JP2007190554A - Drop discharge apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern formation method with improved position accuracy at the time of drop landing on a substrate and a drop discharge apparatus with improved position accuracy. <P>SOLUTION: The pattern formation method includes a step of providing affinity for liquid by means 102 for selectively generating plasma on a liquid-repellent thin film, for example, a semiconductor film, on a substrate having insulating property, for example, a glass substrate, and discharging a drop composition onto the surface having affinity for liquid by drop discharge means 103. As the selectively formed region having affinity for liquid is provided between liquid-repellent parts, a drop can be formed without moving from its impact position after impact. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film pattern manufacturing method and a droplet discharge device.

  In recent years, development of a method for producing a pattern using a droplet discharge method by screen printing or inkjet has been active.

  The droplet discharge method has many advantages such as direct drawing patterning, no mask is required, easy application to large substrates, high material utilization efficiency, etc., so fine patterning is applied to FPD (flat panel display). ) Is becoming popular.

  As applications, formation of not only organic EL (electroluminescence) light emitting layers and LCD (liquid crystal display) color filters but also PDP (plasma display) electrodes and organic transistors has been reported.

  Although the droplet discharge method has many advantages, there are various restrictions on the droplet and the substrate containing the composition in order to actually perform fine patterning.

  The droplets that can be formed at present are as small as 2 pL, and such fine droplets are precisely arranged on the substrate to form pixels, electrodes, wirings, and the like. However, the actual droplet landing accuracy is about several μm to 30 μm, and even after landing, the droplet may deviate from the landing position due to the influence of the landing surface state and the contact angle of the droplet. Therefore, it is often insufficient to form a small FPD pixel portion as patterning.

  Therefore, in the case of an organic EL light emitting layer or a color filter, droplets are discharged into a bank formed by photolithography so that the landing position does not shift.

  In the droplet discharge method, it goes without saying that the droplet including the head and the composition is most important, but in fact, other factors are also large. Unlike normal inkjet, in which an absorbent medium such as paper receives ink, in FPD applications, it is often necessary to eject the ink onto a non-absorbent substrate, which restricts the ejection method. For example, since it spreads greatly when discharged onto a lyophilic substrate, the substrate on which fine patterning is to be performed must be liquid repellent to some extent. However, since the droplet placed on the liquid-repellent substrate easily moves, it is necessary to perform drawing after optimizing the combination of the surface state of the substrate and the discharge conditions.

  Therefore, an object of the present invention is to provide a pattern manufacturing method that improves the positional accuracy when a droplet reaches a substrate. It is another object of the present invention to provide a droplet discharge device with improved positional accuracy.

  The present invention provides a method for producing a pattern with improved positional accuracy when a droplet lands on a substrate, and a droplet discharge apparatus having a plasma generating means.

That is, a substrate having an insulating property, for example, a glass substrate is made lyophilic by means for selectively generating plasma on a liquid-repellent thin film, for example, a semiconductor film, and a liquid is ejected on the lyophilic surface by a droplet discharge means. It includes a step of discharging a droplet composition to produce a pattern. By sandwiching the selectively formed lyophilic region with liquid repellency, the droplet after landing can be formed without moving from the landing position. The power source for plasma generation is a high voltage pulse power source adapted to apply a high frequency or pulsed electric field, the high frequency is a frequency of 10 MHz to 100 MHz, the pulse power source is a frequency of 50 Hz to 100 kHz, and the pulse duration is It is preferably 1 to 100 μsec. The pressure is in the range of atmospheric pressure or near atmospheric pressure, and the pressure range may be 1.3 × 10 ^{1 to} 1.31 × 10 ⁵ Pa. As the reaction gas, an inert gas such as He, Ne, Ar, Kr, or Xe, or one or more of oxygen and nitrogen may be appropriately selected and used. The lyophilic property is defined as a contact angle θ of 0 ° ≦ θ <10 °, and the liquid repellency is defined as 10 ° ≦ θ <180 °.

A groove is selectively formed by means for selectively generating plasma in a lyophilic thin film such as a silicon oxide film on an insulating substrate such as a glass substrate, and a droplet discharge means is formed on the lyophilic surface. And a step of discharging a droplet composition to form a pattern. By selectively forming grooves on the lyophilic surface, the droplet after landing can be formed without moving from the position at the time of landing. The power source for plasma generation is preferably a high frequency power source or a high voltage pulse power source. The high frequency is preferably 10 MHz to 100 MHz, the pulse power source is preferably 50 Hz to 100 kHz, and the pulse duration is 1 to 100 μsec. The pressure is in the range of atmospheric pressure or near atmospheric pressure, and the pressure range may be 1.3 × 10 ^{1 to} 1.31 × 10 ⁵ Pa. The reactive gas may be a reducing gas such as hydrogen, or may be etched so that grooves can be selectively formed using a gas such as CF ₄ , CHF ₃ , or SF ₆ . The lyophilic property is defined as a contact angle θ of 0 ° ≦ θ <10 °, and the liquid repellency is defined as 10 ° ≦ θ <180 °.

  In addition, the present invention can provide a droplet discharge unit having a plasma processing unit, and can provide a droplet discharge apparatus with improved positional accuracy when a droplet is landed by this configuration.

  The droplet discharge method in the present invention means a method of forming a predetermined pattern by discharging droplets containing a predetermined composition from the pores, and includes an ink jet method in its category.

  The present invention having the above configuration can produce a pattern with improved positional accuracy when a droplet composition is landed on a substrate. In addition, it is possible to provide a display device that can be adapted to the global environment and can significantly reduce costs by shortening the process by direct drawing, improving yield, and increasing material utilization efficiency.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it is easily understood by those skilled in the art that modes and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments below. Note that in the structure of the present invention described below, the same symbol is used in different drawings.

  One aspect of the liquid droplet ejection means according to the present invention, in which the liquid repellent surface is selectively made lyophilic, will be described with reference to FIG. A thin film 100 having a liquid repellent surface, such as a semiconductor silicon film, is formed over an insulating substrate such as a glass substrate (FIG. 1A). The droplet discharge scheduled region 101 is selectively irradiated on the surface of the thin film 100 by the plasma irradiation means 102 to make the region 101 lyophilic (FIG. 1B). A droplet composition 106 is discharged onto the lyophilic surface thus formed by the droplet discharge means 103 to produce a pattern (FIGS. 1C and 1D). The plasma irradiation unit 102 and the droplet discharge unit 103 are integrated or arranged at a close position. The plasma irradiation means 102 and the droplet discharge means 103 integrated immediately after the plasma irradiation are moved to the processing position by the moving means 105. The ejected composition 107 landed by moving the droplet ejecting means 103 is lyophilic when the landing position is irradiated with plasma, and the non-landing region 100 is liquid repellent. Since no problem occurs, the discharge composition can be formed with high accuracy. After the plasma irradiation by the plasma irradiation unit 102, it is possible to discharge the droplet to the plasma irradiation position without moving the droplet discharge unit 103. In this case, however, the piezo element or discharge port of the droplet discharge unit 103 is inclined. It is necessary to change the electrical signal.

The power source for plasma generation is preferably a high frequency power source or a high voltage pulse power source. The high frequency is preferably 10 to 100 MHz, the pulse power source is preferably 50 Hz to 100 kHz, and the pulse duration is 1 to 100 μsec. The pressure is in the range of atmospheric pressure or near atmospheric pressure, and the pressure range may be 1.3 × 10 ^{1 to} 1.31 × 10 ⁵ Pa. In a reduced-pressure atmosphere rather than atmospheric pressure, the landing accuracy tends to improve because the probability of collision with gas molecules or suspended matter decreases from discharge to landing. As a reactive gas used for generating plasma for making it lyophilic, an inert gas such as He, Ne, Ar, Kr, or Xe, or one or more of oxygen and nitrogen may be appropriately selected and used.

  The droplet discharge material may be any material that can be discharged as a droplet by dissolving in a solvent. For example, the droplet discharge material is used for a conductive material that becomes a wiring, a resist material, a resin material that becomes an alignment film, and a light-emitting element. A light emitting material, an etching solution used for wet etching, or the like can be used.

  A plurality of integrated plasma irradiation means 102 and droplet discharge means 103 may be combined into one processing mechanism. Moreover, the plasma irradiation means 102 and the droplet discharge means 103 can be used independently for each purpose. Even when they are used independently, a plurality of processing mechanisms can be combined into one processing mechanism. The plasma processing means 102 is intended to modify the surface to be processed in this means, but it can also be used as a plasma processing means for film formation or etching, if necessary.

  Next, an aspect of landing on the lyophilic surface with high accuracy and controlling the position of the discharged composition after landing will be described with reference to FIG. Plasma irradiation is selectively performed on the surface of the thin film 200 by the plasma irradiation 202 means.

In the plasma-irradiated region 201, a groove in which the discharged droplet composition 206 is accommodated is formed by hydrogen as a reducing gas, etching gas CF ₄ , CHF ₃ , SF _6, or the like. The size of the groove is adjusted according to the amount of droplets to be ejected, and is appropriately formed according to the extent to which the droplets are accommodated. Even if the plasma irradiation region 201 is not etched like the groove, the surface unevenness may be changed to improve the adhesion of the discharge composition. A droplet composition 206 is ejected by a droplet ejection means 203 into a groove formed by the plasma irradiation, thereby producing a pattern. The plasma irradiation unit 202 and the droplet discharge unit 203 are integrated or arranged at a close position. The integrated plasma irradiation means 202 and droplet discharge means 203 are moved to the processing position by the moving means 205. Since the plasma irradiation and the droplet discharge location are not the same, the droplet discharge means 203 is moved immediately after the plasma irradiation to discharge the discharge composition. Since the discharged ejection composition 207 has a groove formed at the landing position, there is no problem of the droplets moving after landing in the non-landing area 200. Although it is possible to discharge droplets to the plasma irradiation position without moving the droplet discharge means 203 after the plasma irradiation means 202 is irradiated with the plasma, in this case, the piezo element or discharge port of the droplet discharge means 203 is inclined It is necessary to change the electrical signal.

The power source for plasma generation is preferably a high frequency power source or a high voltage pulse power source. The high frequency is preferably 10 to 100 MHz, the pulse power source is preferably 50 Hz to 100 kHz, and the pulse duration is 1 to 100 μsec. The pressure is in the range of atmospheric pressure or near atmospheric pressure, and the pressure range may be 1.3 × 10 ^{1 to} 1.31 × 10 ⁵ Pa. In a reduced-pressure atmosphere rather than atmospheric pressure, the landing accuracy tends to improve because the probability of collision with gas molecules or suspended matter decreases from discharge to landing.

  FIG. 3 shows the relationship between the plasma irradiation region L and the droplet diameter upon landing. In order that R1 <L, R2 = L, R3> L, the diameter R at the time of landing of the discharge composition is always kept at a stable position, regardless of whether the plasma irradiation region L is lyophilic or groove formation, R It is important to satisfy the relationship of / 2 <L ≦ R.

  FIG. 4 shows a configuration in which a nozzle body suitable for performing surface modification or etching using plasmaized gas or reactive radicals or ion species and a nozzle body for discharging droplets are integrated. . A nozzle body for plasma processing will be described. The gas supplied to the nozzle body from the gas supply means 402, its exhaust means 405, and the gas supply means 402 is converted into plasma or reactive radicals in the inner peripheral gas supply cylinder 400 or gas for surface treatment. Ion species are generated and sprayed from the gas ejection port 403 to the object to be processed. Thereafter, the gas is discharged from the outer peripheral gas exhaust tube 404 by the exhaust means 405.

  Further, a gas refining unit 406 may be provided between the gas supply unit 402 and the gas discharge unit 405 to incorporate a configuration for circulating the gas. By incorporating such a configuration, gas consumption can be reduced. Alternatively, the gas discharged from the exhaust unit 405 may be collected and purified, and used again by the gas supply unit 402.

  In order to maintain a stable discharge at or near atmospheric pressure, the distance between the nozzle body and the object to be processed is preferably 50 mm or less, and preferably 10 mm or less.

  The shape of the nozzle body is most preferably a coaxial cylindrical type centered on the electrode 401 provided inside the inner peripheral gas supply cylinder 400 and the solid dielectric 412 installed on the electrode 401, but is also locally However, the present invention is not limited to this as long as it can supply the plasma-processed processing gas. The distance between the electrodes is determined in consideration of the thickness of the fixed dielectric, the magnitude of the applied voltage, the purpose of using plasma, and the like, but is preferably 1 to 7 mm. The irradiation port for plasma irradiation is narrower than between the electrodes.

  The electrode 401 may be formed of a rod shape, a spherical shape, a flat plate shape, a cylindrical shape, or the like using stainless steel, brass, other alloys, aluminum, nickel, or other single metal. The solid dielectric 412 provided on the electrode 401 needs to completely cover the electrode 401. If there is a portion where the electrodes directly face each other without being covered by the solid dielectric, arc discharge occurs from there. Examples of the solid dielectric include metal oxides such as silicon dioxide, aluminum oxide, zirconium dioxide, and titanium dioxide, plastics such as polyethylene terephthalate and polytetrafluoroethylene, glass, and complex oxides such as glass and barium titanate. The shape of the solid dielectric may be a sheet or a film, but the thickness is preferably 0.05 to 4 mm. If a high voltage is required to generate discharge plasma and the solid dielectric is too thin, dielectric breakdown occurs when voltage is applied, and arc discharge occurs. A DC power source or a high frequency power source can be applied to the power source 407 that supplies power to the electrode 401. When a DC power source is used, it is preferable to supply power intermittently in order to stabilize the discharge, and the frequency is preferably 50 Hz to 100 kHz and the pulse duration is 1 to 100 μsec.

The treatment gas is selected from inert gases such as He, Ne, Ar, Kr, and Xe, or oxygen and nitrogen for the purpose of selectively treating the lyophobic surface to the lyophilic surface. On the other hand, for the purpose of forming grooves by etching the lyophilic surface, a reducing gas such as hydrogen, carbon tetrafluoride (CF ₄ ), nitrogen trifluoride (NF ₃ ), sulfur hexafluoride (SF ₆ ). ), Other fluoride gases and oxygen (O ₂ ) may be used in appropriate combination. In order to stably maintain the discharge, these fluoride gases may be diluted with a rare gas such as helium, argon, krypton, or xenon.

The atmospheric pressure or the pressure in the vicinity of the atmospheric pressure may be 1.30 × 10 ^{1 to} 1.31 × 10 ⁵ Pa. Of these, in order to keep the reaction space at a pressure lower than the atmospheric pressure, the nozzle body and the substrate to be processed may be held in the reaction chamber forming the closed space and the reduced pressure state may be maintained by the exhaust means.

  Next, a nozzle body for discharging droplets will be described. An electric signal 411 is sent to the piezo element 408, and a discharge composition is sent from the droplet cartridge 410 at the timing of the electric signal 411, and discharged from the discharge port 409 to a region where plasma treatment has been performed. At this time, the pressure lower than the atmospheric pressure tends to improve the landing accuracy because the probability of colliding with gas molecules or suspended matter from discharge to landing decreases. In addition, a pattern without droplet movement after landing is formed by discharging into regions or grooves that have been changed to lyophilicity by plasma treatment. Since the droplet discharge means is non-contact with the processing substrate, it is superior in space saving, material utilization efficiency, multi-product compatibility, landing accuracy, and fine dimension pattern as compared with the screen printing method.

  In FIG. 4, the nozzle body that performs plasma processing and the nozzle body that discharges droplets are integrated, but may be separated by an appropriate distance. The plasma processing means is not limited to the purpose of surface modification, and may be used separately from the droplet discharge means for the purpose of film formation or etching.

  FIG. 5 shows a nozzle mechanism when the plasma processing nozzle handles only a gas having no danger, which is simplified from FIG. The gas supplied to the nozzle body from the gas supply means 502, its exhaust means 509, and the gas supply means 502 is a plasma or reactive radical or gas in the inner peripheral gas supply cylinder 500. Ion species are generated and sprayed from the gas ejection port 503 to the object to be processed. Thereafter, the gas is provided with a hood 512 surrounding the apparatus on the outside of the apparatus, and is exhausted by a unified exhaust means 509.

  In order to maintain a stable discharge at or near atmospheric pressure, the distance between the nozzle body and the object to be processed is preferably 50 mm or less, and preferably 10 mm or less.

  The shape of the nozzle body is most preferably a coaxial cylindrical type centered on the electrode 501 provided inside the inner peripheral gas supply cylinder 500 and the solid dielectric 510 installed on the electrode 501, but similarly, However, the present invention is not limited to this as long as it can supply the plasma-processed processing gas. The distance between the electrodes is determined in consideration of the thickness of the fixed dielectric, the magnitude of the applied voltage, the purpose of using plasma, and the like, but is preferably 1 to 7 mm. The irradiation port for plasma irradiation is narrower than between the electrodes.

  The electrode 501 may be formed of a rod shape, a spherical shape, a flat plate shape, a cylindrical shape, or the like using stainless steel, brass, other alloys, aluminum, nickel, or other simple metal. The solid dielectric 510 placed on the electrode 501 needs to completely cover the electrode 501. If there is a portion where the electrodes directly face each other without being covered by the solid dielectric, arc discharge occurs from there. Examples of the solid dielectric include metal oxides such as silicon dioxide, aluminum oxide, zirconium dioxide, and titanium dioxide, plastics such as polyethylene terephthalate and polytetrafluoroethylene, glass, and complex oxides such as glass and barium titanate. The shape of the solid dielectric may be a sheet or a film, but the thickness is preferably 0.05 to 4 mm. A high voltage is required to generate discharge plasma, and if it is too thin, dielectric breakdown will occur when voltage is applied and arc discharge will occur. A DC power source or a high frequency power source can be applied to the power source 504 that supplies power to the electrode 501. When a DC power source is used, it is preferable to supply power intermittently in order to stabilize the discharge, and the frequency is preferably 50 Hz to 100 kHz and the pulse duration is 1 to 100 μsec.

  The treatment gas can be selected only for the purpose of selectively treating the lyophobic surface to the lyophilic surface. As the processing gas, an inert gas such as He, Ne, Ar, Kr, or Xe, or oxygen or nitrogen is used.

The atmospheric pressure or the pressure in the vicinity of the atmospheric pressure may be 1.30 × 10 ^{1 to} 1.31 × 10 ⁵ Pa. Of these, in order to keep the reaction space at a pressure lower than the atmospheric pressure, the nozzle body and the substrate to be processed may be held in the reaction chamber forming the closed space and the reduced pressure state may be maintained by the exhaust means.

  Next, a nozzle body for discharging droplets will be described. An electric signal 508 is sent to the piezo element 505, and a discharge composition is sent from a droplet cartridge 507 at the timing of the electric signal, and discharged from a discharge port 506 to a region where plasma treatment has been performed. At this time, the pressure lower than the atmospheric pressure tends to improve the landing accuracy because the probability of colliding with gas molecules or suspended matter from discharge to landing decreases. In addition, a pattern without droplet movement after landing is formed by discharging into regions or grooves that have been changed to lyophilicity by plasma treatment.

  In FIG. 5, the nozzle body that performs plasma processing and the nozzle body that discharges droplets are integrated, but they may be separated by an appropriate distance.

  FIG. 6 shows a simplified configuration in which the plasma processing means and the droplet discharge means are integrated. FIG. 6 shows a surface on which plasma processing and droplet discharge processing are performed. FIG. 6A shows a configuration in which the integrated cylindrical nozzle 603 has the plasma processing port 600 and the droplet discharge port 601 arranged as close as possible. The amount of plasma and the amount of liquid droplets discharged from each processing port can be appropriately determined according to the size of the pattern to be processed. However, in the case of plasma processing, it varies depending on the gas flow rate and pressure. The droplet discharge also varies depending on the magnitude of the pulse voltage to the piezo element and the switching method. Further, the shape of the processing port is not limited to the circular shape as shown in FIG. 6A, but can be changed according to the application such as an elliptical shape, a rectangular shape, a square shape, or a triangular shape.

  FIG. 6B is a processed tip of the processing port of FIG. 6A, and the shape is changed in order to process more minute and minute regions. The cylindrical nozzle 606 is connected to a plasma processing port 604 and a nozzle 607 having a narrow tip. A nozzle 608 having a narrow tip is also connected to the droplet discharge port 605, and the plasma processing nozzle 607 and the droplet discharge nozzle 608 are arranged as close as possible. As a result, not only the minute region is processed but also the droplets can be discharged to the plasma processing position without moving after the plasma processing.

  FIG. 7 illustrates an embodiment of a pattern drawing unit in which a large number of nozzles in which the plasma processing unit and the droplet discharge unit are integrated. Plasma processing means and droplet discharge means 701 are provided on the substrate 700. In FIG. 7, the plasma processing unit and the droplet discharge unit 701 do not move with respect to the substrate, but the substrate 700 is processed by appropriately rotating a plurality of rotation shafts under the substrate 700. The plasma processing means and the droplet discharge means 701 use a plurality of heads each provided with a plasma irradiation port 711 and a liquid discharge port 712 and are arranged in a uniaxial direction (the width direction of the substrate 700). The imaging means 702 is provided for detecting the marker position on the substrate 700 and observing the pattern. The head of the plasma irradiation port 711 may be any one that controls the amount and timing of plasma irradiation. The head 712 of the droplet discharge means is not limited as long as it can control the amount and timing of the composition to be discharged or dropped, and has a configuration in which the composition is discharged using a piezoelectric element as in an ink jet method, or a needle at the discharge port. A valve may be provided to control the dropping amount.

  The dispenser 703 that constitutes the plasma processing unit and the droplet discharge unit 701 does not necessarily have to perform the discharge operation at the same timing at the same time. The individual heads 711 and 712 discharge the plasma and the composition as the substrate 700 moves. By controlling the timing, the target pattern can be formed.

  The individual heads 712 of the droplet discharge means are connected to the control means, which can draw a pre-programmed pattern under the control of the computer 707. The drawing timing may be performed with reference to a marker 708 formed on the substrate 700, for example. This is detected by the imaging means 702, converted into a digital signal by the image processing means 706, recognized by the computer 707, a control signal is generated and sent to the control means 704. Of course, the information on the pattern to be formed on the substrate 700 is stored in the storage medium 705. Based on this information, a control signal is sent to the control means 704, and the individual heads 712 of the droplet discharge means are controlled. It can be controlled individually.

  The individual heads 711 of the plasma irradiation means are also connected to the control means in the same manner as the droplet discharge means, and can be irradiated to a preprogrammed pattern by being controlled by the computer 707. The plasma irradiation head 711 is connected to a gas supply unit 709 and an electrode power source 710. It should be noted that gas exhaust is not installed in each dispenser 703, but is exhausted in a batch with a hood that covers the apparatus, but is not particularly shown in FIG.

  An embodiment of the present invention will be described with reference to FIGS.

  FIG. 8A shows a step of forming a conductive film in order to form a gate electrode and a wiring.

A substrate having a light-transmitting property such as glass or quartz is used, but other substrates may be used as long as they can withstand the processing temperature in each step. The size of the substrate 1500 is as large as 600 mm × 720 mm, 680 mm × 880 mm, 1000 mm × 1200 mm, 1100 mm × 1250 mm, 1150 mm × 1300 mm, 1500 mm × 1800 mm, 1800 mm × 2000 mm, 2000 mm × 2100 mm, 2200 mm × 2600 mm, or 2600 mm × 3100 mm. It is preferable to use an area substrate to reduce manufacturing costs. A conductive film 11 such as aluminum, titanium, tantalum, or molybdenum is formed on the substrate 10 by a film forming means that includes a nozzle body in which a plurality of jet nozzles are arranged in a uniaxial direction. The conductive material to be discharged is a conductive composition containing metal fine particles with a particle size of about 1 μm, or metal fine particles with a particle size of about 1 μm and nano-micro size ultra fine particles are dispersed in a conductive polymer composition. May be used. Since the conductive film 11 is applied in the state of a solvent-based paste, the adhesion with the glass substrate is poor. Accordingly, the discharge region is subjected to plasma treatment before discharge, and the glass substrate surface is reduced to a reducing gas such as hydrogen, carbon tetrafluoride (CF ₄ ), nitrogen trifluoride (NF ₃ ), sulfur hexafluoride (SF ₆ ), etc. As shown in the embodiment, a minute groove is formed by appropriately combining the fluoride gas and oxygen (O ₂ ), etc., as shown in the embodiment. Even if the groove is not formed, the surface roughness may be increased to improve the adhesion to the substrate. In order to stably maintain the discharge, these fluoride gases may be diluted with a rare gas such as helium, argon, krypton, or xenon. The power source for plasma generation is preferably a high frequency power source or a high voltage pulse power source. The high frequency is preferably 10 to 100 MHz, the pulse power source is preferably 50 Hz to 100 kHz, and the pulse duration is 1 to 100 μsec. The pressure is in the range of atmospheric pressure or near atmospheric pressure, and the pressure range may be 1.3 × 10 ^{1 to} 1.31 × 10 ⁵ Pa. When ejecting droplets, in a reduced-pressure atmosphere rather than atmospheric pressure, the landing probability tends to improve because the collision probability decreases with gas molecules or suspended matter from ejection to landing. A reactive gas used for generating plasma for lyophilicity may be selected from an inert gas such as He, Ne, Ar, Kr, or Xe, or one or more of oxygen and nitrogen as appropriate. The conductive film 11 does not need to be formed over the entire surface of the substrate 10 and may be selectively formed in the vicinity of the region where the gate electrode and the wiring are formed. After discharging the conductive metal liquid onto the substrate, it is dried at 100 ° C. for 3 minutes and baked at 200 to 500 ° C. for 15 to 30 minutes. Prior to drying, the conductive film may be rubbed and flattened with a roller or the like.

  Thereafter, as shown in FIG. 8B, plasma of oxygen, nitrogen, helium or the like is provided by the droplet discharge means 13 in which a plurality of plasma irradiation ports and composition discharge ports are arranged in a uniaxial direction so as to improve adhesion. Then, a resist composition is selectively ejected to form a mask pattern 14 on the conductive film 11 for forming a gate electrode. In this case, since the discharge ports of the droplet discharge means are arranged only in the uniaxial direction, it is only necessary to operate the head only at a necessary position (13a). One of the plasma irradiation unit and the droplet discharge unit 13 or both of them may be moved. Such a process is the same in the following steps.

  FIG. 8C shows a step of forming a gate electrode and a wiring 16 by performing etching using the mask pattern 14. Etching is performed using a film removing means in which a plurality of plasma jets are arranged in a uniaxial direction. Fluoride gas or chloride gas is used for etching the conductive film 11, but in the nozzle body 15, this reactive gas does not need to be sprayed on the entire surface of the substrate 10, and the conductive film 11 is formed in the nozzle body 15. It is only necessary to operate the nozzle body 15a facing the region being processed and process only that region.

  FIG. 8D shows a step of removing the mask pattern 14 and uses a film removing means in which a plurality of plasma nozzles are arranged in a uniaxial direction. In the nozzle body 17, oxygen plasma treatment is performed to perform ashing. However, this need not be performed on the entire surface of the substrate, and the nozzle body 17a is operated only in the vicinity of the region where the mask pattern is formed. This can be done selectively.

  In FIG. 9A, a gate insulating film 19, a non-single crystal silicon film 20, and a protective film 21 are formed. These laminates may be formed by continuously preparing a plurality of nozzle bodies 18 in charge of forming each film, or by changing the reactive gas species every time the nozzle body 18 is scanned once. The layers may be sequentially stacked by switching. Since the region where the film is to be formed is not the entire surface of the substrate 10, for example, the plasma is formed from the entire surface of the nozzle body 18 to form the film only in the region where the TFT is to be formed. Also good. In the case of forming a silicon oxide film, there are options of using an oxide gas such as silane and oxygen or using TEOS. The gate insulating film 19 may be formed on the entire surface of the substrate, or of course, may be selectively formed in the vicinity of the region where the TFT is formed.

  FIG. 9B shows a step of forming a mask pattern 23, in which oxygen and nitrogen are improved so that the adhesion is improved by the plasma processing means and the droplet discharge means 22 in which a plurality of composition discharge ports are arranged in a uniaxial direction. Then, after irradiating plasma such as helium, a resist composition is selectively discharged to form a mask pattern 23 for forming a protective film for the channel portion.

FIG. 9C shows a process of forming the protective film 25 in the channel portion by etching the protective film 21 using the mask pattern 23. Channel protection film formed of a silicon nitride film may be performed using a fluoride gas such as SF _6.

  Thereafter, the mask pattern 23 is removed by the film removing means as in the case of FIG.

  FIG. 9D shows a step of forming a non-single crystal silicon film 27 of one conductivity type for forming the source and drain of the TFT. Typically, an n-type non-single-crystal silicon film is formed, but the reactive gas supplied from the nozzle body 26 includes a silicide gas such as silane and a periodic group 15 element represented by phosphine. What is necessary is just to mix gas.

  FIG. 10A shows a process of forming a source and drain wiring by improving the adhesion by plasma treatment and then applying a solvent-based conductive paste. The plasma processing unit and the droplet discharge unit 28 may be configured to discharge droplets using a piezoelectric element after irradiation with plasma of oxygen, nitrogen, helium or the like so as to improve adhesion, or as a dispenser type. good. In any case, a conductive composition containing metal fine particles having a particle diameter of about 1 μm is selectively dropped to directly form the wiring patterns of the source 29 and the drain 30. Alternatively, metal fine particles having a particle diameter of about 1 μm and nano-micro size ultra fine particles dispersed in a conductive polymer composition may be used. By using this, there is a significant effect that the contact resistance with the non-single crystal silicon film 27 of one conductivity type can be reduced. Thereafter, in order to volatilize the solvent of the composition and cure the wiring pattern, a heated inert gas may be sprayed from the nozzle body in the same manner, or a halogen lamp heater, an oven, or a furnace is used. You may heat. Baking temperature is 100 degreeC, it is dried for 3 minutes, and 200-500 degreeC and 15-30 minutes are baked. Prior to drying, the conductive film may be rubbed with a roller or the like to be flattened so that the surface of the conductive film is free from unevenness.

  10B, using the formed source wiring 29 and drain wiring 30 as a mask, the one-conductivity-type non-single-crystal silicon film 27 and non-single-crystal semiconductor film 20 located on the lower layer side are etched. Etching is performed by irradiating the gas fluoride gas from the nozzle body 31. Etching is performed by irradiating the gas fluoride gas from the nozzle body 31. Also in this case, the amount of reactive gas to be blown is different in the amount of jetting in the vicinity of the wiring formation region and in other regions, and by jetting a large amount in the region where the non-single crystal silicon film is exposed, Etching is balanced and consumption of reactive gas can be suppressed.

  FIG. 10C shows a step of forming a protective film on the entire surface. Typically, a reactive gas converted into plasma is ejected from the nozzle body 32 to typically form a film of the silicon nitride film 33. Since the conductive film is an ultrafine particle having a particle diameter of about 1 μm, there is a concern that the conductive film may be thermally diffused into the contacted thin film. However, the silicon nitride film is effective because it is superior in diffusion prevention and protection ability compared with the oxide film. Further, Ar or the like may be doped into the silicon nitride film in order to make the silicon nitride film a harder barrier film.

  FIG. 10D shows the formation of a contact hole. The nozzle body 34 is used to form the contact hole 35 in a maskless manner by ejecting a reactive gas that is selectively converted into plasma into a place where the contact hole is to be formed. It can be performed. Alternatively, local wet etching may be performed using an HF-based wet etching solution instead of plasma gas. At this time, pure water is dropped to remove the etching solution after dropping the etching droplet so that the etching does not proceed excessively.

  Thereafter, as shown in FIG. 11, a transparent electrode 37 is formed. The plasma processing unit and the droplet discharge unit 36 irradiate the droplet discharge region with plasma such as oxygen, nitrogen, and helium so as to improve adhesion, and then discharge droplets that become transparent electrodes. Also in this case, a configuration in which droplets are ejected using a piezoelectric element may be used, or a dispenser method may be used. The transparent electrode material to be discharged is a conductive composition containing metal fine particles with a particle size of about 1 μm, or metal fine particles with a particle size of about 1 μm and nano-micro size ultra fine particles dispersed in a conductive polymer composition. You may use what was made to do. A composition containing a powder of conductive particles such as indium tin oxide, tin oxide, and zinc oxide is formed by droplet discharge means, and in particular, the resistance of the contact portion with the non-single crystal silicon film 27 of one conductivity type is reduced. can do. In this process, a pixel electrode is formed. After the transparent electrode material is discharged, the solvent of the composition is volatilized to cure the wiring pattern. As a heating means, a heated inert gas may be sprayed from the nozzle body in the same manner, a halogen lamp heater, an oven, Heating may be performed using a furnace. Baking temperature is 100 degreeC, it is dried for 3 minutes, and 200-500 degreeC and 15-30 minutes are baked. Prior to drying, the conductive film may be rubbed with a roller or the like to flatten the surface of the transparent electrode so that there are no irregularities.

  The subsequent steps are steps required when manufacturing a liquid crystal display device, but the following steps also use non-contact droplet discharge means. As shown in FIG. 12, an alignment film is formed by the plasma processing unit 120, the droplet discharge unit 121 and the heating unit 122, and a rubbing process is performed by the rubbing unit 124. Further, after the seal material is drawn by the droplet discharge means 125 and the spacer is sprayed by the spraying means 126, the liquid crystal is dropped on the substrate by the liquid crystal dropping means 127.

  The substrate is supplied from another unwinding roller 128 and bonded to the opposite side. By curing the sealing material by the curing means 129, the two substrates are fixed. Furthermore, the dividing means 130 can cut out the panel size as appropriate, and the liquid crystal panel 131 can be manufactured.

  As described above, a display device using the method for manufacturing a semiconductor device of the present invention is manufactured.

  A television receiver, a computer, a video reproduction device, and other electronic devices illustrated in FIG. 13 can be completed using a display device formed by implementing the present invention.

  FIG. 13A illustrates an example in which a television receiver is completed by applying the present invention, which includes a housing 2001, a support base 2002, a display portion 2003, a speaker portion 2004, a video input terminal 2005, and the like. By using the present invention, a television receiver having a screen size of 30 inches or more can be manufactured at low cost. Furthermore, a television receiver can be completed by using the apparatus of the present invention.

  FIG. 13B is an example in which a laptop personal computer is completed by applying the present invention, which includes a main body 2201, a housing 2202, a display portion 2203, a keyboard 2204, an external port 2205, a pointing mouse 2206, and the like. ing. By using the present invention, a personal computer having a display unit 2203 of 15 to 17 type class can be manufactured at low cost.

  FIG. 13C is an example in which an image device is completed by applying the present invention, and includes a main body 2401, a housing 2402, a display portion A 2403, a display portion B 2404, a recording medium reading portion 2405, operation keys 2406, and a speaker portion 2407. Etc. By using the present invention, it is possible to manufacture a video reproducing apparatus which has a display unit 2203 of 15 to 17 type class and is reduced in weight at a low cost.

  In this example, a method of filling a contact hole (opening) with a droplet composition by using a droplet discharge method will be described with reference to FIGS.

  14A, a semiconductor 3001 is provided over a substrate 3000, an insulator 3002 is provided over the semiconductor 3001, and the insulator 3002 has a contact hole 3003. As a method for forming the contact hole, a known method may be used, but a droplet discharge method may be used. In that case, the contact hole 3003 is formed by discharging a wet etching solution from the nozzle. Then, contact hole formation and wiring formation can be continuously performed by a droplet discharge method.

  Then, the nozzle 3004 is moved above the contact hole 3003, the droplet composition is continuously discharged into the contact hole 3003, and the contact hole 3003 is filled with the droplet composition (FIG. 14B). . After that, by resetting the position of the nozzle 3004 and selectively discharging the droplet composition, a conductor 3005 in which the contact hole 3003 is filled with the droplet composition can be formed (FIG. 14C )). In this method, the nozzle 3004 scans the same portion a plurality of times.

  Next, a method different from the above will be described with reference to FIG. In this method, the nozzle 3004 is moved, and a droplet composition is selectively discharged only to a region where a wiring is to be formed, so that a conductor 3006 is formed (FIG. 15B). Next, the liquid crystal moves to above the contact hole 3003 and continuously discharges a droplet composition into the contact hole 3003. As a result, a conductor 3007 in which the contact hole 3003 is filled with the droplet composition can be formed (FIG. 15C). In this method, the nozzle 3004 scans the same portion a plurality of times.

  Next, a method different from the above will be described with reference to FIG. In this method, first, the nozzle 3004 is moved to selectively discharge a droplet composition (FIG. 16A). When the nozzle 3004 reaches above the contact hole 3003, the droplet composition is continuously discharged, and the contact hole is filled with the droplet composition (FIG. 16B). As a result, a conductor 3008 in which the contact hole 3003 is filled with a droplet composition can be formed (FIG. 16C). In this method, the nozzle 3004 does not scan the same location multiple times.

  By using any of the methods described above, a conductor in which the contact hole is filled with the droplet composition can be formed.

  Note that when the droplet discharge method is used, a circuit wiring input to a personal computer or the like can be immediately produced. The system at this time will be briefly described with reference to FIG.

  As basic components, a droplet discharge apparatus including a CPU 3100, a volatile memory 3101, a nonvolatile memory 3102, an input unit 3103 such as a keyboard and operation buttons, and a droplet discharge unit 3104 can be cited. The operation will be briefly described. When circuit wiring data is input by the input unit 3103, the data is stored in the volatile memory 3101 or the nonvolatile memory 3102 via the CPU 3100. Based on this data, the droplet discharge means 3104 selectively discharges the droplet composition, whereby a wiring can be formed.

  With the above configuration, a mask for the purpose of exposure becomes unnecessary, and steps such as exposure and development can be greatly reduced. As a result, throughput is increased and productivity can be greatly improved. Moreover, you may use this structure for the purpose of repairing the disconnection location of a wiring, the defective location of the electrical connection between a wiring and an electrode, etc. In this case, for example, it is preferable to input a repair location to a personal computer or the like and discharge the droplet composition from the nozzle to the location. In addition, wiring can be easily formed even on a large-sized board with a meter angle, and since only a necessary amount of material needs to be applied to a desired location, the amount of wasted material is reduced. Improve usage efficiency and reduce production costs.

FIG. 1 is a diagram showing a configuration of means for selectively forming a lyophobic surface as a lyophilic surface. FIG. 2 is a diagram showing a configuration of means for selectively forming grooves on the lyophilic surface. FIG. 3 is a conceptual diagram regarding the plasma processing region and the droplet diameter upon landing. FIG. 4 is a diagram showing an example of pattern drawing means according to the present invention. FIG. 5 is a diagram showing an example of pattern drawing means according to the present invention. FIG. 6 is a view showing a plasma processing port and a droplet discharge port. FIG. 7 is a diagram showing an example of the drawing means according to the present invention. FIG. 8 is a cross-sectional view illustrating the manufacturing process of the display device according to the present invention. FIG. 9 is a cross-sectional view illustrating a manufacturing process of the display device according to the present invention. FIG. 10 is a cross-sectional view illustrating the manufacturing process of the display device according to the present invention. FIG. 11 is a cross-sectional view illustrating a manufacturing process of the display device according to the present invention. FIG. 12 is a diagram showing a manufacturing process of the display device according to the present invention. FIG. 13 is a diagram illustrating one mode of a display device according to the present invention. FIG. 14 is a diagram showing an example of a means for filling the opening according to the present invention with a droplet composition. FIG. 15 is a diagram showing an example of a unit for filling the droplet composition with the opening according to the present invention. FIG. 16 is a diagram showing an example of means for filling the apertures with the droplet composition according to the present invention. FIG. 17 is a diagram illustrating an example of a control device according to the present invention.

Claims (9)

Using a plasma generated by applying a high-frequency or pulsed voltage to the first electrode or the second electrode with a process gas introduced between the first electrode and the second electrode, repelling is performed. Plasma generating means for selectively lyophilic liquid thin film surface;
Droplet discharging means for discharging the droplet composition onto the lyophilic surface of the thin film to produce a pattern,
A droplet discharge apparatus having a configuration in which the plasma generating unit and the droplet discharge unit are integrated or capable of continuous processing. In claim 1,
The liquid droplet ejection apparatus, wherein the liquid repellent thin film is any one of a semiconductor film, a conductive film, and a polymer film. In claim 1 or 2,
The liquid-repellent thin film surface has a contact angle θ of 10 ° ≦ θ <180 °. Using a plasma generated by applying a high frequency or pulsed voltage to the first electrode or the second electrode in a state where a process gas is introduced between the first electrode and the second electrode, Plasma generating means for selectively forming grooves or holes in the liquid thin film surface;
Droplet ejection means for producing a pattern by ejecting a droplet composition into the groove of the thin film,
A droplet discharge apparatus having a configuration in which the plasma generating unit and the droplet discharge unit are integrated or capable of continuous processing. In claim 4,
The droplet discharge apparatus, wherein the lyophilic thin film is any one of a silicon oxide film, a silicon nitride film, a silicon oxynitride film, and a metal oxide film. In claim 4 or 5,
The droplet discharge device, wherein the lyophilic thin film surface has a contact angle θ of 0 ° ≦ θ <10 °. In any one of Claims 1 thru | or 6,
The method for producing a pattern, wherein the droplet composition is a conductive material, a resist material, a polymer material, or a luminescent material. In any one of Claims 1 thru | or 7,
The plasma generating means has an electrode provided with a pair of solid dielectrics and a high frequency or pulse power source, and introduces a processing gas between the electrodes. In any one of Claims 1 thru | or 8,
Regarding the plasma generation unit and the droplet discharge unit, the pressure of the processing unit is in the range of 1.3 × 10 ^{1 to} 1.31 × 10 ⁵ Pa.

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