CN1768161A - Thin film forming apparatus and method for forming thin film - Google Patents
Thin film forming apparatus and method for forming thin film Download PDFInfo
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- CN1768161A CN1768161A CN 200480008610 CN200480008610A CN1768161A CN 1768161 A CN1768161 A CN 1768161A CN 200480008610 CN200480008610 CN 200480008610 CN 200480008610 A CN200480008610 A CN 200480008610A CN 1768161 A CN1768161 A CN 1768161A
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Abstract
A thin film forming apparatus comprising first and second electrodes and a gas supply portion is disclosed. Discharge surfaces of the first and second electrodes are opposite to each other so as to form a discharge space where a high frequency electric field is generated. The gas supply portion supplies a gas containing a thin film forming gas into the discharge space so that the gas is activated by the high frequency electric field and a thin film is formed on a base material by exposing the base material to the activated gas. The thin film forming apparatus also comprises a film carrying mechanism for carrying a cleaning film which prevents at least one of the first and second electrodes from being exposed to the activated gas. The film carrying mechanism carries the cleaning film so that the film is in close contact with the discharge surface of at least one of the first and second electrodes and at least a part of other surface continued to the discharge surface.
Description
Technical field
The present invention relates to film forming device and film formation method, particularly sharp atmos plasma discharge process, film forming film forming device and film formation method on substrate.
Background technology
Now, in various goods such as LS1, semi-conductor, indicating meter, magnetic recording system, photoelectric transformer, solar cell, Josephson device, photo-thermal umformer, make the material that high performance film is set on substrate.In film forming method on substrate, for example, have: be the film by wet method of representative with the coating and be the dry type system embrane method of representative with sputtering method, vacuum vapour deposition, ion plating method etc., perhaps, the atmos plasma film-forming method of sharp atmos plasma discharge process etc.Yet in recent years, special hope allows to keep high productivity can form the atmos plasma film-forming method of high-quality thin film again.
The atmos plasma film-forming method with the state of placement substrate between electrode of opposite, is supplied with film and is formed gas and apply electric field at two electrodes.Thus, plasma discharging takes place, exposure of substrates is formed film in plasma discharging.Therefore, owing to produce plasma discharging,, just can not evenly form film if the discharge face of electrode is contaminated.As can prevent this pollution, can effective film forming film forming device, for example have the spy to open the film forming device described in the 2000-212753 communique.In this film forming device device, have: with respect to two electrodes; The high voltage pulse power supply that adds pulsed electrical field at these two electrodes; Discharge face with two electrodes is adjacent to the film conveyer that transports substrate respectively; Between electrode, supply with the film formation gas supply part that film forms gas.And this film forming device is supplied with film and is formed after the gas between electrode, by adding pulsed electrical field generation plasma discharging, with the substrate of two electrode securements on form film.In a word, when plasma discharging took place, the discharge face of two electrodes was covered by substrate all the time, thereby, prevent that discharge face from polluting.
Yet, research according to present inventors, promptly use the discharge face of a substrate coated electrode, as shown in figure 13, because the plasma space h of generation plasma discharging overflows from discharge face 101a, the 102a of electrode 101,102, so substrate 103,104 enters plasma space h with before discharge face 101a, 102a contact with no bearing state, excessively and the anxious poly-heat affecting that is subjected to plasma discharging.Like this, base material 103,104 shrinks, and wrinkle and distortion take place, and forms uneven film.
Summary of the invention
Problem of the present invention provides the form of film device and the form of film method that can form high-quality film.
In order to solve above-mentioned problem, film forming device of the present invention has: first electrode and second electrode, and its mutual discharge face forms discharge space relatively, and in above-mentioned discharge space high-frequency electric field takes place; Gas supply part, it is supplied with to above-mentioned discharge space and contains the gas that film forms gas so that this gas is activated by high-frequency electric field, and exposure of substrates in the above-mentioned gas that is activated, on aforesaid substrate, to form film; The film conveyer, it is used for preventing that at least one side of above-mentioned first electrode and above-mentioned second electrode is exposed to the purification membrane of above-mentioned activated gas, with at least one side's of above-mentioned first electrode and above-mentioned second electrode discharge face and in succession at least a portion on the surface beyond the above-mentioned discharge face of above-mentioned discharge face be adjacent to and transport.
In addition, film formation method of the present invention, supply with to the discharge space that constitutes by relative first electrode of mutual discharge face and second electrode from gas supply part and to contain the gas that film forms gas, by activating above-mentioned gas at above-mentioned discharge space generation high-frequency electric field, and exposure of substrates in above-mentioned activated gas and on aforesaid substrate, form film; In said process, at least one side who is used for preventing above-mentioned first electrode and above-mentioned second electrode is exposed to the purification membrane of above-mentioned activated gas, is adjacent to and transports with at least one side's of above-mentioned first electrode and above-mentioned second electrode discharge face and at least a portion of connecting the surface beyond the above-mentioned discharge face of above-mentioned discharge face.
Membrane according to the invention forms device and film formation method, since purification membrane at least one side's of first electrode and second electrode discharge face be adjacent in the discharge face of above-mentioned discharge face surface in addition in succession and transport, thereby, at least one side of first electrode and second electrode is not exposed in the activated gas, can prevent that the discharge face of first electrode and second electrode from polluting.
In addition, transporting purification membrane by the film conveyer, thereby, can change the purification membrane of at least one side's who is closely attached on first electrode and second electrode discharge face and new purification membrane continuously.
At this, wrinkle or distortion take place on the purification membrane of discharge face if be positioned at, the homogeneity the plasma space in will disorder, forms uneven film.The reason that this wrinkle and distortion take place, identical with the occasion of aforesaid substrate, owing to enter the plasma space that plasma discharging takes place, be influenced by heat and cause contraction with no bearing state.Yet,,, enter the plasma space with state by the surface bearing beyond the above-mentioned discharge face because purification membrane is adjacent at discharge face with in succession on the surface beyond the discharge face of above-mentioned discharge face as above-mentioned.Like this,, also can keep smooth, therefore, can prevent that wrinkle and distortion from taking place even purification membrane is influenced by heat.Thereby, can keep the homogeneity in the plasma space, can form high-quality film.
And purification membrane is closely attached at least one side's of first electrode and second electrode discharge face, thereby, do not make system film gas flow at discharge space, only during mobile discharge gas, can protect at least one side of first electrode and second electrode.
Like this, purification membrane prevents that discharge face from polluting, and protects discharge face simultaneously, thereby, can steady in a long-termly form film.
For example, among pair of electrodes relative to each other, with with the electrode of system film substrate contacts as first electrode, when being second electrode with the opposing party's electrode of opposite, as film forming device of the present invention, above-mentioned film transporter also can above-mentioned purification membrane be adjacent to the discharge face of above-mentioned second electrode and in succession at least a portion on the surface beyond the above-mentioned discharge face of above-mentioned discharge face transport.
On the other hand, in film formation method of the present invention, also can above-mentioned purification membrane be adjacent to the discharge face of above-mentioned second electrode and in succession at least a portion on the surface beyond the above-mentioned discharge face of above-mentioned discharge face transport.
Like this, the discharge face of the purification membrane and second electrode is adjacent to, thereby, can reliably prevent the gas contamination that the discharge face of second electrode is activated.If do not pollute on the discharge face of second electrode, muddiness do not take place on substrate can be made into high-quality film.
In addition, in film forming device of the present invention, above-mentioned first electrode and above-mentioned second electrode also can make high-frequency electric field takes place in the above-mentioned discharge space at normal atmosphere or near under the atmospheric pressure.
On the other hand, in film formation method of the present invention, also can at normal atmosphere or near under the atmospheric pressure, make high-frequency electric field takes place in the above-mentioned discharge space by above-mentioned first electrode and above-mentioned second electrode.
Like this, can be at normal atmosphere or near making film under the atmospheric pressure, thereby, and compare in the occasion of vacuum system film, can make film at a high speed, simultaneously, can continuous production.And, the also unnecessary device that is used to vacuumize etc., so, installation cost can be reduced.
In addition, in film forming device of the present invention,, the heater block of the above-mentioned purification membrane of heating can be set with respect to the discharge face of above-mentioned second electrode, at the upstream side of the carriage direction of above-mentioned purification membrane.
On the other hand, in film formation method of the present invention, can be with respect to the discharge face of above-mentioned second electrode, the upstream side at the carriage direction of above-mentioned purification membrane heats above-mentioned purification membrane.
Like this, if, just can before the discharge face that contacts second electrode, heat purification membrane in the upstream side heating purification membrane of the discharge face of second electrode.Therefore,, also can prevent from anxious poly-exceedingly to be subjected to heat affecting, can suppress the contraction that the heat because of plasma discharging causes even purification membrane has entered in the plasma space.Thereby, can further prevent from purification membrane, to take place wrinkle and distortion.
In addition, in film forming device of the present invention, above-mentioned heater block can intermittently or heat this purification membrane continuously before above-mentioned purification membrane arrives above-mentioned discharge face.
On the other hand, in film formation method of the present invention, above-mentioned purification membrane can intermittently or continuously be heated before arriving above-mentioned discharge face.
Like this, purification membrane intermittently or was continuously heated before arriving discharge face, thereby, can not suppressed to take place wrinkle and distortion more by anxious poly-heating.
In addition, in form of film device of the present invention, also can have aforesaid substrate is adjacent to the substrate conveyer that the discharge face at above-mentioned first electrode transports.
On the other hand, in film formation method of the present invention, also can the discharge face that aforesaid substrate is close to above-mentioned first electrode be transported.
Like this, the discharge face that substrate is adjacent at first electrode transports, thereby, can prevent the gas contamination that the discharge face of first electrode is activated.
In addition, in film forming device of the present invention, the aforesaid substrate conveyer, also can aforesaid substrate be adjacent to the discharge face above-mentioned discharge face in succession of above-mentioned first electrode beyond the surface after, the discharge face that is adjacent at above-mentioned first electrode transports.
On the other hand, in film formation method of the present invention, also can aforesaid substrate be adjacent to the discharge face above-mentioned discharge face in succession of above-mentioned first electrode beyond the surface after, the discharge face that is adjacent at above-mentioned first electrode transports.
Thus, substrate had been adjacent to before the discharge face of first electrode, by be adjacent to the discharge face discharge face in succession of first electrode beyond the surface, so, enter in the plasma space with the state that is supported on the surface beyond the above-mentioned discharge face.Thereby, even being influenced by heat, substrate also keeps smooth, therefore, can prevent that wrinkle and distortion from taking place, and can form high-quality film.
In addition, in film forming device of the present invention, the bight in succession on the surface beyond the discharge face of above-mentioned second electrode and the above-mentioned discharge face can form circular arc.
On the other hand, in film formation method of the present invention, can form circular arc to the bight in succession on the surface beyond the discharge face of above-mentioned second electrode and the above-mentioned discharge face.
Like this, if the bight in succession on the surface beyond the discharge face of second electrode and the above-mentioned discharge face is formed circular arc, can prevent that purification membrane from tangling when discharge face moves on the surface beyond above-mentioned discharge face, can smoothly transport.
In addition, in film forming device of the present invention, the discharge face of above-mentioned second electrode also can form the curved surface to the discharge face protrusion of above-mentioned first electrode.
On the other hand, in film formation method of the present invention, the discharge face of above-mentioned second electrode also can form the curved surface to the discharge face protrusion of above-mentioned first electrode.
Like this, if the discharge face of second electrode is formed the curved surface to the discharge face protrusion of above-mentioned first electrode, just can improve the degree of being adjacent to of the discharge face of the purification membrane and second electrode.
In addition, in film forming device of the present invention, above-mentioned second electrode is formed by a plurality of small electrodes, also can above-mentioned film conveyer be set at above-mentioned each small electrode.
On the other hand, in film formation method of the present invention, above-mentioned second electrode is formed by a plurality of small electrodes, also can transport above-mentioned purification membrane to each small electrode.
Like this, if transport purification membrane, just can prevent pollution to each small electrode to each small electrode.
In addition, in film forming device of the present invention, above-mentioned small electrode is fixed, and above-mentioned film conveyer also can transport on the surface of above-mentioned small electrode above-mentioned purification membrane in the sliding friction mode.
On the other hand, in film formation method of the present invention, fixing above-mentioned small electrode also can transport on the surface of above-mentioned small electrode above-mentioned purification membrane in the sliding friction mode.
In the occasion that small electrode is fixed, purification membrane is transported in the sliding friction mode on the surface of small electrode, thereby, can do one's utmost to suppress wrinkle and distortion generation.
In addition, in film forming device of the present invention, above-mentioned small electrode is a roller electrode, can corresponding by above-mentioned film conveyer transporting of above-mentioned purification membrane be rotated.
On the other hand, in film formation method of the present invention, above-mentioned small electrode is a roller electrode, can transporting of corresponding above-mentioned purification membrane and rotate.
Like this, if small electrode is a roller electrode, also transporting of corresponding purification membrane and rotating just can be transported purification membrane smoothly.
In addition, in film forming device of the present invention, above-mentioned first electrode is a roller electrode, and above-mentioned a plurality of small electrodes also can be the clavate electrodes with respect to the side face configuration of above-mentioned rollers electrode.
On the other hand, in film formation method of the present invention, above-mentioned first electrode is a roller electrode, and above-mentioned a plurality of small electrodes also can be the clavate electrodes with respect to the side face configuration of above-mentioned rollers electrode.
Like this, with first electrode being roller electrode and when disposing a plurality of small electrode, also can prevent first electrode and second electrode fouling with respect to its side face.
In addition, at film forming device of the present invention, configuration above-mentioned gas supply unit with first small electrode among above-mentioned a plurality of small electrodes with adjacent to the stream that is spaced apart between second small electrode of above-mentioned first small electrode, is supplied with above-mentioned gas to above-mentioned discharge space.
The above-mentioned film conveyer separately of above-mentioned first small electrode and above-mentioned second small electrode also can be adjacent to above-mentioned purification membrane on the surface of the above-mentioned small electrode that forms above-mentioned stream and transport.
On the other hand, in film formation method of the present invention, configuration above-mentioned gas supply unit with first small electrode among above-mentioned a plurality of electrodes with adjacent to the stream that is spaced apart between second small electrode of above-mentioned first small electrode, is supplied with above-mentioned gas to above-mentioned discharge space.
To each above-mentioned first small electrode and above-mentioned second small electrode, above-mentioned purification membrane is transported on the surface that also can be closely attached on the above-mentioned small electrode that forms above-mentioned stream respectively.
Therefore, purification membrane is adjacent to the surface at the small electrode that forms gas flow path, so, can prevent to form the surface contamination of the small electrode of this stream.
In addition, in film forming device of the present invention, the surface that forms the above-mentioned small electrode of above-mentioned stream also can form the curved surface that protrudes to the central authorities of above-mentioned stream.
On the other hand, in film formation method of the present invention, the surface that forms the above-mentioned small electrode of above-mentioned stream also can form the curved surface that protrudes to the central authorities of above-mentioned stream.
Be formed the curved surface that protrudes to stream central authorities because form the surface of the above-mentioned small electrode of stream, so, even in stream, also can be adjacent to purification membrane on small electrode and smoothly transport, can suppress to take place wrinkle and distortion.
In addition, in film forming device of the present invention, the above-mentioned film conveyer separately of above-mentioned first small electrode and above-mentioned second small electrode also can be transported to the surface of the above-mentioned small electrode that forms above-mentioned stream again after at least a portion of above-mentioned purification membrane contact above-mentioned gas supply unit.
On the other hand, in film formation method of the present invention, also can after at least a portion of above-mentioned purification membrane contact above-mentioned gas supply unit, be transported to the surface of the above-mentioned small electrode that forms above-mentioned stream again to each above-mentioned first small electrode and above-mentioned second small electrode.
Like this, after the periphery of purification membrane contact gas supply part, be transported to the surface of the small electrode that forms stream again, thereby the space from the gas supply part to the stream is separated by purification membrane, can prevent outside the gas flow stream.
In addition, in film forming device of the present invention, above-mentioned high-frequency electric field is that overlapping first high-frequency electric field that is produced by above-mentioned first electrode and second high-frequency electric field that is produced by above-mentioned second electrode form, the frequencies omega 2 of above-mentioned second high-frequency electric field is higher than the frequencies omega 1 of above-mentioned first high-frequency electric field, the relation of the strength of electric field V2 of the strength of electric field V1 of above-mentioned first high-frequency electric field, above-mentioned second high-frequency electric field and discharge beginning strength of electric field IV satisfies V1 〉=IV＞IV2, or V1＞IV 〉=V2.
On the other hand, in film formation method of the present invention, above-mentioned high-frequency electric field is that overlapping first high-frequency electric field that is produced by above-mentioned first electrode and second high-frequency electric field that is produced by above-mentioned second electrode form, the frequencies omega 2 of above-mentioned second high-frequency electric field is higher than the frequencies omega 1 of above-mentioned first high-frequency electric field, and the relation of the strength of electric field V2 of the strength of electric field V1 of above-mentioned first high-frequency electric field, above-mentioned second high-frequency electric field and discharge beginning strength of electric field IV also can satisfy V1 〉=IV＞V2 or V1＞IV 〉=V2.
Like this, because being overlapping first high-frequency electric field and second high-frequency electric field, high-frequency electric field forms, the efficient ω 2 of second high-frequency electric field is higher than the frequencies omega 1 of first high-frequency electric field, the relation of the strength of electric field V2 of the strength of electric field V1 of first high-frequency electric field, second high-frequency electric field and discharge beginning strength of electric field IV satisfies V1 〉=IV＞V2 or V1＞IV 〉=V2, so, even in the occasion of using cheap gas such as nitrogen, also film-forming discharge can be produced, the high-density plasma of the necessity that forms the higher-grade film can be produced.
In addition, in film forming device of the present invention, also can form above-mentioned purification membrane by polyester.
On the other hand, in film formation method of the present invention, also can form above-mentioned purification membrane by polyester.
Here, polyester is better than other production of resins rates, and price is low.Therefore, as mentioned above, can boost productivity if form purification membrane by polyester.
In addition, in film forming device of the present invention, the whole width that also can set above-mentioned purification membrane is bigger than above-mentioned discharge space.
On the other hand, in film formation method of the present invention, the whole width that also can set above-mentioned purification membrane is bigger than above-mentioned discharge space.
Like this, the whole width of setting purification membrane increases than discharge space, thereby second electrode is cleaned film and covers, and therefore, can not be exposed in the plasma discharging, can prevent the pollution to second electrode.And then, because the purification membrane edge does not enter in the discharge space, so, can prevent owing to concentrate the arc-over of discharge generation.
In addition, in film forming device of the present invention, at the above-mentioned gas supply unit, along above-mentioned small electrode axially, arrange a plurality of spouts, the ejection condition in the time of can setting ejection gas to each spout of above-mentioned a plurality of spouts respectively to above-mentioned stream ejection gas.
Can be among above-mentioned a plurality of spouts, forming no unstripped gas for ejection does not contain film with raw material with respect at least more than one the above-mentioned ejection condition enactment of spout that is positioned at both ends, simultaneously, the ejection condition enactment of the spout beyond at least more than one the spout that is positioned at above-mentioned both ends for containing film, ejection is formed unstripped gas with gas.
In addition, in film formation method of the present invention, at the above-mentioned gas supply unit, along the axial array of above-mentioned small electrode a plurality of spouts to above-mentioned stream ejection gas, the ejection condition in the time of can setting ejection gas to each spout of above-mentioned a plurality of spouts respectively.
Can be among above-mentioned a plurality of spouts, at least more than one the above-mentioned ejection condition enactment of spout that is positioned at both ends is not contained the no unstripped gas that film forms the raw material of usefulness for ejection, simultaneously, the ejection condition enactment of the spout beyond at least more than one the spout that is positioned at above-mentioned both ends for containing film, ejection is formed unstripped gas with gas.
Like this, can be respectively each spout of a plurality of spouts be set ejection condition, thereby, can set to make and contain the gas that film forms with raw material and be difficult to effusive each the ejection condition of stream.Like this, can prevent that gas from flowing out the restraining device internal contamination.And, to being positioned at least more than one the ejection condition of spout at both ends, be set at ejection and do not contain the no unstripped gas of film formation with raw material, thereby, the unstripped gas that spout beyond above-mentioned spout sprays is not had unstripped gas and is blocked, and can prevent to flow out with raw material as the film formation of pollution cause.
In addition, in film forming device of the present invention, at the above-mentioned gas supply unit, along the axial array of above-mentioned small electrode a plurality of spouts, also can have at least one side of being configured in above-mentioned small electrode, attract at least one gas attraction portion from above-mentioned stream effluent air to above-mentioned discharge space ejection gas.
On the other hand, in film formation method of the present invention, at the above-mentioned gas supply unit, along the axial array of the above-mentioned small electrode a plurality of spouts to above-mentioned stream ejection gas, the gas attraction portion of at least one side that also can be by being configured in above-mentioned small electrode attracts from above-mentioned discharge space effluent air.
Like this, at least one gas attraction portion is set at least one side of small electrode, thereby, by this gas attraction portion, can attract side effluent air from small electrode, can suppress the pollution of film forming device inside.
In addition, in film forming device of the present invention, also can set the attraction condition when attracting gas to each attraction portion of above-mentioned at least one gas attraction portion.
On the other hand, in film formation method of the present invention, also can set the attraction condition when attracting gas to each attraction portion of above-mentioned at least one gas attraction portion.
Like this, to each attraction portion setting attraction condition of at least one gas attraction portion, thereby, can set each attraction condition in the mode of more effective attraction effluent air.Thus, pollution that can restraining device inside.
In addition, in film forming device of the present invention, also can be closely attached on the filler of above-mentioned first small electrode and above-mentioned second small electrode with the mode setting that can cover above-mentioned stream at the both ends of above-mentioned stream.
On the other hand, in film formation method of the present invention, also can be closely attached on the filler of above-mentioned first small electrode and above-mentioned second small electrode with the mode setting that can cover above-mentioned stream at the both ends of above-mentioned stream.
Like this, filler is set at the both ends of the stream that forms by first small electrode and second small electrode, thereby, by the filler barrier gas, can prevent that gas from flowing out from the gap of electrode.
Description of drawings
Fig. 1 is the side elevational view that expression relates to the general structure of film forming device of the present invention;
Fig. 2 is the stereographic map of first electrode that film forming device had in the presentation graphs 1;
Fig. 3 is that the film in the film forming device of presentation graphs 1 forms unitary side elevational view;
Fig. 4 is that the film of presentation graphs 3 forms unitary side elevational view;
Fig. 5 is the stereographic map that the film of presentation graphs 3 forms the small electrode in the unit;
Fig. 6 is the main control functional diagram partly of the film forming device of presentation graphs 1;
Fig. 7 is the stereographic map of the variation of expression film forming device;
Fig. 8 is that the film in the film forming device of presentation graphs 7 forms unitary front elevation;
Fig. 9 is the side elevational view of the contact condition of purification membrane in the film forming device of presentation graphs 7 and small electrode;
Figure 10 is the stereographic map that expression has the gas supply part of a plurality of spouts;
Figure 11 is the gas supply part of expression Figure 10 and the side elevational view of a pair of small electrode;
Figure 12 is the gas supply part of expression Figure 10 and the stereographic map of gas attraction portion;
Figure 13 is the explanatory view of the contact condition of present electrode when film forms of expression and substrate.
Embodiment
Below, with reference to the description of drawings embodiments of the present invention.Fig. 1 is the side elevational view of the general structure of expression film forming device 1.
This film forming device 1 is at normal atmosphere or approach under the atmospheric pressure, activates gas by plasma discharging takes place, and exposure of substrates in the gas of this sensitization, is formed film on substrate.In film forming device 1, as shown in Figure 1, rotate first electrode 10 is set freely, be used for that flaky substrate 2 is adjacent to its side face and transport.
Fig. 2 is the stereographic map of expression first electrode 10, and this first electrode 10 is the roller shape electrodes at the surface coverage dielectric medium 12 of conductive metal parent 11.In the inside of first electrode 10, be attemperation, for example, can make the medium circulation of attemperation such as water and silicone oil, as shown in Figure 1, temperature control equipment 4 is connected in this cyclic part by pipe arrangement 3.In addition, first power supply 14 is connected with first electrode 10 by first wave filter 13.At the periphery of first electrode 10, be provided for that substrate 2 is closely attached on the substrate conveyer 15 that the side face of first electrode 10 transports and be used for that film forming a plurality of films form unit 20 on substrate 2.
In substrate conveyer 15, be provided with: first orienting roll 16 and first of the side face of substrate 2 guiding first electrode 10 is flattened roll 17; The substrate 2 that is closely attached on above-mentioned side face is peeled off, be directed to second orienting roll 18 of next stroke; Make first orienting roll 16, second orienting roll 18 and the rotating drive sources 51 of first electrode, 10 interlocks (with reference to Fig. 6).
Fig. 3 is the side elevational view that film forms unit 20, and Fig. 4 is the front elevation that film forms unit 20.In film forms unit 20, with respect to the side face of first electrode 10, devices spaced apart a configuration width a pair of small electrode (second electrode) 21 greater than first electrode 10.That is, among this a pair of small electrode 21, a small electrode 21 is first small electrode 21A, and another small electrode 21 is second small electrode 21Bs adjacent with the first small electrode 21A.And, above-mentioned interval a discharge space A, respectively first electrode 10 that forms discharge space A be discharge face 10a, 21a with the relative face of small electrode 21.In addition, between a pair of small electrode 21, establish gap b.Fig. 5 is the stereographic map of expression small electrode 21, and small electrode 21 is the clavate electrodes at the surface coverage dielectric medium 212 of conducting metal parent 211.Small electrode 21 inside are hollow, connect temperature control equipment 6 at this hollow space 213 by pipe arrangement 5.Because at the adjusting of hollow space 213 yield temperatures medium, the temperature that can regulate electrode surface.In addition, the bight of small electrode 21 (connection bight) 215 forms circular arc.In a word, the four sides of small electrode 21 is continuous by bight 215, therefore, and continuous outwardly beyond discharge face 10 and the discharge face 10a.And, form at each film on the small electrode 21 of unit 20, as shown in Figure 1, connect second source 23 by second wave filter 22.
In addition, in film forms unit 20, as shown in Figure 3, dispose with respect to above-mentioned gap b towards the gas supply part 24 of the gap b ejection gas of a pair of small electrode 21.Like this, gap b becomes the stream B to discharge space A supply gas.In gas supply part 24, be arranged on the nozzle body 25 of inner formation gas flow path and be communicated with the gas ejection portion 26 that sprays gas to stream B protrusion and with gas flow path from nozzle body 25.
In addition, in film formed unit 20, with each small electrode 21 corresponding film conveyer 30 that are provided with, its purification membrane 27 that prevents that small electrode 21 from polluting was closely attached on small electrode 21, transports continuously or off and on.In this film conveyer 30, the first film orienting roll 31 of guiding purification membrane 27 is set near gas supply part 24.At the upstream side of this first film orienting roll 31, the reel that the volume that does not have illustrated purification membrane 27 is put roller or purification membrane 27 is set.
In addition, for gas supply part 24, the take-up roller 33 (with reference to Fig. 6) of batching purification membrane 27 by the second film guide roll 32 is being set than the first film orienting roll, 31 positions far away.As shown in Figure 4, it is longer than the overall with of first electrode 10 to set the overall with of the first film orienting roll 31, the second film orienting roll 32 and purification membrane 27.The concrete overall with of setting purification membrane 27 is that two ends surpass first electrode, 10 two ends, 1～100mm for desirable.Like this, purification membrane 27 width are empty longer to A than discharge.That is, small electrode 21 is cleaned film 27 and covers, and just can not be exposed in the plasma discharging, can prevent the pollution to small electrode 21.In addition, because the edge of purification membrane 27 does not enter in the discharge space A, so, can prevent owing to concentrate the electric arc of discharge generation.
By this film conveyer 30, after purification membrane 27 is put rolling drawing and is gone out from volume, by 31 guiding of the first film orienting roll, after the periphery of the nozzle body 25 of contact gas supply part 24, be adjacent to the surperficial 21b of the formation stream B of small electrode 21, then, be adjacent to discharge face 21a by bight 215, by 32 guiding of the second film orienting roll, be wound on the take-up roller 33.At this moment, bight 215 forms circular arc, thereby, can prevent that purification membrane 27 is blocked and can smoothly transports when the surperficial 21b beyond the above-mentioned discharge face 21a moves to discharge face 21a.In addition, in present embodiment, the discharge face 21a of small electrode 21 is planes, yet, also can form the curved surface that protrudes towards the discharge face 10a of first electrode 10 to this discharge face 21a.At this moment, more can improve the discharge face 21a of small electrode 21 and the degree of being adjacent to of purification membrane 27.In addition, in present embodiment, the surface that forms the small electrode 21 of stream B also is the plane, yet, also can form the curved surface that protrudes to the central authorities of stream B to this surface.Like this, in stream B, also can be closely attached on small electrode 21 to purification membrane 27 and smoothly transport, can suppress wrinkle and distortion generation.
And as above-mentioned, purification membrane 27 contacts with nozzle body 25, thereby the space from gas supply part 24 to stream B is isolated by purification membrane 27, and can prevent outside the gas flow stream B.
At this, when purification membrane 27 was not adjacent on small electrode 21, as above-mentioned, the surface of small electrode 21 became discharge face 21a, yet when purification membrane 27 was adjacent on small electrode 21, the surface that is adjacent to the purification membrane 27 on above-mentioned discharge face 21a became discharge face.Equally, when substrate 2 was not adjacent on first electrode, 10 surfaces, as above-mentioned, the surface of first electrode 10 became discharge face 10a, yet when substrate 2 was adjacent on first electrode 10, the surface that is adjacent to the substrate 2 on above-mentioned discharge face 10a became discharge face.Thereby when substrate 2 and purification membrane 27 were adjacent to respectively on first electrode 10 and small electrode 21, discharge space A was formed by the surface of substrate 2 and purification membrane 27.
As shown in Figure 6, in film forming device 1, the control device 50 of each driving part of control is set.Drive source 51, storage part 52, first power supply 14, second source 23, gas supply part 24, temperature control equipment the 46, the 2nd film orienting roll 32 are electrically connected with control device 50.In addition, each driving part of film forming device 1 etc. also is connected with control device 50.And control device 50 is controlled each journey machine according to the sequence of control and the control data that deposit in the storage part 52.
Below, the gas of supplying with discharge space A is described.
The gas of supplying with discharge space A contains discharge gas and film formation gas at least.Discharge gas and film form gas, both can spray with admixture, also can spray respectively.In addition, except that above-mentioned gas, also can add interpolation gas.The volume ratio which kind of situation no matter, the amount of discharge gas account for total gas volume of supplying with discharge space A is 90～99.99% for desirable.
Discharge gas be can cause can film forming glow discharge gas.As discharge gas, nitrogen, rare gas, air, hydrogen, oxygen etc. are arranged, both can use these gases separately also as discharge gas and can mix use.In present embodiment, use less expensive nitrogen.At this moment, 50～100% of discharge gas volume, nitrogen are desirable, in addition, as with nitrogen blended gas, use rare gas, content be ideal less than 50% of discharge gas.
Form gas as film, for example have, organometallic compound, halogen metal compound, metal hydride etc.
As organometallic compound, the material of representing with following general expression (I) is desirable.General expression (I) R
1xMR
2yR
3zIn the formula, M is a metal, R
1Be alkyl, R
2Be alkoxyl group, R
3It is the base of from beta-diketon complex compound base, β-esters of keto-carboxylic acid complex compound base, β-keto-earboxylic acid complex compound base and wooden ketone group (wooden ketone complex compound base), selecting.When the valence mumber of metal M is m, x+y+z=m, x=0～m or x=0～m-1, y=0～m, z-0～m is 0 or positive integer.As R
1Alkyl, methyl, ethyl, propyl group, butyl etc. are for example arranged.As R
2Alkoxyl group, for example have methoxyl group, oxyethyl group, propoxy-, butoxy, 3,3,3-trifluoro to close propoxy-etc.In addition, also can convert the hydrogen atom of alkyl to fluorine atom.As R
3From beta-diketon complex compound base; β-ketone carboxylic ester complex compound base; the base of selecting in β-keto-earboxylic acid complex compound base and the wooden ketone group (wooden ketone complex compound base); as beta-diketon complex compound base; for example have 2; 4 Skellysolve As (methyl ethyl diketone); 1.1.1.5.5.5-the positive diacetylmethane of cyclohexane-2.4-; 2.2.6.6-tetramethyl--3.5-heptadione; 1.1.1-trifluoro closes-the positive diacetylmethane of 2.4-etc.; as β-esters of keto-carboxylic acid complex compound base; methyl acetoacetate is for example arranged; ethyl 3-oxobutanoate; the acetoacetic acid propyl ester; the Trimethylamine 99 ethyl 3-oxobutanoate; trifluoro closes methyl acetoacetate etc.; as β-ketone hydroxy acid; acetoacetic acid is for example arranged; Trimethylamine 99 acetoacetic acid etc.; in addition; as wooden ketone group, acetone alkyl (or acetoxyl) is for example arranged; propionyloxy; butyryl radicals; the acryl alkyl; methacryloyl alkyl etc.The carbonatoms that these are basic comprises above-mentioned routine organometallic compound, is for desirable below 18.In addition, as illustration, can be straight chain or branch's compound, also can convert hydrogen atom to fluorine atom.
In the present invention, consider that from the problem of handling the dangerous little organometallic compound of blast is desirable, there is the organometallic compound of at least more than one oxygen to be ideal at intramolecularly.As this organic compound, contain at least one R
2The organometallic compound of alkoxyl group, perhaps, contain from R
3Beta-diketon complex compound base, β-esters of keto-carboxylic acid complex compound base, β-keto-earboxylic acid complex compound base and wooden ketone group (wooden ketone complex compound base) at least one basic organometallic compound of selecting be ideal.
In addition, the organometallic compound that is used for film formation property gas, metal as halogen metal compound, metal hydride for example has: Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ra, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu etc.
In addition, mixing the occasion of adding gas, as adding gas, for example have: oxygen, ozone, hydrogen peroxide, carbonic acid gas, carbon monoxide, hydrogen, ammonia etc., yet, be ideal with oxygen, carbon monoxide and hydrogen, selection, blended gas are desirable from above-mentioned gas.It is 0.01～5% for desirable that its content accounts for the gas volume full dose.Thus, can promote to react and can form accurate fine film.
Below, substrate 2 is described.As long as form the planar shaped thing of plate shape, sheet shape or film shape at its surface energy, perhaps the film of solid figure thing such as lens and other shaping things etc. just is not particularly limited as substrate 2.Substrate 2, so long as in static condition or mobile status, be exposed to that to form uniform film in the gas mixture of isoionic state just passable, the form and the material of substrate 2 do not limited.As for material, for example, can use glass, resin, pottery, metal, nonmetal etc.Specifically be that as glass, for example sheet glass and lens etc. for example have resin lens, resin molding, resin sheet, resin board etc. as resin.
Resin molding can form nesa coating moving between the electrode that relates to film forming device 1 of the present invention or near the electrode, thereby, not the intermittent type of the such vacuum system of sputter, suitable to mass production, the mode of production that successive productivity is high.
As material by the substrate 2 of resin formation, for example have: as cellulose triacetate, cellulose diacetate, the cellulose ester that cellulose acetate propionic ester or cellulose acetate-butyrate are such, as polyethylene terephthalate, the polyester that polyethylene naphthalenedicarboxylate is such, polyalkenes as polyethylene and polypropylene, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, the ethylene-vinyl alcohol co-polymer, syndiotactic polystyrene, polycarbonate, the norbornane resin, poly-methylpentane, polyetherketone, polyimide, polyether sulphur, polysulfones, polyimide, polymeric amide, fluoro-resin, polymethacrylate, acrylate copolymer etc.
In addition, the used substrate 2 of the present invention, thickness are 10～1000 μ m, the better membranaceous substrate that is to use 40～200 μ m.
Below, purification membrane 27 is described.
Below, the metal matter parent 11,211 and the dielectric medium 12,212 that form first electrode 10 and small electrode 21 are described.
As metal matter parent 11,211 and dielectric medium 12,22 subassemblies, characteristic adapts and is that ideal, one of its characteristic are that the difference of the thermal linear expansion coefficient of metal matter parent 11,211 and dielectric medium 12,212 is 10 * 10 between the two
-1/ ℃ below combination.Ideal is 8 * 10
-6/ ℃ below, better be 5 * 10
-6/ ℃ so that 2 * 10
-6/ ℃ below.In addition, thermal linear expansion coefficient is the distinctive physics value of well-known material.
As conductive metal matter parent and the dielectric combination of the difference of thermal linear expansion coefficient in this scope, for example have: 1. metal matter parent is pure titanium or titanium alloy, dielectric medium is ceramic scorching flame spraying film forming, 2. metal matter parent is pure titanium or titanium alloy, dielectric medium is the glass lined face, 3. metal matter parent is a stainless steel, dielectric medium is ceramic scorching flame spraying film forming, 4. metal matter parent is a stainless steel, dielectric medium is the glass lined face, 5. metal matter parent is the matrix material of pottery and iron, dielectric medium is ceramic flame plating film forming, 6. metal matter parent is the matrix material of pottery and iron, dielectric medium is the glass lined face, 7. metal matter parent is the matrix material of pottery and aluminium, dielectric medium is ceramic flame plating film forming, and 8. metal matter parent is the matrix material of pottery and aluminium, dielectric medium is a glass lined face etc.With the such viewpoint of the difference of thermal linear expansion coefficient, 1. above-mentioned or 2. and 5.～8. be desirable, 1. desirable especially.
And, titanium or titanium alloy are particularly useful for metal matter parent 11,211, metal matter parent 11,211 is that titanium or titanium alloy, dielectric medium 12,211 are corresponding material in the aforesaid combination, like this, in can not using electrode aging, particularly can not take place crackle, ftracture, come off etc., can in harsh conditions, use for a long time.
To the metal matter parent 11,211 of the useful electrode of the present invention, be titanium alloy or the titanium metal of titaniferous quality more than 70%.In the present invention, the content of the titanium in titanium alloy or the titanium metal if quality more than 70% just can use by no problem, yet, be ideal to contain the titanium of quality more than 80%.Titanium alloy or the titanium metal useful to the present invention can use general-purpose industrial with pure titanium, corrosion-resistant titanium, high strength titanium etc.As industrial pure titanium, for example, TiA, TiB, TiC, TiD etc. are arranged, all be the material that contains denier iron atom, carbon atom, nitrogen-atoms, Sauerstoffatom, hydrogen atom etc., its titanium content is that quality is more than 99%.As erosion resistant titanium alloy, use T15PB to be ideal, this alloy is except that containing above-mentioned atom, and is also leaded, and titanium content is that quality is more than 98%.In addition, as titanium alloy, remove delead, contain for example aluminium outside the above-mentioned atom, in addition, also contain T64, T325, T525, the TA3 etc. of vanadium and tin, can desirablely use, the titanium content of these alloys is that quality is more than 85%.These titanium alloys and titanium metal and stainless steel, for example, A1S1316 compares, and thermal expansivity is little by about 1/2nd, good with the combination that is applied to as the dielectric medium 12,212 on metal matter parent 11,211 titanium alloys or the titanium metal, can in high temperature, use for a long time.
On the other hand, as dielectric medium 12,212 desired characteristics, specifically be to be that 6～45 mineral compound is for desirable than specific inductivity, in addition, as this dielectric medium, for example, potteries such as aluminum oxide, silicon nitride are arranged, and perhaps silicate is the glass lined plane materiel of glass, borate-based glass etc. etc.Wherein, with ceramic flame plating with the glass lined face is set is ideal.Especially, the dielectric medium 12,212 that forms with the flame plating aluminum oxide is an ideal.
In addition, as one of specification that can anti-high-power electric, to such an extent as to the space rate of dielectric medium 12,212 is volumes below 10%, it is desirable to volume volume below 8% 0% with upper volume below 5%.In addition, as another desired gauge of anti-high-power electric, the thickness of dielectric medium 12,212 is 0.5～2mm.This film thickness change rate is to be desirable below 5%, it is desirable to below 3%, and better is below 1%.
Below, the effect when the film forming device 1 with present embodiment carries out film formation is described, simultaneously, illustrate film is formed suitable various conditions.
At first, along with film forms beginning, control device 50 controls are from each gas supply part 24 ejection gas, to discharge space A supply gas.At this moment, from the gas of gas supply part 24 ejections, by arriving discharge space A through the stream B that forms by a pair of small electrode 21 by purification membrane 27 isolated spaces.On the surperficial 21b of the small electrode 21 of formation stream B, be adjacent to purification membrane 27 all the time, thereby, can prevent that this surface 21b is by the gas contamination in the process stream B.
And, when to discharge space A supply gas, control device 50 control drive sources 51, first orienting roll 16, second orienting roll 18 and first electrode 10 are rotated, the side face that substrate 2 is closely attached on first electrode 10 transports, simultaneously, control take-up roller 33 is closely attached on small electrode 21 surfaces to purification membrane 27 and transports.At this, the velocity of rotation of control take-up roller 33, transporting purification membrane 27 with the travelling speed of 200mm/min～200m/min is ideal.At this, the tension force of the purification membrane 27 on the small electrode 21, because the material of purification membrane 27 is different with thickness, its appropriate value change, however for example, when the material of purification membrane 27 is PET, thickness when being 38 μ m, the tensile appropriate value is 25gf/mm～75gf/mm.When tension force during less than 25gf/mm, purification membrane 27 suspends from small electrode 21, if greater than 75gf/mm, be directed at device and maximize, and local elongation significantly deforms.
When transporting substrate 2, control device 50 is connected first power supply 14 and second source 23.Like this, apply first high-frequency electric field of the frequencies omega 1 supplied with from first power supply 14, strength of electric field V1, electric current I 1 by first electrode 10.On the other hand, apply second high-frequency electric field of the frequencies omega 2 supplied with from second source 23, strength of electric field V2, electric current I 2 by small electrode 21.At this, setpoint frequency ω 2 is than frequencies omega 1 height.
Specifically be, frequencies omega 1 is that 200KHz is following for desirable, and lower limit is 1KHz.The waveform of this electric field can be that continuous wave also can be a pulse wave.On the other hand, frequencies omega 2 is that 800KHz is above for desirable, and frequency higher ion density more just increases more, on be limited to about 200MHz.
In addition, to between electrode, supply with discharge gas, increase this interelectrode strength of electric field, the strength of electric field that begins to discharge is defined as discharge beginning strength of electric field IV, so the relation that setting strength of electric field V1, V2 and discharge begin strength of electric field IV satisfies: formula V1 〉=IV＞V2 or V1＞IV 〉=V2.For example, be the occasion of nitrogen at discharge gas, this discharge beginning strength of electric field IV is about 3.7kv/mm, by above-mentioned relation, applying strength of electric field V1 is that V1 〉=3.7kv/mm, strength of electric field V2 are V2＜3.7kv/mm, so, activate nitrogen, can form isoionic state.
And, the relation of electric current I 1, I2 is ideal with I1＜I2.The electric current I 1 of first high-frequency electric field is desirably 0.3mA/cm
2～20mA/cm
2, better be 1.0mA/cm
2～20mA/cm
2In addition, the electric current 12 of second high-frequency electric field is desirably 10mA/cm
2～100mA/cm
2, better is 20mA/cm
2～100mA/cm
2
Like this, when taking place by first high-frequency electric field of first electrode 10 and during by second high-frequency electric field of small electrode 21, the high-frequency electric field of overlap in discharge space A first high-frequency electric field and second high-frequency electric field is with gas reaction generation plasma discharging.The plasma Space H that plasma discharging takes place, as shown in Figure 3 and Figure 4, though overflow from the discharge face 10a of first electrode 10 and the discharge face 21a of small electrode 21, but substrate 2 and purification membrane 27 with the discharge face 10a of first electrode 10 and small electrode 21, before 21a is adjacent to, with in succession in the discharge face 10a of first electrode 10 and small electrode 21, the discharge face 10a of 21a, surface beyond the 21a is adjacent to, therefore, with by above-mentioned discharge face 10a, the state of the surface bearing beyond the 21a enters the plasma Space H, like this, even it is also smooth that substrate 2 and purification membrane 27 are influenced by heat, therefore, can prevent that wrinkle and distortion from taking place.
And then, first electrode 10 and small electrode 21, its surface temperature is respectively by temperature control equipment 4,6 control, so substrate 2 and purification membrane 27 were given heat by the surface beyond discharge face 10a, the 21a before entering the plasma Space H.Therefore,, also can prevent from sharply and excessively to be subjected to heat affecting, can suppress because the contraction that the heat of plasma discharging causes even substrate 2 and purification membrane 27 enter the plasma Space H.Thereby, can further prevent from substrate 2 and purification membrane 27, to take place wrinkle and distortion.Especially on small electrode 21, guarantee that purification membrane 27 enters the regulation area on the discharge face 21a surface in addition of plasma Space H contact in the past, thereby, before arriving discharge face 21a, can heat purification membrane 27 continuously, can sharply not heat at small electrode 21 yet, can further suppress to take place wrinkle and distortion.In addition, also can not heat continuously and carry out intermittence and heat.
And, in the process that substrate 2 passes through in the plasma Space H, on substrate 2, form film.Because the temperature variation of the substrate 2 in the plasma discharge treatment, the physical properties and the composition of the film that obtains can change, thereby, when forming film, make by temperature control equipment 4 and carry out temperature controlled medium at first electrode, 10 internal recycle, control the surface temperature of first electrode 10, the temperature of suitably regulating substrate 2 is ideal.At this, temperature control equipment 4 is temperature regulation 20 ℃～300 ℃, is desirably 80 ℃～100 ℃ with the medium temperature regulation, so that substrate 2 is able to bring into play the temperature of the performance of regulation.On the other hand, at temperature control equipment 6, also temperature regulation is 20 ℃～300 ℃, is desirably 80 ℃～100 ℃ with the medium temperature regulation.But,, must be above-mentioned medium temperature regulation the gasification condition temperature that is not less than the gas of use as lower limit temperature.
Then, formed the substrate 2 of film, and be transported to down stroke by orienting roll 18.
As above-mentioned, film forming device 1 according to present embodiment, film conveyer 30 purification membrane 27 be adjacent to the discharge face 21a discharge face 21a in succession of small electrode 21 beyond surperficial 21b after, transport the discharge face 21a that is adjacent at above-mentioned small electrode 21, thereby, at small electrode 21, its surface is capped by being adjacent to of purification membrane 27.Thereby, can prevent that the discharge face 21a of small electrode 21 is contaminated by the gas that is activated.In addition, purification membrane 27 is transported by film conveyer 30, thereby, can be replaced with new film to the purification membrane 27 of the discharge face 21a that is closely attached on small electrode 21 continuously.
In addition, film conveyer 30 is set at each small electrode 21, thereby, transport purification membrane 27 at each small electrode 21, like this, can prevent pollution to each small electrode 21.
And purification membrane 27 is closely attached on the surface beyond the discharge face 21a of small electrode 21 and the discharge face, thereby, when flow system film gas only flows discharge gas, can protect small electrode 21 at discharge space A.
And substrate conveyer 15 transports the discharge face 10a that substrate 2 is adjacent at first electrode 10, thereby the discharge face 10a that can prevent first electrode 10 is by the gas contamination that is activated.And then, this substrate conveyer 15, be adjacent at substrate 2 before the discharge face 10a of first electrode 10, substrate 2 be adjacent to the discharge face 10a discharge face 10a in succession of first electrode 10 beyond the surface, therefore, substrate 2 enters and waits from capable subspace H with the state by the surface bearing beyond the above-mentioned discharge face 10a.Like this, also smooth even substrate 2 is influenced by heat, therefore, can prevent wrinkle and distortion, can form high-quality film.
And then, can be at normal atmosphere or near making film under the atmospheric pressure, thereby, and compare in the occasion of vacuum system film, can make film at a high speed, simultaneously, can continuous production.And, because do not need to be used to form the device of vacuum, so, installation cost can be reduced.
In addition, the present invention is not limited to above-mentioned embodiment, certainly suitably change.
For example, in present embodiment, illustration by transporting purification membrane 27 at direction of principal axis, purification membrane 27 being closely attached on the situation that the discharge face 21a of small electrode 21 transports simultaneously perpendicular to small electrode 21, describe.Yet, transport as long as can be adjacent at discharge face 21a from the surface beyond the discharge face 21a of the discharge face 21a of small electrode 21 in succession, transporting purification membrane 27 in any direction can.For example, can enumerate and axially transport purification membrane 27A along small electrode 21.Below, specify the situation of axially transporting purification membrane 27A with reference to Fig. 7～Fig. 9 along small electrode 21.Fig. 7 is the stereographic map of the general configuration of expression film forming device 1A, Fig. 8 represents that the film among the film forming device 1A forms the front elevation of unit 20A, in addition, Fig. 9 represents the side elevational view of the contact condition of purification membrane 27A among the film forming device 1A and small electrode 21.In addition, the integrant additional phase identical with above-mentioned embodiment with numbering, omitted its explanation.
As shown in Figure 7 and Figure 8, film in this film forming device 1A forms unit 20A, corresponding to each small electrode 21 film conveyer 30A is set, its direction of principal axis along small electrode 21 transports purification membrane 27A continuously or intermittently, makes purification membrane 27 be closely attached on small electrode 21 simultaneously.As shown in Figure 9, corresponding to the width of the discharge face 21a of the equidirectional vertical direction of small electrode 21, set the whole width of the purification membrane 27A that transports by this film conveyer 30A.And, in film conveyer 30, as shown in Figure 8, the first film orienting roll 31A that revolution keeps being wound into the purification membrane 27A of web-like freely is set in a side of small electrode 21.In addition, at the opposite side of small electrode 21, the second film orienting roll 32A that batches purification membrane 27A is set.By this film conveyer 30A, purification membrane 27A pulls out from the first film orienting roll 31A, be adjacent to the discharge face discharge face 21a in succession of small electrode 21 beyond surperficial 21c after, be adjacent at discharge face 21a, batched in the second film orienting roll 32A.Like this, purification membrane 27A enters the plasma Space H with the state by the surperficial 21c supporting beyond the discharge face 21a of small electrode 21.Thereby, also smooth even purification membrane 27A is subjected to heat affecting, therefore, can prevent wrinkle and distortion.
In addition, at above-mentioned embodiment, small electrode 21 plays the heater block of the purification membrane 27 among heating the present invention, yet, as long as the discharge face 21a to small electrode 21 can heat at the upstream side of the carriage direction of purification membrane 27, no matter which kind of structure can, in addition, for example can enumerate discharge face 21a, in the mode of the upstream side configuration heating special-purpose member of the carriage direction of purification membrane 27 to small electrode 21.
In addition, at the foregoing description, small electrode 21 becomes prismatic substantially fixing, yet small electrode also can be to turn round the roller that is provided with freely.At this moment, the corresponding purification membrane of small electrode body is transported revolution, therefore can transport purification membrane smoothly.And then the small electrode body is the structure that revolution drives, and can carry out transporting of purification membrane effectively.
In addition, if gas supply part has a plurality of spouts, can prevent that also film from forming gas and flowing out from stream.Below, illustrate that gas supply part has the situation of a plurality of spouts.In the part identical with above-mentioned film forming device 1, additional phase is omitted its explanation with numbering.
Figure 10 is the stereographic map that expression has the gas supply part of a plurality of spouts.As shown in figure 10, at the front end of gas supply part 44, a plurality of spouts 441,442,443 assortments that the spray gas respectively shape that is in line.In a word, these spouts 441,442,443, when gas supply part 44 disposes with respect to gap b, along the axial assortment of small electrode 21 with respect to gap b.
Rearward end at gas supply part 44, connect a plurality of flues 444,445,446, these flues 444,445,446, the gas regulation portion (omitting diagram) of flow, flow velocity, gaseous constituent and concentration etc. by regulating inflow gas pipe 444,445,446 gas inside connects a plurality of gas tanks (omitting diagram) that store gas with various respectively.Gas regulation portion is based on the control of control device 50, the gas that flows into from a plurality of gas tanks separately or be mixed into after promoting the circulation of qi body composition and the concentration adjustment, also carries out adjustings such as flow and flow velocity, then, sends into each tracheae 444,445,446.
And in these a plurality of gas tanks, storage contains the unstripped gas of film formation with raw material in a gas tank at least, simultaneously, stores the no unstripped gas that does not contain above-mentioned raw materials at least in a gas tank.And, when unstripped gas contains discharge gas, at the state that applies electric field by first electrode 10 and small electrode 21, if pass through stream B to discharge space A base feed gas, plasma discharging just takes place activate raw material, yet, when unstripped gas does not contain discharge gas, the gas tank that stores discharge gas must be set.At this moment, unstripped gas and discharge gas are supplied with discharge space A by stream B separately respectively, yet, because in discharge space A, mix, so, if apply electric field at first electrode 10 and small electrode 21, plasma discharging just can take place, activate raw material.
Now, unstripped gas and no unstripped gas are described.
Unstripped gas is the mixed gas that contains discharge gas and film formation gas at least, in addition, in addition, also can add interpolation gas.The sort of occasion no matter, the amount of discharge gas is that volume 90～99.99% is for desirable to the ratio of all gas amount of supplying with discharge space A.
As no unstripped gas, use and not contain the gas that forms the compound that is contained in the property gas at film as the raw material of film.The above-mentioned in this way discharge gas of concrete example, oxygen, carbon monoxide, air etc.As no unstripped gas, when using discharge gas, can make the plasma discharging that in discharge space B, takes place even.
In addition,, dividing plate 448,449 is set, so that before arriving spout 441,442,443, do not mix from each flue 444,445,446 gas supplied in gas supply part 44 inside.
Figure 11 represents the side elevational view of a pair of small electrode 21A, 21B and gas supply part 44.As shown in figure 11, at the both ends of the gap b of a pair of small electrode 21A, 21B, fill up b ground, gap the filler 46 that is adjacent to a pair of small electrode 21A, 21B is set.This filler 46 by having the thermotolerance that is enough to bear the temperature of plasma discharging when taking place, having the insulativity material simultaneously and forms, is set at the scope that a pair of little electricity is weighed the discharge face 21a of 21A, 21B that do not cover.
In addition, as shown in figure 11,, prevent that gas effluent air partition walls 47 from clipping purification membrane 27 and uprightly being provided with at the both ends of a pair of small electrode 21A, 21B.And, in the both sides of a pair of small electrode 21A, 21B, the gas attraction portion 48 of attraction from the stream effluent air is set.In addition, if be provided with few gas attraction portion 48, just can obtain and prevent the effusive effect of gas at least one side of a pair of small electrode 21A, 21B.
Figure 12 is the stereographic map of expression gas attraction portion 48.In addition, in Figure 12, omit the gas partition walls 47 of small electrode 21A and the diagram of the gas attraction portion 48 of the opposite side that is configured in a pair of small electrode 21A, 21B.
In gas attraction portion 48, suction oral area 43 that attracts gas and the suction pump (omitting diagram) that is connected in suction oral area 43 by air suction pipe 431 are set.This suction pump is by control device 50 controls.In addition, suck oral area 43, as long as have the suction port that sucks gas, whatsoever shape can.
Below, the effect of gas attraction portion 48 and gas supply part 44 is described.
At first, follow to begin to form film, control device 50 drives suction pump.At this moment, control device 50 is set the attraction condition, so that can effectively attract when attracting.Based on this attraction condition control suction pump.At this, the attraction condition is meant, attracts flow, attracts flow velocity, ambient air pressure etc., is set at that can to stablize the value of making film when attracting be ideal.These values wait with simulation by experiment and obtain.
And, control device 50, control is given discharge space A gas from gas supply part 44 ejection gases.At this, control device 50 is set the ejection condition of each spout 441,442,443, doing one's utmost to reduce the unstripped gas of leaking from gap b, and corresponding to this ejection condition pilot-gas adjusting portion.Specifically be that the ejection condition of setting the spout 441,443 that is positioned at both ends is the no unstripped gas of ejection.In addition, set the ejection condition of these spouts that are positioned at both ends 441,443 spout 442 in addition for spraying unstripped gas.Like this, from gas supply part 44 during to discharge space A supply gas, unstripped gas and extraneous gas are cut off by no unstripped gas, can prevent that unstripped gas from flowing out from the gap.
In addition, in this ejection condition that exemplifies, be the minimum prerequisite that is used to reduce from the effusive unstripped gas of gap b, for further reducing discharge, each condition of adjustments of gas flow, flow velocity, gas composition and concentration is an ideal.These conditions wait with simulation by experiment and obtain.
And the gas from gas supply part 44 ejections by the space that is separated by purification membrane 27, flows to the stream B that is formed by a pair of small electrode 21A, 21B.At this moment, even gas flows out from stream B, this gas also nearly all is no unstripped gas, therefore, is atomic little to installing inner influence.And then, even effluent air includes unstripped gas, because gas attraction portion 48 attracts, so, also can prevent polluting device inside.
As mentioned above, can set the ejection condition respectively to a plurality of ejiction openings 441,442,443, thereby, can set each ejection condition, make to contain the gas that film forms with raw material and be difficult to from stream and discharge space A outflow.Like this, can prevent that gas from flowing out the restraining device internal contamination.
In addition, gas attraction portion 48 is set in the both sides of small electrode 21A, 21B also, thereby, the side effluent air from small electrode 21A, 21B, the pollution of inhibition film forming device inside can be attracted by this gas attraction portion 48.
In addition, at above-mentioned embodiment, thereby so that substrate 2 by in the plasma Space H that between first electrode 10 and small electrode 21A, forms on base material 2 film forming direct plasma mode be that example is illustrated, yet, also go for the remote plasma mode.As the remote plasma mode, for example have the spy and open flat 5-23579 communique and the described method of Te Kai 2003-49272 communique.Promptly by with respect to pair of electrodes between ejection mixed gas and apply electric field, by spraying plasma discharging between electrode, the exposure of substrates with respect to above-mentioned plasma discharging setting is made film in plasma discharging.For the discharge face of above-mentioned electrode at this moment, can use present technique.
[embodiment]
[electrode]
At this, small electrode 21 makes the curvature of the face that forms stream B and discharge face 21a in R20mm～R2000mm scope, makes the curvature that connects bight 215 in the scope of R1mm～R20mm, covering dielectric.In addition, the curvature ideal scope in connection bight 215 is R3mm～R8mm.Specifically in the present embodiment, it is R500mm that small electrode 21 makes the face of formation stream B and the curvature of discharge face 21a, and making the curvature that connects bight 215 is R5mm, covering dielectric.
[film forming device]
Use the film forming device 1 in the above-mentioned embodiment, making at the interval a of above-mentioned first electrode 10 that makes and small electrode 21 is that 1mm is configured this two electrode.At this, at the composition of gas, discharge gas (nitrogen) is that volume 97.9%, film form the gas tetra isopropyl titanium) be that volume 0.01%, interpolation gas (hydrogen) they are volumes 2.0%.In addition, as substrate 2, use コ ニ カ Star Network KC8UX.As purification membrane 27, use the PET film of Mitsubishi Chemical polyester film company or Supreme Being people デ ュ Port Application film corporate system.And, making discharge beginning strength of electric field IV is that the frequencies omega 1 of first high-frequency electric field of 3.7kv/mm, first electrode 10 is 12kv/mm for 5KHz, strength of electric field V1, the frequencies omega 2 of second high-frequency electric field of small electrode 21 is 800KHz, and strength of electric field V2 is 1.2kv/mm, makes film.
As a comparative example, use, use substrate identical and gas to carry out film and form with embodiment at the illustrative film forming device of prior art.
Repeatedly carry out repeatedly after film forms, the film that forms by both of embodiment and comparative example relatively, the result at embodiment, is formed uniformly film on substrate, in contrast, at comparative example, deform on substrate and wrinkle, and film is also inhomogeneous.
Claims (42)
1. film forming device is characterized in that having: first electrode and second electrode, and its mutual discharge face forms discharge space relatively, and in above-mentioned discharge space high-frequency electric field takes place; Gas supply part, it is supplied with to above-mentioned discharge space and contains the gas that film forms gas so that above-mentioned gas is activated by high-frequency electric field, and exposure of substrates in the above-mentioned gas that is activated, on aforesaid substrate, to form film; The film conveyer, it is used for preventing that at least one side of above-mentioned first electrode and above-mentioned second electrode is exposed to the purification membrane of above-mentioned activated gas, with at least one side's of above-mentioned first electrode and above-mentioned second electrode discharge face and in succession at least a portion on the surface beyond the above-mentioned discharge face of above-mentioned discharge face be adjacent to and transport.
2. film forming device as claimed in claim 1 is characterized in that, above-mentioned film transporter, and the discharge face that above-mentioned purification membrane is adjacent at above-mentioned second electrode transports with at least a portion on the above-mentioned discharge face that is connected in above-mentioned discharge face surface in addition.
3. film forming device as claimed in claim 1 is characterized in that, above-mentioned first electrode and above-mentioned second electrode at normal atmosphere or near under the atmospheric pressure, make high-frequency electric field takes place in the above-mentioned discharge space.
4. as film forming device as described in the claim 2, it is characterized in that,, the heater block of the above-mentioned purification membrane of heating is set with respect to the discharge face of above-mentioned second electrode, at the upstream side of the carriage direction of above-mentioned purification membrane.
5. film forming device as claimed in claim 4 is characterized in that, above-mentioned heater block before above-mentioned purification membrane arrives above-mentioned discharge face intermittently or heat this purification membrane continuously.
6. film forming device as claimed in claim 2 is characterized in that, has aforesaid substrate is adjacent to the substrate conveyer that the discharge face at above-mentioned first electrode transports.
7. film forming device as claimed in claim 6, it is characterized in that, the aforesaid substrate conveyer, aforesaid substrate be adjacent to the discharge face above-mentioned discharge face in succession of above-mentioned first electrode beyond the surface after, the discharge face that is adjacent at above-mentioned first electrode transports.
8. film forming device as claimed in claim 2 is characterized in that, the bight in succession on the surface beyond the discharge face of above-mentioned second electrode and the above-mentioned discharge face forms circular arc.
9. film forming device as claimed in claim 2 is characterized in that, the discharge face of above-mentioned second electrode forms the curved surface to the discharge face protrusion of above-mentioned first electrode.
10. film forming device as claimed in claim 2 is characterized in that, above-mentioned second electrode is formed by a plurality of small electrodes, at above-mentioned each small electrode above-mentioned film conveyer is set.
11. film forming device as claimed in claim 10 is characterized in that, above-mentioned small electrode is fixed, and above-mentioned film conveyer transports on above-mentioned small electrode surface above-mentioned purification membrane in the sliding friction mode.
12. film forming device as claimed in claim 10 is characterized in that, above-mentioned small electrode is a roller electrode, and correspondence is rotated transporting of above-mentioned purification membrane by above-mentioned film conveyer.
13. film forming device as claimed in claim 10 is characterized in that, above-mentioned first electricity is a roller electrode, and above-mentioned a plurality of small electrodes are the clavate electrodes with respect to the side face configuration of above-mentioned rollers electrode.
14. film forming device as claimed in claim 10, it is characterized in that: configuration above-mentioned gas supply unit, with first small electrode among above-mentioned a plurality of small electrodes with adjacent to the stream that is spaced apart between second small electrode of above-mentioned first small electrode, supply with above-mentioned gas to above-mentioned discharge space;
The above-mentioned film conveyer separately of above-mentioned first small electrode and above-mentioned second small electrode is adjacent to above-mentioned purification membrane on the surface of the above-mentioned small electrode that forms above-mentioned stream and transports.
15. film forming device as claimed in claim 14 is characterized in that, the above-mentioned small electrode surface that forms above-mentioned stream forms the curved surface that protrudes to the central authorities of above-mentioned stream.
16. film forming device as claimed in claim 14, it is characterized in that, the above-mentioned film conveyer separately of above-mentioned first small electrode and above-mentioned second small electrode, after at least a portion of above-mentioned purification membrane contact above-mentioned gas supply unit, be transported to the surface of the above-mentioned small electrode that forms above-mentioned stream again.
17. film forming device as claimed in claim 1 is characterized in that, above-mentioned high-frequency electric field is the electric field that overlapping first high-frequency electric field that is produced by above-mentioned first electrode and second high-frequency electric field that produced by above-mentioned second electrode form; The frequencies omega 2 of above-mentioned second high-frequency electric field is higher than the frequencies omega 1 of above-mentioned first high-frequency electric field; The relation of the strength of electric field V2 of the strength of electric field V1 of above-mentioned first high-frequency electric field, above-mentioned second high-frequency electric field and discharge beginning strength of electric field IV satisfies V1 〉=IV＞V2 or V1＞IV 〉=V2.
18. film forming device as claimed in claim 1 is characterized in that, forms above-mentioned purification membrane by polyester.
19. film forming device as claimed in claim 1 is characterized in that, the whole width of setting above-mentioned purification membrane is bigger than above-mentioned discharge space.
20. film forming device as claimed in claim 10 is characterized in that, at the above-mentioned gas supply unit, sprays a plurality of spouts of gas to above-mentioned discharge space along the axial array of above-mentioned small electrode; Ejection condition in the time of can setting ejection gas to each spout of above-mentioned a plurality of spouts respectively; Among above-mentioned a plurality of spouts, forming no unstripped gas for ejection does not contain film with raw material with respect at least more than one the above-mentioned ejection condition enactment of spout that is positioned at both ends, simultaneously, the ejection condition enactment with respect to the spout beyond at least more than one the spout that is positioned at above-mentioned both ends is contained the unstripped gas that film forms usefulness gas for ejection.
21. film forming device as claimed in claim 14, it is characterized in that: at the above-mentioned gas supply unit, along the axial array of above-mentioned small electrode a plurality of spouts, have at least one side of being configured in above-mentioned small electrode, attract at least one gas attraction portion from above-mentioned stream effluent air to above-mentioned discharge space ejection gas.
22. film formation method, it is characterized in that: supply with to the discharge space that constitutes by relative first electrode of mutual discharge face and second electrode from gas supply part and contain the gas that film forms gas, by activating above-mentioned gas at above-mentioned discharge space generation high-frequency electric field, exposure of substrates in above-mentioned activated gas and on aforesaid substrate, form film; When above-mentioned formation film, at least one side who is used for preventing above-mentioned first electrode and above-mentioned second electrode is exposed to the purification membrane of above-mentioned activated gas, with at least one side's of above-mentioned first electrode and above-mentioned second electrode discharge face and in succession at least a portion on the surface beyond the above-mentioned discharge face of above-mentioned discharge face be adjacent to and transport.
23. film formation method as claimed in claim 22 is characterized in that, above-mentioned purification membrane is adjacent at the discharge face of above-mentioned second electrode with at least a portion on above-mentioned discharge face above-mentioned discharge face in succession surface in addition transports.
24. film formation method as claimed in claim 22 is characterized in that, by above-mentioned first electrode and above-mentioned second electrode, at normal atmosphere or near under the atmospheric pressure, makes high-frequency electric field takes place in the above-mentioned discharge space.
25. film formation method as claimed in claim 23 is characterized in that, with respect to the discharge face of above-mentioned second electrode, heat above-mentioned purification membrane at the upstream side of the carriage direction of above-mentioned purification membrane.
26. film formation method as claimed in claim 25 is characterized in that, above-mentioned purification membrane intermittently or was continuously heated before arriving above-mentioned discharge face.
27. film formation method as claimed in claim 23 is characterized in that the discharge face that aforesaid substrate is adjacent at above-mentioned first electrode transports.
28. film formation method as claimed in claim 27 is characterized in that, aforesaid substrate be adjacent to the discharge face above-mentioned discharge face in succession of above-mentioned first electrode beyond the surface after, the discharge face that is adjacent at above-mentioned first electrode transports.
29. film formation method as claimed in claim 23 is characterized in that, the bight in succession on the surface beyond the discharge face of above-mentioned second electrode and the above-mentioned discharge face is formed circular arc.
30. film formation method as claimed in claim 23 is characterized in that, the discharge face of above-mentioned second electrode forms the curved surface to the discharge face protrusion of above-mentioned first electrode.
31. film formation method as claimed in claim 23 is characterized in that, above-mentioned second electrode is formed by a plurality of small electrodes, transports above-mentioned purification membrane to each small electrode.
32. film formation method as claimed in claim 31 is characterized in that above-mentioned small electrode is fixed, and above-mentioned purification membrane is being slided on the surface of above-mentioned small electrode transporting.
33. film formation method as claimed in claim 31 is characterized in that above-mentioned small electrode is a roller electrode, transporting of its corresponding above-mentioned purification membrane and rotating.
34. film formation method as claimed in claim 31 is characterized in that, above-mentioned first electrode is a roller electrode, and above-mentioned a plurality of small electrodes are the clavate electrodes with respect to the side face configuration of above-mentioned rollers electrode.
35. film formation method as claimed in claim 31, it is characterized in that: configuration above-mentioned gas supply unit, with first small electrode among above-mentioned a plurality of small electrodes with adjacent to the stream that is spaced apart between second small electrode of above-mentioned first small electrode, supply with above-mentioned gas to above-mentioned discharge space
With respect to each above-mentioned first small electrode and above-mentioned second small electrode, above-mentioned purification membrane is transported in the mode on the surface that is closely attached on the above-mentioned small electrode that forms above-mentioned stream.
36. film formation method as claimed in claim 35 is characterized in that, the surface that forms the above-mentioned small electrode of above-mentioned stream forms to the central curved surface that protrudes of above-mentioned stream.
37. film formation method as claimed in claim 35, it is characterized in that, with respect to each above-mentioned first small electrode and above-mentioned second small electrode, after at least a portion of above-mentioned purification membrane contact above-mentioned gas supply unit, be transported to the surface of the above-mentioned small electrode that forms above-mentioned stream again.
38. film formation method as claimed in claim 22 is characterized in that: above-mentioned high-frequency electric field is the high-frequency electric field that overlapping first high-frequency electric field that is produced by above-mentioned first electrode and second high-frequency electric field that produced by above-mentioned second electrode form; The frequencies omega 2 of above-mentioned second high-frequency electric field is higher than the frequencies omega 1 of above-mentioned first high-frequency electric field; The relation of the strength of electric field V2 of the strength of electric field V1 of above-mentioned first high-frequency electric field, above-mentioned second high-frequency electric field and discharge beginning strength of electric field 1V satisfies V1 〉=IV＞V2 or V1＞IV 〉=V2.
39. film formation method as claimed in claim 22 is characterized in that, forms above-mentioned purification membrane by polyester.
40. film formation method as claimed in claim 22 is characterized in that, the whole width of setting above-mentioned purification membrane is bigger than above-mentioned discharge space.
41. film formation method as claimed in claim 31 is characterized in that, at the above-mentioned gas supply unit, sprays a plurality of spouts of gas to above-mentioned discharge space along the axial array of above-mentioned small electrode; Ejection condition in the time of can setting ejection gas to each spout of above-mentioned a plurality of spouts respectively; Among above-mentioned a plurality of spouts, forming no unstripped gas for ejection does not contain film with raw material with respect at least more than one the above-mentioned ejection condition enactment of spout that is positioned at both ends, simultaneously, the ejection condition enactment with respect to the spout beyond at least more than one the spout that is positioned at above-mentioned both ends is contained the unstripped gas that film forms usefulness gas for ejection.
42. film formation method as claimed in claim 35, it is characterized in that: at the above-mentioned gas supply unit, spray a plurality of spouts of gas to above-mentioned discharge space along the axial array of above-mentioned small electrode, the gas attraction portion of at least one side by being configured in above-mentioned small electrode attracts from above-mentioned stream effluent air.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP095367/2003 | 2003-03-31 | ||
| JP2003095367 | 2003-03-31 | ||
| JP195845/2003 | 2003-07-11 | ||
| JP201172/2003 | 2003-07-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1768161A true CN1768161A (en) | 2006-05-03 |
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ID=36743323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480008610 Pending CN1768161A (en) | 2003-03-31 | 2004-02-23 | Thin film forming apparatus and method for forming thin film |
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| Country | Link |
|---|---|
| CN (1) | CN1768161A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106449342A (en) * | 2015-08-06 | 2017-02-22 | 财团法人工业技术研究院 | Electrode antifouling device and coating system |
| CN109964299A (en) * | 2016-11-16 | 2019-07-02 | 涂层等离子创新公司 | For handling processing unit, corresponding facility and the implementation method of the facility of the substrate surface in movement |
-
2004
- 2004-02-23 CN CN 200480008610 patent/CN1768161A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106449342A (en) * | 2015-08-06 | 2017-02-22 | 财团法人工业技术研究院 | Electrode antifouling device and coating system |
| CN106449342B (en) * | 2015-08-06 | 2018-11-20 | 财团法人工业技术研究院 | Electrode antifouling device and coating system |
| CN109964299A (en) * | 2016-11-16 | 2019-07-02 | 涂层等离子创新公司 | For handling processing unit, corresponding facility and the implementation method of the facility of the substrate surface in movement |
| CN109964299B (en) * | 2016-11-16 | 2021-08-03 | 涂层等离子创新公司 | Processing unit for a facility for processing a surface of a substrate in motion, corresponding facility and method for implementing the same |
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