the processing area of primary treatment.This has improved processing efficiency.In addition, when the object 5 that is being transported was carried out surface treatment, object 5 can be exposed to the activatory plasma body and generate the time period that gas G one prolongs.Therefore, can effectively implement surface treatment with the airshed that reduces.In other words, can not increase airshed, improve the surface treatment ability by prolonging the duration of contact between activation particle and the object 5.As a result, can prevent that the operating cost of surface processing device from increasing, so that the good ratio of performance to price to be provided.
In the above-described embodiments, by using the insulating element 1 that in plan view, has rectangular shape, obtain the rectangle processing area.Can the appropriate change processing area according to object 5.For example,, perhaps revise the arrangement of through hole 2, can obtain required processing area by changing the size or the shape of insulating element 1.
In addition, form reaction vessel R by making up a plurality of insulating elements 1, with further increase processing area.In addition, the arranged in patterns that insulating element 1 can be required is the specific region for object 5 only to carry out surface treatment.And, when setting and object 5 have the insulating element 1 of different distance, can handle simultaneously need the crust zone of handling and the zone that needs pressure release surface to handle of object 5.Therefore, these are as the treatment effect setting device.
For example, shown in Figure 15 A, can form reaction vessel R by arranging a plurality of insulating elements 1.Alternatively, shown in Figure 15 B, can form reaction vessel R by insulating element 1 is arranged in matrix pattern.In these cases, can realize the further increase of processing area.In addition, when insulating element 1 is aligned to required pattern, can be to carrying out surface treatment with the corresponding treatment zone of the arrangement of insulating element 1.In this case, can only carry out surface treatment to the specific region of object 5.For example, shown in Figure 15 C, when insulating element 1 is arranged in L shaped pattern with formation reaction vessel R, can carry out surface treatment to the L shaped zone of object 5.And, shown in Figure 15 D, can form reaction vessel R by arranging like this insulating element 1, make distance between an insulating element and the object 5 be different from the distance between another insulating element and the object 5.In this case,, compare, obtain relatively low treatment effect with another treatment zone being separated by on the treatment zone of object 5 of big distance with insulating element 1.On the contrary,, compare, obtain relative high processing effect with another treatment zone being separated by on the treatment zone of object 5 of small distance with insulating element 1.Thus, according to pending object 5, can form the treatment zone that higher treatment effect is provided and provide the lower to manage the treatment zone of effect according to purpose.
In addition, when forming reaction vessel R,, can easily carry out various modifications, such as the size that changes treatment zone and shape or control processing horizontal by quantity or its arrangement of simple change insulating element 1 by a plurality of insulating elements 1 of combination.
Under the situation of combined insulation parts 1, can in each insulating element 1, form scatterer 7 and gas reservoir 11.Alternatively, form single right scatterer 7 and gas reservoir 11, with to insulating element 1 simultaneously supplying plasma generate gas G or from insulating element 1 distribute heat simultaneously.
Forming under the situation of reaction vessel R by combined insulation parts 1, preferably supplying electric power from same power source 6 to insulating element 1.For example, shown in Figure 16 A, when utilization comprises the unit A of single insulating element 1A and electric power source 6A and comprise the unit B formation reaction vessel R of single insulating element 1B and electric power source 6B, by utilizing power supply 6A between the electrode 3,4 of the insulating element 1A of unit A, to apply high-frequency voltage, and by utilizing power supply 6B between the electrode 3,4 of the insulating element 1B of unit B, to apply high-frequency voltage.Yet, between high-frequency voltage that produces by the power supply 6A of unit A and the high-frequency voltage that produces by the power supply 6B of unit B, be difficult to realize synchronously.For example, shown in Figure 16 B, phase-shifted often appears.Thereby have such worry, because the interference between the voltage that power supply 6A and 6B produce can not be supplied the voltage with required waveform.
In the present invention, as shown in figure 17, preferably supply electric power such as high frequency electric source to insulating element 1 from same power supplies 6.In Figure 17, a plurality of transformer 32a, 32b, 32c are electrically connected on single power supply 6 by parallel connection, and a plurality of insulating element 1 is electrically connected on each transformer 32a, 32b, 32c by parallel connection.According to this reaction vessel R, can prevent between the voltage that applies to insulating element 1, phase-shifted to occur.That is to say, can prevent the interference between the voltage that applies to insulating element 1, thereby supply has the voltage of required waveform.
In the present invention, when many counter electrode 3,4 in through hole 2 when being parallel to direction that plasma body generates the flow direction of gas G and arranging, can in discharge space, produce hyperpycnal flow and discharge.In this case, can produce the electric power that discharge is applied, improve the surface treatment ability by increasing to activate Particle Density in the gas and do not increase to.In addition,, improve the surface treatment ability, therefore can prevent the handled object prolongation in 5 needed treatment times owing to can generate under the condition of supply time of air-flow of gas G not prolonging to object 5 supply activatory plasma bodys.As a result, there is the advantage that the productivity reduction can not occur.
In addition, because the activation particle density that the plasma body that sprays generates among the gas G is increased,, therefore do not need to shorten the distance between object 5 and the gas outflow port 2b on object 5 to improve the surface treatment ability.Therefore, can minimize, thereby prevent that object is subjected to the damage of arc-over from the occurrence rate of discharge space towards the arc-over of object 5.In addition, need between gas stream outbound port 2b and object 5, wire netting be set to prevent arc-over.Therefore, can not hinder the air-flow that plasma body generates gas G owing to the existence of wire netting, thereby can stably keep the surface treatment ability.And can eliminate such problem: the Corrosion of Metallic Materials by electrode 3,4 causes oxide compound (rust), and it pollutes object 5.
The present invention can be used for various object surfaces and handles.Especially, this surface treatment is applicable to the glass material (such as the glass material that is used for liquid crystal, plasma display and organic electric lighting displaying device) that is used for various flat-panel monitors, and printed wiring board or various resin molding are such as polyimide film.These objects 5 are being carried out having these advantages under the surface-treated situation: clean impurity such as organic materials, remove or the etching resist, improve the adhesivity of organic membrane, reducing metal oxide forms film, pre-treatment before water cleans is electroplated or is applied, and other surfaces are revised.Such as the glass material that is used for liquid crystal,, need big area to handle uniformly about the glass material that is used for flat-panel monitor because pending processing area increases continuously.Therefore since can flexible design the processing area of expection, expect that plasma processing apparatus of the present invention and method of plasma processing are preferably used for during these use.
Glass material is being carried out under the surface-treated situation, the glass material with transparency electrode, TFT (thin film transistor) liquid crystal or color filter (CF) of being made by indium tin oxide (ITO) is being carried out surface treatment.Resin molding is being carried out under the surface-treated situation, can handle the resin molding continuous surface that transports in (roll-to-roll) mode of rolling.
Example
According to example in detail the present invention.
(example 1)
By being printed on first plate (thickness: form conducting film on surface 0.4mm), on this conducting film, place the second plate (thickness: 1.4mm) then.In addition, by forming conducting film on the surface that is printed on second plate, on this conducting film, place the 3rd plate (thickness: 1.4mm) then.In this embodiment, obtain each first to the 3rd plate by the forming materials that will contain alumina powder for plate shape.Each plate has a plurality of holes, and each hole has the diameter of 1mm.These plates are placed in the layer, make that the aperture position of each plate is corresponding mutually.Form conducting film by printing tungsten layer.A plurality of holes 8 (diameter that all has 3mm is greater than the hole of plate) are formed in the conducting film, make each holes of these plates all place each hole of conducting film.Thus obtained lamination is sintered, obtaining reaction vessel R, shown in the viewgraph of cross-section of the plan view of Fig. 2 A and Fig. 2 B.
In this embodiment, the insulating element 1 of reaction vessel has the thickness of 3.2mm, and 55 through holes 2 that all have the 1mm diameter.These 55 through holes 2 are arranged in the plane domain of 45 * 22mm, make between the adjacent through-holes 2 to be 4.5mm at interval.In addition, form electrode 3,4, make each through hole 2 be placed in each hole 8 of electrode 3,4 by the upper and lower tungsten conductive layer that all has 30 μ m thickness.Distance on (that is, between the discharge plane) between the upper and lower electrode 3,4 is 1.4mm.Electrode (3,4) with hole 8 is not exposed to the inside of through hole 2.By using the insulating material (dielectric materials) identical with insulating element 1, the insulating coating that will have 1mm thickness is formed on the internal surface of hole 8 of electrode 3,4.Top electrode 4 is connected in electric power source 6, and lower electrode 3 ground connection.
As shown in Figure 9, the gas reservoir 11 with copper radiator 7 is placed on the top of insulating element 1.Plasma body generates gas G and introduces from the gas inlet 10 that is formed at gas reservoir 11 tops, and is allowed to flow in the through hole 2 of insulating element 1.Recirculated cooling water among the flow passage 7c in being formed at scatterer 7, overheated to prevent insulating element 1.
(example 2)
By being printed on first plate (thickness: form conducting film on surface 0.7mm), on this conducting film, place the second plate (thickness: 1.5mm) then.Form each first and second plate by the forming materials that will contain aluminum oxide for plate shape, as the situation of example 1.Each first and second plate has a plurality of slit-shaped holes, all has the length of width and the 22mm of 1mm in its plan view.These plates are placed in the layer, make that the position of slit-shaped hole of each plate is corresponding mutually.Form conducting film by printing tungsten layer, as the situation of example 1.In this embodiment, each conducting film all forms comb pattern.Thus obtained lamination is sintered, to obtain reaction vessel R with the structure shown in Fig. 3 A and 3B.
In this embodiment, the insulating element 1 of reaction vessel has the thickness of 2.2mm, and 11 slit-shaped through holes 2 that all have 1mm width and 22mm length.These 11 through holes 2 are arranged in the plane domain of 45 * 22mm, make between the adjacent through-holes 2 to be 3.5mm at interval.In addition, electrode 3,4 thickness with 100 μ m are formed on the same level of insulating element 1, make electrode 4 be positioned at a side of each through hole 2, and electrode 3 is positioned at a relative side of each through hole.The distance of (promptly discharging between the plane) is 2mm between the electrode 3,4.In this embodiment, electrode 3,4 is not exposed to the inside of through hole 2.By using the insulating material (dielectric materials) identical with insulating element 1, formation has the insulating coating of 0.5mm thickness on the side surface of electrode 3,4, thereby flushes with the internal surface of through hole 2.Electrode 4 is connected in electric power source 6, and electrode 3 ground connection.
Shown in Fig. 3 A and 3B, the gas reservoir 11 with scatterer 7 of being made by aluminium nitride places the top of insulating element 1.Plasma body generates gas G and is introduced into from the gas inlet 10 on the top that is formed at gas reservoir 11, and is allowed to flow into the through hole 2 of insulating element 1.Recirculated cooling water among the flow passage 7c in being formed at scatterer 7, overheated to prevent insulating element 1.
(example 3)
The device with example 1 is identical basically for the plasma processing apparatus of Shi Yonging in the present embodiment, and except the hole 8 of electrode 3,4 and the diameter of through hole 2 are 1mm, and the internal surface of the hole 8 of electrode 3,4 is exposed to the inside of through hole 2, as shown in figure 10.
(comparative example 1)
Use has the plasma processing apparatus of cross section as shown in figure 18.The reaction vessel 21 of this device is configured to rectangular tubular, and is made by the silica glass with 1mm thickness.Discharge slit (slit) width is 1mm, and inside (width) size that it is defined as the discharge generation part 22 that is provided with in the reaction vessel 21 equals to be formed at the gas stream inbound port 22a of opposite end of reaction vessel 21 and the slit width of gas outflow port 22b.In addition, the length scale of reaction vessel 21 is 45mm.The bottom of electrode 23,24 is positioned at the upstream side 5mm place of gas stream outbound port 22b.
Pair of electrodes 23,24 is made of copper, and forms gold-plated thereon.Electrode 23,24 is provided with like this, makes reaction vessel 21 place therebetween.Recirculated cooling water in the flow passage 27 in being formed at electrode 23,24 is with cooling electrode.Left electrodes 23 is connected to electric power source 6, and right electrodes 24 ground connection.
(assessment 1)
Use aforesaid each plasma treatment appts, apply voltage (6kHz, 13kV, 50% dutycycle) by utilizing electric power source 6 between electrode 3,4 (23,24), this voltage has the pulse type waveform of resting stage as shown in figure 11; Under atmospheric gas pressure, plasma body generated simultaneously gas G (10 liters/minute nitrogen and 0.02 liter/minute oxygen) and introduce reaction vessel; And will contain air-flow that the plasma body that activates particle generates gas and be ejected on the object that transports with the speed of 100mm/s, implement surface treatment.As object, be used for the rare glass of liquid crystal.Distance between this object and gas outflow port 2b (22b) is 5mm.The water contact angle of the rare glass of measuring before surface treatment is 68 degree.
For each example 1 to 3 and comparative example 1, the water contact angle of Measuring Object 5 after surface treatment.The result is shown in the table 1.As shown in table 1, in example 1 and 2, observe the abundant minimizing of water contact angle.Especially, water contact angle significantly reduces in example 1.On the contrary, water contact angle is difficult to change in comparative example 1.Thus, these presentation of results examples 1 and 2 can provide frequently and want high surface treatment effect than example 1.
Table 1
Water contact angle
Example 1 ??8.3°
Example 2 ??9.8°
Comparative example 1 ??65.0°
(assessment 2)
For each example 1,2 and comparative example 1, has the voltage (6kHz of the pulse type waveform of resting stage as shown in figure 12 except between electrode 3,4 (23,24), applying, 13kV, 5% dutycycle), under the condition identical, object 5 is carried out surface treatment with assessment 1.In this assessment, repeat surface treatment, water contact angle becomes 10 degree or littler on object 5.
Until object 5 on water contact angle become 10 the degree or littler institute multiple surface-treated number of times shown in the table 2.As shown in table 2, to handle by in example 1 and 2, carrying out one-time surface, water contact angle becomes less than 10 degree.On the other hand, in comparative example 1, repeat surface treatment 7 times, to obtain water contact angle less than 10 degree.These presentation of results examples 1 and 2 can provide the processing efficiency that is higher than comparative example 1.
Table 2
Number of processes
Example 1 ??1
Example 2 ??1
Comparative example 1 ??7
(assessment 3)
About example 3, has the voltage (6kHz of the pulse type waveform of resting stage as shown in figure 11 by utilizing electric power source 6 between electrode 3,4, to apply, 50% dutycycle), simultaneously introduce plasma body and generate gas (10 liters/minute nitrogen and 0.02 liter/minute oxygen) at atmospheric gas pressure downhill reaction container, and will contain air-flow that the plasma body that activates particle generates gas and be ejected on the object that transports with the speed of 100mm/s, implement surface treatment.In this assessment, carry out surface treatment for voltage 8kV, 9kV and the 10kV that each applied.As object, can use the rare glass that is used for liquid crystal.Distance between object 5 and gas outflow port 2b is 5mm.The water contact angle rare on glass that recorded before surface treatment is 68 degree.
Water contact angle on the object 5 that records after each surface treatment is shown in the table 3.As shown in table 3, in example 3, can be observed fully reducing of water contact angle.Thus, example 3 can provide high processing efficient.In addition, the voltage by increase applies can further reduce water contact angle.Yet when the voltage that applies was 10kV, it is unstable that discharge becomes, and be not suitable for surface treatment.
Table 3
The voltage that applies Water contact angle
??8kV ??22.5°
??9kV ??15.3°
??10kV Non stationary discharge
(assessment 4)
About example 1, has the voltage (12kHz of the pulse type waveform of resting stage as shown in figure 13 by utilizing neutral earthing power supply 6A, 6B between electrode 3,4, to apply, 30% dutycycle), simultaneously introduce plasma body and generate gas G (10 liters/minute nitrogen and 0.1 liter/minute dry air) at atmospheric gas pressure downhill reaction container, and will contain air-flow that the plasma body that activates particle generates gas G and be ejected on the object that transports with the speed of 50mm/s, implement surface treatment.As object 5, can use resin molding or printed circuit board (PCB).Distance between object 5 and the gas outflow port 2b is 5mm.
After Cement Composite Treated by Plasma,, and measure adhesion strength at the enterprising electroplating of the treat surface of object 5.The result is shown in the table 4.As shown in table 4, utilize the Cement Composite Treated by Plasma of the device of example 1 that such effect is provided: significantly increase the adhesion strength of electroplating film on the object 5, improve surface treatment efficient, and the reliability of improving electroplating film.
Table 4
Adhesion strength
Non-processor ??0.006N/mm 2
Example 1 ??0.070N/mm 2
Industrial applicability
As mentioned above, according to plasma processing apparatus of the present invention, in each through hole, carry out gas discharge, and the plasma that contains the activation that activates particle that is produced by this gas discharge from through hole to the object supply generates the air-flow of gas. Therefore, can effectively carry out uniform plasma surface treatment with the larger area that little throughput is treated handled object.
Carry out when transporting object in the surface-treated situation, the plasma that object can be exposed to activation generates the time period that prolongs in the air-flow of gas, and utilizes less gas flow effectively to carry out surface treatment. Thus, do not increase throughput by prolonging object with the time of contact of activation particle, can improve surface treatment efficient, and prevent the increase of the operating cost of surface processing device.
And, reaction vessel can be easily formed by making up a plurality of insulating elements, and by changing arrangement and the quantity of insulating element, the design freedom of device can be increased. Therefore, can provide suitable plasma processing apparatus with size according to the shape of object.
Thus, plasma processing apparatus of the present invention has the ability of effectively carrying out the Large-Area-Uniform Cement Composite Treated by Plasma, because except conventional object to having the pending object of larger area, such as the glass that is used for liquid crystal panel, can suitably carry out surface treatment, thereby expection can be used in the various application.

Claims (28)

1. plasma processing apparatus, be used for generating gas by the discharge activate plasma, and the activatory plasma body is generated gas injection to object, described device has the reaction vessel that is formed by insulating element, and this reaction vessel comprises: a plurality of through holes, each through hole has the inlet opening that is used for plasma body generation gas at the one end, and has the outflow opening that is used for activatory plasma body generation gas in its opposite end; And be used for the electrode that discharges at each described through hole.
2. plasma processing apparatus as claimed in claim 1, wherein said insulating element is configured to plate shape.
3. plasma processing apparatus as claimed in claim 1, wherein said electrode is embedded in the described insulating element.
4. plasma processing apparatus as claimed in claim 1, wherein said electrode is exposed to the inside of described through hole.
5. plasma processing apparatus as claimed in claim 1, wherein said electrode is not exposed to the inside of described through hole.
6. plasma processing apparatus as claimed in claim 1, wherein said electrode is set up, and makes in described through hole to produce line of electric flux generating on the direction that gas flow direction intersects with this plasma body.
7. plasma processing apparatus as claimed in claim 1, wherein said electrode is set up, and makes to produce line of electric flux on the direction parallel with this plasma body generation gas flow direction in described through hole.
8. plasma processing apparatus as claimed in claim 1, the interval between the wherein said electrode is in 0.01 to 5mm scope.
9. plasma processing apparatus as claimed in claim 1, the opening of wherein said through hole forms the circle with 0.01 to 15mm diameter.
10. plasma processing apparatus as claimed in claim 1, the opening of wherein said through hole form the slit shape with 0.01 to 15mm minor face size.
11. plasma processing apparatus as claimed in claim 1, wherein said electrode are formed in the layer in the described insulating element, and have hole in the position corresponding to described through hole, and wherein do not have the vacancy part between the adjacent pores in described electrode.
12. plasma processing apparatus as claimed in claim 1, wherein said electrode is formed in the layer, with towards described insulating element, and it is outwards outstanding with respect to the peripheral portion of another electrode that is positioned at this air flow line upstream side to be positioned at the peripheral portion of a described electrode in air flow line downstream side.
13. plasma processing apparatus as claimed in claim 1, wherein said insulating element is made by pottery.
14. plasma processing apparatus as claimed in claim 13, wherein said insulating element is made by aluminum oxide.
15. plasma processing apparatus as claimed in claim 1 comprises electric power source, is used for applying between described electrode the pulse-like voltage with resting stage.
16. plasma processing apparatus as claimed in claim 1 comprises electric power source, is used for applying between described electrode the voltage with 1Hz to 200kHz frequency.
17. plasma processing apparatus as claimed in claim 1 comprises electric power source, is used for applying between described electrode the pulse-like voltage with 0.01 to 80% dutycycle.
18. plasma processing apparatus as claimed in claim 1, wherein said electrode neutral earthing.
19. plasma processing apparatus as claimed in claim 1, comprise gas supply device, it is configured to and will contains gas at least a in rare gas element, nitrogen, oxygen and the air, or contain two or more mixed gas among them, be fed in the described reaction vessel, generate gas as plasma body.
20. plasma processing apparatus as claimed in claim 1 comprises the scatterer that is used to cool off described insulating element.
21. plasma processing apparatus as claimed in claim 1 comprises thermoswitch, it is configured to the temperature of described insulating element is controlled at the temperature of launching secondary electron easily.
22. plasma processing apparatus as claimed in claim 1 comprises the gas uniform device, it is configured to even velocity of flow plasma body to be generated gas and is fed in all described through holes.
23. plasma processing apparatus as claimed in claim 1, wherein said reaction vessel forms by making up a plurality of insulating elements.
24. a manufacturing is applicable to the method for the described reaction vessel of the described plasma processing apparatus of claim 1, described method comprises the steps:
Between the plate that has a plurality of openings and form, place the conducting film that forms by electro-conductive material, make that the opening of described plate is corresponding mutually by insulating material; And
The global formation that synthesizes lamination, thus described insulating element, electrode and described through hole provided by the opening of described plate, conducting film and described plate respectively.
25. a method of plasma processing that uses the described plasma processing apparatus of claim 1, described method comprises the steps:
By in described through hole, discharging to described electrode application voltage, make this plasma body generation gas flow to its other end simultaneously from an end of described through hole, in described through hole, produce plasma body thus and generate gas with activate plasma; And
Spray activatory plasma body generation gas from the other end of described through hole in object surfaces.
26. method of plasma processing as claimed in claim 25, wherein this object comprises glass material, printed circuit board (PCB) and the resin molding that is used for flat-panel monitor.
27. a plasma processing apparatus comprises:
The pair of electrodes plate has a plurality of through holes;
Insulcrete has a plurality of through holes, and this insulcrete is arranged between the described battery lead plate, makes the lead to the hole site of described battery lead plate corresponding to the lead to the hole site of described insulcrete;
Gas supply device is configured to that plasma body is generated gas and is fed in a plurality of discharge spaces, and described discharge space is formed by the through hole of described battery lead plate and the through hole of described insulcrete; And
Voltage bringing device is configured to apply voltage between described battery lead plate, to generate the plasma body that plasma body generates gas simultaneously in described discharge space.
28. a plasma processing apparatus comprises: tubular vessel has pair of electrodes and is arranged at insulcrete between the described electrode; Gas supply device is configured to generate gas from an end supplying plasma of described tubular vessel; And voltage bringing device, be configured to applying voltage between the described electrode in described tubular vessel, to generate the plasma body that this plasma body generates gas, utilize the plasma body that ejects from the other end of described tubular vessel that object is carried out surface treatment thus
Wherein, described electrode is provided by the pair of electrodes plate with a plurality of through holes, described insulcrete has a plurality of through holes, described tubular vessel has a plurality of discharge spaces that the through hole by the through hole of described battery lead plate and described insulcrete forms, and the plasma body that plasma body generates gas generates in described discharge space simultaneously by apply voltage between described battery lead plate, and ejects from the other end of described tubular vessel.
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