JP2018076591A - Film deposition apparatus according to mist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable a material substance for an electronic device to be formed finely in a high accuracy on a substrate such as a film.SOLUTION: A film deposition apparatus for depositing and filming particles contained in a mist on the surface of a substrate, by spraying a gas containing a mist on the surface of a substrate comprises: a carrier mechanism for moving a substrate formed with a familiar liquid portion, continuously in a predetermined transportation direction thereby to carry continuously at a predetermined transportation speed; and a chamber disposed to pass the substrate over a predetermined length along the transportation direction, and spraying the gas, which is misted from a functional solution containing molecules or particles of a material substance for an electronic device, so that the gas may be flown along the surface of the substrate at a flow velocity adjusted according to the transportation velocity.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film forming apparatus using mist.

  In a large-screen display element (display panel) such as a liquid crystal display element, a transparent electrode layer such as ITO, a semiconductor material layer such as Si, an insulating film layer, or a metal film layer for wiring is provided on a flat glass substrate. A circuit pattern is transferred by applying a photoresist on the deposited film, and a circuit pattern is formed by etching after developing the photoresist after the transfer. However, since the glass substrate is enlarged with an increase in the screen size of the display element, there has been a problem that the substrate transfer device and the processing device are also enlarged, and the production line (factory) is enlarged. Therefore, a roll-to-roll method (hereinafter simply referred to as “roll method”) in which a display element is directly formed on a flexible substrate (for example, a film member such as polyimide, PET, metal foil, or an ultrathin glass sheet material). Has been proposed (for example, see Patent Document 1).

  When processing flexible film members using the roll method, the amount of various materials used for manufacturing and the amount of various utility power (electric power, air pressure, refrigerant, etc.) are reduced compared to conventional production methods. Therefore, an additive manufacturing method with less environmental load is desired. The manufacturing method disclosed in Patent Document 1 also does not use a conventional lithography method using a photoresist, and deposits necessary materials only on necessary portions during fine patterning of TFTs (thin film transistors) and wirings. Mainly the manufacturing method by the inkjet method etc. to make.

  Patent Document 2 discloses a self-assembled monomolecular film (SAM) when an electrode layer or a wiring layer is formed by selectively applying a conductive ink material on a film material by such an ink jet method. Layer) is uniformly formed, and then the surface of the SAM layer is irradiated with ultraviolet rays patterned corresponding to the shape of the electrodes and wirings to improve the wettability (lyophilicity). A method of coating is disclosed.

  Patent Document 3 discloses a method of applying and patterning a mist of a material solution to be formed on a substrate through a shadow mask as a method that can be expected to have high productivity. This Patent Document 3 also discloses that a pattern is formed by overlaying a shadow mask on a substrate after previously imparting lyophilic and lyophobic contrast to the surface of the substrate, as in the ink jet method. In the experimental example, it is assumed that an opening pattern of 0.5 mm × 12 mm on the shadow mask is formed on the substrate with the same dimensions.

International Publication No. WO2008 / 1229819 Pamphlet International Publication WO2010 / 001537 Pamphlet Japanese Patent No. 4387775

  However, in the inkjet method, a functional material such as a nano-ink conductive material is selectively applied to a specified region on the substrate in the form of small droplets from the ink discharge head, so that the pattern size (line width or If the dot size is as small as 20 μm or less, for example, the ink droplet landing accuracy from the head is poor, so that a contrast due to lyophilicity and lyophobic properties is provided on the substrate in advance. There is a problem that clean patterning is difficult even if the ink is concentrated. Of course, it is conceivable to devise an ink discharge head and ink material to further reduce the number of ink droplets discharged from the nozzles of the head at one time, but there is a problem that productivity is significantly reduced.

  On the other hand, in the method disclosed in Patent Document 3, since the shadow mask is arranged at a distance from the substrate, the pattern size formed on the substrate is generally larger than the opening pattern on the shadow mask. There is a problem. In Patent Document 3, since a large pattern of 500 μm × 1200 μm is transferred, even if the pattern edge is thickened by about 5 μm or 10 μm, the influence is small. However, in the case of a fine pattern of 20 μm or less, it is a big problem that the pattern edge is as thick as 5 μm or 10 μm, and when a plurality of such fine patterns are adjacent to each other, the adjacent patterns are connected. There is also a problem that is said to end.

  Furthermore, even when a lyophilic and lyophobic contrast is given to the substrate surface and a shadow mask is used in combination, a relative alignment error occurs between the shadow mask and the lyophilic substrate. The pattern is limited by the accuracy of the shadow mask. In addition, it is necessary to prepare a liquid repellent layer of a liquid repellent material uniformly on the surface of the lyophilic substrate in advance, and selectively remove the liquid repellent layer using photolithography technology for patterning. there were. In addition, there is a problem that it is difficult to manufacture a linear pattern or contact hole (via hole) pattern with a fine line width of 20 μm or less as a shadow mask.

  The present invention has been made in consideration of the above points, and provides a film forming apparatus using a mist capable of forming a material substance for an electronic device on a substrate such as a film with high precision. The purpose is to do.

  According to a first aspect of the present invention, there is provided a film forming apparatus using mist that forms a film by spraying a gas containing mist on a surface of a substrate and depositing particles contained in the mist on the surface of the substrate. A substrate having a lyophilic portion formed on the surface as a substrate is moved in a predetermined conveyance direction continuously at a constant conveyance speed, and the substrate is passed over a predetermined length along the conveyance direction. And a misted gas of a functional solution containing molecules or particles of a material substance for an electronic device is caused to flow along the surface of the substrate at a flow rate adjusted according to the transport speed. And a chamber for spraying on a mist.

  According to the present invention, it is possible to form a fine pattern on a substrate with higher accuracy than a printing method or an ink jet method, and a thin film layer made of a material to be selectively patterned with a uniform thickness can be easily used. Can be formed.

FIG. 1 is a diagram illustrating a schematic configuration of a substrate processing apparatus according to the first embodiment. FIG. 2 is a diagram showing the chemical structure of the photosensitive silane coupling agent deposited on the substrate. FIG. 3 is a diagram illustrating an example of a pixel circuit of an active matrix display. 4A is a plan view illustrating a transistor structure of the pixel circuit of FIG. 4B is a cross-sectional view taken along 4B-4B in FIG. 4A. FIG. 5 is a diagram showing an overall configuration of the substrate processing apparatus according to the second embodiment. FIG. 6 is a diagram showing a configuration of a part of the substrate processing apparatus according to the third embodiment. FIG. 7 is a diagram showing various patterns formed on a sheet as a substrate to be processed. FIG. 8 is a diagram showing a configuration of a part of the substrate processing apparatus according to the fourth embodiment.

(First embodiment)
A substrate processing apparatus according to a first embodiment of the present invention will be described below with reference to FIGS. 1 to 4B. FIG. 1 shows a schematic overall configuration of a substrate processing apparatus. In this embodiment, a flexible substrate P supplied from a supply roll FR1 is typically sent sequentially to four processing units U1, U2, U3, and U4. After that, it is configured to be wound by the collection roll FR2, and while the substrate P is sent from the supply roll RF1 to the collection roll RF2, a fine pattern made of a functional material is precisely formed on the substrate P.

  The processing unit (functional layer forming unit) U1 includes, for example, a printing transfer drum Gpa and the like, and is a photosensitive lyophobic coupling agent, for example, silane coupling having a fluorine group having liquid repellency in nitrobenzyl. The agent is uniformly applied to at least the entire pattern formation region on the surface of the substrate P. Since a pattern is not normally formed on the back surface of the substrate P, a water-repellent film is applied to the back surface of the substrate P by a transfer drum Gpb so that unnecessary deposition does not occur in mist deposition in a subsequent process. You can keep it.

  As an example, the photosensitive silane coupling agent (photosensitive SAM) used in the present embodiment is configured by a chemical formula as shown in FIG. 2. Details of the photosensitive silane coupling agent (photosensitive SAM) are as follows. Paper 1: Presented at “New Technology Briefing” held by the Japan Science and Technology Agency: “Cell patterning technology using near-ultraviolet light using a surface modifier”, or Japanese Patent Application Laid-Open Nos. 2003-321479 and 2008-050321 It is disclosed in the gazette.

  In FIG. 2, the silane coupling agent having a fluorine group applied to the surface of the substrate P is a liquid repellent region HPB having a fluorine group when the solvent is dried after application. When the surface is irradiated with patterning ultraviolet rays UV at a predetermined illuminance for a predetermined period of time, the fluorine group bond is released, and the portion becomes a region HPR that is relatively lyophilic with relatively low liquid repellency. In the experimental example disclosed in Japanese Patent Laid-Open No. 2008-050321, the contact angle of the surface of the substrate in the unirradiated region of ultraviolet rays is 110 ° (water repellency), and the substrate is made of tetramethylammonium hydroxide (TMAH) after ultraviolet irradiation. It is disclosed that the contact angle of the region irradiated with ultraviolet rays is reduced to about 20 ° (changed to lyophilicity) by washing with an aqueous solution.

  The substrate P coated with the coupling agent is sufficiently dried (heat treatment at 200 ° C. or less) in the next processing unit U2, and then sent to the processing unit U3 (patterning unit). A predetermined amount of the converted ultraviolet light energy is applied to the layer (functional layer) made of the coupling agent on the surface of the substrate P. The processing unit U3 includes a drum mask DM on which a fine pattern mask is formed, a light source in the ultraviolet region (wavelength 400 nm or less), an illumination system IU that irradiates the drum mask DM with ultraviolet illumination light, and a drum mask DM. Is provided with a projection optical system PL that forms an image of the ultraviolet rays patterned by the above on the substrate P. The processing unit U3 is a stepper type or scanning type exposure apparatus, but may be a beam scanning type drawing machine, a maskless exposure machine using DMD, or the like.

  As shown in FIG. 2, immediately after the photosensitive silane coupling agent is applied to the surface of the substrate P and dried, the fluorine group having liquid repellency is bonded to nitrobenzyl, and the portion is a liquid repellant region. Although it is HPB, when ultraviolet UV is irradiated with a predetermined energy amount, the irradiated portion of the nitrobenzyl group reacts to dissociate the fluorine group, and the liquid repellency of that portion decreases, resulting in a lyophilic solution. It becomes the sex region HPR. In other words, the light pattern generated by the drum mask DM is transferred on the substrate P as a pattern having a contrast due to the difference in lyophilicity.

  In order to remove the unbonded fluorine group from the surface of the substrate P, the substrate P exposed by the processing unit U3 is washed with TMAH as disclosed in Japanese Patent Laid-Open No. 2008-050321 and then dried. It is desirable to make it. For this purpose, a TMAH cleaning tank, a pure water cleaning tank, a drying unit, and the like are provided between the processing unit U3 and the processing unit U4.

  The substrate P that has undergone the exposure process (or cleaning / drying process) is then sent to the processing unit (mist deposition unit) U4. In the processing unit U4, a so-called film formation method called mist deposition is applied, and a fundamental apparatus configuration for that purpose is disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-307238, and the mist deposition method is used. An experimental example of depositing a thin film of zinc oxide (ZnO) was published in the paper 2: “Research on mist CVD method and its application to the growth of zinc oxide thin film” (published March 24, 2008) [ URI: http://hdl.handle.net/2433/57270], pages 35-43-65.

In the processing unit U4, an atomizer that makes a liquid (functional solution) containing molecules and particles of a raw material substance to be deposited on the lyophilic region HPR of the substrate P into a mist with an ultrasonic vibrator. GS1, a gas supply unit GS2 for supplying a carrier gas such as nitrogen (N ₂ ), argon (Ar), air (O ₂ ) or the like at a predetermined flow rate, and a mist of a functional solution are mixed with the carrier gas at a predetermined concentration. A mixer ULW, a reaction chamber TC for bringing the mixed gas into contact with the surface of the substrate P at a predetermined flow rate, and a recovery port part De for recovering the gas in the chamber TC are provided.

As the raw material, a solution containing a molecule that becomes an oxide semiconductor or an organic semiconductor, a carbon nanotube, a solution for an electrode or wiring containing metal nanoparticles, or a solution having a molecular structure that becomes an insulating film is selected. When zinc oxide (ZnO) is selected as the raw material, as disclosed in the previous paper 2, the atomizer GS1 is supplied with a ZnAc ₂ , 98% H ₂ O solution, and an internal 2. The ZnAc ₂ solution is misted by the 4 MHz ultrasonic transducer. The mist is sent into the reaction chamber TC together with the carrier gas, and the raw material substance (mist) is selectively captured in the lyophilic region HPR on the surface of the substrate P that travels in the chamber TC at a constant speed.

  The substrate P that has been subjected to mist / deposition processing in the processing unit U4 is sent to a drying (heating) unit (not shown) and the like, and solvent components and the like are removed from the raw material deposited in the lyophilic region HPR on the surface of the substrate P. Then, it is sent to a downstream processing step, and after an appropriate processing step, it is wound around the collection roll FR2. Thus, on the substrate P that has passed through the processing unit U4, a thin film layer made of the raw material is deposited as a pattern having a shape that follows the lyophilic region HPR.

  Incidentally, in general, in an active matrix display panel (AMOLED) using an organic EL as a light emitter, a pixel circuit by a thin film transistor (TFT) as shown in FIG. 3 is provided for each pixel (subpixel). . In FIG. 3, a light emitting diode OLED as an organic EL element is driven by two transistors, a pixel switching transistor TR1 and a current driving transistor TR2. A luminance signal Yc corresponding to the pixel is applied to the drain electrode D1 of the transistor TR1, and the transistor TR1 is turned on / off in response to a synchronous clock pulse Hcc applied to the gate electrode G1 of the transistor TR1.

  When the transistor TR1 is turned on, the voltage level of the luminance signal Yc is held in the capacitor Cg and applied to the gate electrode G2 of the transistor TR2. The transistor TR2 performs voltage / current conversion such that a driving current corresponding to the voltage applied to the gate electrode G2 flows from the drain electrode D2 to the source electrode S2. As a result, a current corresponding to the luminance signal Yc is supplied from the power supply bus line Vdd to the light emitting diode OLED, and the light emitting diode OLED emits light with a luminance corresponding to the magnitude of the current.

  Such a pixel circuit is configured as shown in FIGS. 4A and 4B, for example. 4A shows a planar arrangement of only the transistors TR1 and TR2 in one pixel circuit, and FIG. 4B is a cross-sectional view taken along 4B-4B in FIG. 4A. The transistors shown in FIGS. 4A and 4B are of bottom gate type. First, in a recess formed on the upper surface of the substrate P by an imprint method or the like, a printing method using a conductive ink or an electroless plating method is used. Thus, the gate electrodes G1 and G2 are formed. A gate insulating film Is is stacked thereon as shown in FIG. 4B. Here, the source electrode S1 of the transistor TR1 and the gate electrode G2 of the transistor TR2 are not electrically connected to the entire surface of the substrate P. The opening HA for connection is formed by a selective deposition technique such as a printing method or an inkjet method so that the opening HA is formed between the transistors TR1 and TR2. The gate electrode layer may be formed by a mist deposition method.

  On the insulating film Is, a semiconductor layer MS made of an organic, oxide, or carbon nanotube provided as a solution is selectively formed by a printing method, an inkjet method, or the like corresponding to each transistor formation region. Is deposited. When low-temperature annealing (200 ° C. or less) for crystallization (orientation) of the semiconductor layer MS is completed, a pattern corresponding to the drain electrodes D1 and D2 and the source electrodes S1 and S2 is applied using conductive ink or the like. The At this time, the gate electrode G2 of the transistor TR2 is exposed in the opening HA of the insulating film Is, and when the pattern corresponding to the source electrode S1 of the transistor TR1 is applied with conductive ink or the like, the opening HA The source electrode S1 and the gate electrode G2 are connected.

  In the pixel circuit configured as described above, the process according to the present embodiment includes, for example, a step of forming the gate electrodes G1 and G2, a step of forming the semiconductor layer MS, or the drain electrodes D1 and D2 and the source electrodes S1 and S2. Can be applied. However, in the thin film formation by the mist deposition method, the mist size when the solution containing the raw material is made mist, the concentration of the raw material contained in the mist and the concentration of the mist in the carrier gas (hereinafter collectively referred to as the mist concentration) It is desirable to optimize the flow rate of the carrier gas, the temperature in the reaction chamber TC, etc., in the size of the pattern to be formed.

  In this embodiment, in order to efficiently form a fine pattern similar to the conventional photolithographic method by the mist deposition method, a material (silane coupling) in which the lyophilicity and lyophobic properties change on the substrate P due to photosensitivity. Agent) and finely patterned light is irradiated onto the substrate P to form a high-definition pattern having a hydrophilic / hydrophobic contrast. For this reason, the region HPR having a high lyophilic property on the surface of the substrate P has a higher surface energy than the region HPB having a high liquid repellency. Deposition is possible.

Here, the surface energy of the highly liquid-repellent region HPB is Epb, the surface energy of the highly lyophilic region HPR is Epr, the surface energy of the mist solvent is Eem, the mist diameter is φm, and the dimension of the pattern to be formed ( When ΔDp is set as the minimum line width or the like, the relationship is set so as to satisfy one or both of the following relationships I and II.
Relationship I: Surface energy Epb <Eem <Epr
Relationship II: Mist size (diameter) 0.2 · ΔDp <φm <ΔDp

  When the mist diameter φm is larger than the minimum line width ΔDp to be patterned, the mist protrudes and adheres to the highly lyophilic region HPR (line width ΔDp). The surface energy may grow into a large mist and flow out of the highly lyophilic region HPR. Therefore, a mist diameter that is larger than the pattern dimension (ΔDp) to be formed is not preferable. On the other hand, if it is too small, it takes too much deposition time for pattern formation, and productivity is lowered.

  As an example, in the pixel circuit shown in FIGS. 4A and 4B, the pattern line width of the drain electrode and the source electrode constituting the transistors TR1 and TR2 is about 20 μm, the pattern line width of the gate electrode is about 6 μm, and the size of the semiconductor layer MS. Is about 40 × 30 μm, the mist size φm when the gate electrode is formed by the mist deposition method is 1.2 μm <φm <6 μm, and when the semiconductor layer MS is formed by the mist deposition method The mist size φm is 6 μm <φm <30 μm. Note that the electrode (wiring) layer, the semiconductor layer, the insulating film, and the like for forming the TFT have different optimum thicknesses in terms of electrical performance, and therefore, in the reaction chamber TC depending on the thickness of the pattern to be deposited. Adjustments such as changing the mist concentration, changing the transport speed of the substrate P and the flow rate of the mist gas, and changing the temperature in the reaction chamber TC are required.

  The process shown in FIG. 1 is for forming one layer by a mist deposition method, and for forming several layers of a device having a multi-layer structure by a mist deposition method. 1 may be serially connected as many as the number of layers of the processing units U1 to U4 in FIG.

(Second Embodiment)
Next, a device manufacturing system embodying the substrate processing apparatus will be described with reference to FIG. FIG. 5 is a diagram showing a partial configuration of a device manufacturing system (flexible display manufacturing line). A flexible substrate P (sheet, film, etc.) drawn out from the supply roll FR1 is successively wound around the collection roll FR2 via n processing devices U1, U2, U3, U4, U5,. Examples are shown. The host control device 5 performs overall control of the processing devices U1 to Un constituting the production line.

  In FIG. 5, the orthogonal coordinate system XYZ is set so that the front surface (or back surface) of the substrate P is perpendicular to the XZ plane, and the width direction orthogonal to the transport direction (long direction) of the substrate P is set to the Y direction. Shall be. In addition, the substrate P is subjected to a predetermined pretreatment in advance and subjected to a surface modification for strengthening the deposition of the photosensitive silane coupling agent, or a fine surface for precise patterning on the surface. What formed the partition structure (uneven structure) may be used.

  The substrate P wound around the supply roll FR1 is pulled out by the nipped drive roller DR1 and conveyed to the processing device U1, and the center of the substrate P in the Y direction (width direction) is set by the edge position controller EPC1. Servo control is performed so as to be within a range of about ± 10 μm to several tens μm relative to the position.

  The processing device U1 is a coating device that continuously or selectively applies a photosensitive functional liquid (photosensitive silane coupling agent) to the surface of the substrate P in the printing method in the transport direction (long direction) of the substrate P. . In the processing apparatus U1, a pressure drum DR2 around which the substrate P is wound, a coating roller for uniformly coating the photosensitive functional liquid on the surface of the substrate P on the pressure drum DR2, or a photosensitive function An application mechanism Gp1 including a printing plate cylinder roller for patterning and applying the liquid, a drying mechanism Gp2 for rapidly removing the solvent or moisture contained in the photosensitive functional liquid applied to the substrate P, and the like are provided. It has been.

  The processing device U2 heats the substrate P conveyed from the processing device U1 to a predetermined temperature (for example, about several tens to 120 ° C.), and stabilizes the photosensitive functional layer applied to the surface. It is. In the processing apparatus U2, a plurality of rollers and an air turn bar for returning and conveying the substrate P, a heating chamber portion HA1 for heating the substrate P that has been carried in, and the temperature of the heated substrate P are set in a post-process ( A cooling chamber HA2 and a nipped drive roller DR3 are provided for lowering the temperature so as to match the environmental temperature of the processing apparatus U3).

  The processing apparatus U3 that performs patterning is an exposure apparatus that irradiates the photosensitive functional layer of the substrate P conveyed from the processing apparatus U2 with ultraviolet patterning light corresponding to a circuit pattern or a wiring pattern for display. In the processing apparatus U3, an edge position controller EPC that controls the center of the substrate P in the Y direction (width direction) to a fixed position, the nipped drive roller DR4, and the substrate P are partially wound with a predetermined tension, and the substrate A rotating drum DR5 (impression body) for supporting a pattern exposed portion on P in a uniform cylindrical surface, and two sets of driving rollers DR6 and DR7 for giving a predetermined slack (play) DL to the substrate P Etc. are provided.

  Further, in the processing apparatus U3, a transmission type cylindrical mask DM (mask unit) and an illumination mechanism IU (inside the cylindrical mask DM, which illuminates a mask pattern formed on the outer peripheral surface of the cylindrical mask DM with ultraviolet rays) In order to relatively align (align) the image of a part of the mask pattern of the cylindrical mask DM and the substrate P to the illumination unit 10) and a part of the substrate P supported in a cylindrical surface by the rotary drum DR5. Alignment microscopes AM1 and AM2 for detecting an alignment mark or the like formed in advance on the substrate P are provided.

  The processing device U4 is a processing device that performs mist deposition on the photosensitive functional layer of the substrate P conveyed from the processing device U3, and supplies the atomizer GS1 and carrier gas shown in FIG. In addition to the part GS2, the mixer ULW, the reaction chamber TC, and the recovery port part De, differential exhaust chambers DE1 and DE2 provided at the front and rear stages of the reaction chamber TC, and the mist material that passes through the reaction chamber TC A temperature control mechanism HP for adjusting the temperature of the gas of the substance and the temperature of the substrate P to be transported, and a dust collection mechanism RT for capturing molecules and particles of the raw material contained in the gas recovered via the recovery port De A unit control unit CUC that comprehensively controls the operation of the processing device U4 is provided.

  In mist deposition, it is possible to atomize a solution of various raw material substances. Among these substances, especially carbon nanotubes (hereinafter referred to as CNT) are harmful to the human body if they are scattered in the atmosphere. There is also. Therefore, the reaction chamber TC has a highly airtight structure, and the difference between the upstream and downstream stages is that the substrate P can be transported and the mist gas containing the raw material is sealed so as not to leak out of the apparatus. Dynamic exhaust chambers DE1 and DE2 are provided. As for the configuration of the atomizer GS1, the carrier gas supply unit GS2, etc., those disclosed in the previous paper 2 can be used, and an ultrasonic transducer is provided in the atomizer GS1. The oscillation frequency and the oscillation intensity are adjusted according to the required mist size.

  The processing apparatus U5 warms the substrate P transported from the processing apparatus U4, and dries the raw material deposited on the lyophilic region HPR of the substrate P by the mist deposition method, so that the moisture content is predetermined. Although it is a heat drying apparatus adjusted to a value, details are omitted. After that, the substrate P that has passed through several processing devices and passed through the last processing device Un in the series of processes is wound up on the collection roll FR2 via the nipped drive roller DR1. Also during the winding, the edge position controller EPC2 controls the Y of the drive roller DR1 and the recovery roll FR2 so that the center in the Y direction (width direction) of the substrate P or the substrate end in the Y direction does not vary in the Y direction. The relative position in the direction is successively corrected and controlled.

  The host control device 5 comprehensively controls each of the processing devices U1 to Un in FIG. 5, but various measurement sensors for measuring the state of the pattern formed on the substrate P, and the transport state of the substrate P In response to signals from various sensors to be monitored, process feedback / feedback and feedforward control are also performed at key points. In the device manufacturing system, an exposure apparatus capable of precisely patterning a fine pattern is used as the processing apparatus U3. Therefore, the boundary between the lyophilic and liquid-repellent portions formed on the substrate P becomes extremely clear and the substrate P Since a raw material material that has been misted is deposited on the lyophilic region HPR, a fine pattern can be formed with high accuracy.

  According to the manufacturing method using the manufacturing system as described above, since the same exposure method as the photolithographic method is applied to the photosensitive functional material, the printing method, the ink jet method and the metal mask (shadow mask) are used. Compared with the method, fine patterning can be performed with high accuracy. In addition, it eliminates the need for expensive equipment used in conventional photolithographic processes such as vacuum deposition equipment and etching equipment, and the raw material can be deposited only on the part where it is to be deposited. There is no need to do so, and there is an advantage that the environmental load is small.

(Third embodiment)
In the processing apparatus U4 for mist deposition shown in FIG. 5, the above relationship I or II is satisfied, and the mist concentration, gas flow rate, temperature, substrate P transfer speed, etc. in the reaction chamber TC are set. It is preferable to set it as an adjustment parameter. This is to control the film thickness and denseness of the raw material deposited on the highly lyophilic region HPR on the substrate P. Furthermore, a function to measure the film thickness of raw material deposited in the highly lyophilic region HPR is provided, and the processing time and conditions (adjustment parameters) of mist deposition are dynamically changed according to the measured values. Is also useful.

  FIG. 6 shows an example in which the processing device U4 for mist / deposition shown in FIG. 5 is provided with a function of measuring the thickness of the deposited pattern, and the configuration of the same function as the members in FIG. The same reference numerals are given. In FIG. 6, the substrate P is maintained in a predetermined tension in the reaction chamber TC by a driving roller DR8 provided in the differential exhaust chamber DE1 and a drive roller DR9 provided in the differential exhaust chamber DE2. Sent in the direction.

  In the present embodiment, a first nozzle NZ1 that ejects a gas that is a mist of a solution containing a raw material substance on the surface of the substrate P is connected from the mixer ULW1 to a position near the differential exhaust chamber DE1 in the reaction chamber TC. Also downstream thereof, a second nozzle NZ2 for ejecting a mist gas of the solution containing the raw material is connected from the mixer ULW2. The two mixers ULW1 and ULW2 are appropriately controlled by the unit controller CUC so as to make the mist concentrations contained in the gas ejected from the nozzles NZ1 and NZ2 the same or different. The mist concentration changes the mixing ratio of the carrier gas supplied from the supply unit GS2 (see FIG. 5) and the mist gas supplied from the atomizer GS1 (see FIG. 5) to each of the mixers ULW1 and ULW2. Can be realized.

  A nozzle VT for sucking and collecting the gas ejected from the nozzles NZ1 and NZ2 is provided downstream of the reaction chamber TC and close to the differential exhaust chamber DE2, and the gas in the chamber TC is an exhaust unit. A flow rate controlled by Exo is sent to the recovery port De. By adjusting the total flow rate of the gas ejected from the nozzles NZ1 and NZ2 and the gas flow rate sucked by the nozzle VT, a gas flow along the transport direction (X direction) of the substrate P is created in the chamber TC. be able to. The flow can be slow, fast, or the same as the transport speed of the substrate P.

  In the configuration of FIG. 6, the mist deposition is performed between the flow paths from the nozzle NZ1 or the nozzle NZ2 to the nozzle VT in the chamber TC, but the adjustment range of the mist concentration is large, and the gas flow rate is set to the substrate. Since it can be adjusted according to the transport speed of P, it is possible to form (deposit) a pattern with a desired film thickness.

  In the present embodiment, the layer thickness of the solution containing the raw material substance deposited as mist on the substrate P at the most downstream position in the reaction chamber TC is downstream of the gas recovery nozzle VT. A measurement sensor TMS for measurement is provided, and the measurement value is sent to the unit control unit CUC. The unit control unit CUC determines whether to adjust the processing conditions (mist concentration, gas flow rate, temperature, etc.) in the chamber TC based on the measured value. As adjustment of the processing conditions, when changing the conveyance speed of the substrate P, the unit control unit CUC outputs the signal Ds1 to the drive motor for the drive roller DR9 (or DR8), and the rotation speed is adjusted.

  As the measurement sensor TMS, an optical interference type film thickness measuring instrument, a spectroscopic ellipsometer, or the like is used. However, since the mist deposited on the substrate P contains a solvent (moisture) even at the most downstream position of the reaction chamber TC, In some cases, it is not possible to accurately determine the thickness of a pattern that is densely formed of raw material substances. Therefore, as shown in FIG. 6, a pair of nip drive rollers NR1 and NR2 are provided after the processing device U5 for heating and drying the substrate P after the processing device U4 for mist deposition (after the differential exhaust chamber DE2). It is preferable to provide a reservoir for the substrate P constituted by the dancer roller DSR, and immediately after that, provide a film thickness measurement sensor TMS.

  In this way, immediately after the reservoir portion of the substrate P, the pattern to be measured on the substrate P can be positioned immediately below the measurement sensor TMS, and the substrate P can be kept stationary for a certain time (for example, several seconds). TMS measurement time can be secured. The time during which the substrate P can be stopped is determined by the speed Vo of the substrate P carried out of the processing apparatus U5 and the swing stroke Ld of the dancer roller DSR in the Z direction. For example, if the velocity Vo of the substrate P is 5 cm / s and the stroke Ld is 50 cm, the substrate P can be kept stationary for up to 20 seconds at the position of the measurement sensor TMS immediately after the reservoir.

  In the measurement sensor TMS after the processing device U5, since the liquid component is removed from the pattern layer of the raw material substance deposited by the mist deposition, the thickness can be accurately measured. The measurement sensor TMS in the reaction chamber TC and the measurement sensor TMS after the processing device U5 are preferably capable of measuring the film thickness of a fine pattern (for example, a line width of 20 μm or less). For example, the optical interference film thickness meter products ST2000-DLXn and ST4000-DLX sold by K-MAC in South Korea are easy to incorporate because they are microscope types, and the diameter of the light spot for measurement is several μm. The measurement time is less than a few seconds. In addition, Dainippon Screen Mfg. Co., Ltd.'s product name Lambda Ace VM-1020 / 1030, a product name RE-8000 equipped with a spectroscopic ellipsometer, etc. are used as measurement sensors TMS after the processing unit U5. It can also be used.

  When measuring the thickness of the pattern of the raw material substance deposited on the substrate P by the measurement sensor TMS as described above, the TFT portion of the device (display panel) formed on the substrate P and a specific layer of the wiring portion are arranged. Although it may be directly measured, a test pattern (mark) forming region for thickness measurement is provided outside the device forming region on the substrate P, and the thickness of the raw material substance deposited thereon is measured. Also good. An example of providing such a test pattern will be described with reference to FIG.

  FIG. 7 is a plan view showing the arrangement of a plurality of device (display panel) regions 100 formed on the substrate P and a plurality of marker regions MK1 to MK5 on which test patterns are formed. Here, a television display panel having an aspect ratio of 16: 9 and a screen size of 32 inches is manufactured, and the longitudinal direction of the display panel region 100 is arranged in the longitudinal direction (X direction) of the substrate P. Each panel region 100 is arranged with a predetermined margin in the longitudinal direction of the substrate P, and margins having a constant width are also set on both sides in the width direction (Y direction) of the substrate P. Three marker regions MK1, MK2, and MK3 are provided in the margin between the panel regions 100 so as to be separated from each other in the Y direction. Two marker regions MK4, MK4, MK5 is provided.

  Here, three measurement sensors TMS shown in FIG. 6 are provided in the width direction of the substrate P so as to correspond to the arrangement of the marker regions MK1 to MK5. The marker areas MK1 to MK5 can be observed by any one of the measurement visual fields St1, St2, and St3 of each measurement sensor TMS. Of the marker areas MK1 to MK5, similar test patterns are formed in the three marker areas MK1 to MK3 arranged in the Y direction.

  An example of the test pattern is shown in the lower dotted circle in FIG. 7 as a representative example of the marker area MK1. A large number of test patterns can be formed in the marker area MK1, but line & space test patterns MPa, MPd, MPe, MPg, and MPh having different line widths, a circular test pattern MPb, and a large rectangular test A pattern MPc, a two-dimensional dot-like test pattern MPf, and the like can be arranged. The line & space test pattern is a set in which the pitch direction is the X direction and the Y direction. Further, the test pattern MPe is formed by arranging a plurality of L-shaped lines in a 45 ° oblique direction, and the test pattern MPh is formed as a 45 ° oblique lattice pattern.

  The line width of the line & space can be determined corresponding to the size of the pattern formed by mist deposition. For example, when an electrode pattern or wiring pattern having a line width of 20 μm is generated on the panel region 100 of the substrate P by mist deposition, the line width is changed to 40 μm, 30 μm, 20 μm, 15 μm, for example, as the test pattern line and space. The four sets are exposed together with the mask pattern for the panel region 100 in the exposure process of the processing apparatus U3. As for the other test patterns MPb, MPc, and MPf, those necessary for measurement are exposed together in the exposure process of the processing device U3.

  The marker areas MK4 and MK5 arranged on both sides in the Y direction of the panel area 100 have a single line-shaped test pattern having a width in the Y direction of about several millimeters and a length in the X direction of several tens of millimeters. You may make it form only. Thus, when the test pattern is elongated in the longitudinal direction of the substrate P, for example, the measurement sensor TMS in the reaction chamber TC shown in FIG. 6 forms the marker regions MK4 and MK5 without stopping the conveyance of the substrate P. It becomes easy to measure the film thickness of the test pattern.

  By the way, the marker region MK1 and the marker region MK4 can be observed by the measurement sensor TMS having the measurement visual field St1, and the marker region MK2 can be observed by the measurement sensor TMS having the measurement visual field St2, and the marker region MK3 and the marker region MK5 can be observed by the measurement sensor TMS having the measurement visual field St3, but the film thickness measurement of the test pattern of the marker areas MK1 to MK3 is performed by the measurement sensor TMS after the processing unit U5 in FIG. The film thickness measurement of the test patterns MK4 and MK5 may be shared so as to be performed by the measurement sensor TMS in the reaction chamber TC. In addition, since a test pattern is formed in each marker area MK1 to MK5 by one mist deposition, when patterning mist deposition over a plurality of layers, a marker is provided for each layer. It is preferable to shift the positions of the areas MK1 to MK5.

  Since there are no other underlying pattern layers in the marker areas MK1 to MK5 as described above, the thicknesses of various test patterns formed by the processing apparatus U4 (mist deposition) are accurately measured. Can do. In addition, since the size (line width, etc.) of the test pattern used for measurement can be selected (changed) according to the size of the device pattern (pattern in the display panel area 100), it is possible to precisely control the film thickness condition. Become. Further, by comparing the film thicknesses of the same kind of test patterns in each of the three marker areas MK1 to MK3 between the panel areas 100, a difference in film forming conditions in the width direction of the substrate P (such as uneven mist concentration) can be obtained. It can also be confirmed and corrected. The measurement sensor TMS may be provided with a sensor for measuring not only the thickness of the formed pattern but also the line width thereof.

(Fourth embodiment)
FIG. 8 shows a mist / deposition treatment apparatus U4 shown in FIG. 5 and a treatment apparatus U5 for performing a heating / drying process integrated with each other, while the substrate P is wound around a rotating drum and conveyed. An example of the apparatus which performs is shown.

  In FIG. 8, a flexible substrate P to be carried is wound around a rotary drum RD that rotates about an axis AX1 through a nip driving roller NDR and a tension roller DR10 for more than half a cycle. It is folded back by the air turn bar ATB in the heating and drying unit 20 as the apparatus U5, and is carried out through the roller DR11, the tension roller DR12, and the nip driving roller NDR. Cylindrical partition walls constituting the reaction chamber TC are provided in a circumferential range around the rotating drum RD around which the substrate P is wound, and mist gas in the chamber TC is formed at both ends of the partition wall in the circumferential direction. An air seal bearing Pd is provided so as not to flow into the environment. Of course, an air seal bearing for closing the gap with the rotary drum RD is also provided at the end of the cylindrical partition wall constituting the chamber TC in the axis AX1 direction (Y direction).

  As shown in FIG. 1, FIG. 5, and FIG. 6, the mist from the atomizer GS1 and the gas from the carrier gas supply unit GS2 are mixed in the mixer ULW to become a mist-containing gas, and the cylinder. Is supplied to one end side (a portion where the substrate P is in contact with the rotating drum RD) of the reaction chamber TC having a shape. The mist-containing gas travels along a narrow cylindrical space along the surface of the substrate P wound around the rotating drum RD, and the other end side of the cylindrical reaction chamber TC (part where the substrate P separates from the rotating drum RD). Thus, the gas is exhausted from the recovery port portion De.

  In this embodiment, since the back surface of the substrate P is brought into close contact with the outer peripheral surface of the rotating drum RD and unnecessary mist does not wrap around the back surface of the substrate P, the back surface can be kept clean. Further, when a temperature control mechanism is provided along the outer periphery in the rotary drum RD, temperature control with high responsiveness of the substrate P can be performed.

  Along with the rotation of the rotating drum RD, the substrate P on which mist is deposited in the lyophilic part HPR on the surface is linearly sent to the first space AT1 of the heating and drying unit 20, and an electric heater, a hot air heater, etc. The pattern of the solution deposited by mist deposition is dried by the temperature control mechanism HP. The substrate P that has passed through the drying space AT1 is folded back at approximately 180 ° by the air turn bar ATB disposed in the second space AT2, and linearly proceeds in the third space AT3 to reach the roller DR11. A partition wall is partitioned between the spaces AT1, AT2, AT3, and a slit-shaped opening through which the substrate P passes is provided in the partition wall. A recovery port portion De is connected to each of the spaces AT2 and AT3, and the remaining mist-containing gas is recovered. When the raw material deposited by mist deposition is a semiconductor material, the space AT1 functions as an annealing furnace for crystallizing and orienting the semiconductor material.

  The air turn bar ATB has an outer peripheral surface that is substantially half the circumference of a cylinder, and an infinite number of fine gas ejection holes and suction holes are provided on the outer peripheral surface. As a result, the substrate P is folded without the surface (the surface on which the raw material is deposited) contacting the surface of the air turn bar ATB. The gas ejected from the air turn bar ATB also has an action of further drying the pattern of the raw material substance deposited on the surface of the substrate P.

  The substrate P folded back by the air turn bar ATB is controlled to a predetermined temperature by the temperature adjusting gas ejected from the nozzle ANZ in the space AT3, reaches the roller DR11, and the rollers DR12 in the space partitioned by the partition walls, It passes through the nip drive roller NDR, passes through an air seal bearing Pd disposed so as to sandwich the substrate P, and is sent to the next processing apparatus or a film thickness and line width measurement sensor unit.

  As described above, when the substrate P is transported using the rotating drum RD as shown in FIG. 8, when the diameter of the rotating drum RD is about 50 cm and the range in which the substrate P is in close contact with the outer peripheral surface of the rotating drum RD is about 240 °, The substantial length of the reaction chamber TC is about 100 cm (50 × π × 240/360), and the footprint of the apparatus can be made smaller than making the reaction chamber TC straight as shown in FIGS. Further, since the substrate P is sent in close contact with the outer periphery of the rotary drum RD, the substrate P does not vibrate up and down during conveyance, and stable mist deposition can be realized.

  As described above, the preferred embodiments according to the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the examples. Various shapes, combinations, and the like of the constituent members shown in the above-described examples are examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention. For example, the substrate P is not limited to a thin film or sheet having flexibility, but may be a glass substrate, a silicon wafer, a plastic substrate, or a resin substrate. Further, the substrate P does not need to be processed by a roll-to-roll method for a long one wound around a roll, and may be a single-sheet processing method that is cut into a predetermined size (A4, B5, etc.).

  In each of the above embodiments, the mist deposition method is used as a method for selectively forming a semiconductor layer, an electrode layer, or a wiring layer in a desired region on the substrate P. Alternatively, a film formation method such as a dip coating method can be used. As with the mist deposition method, the spray method applies a spray-like material solution sprayed from a nozzle onto the substrate P, and the dip coating method applies the substrate P to the material solution tank for a certain period of time. It is dipped and pulled up.

  In either case, for example, as described in the third embodiment (FIG. 7), optical patterning is performed so that marker regions MK1 to MK5 are formed at appropriate positions on the substrate P, and a spray method is performed. After the deposition process of the material solution by the dip coating method, the spraying method is performed by confirming the deposition state (attachment state) with various test patterns in the marker areas MK1 to MK5 with the measurement sensor TMS as shown in FIG. And various conditions of the dip coating method can be fed back and corrected. The various conditions of the spray method are the fine pore diameter of the nozzle for spraying, the spraying pressure, the distance between the substrate P and the nozzle, the relative movement speed between the nozzle and the substrate P, etc. The various conditions of the dip coating method are the material solution Temperature, immersion time of the substrate P, pulling speed, and the like.

  Further, when a conventional photolithography process is performed in which a photoresist layer is subjected to photopatterning (exposure processing) and then developed, and the resist layer is etched according to the pattern, the surface of the substrate P (when there is an underlayer) After the surface is made highly lyophilic, a highly lyophobic photoresist material is applied to the surface of the substrate P with a uniform thickness. Thereafter, by performing development processing, the portion from which the resist layer has been removed (the surface of the substrate P or the surface of the underlayer) is exposed as a highly lyophilic surface, so the mist deposition method (or spray method) The dip coating method) forms a precise pattern with the material solution.

FR1 ... Supply roll, FR2 ... Recovery roll, P ... Substrate, U1, U2, U3, U4, U5, Un ... Processing unit (processing device), Gpa ... Rotating drum for application of photosensitive silane coupling agent, Gp1 ... Application Mechanism, IU ... UV illumination system, DM ... Drum mask,
PL ... Projection optical system, DE1, DE2 ... Differential exhaust chamber, TC ... Reaction chamber, GS1 ... Material material atomizer, GS2 ... Carrier gas supply unit, ULW ... Mixer, HPB ... Liquid repellent unit, HPR ... Parent Liquid part, RD ... Rotating drum, MK1 to MK5 ... Marker area, 20 ... Heat drying unit, 100 ... Display panel area

Claims (8)

A film forming apparatus using a mist that forms a film by spraying a gas containing mist on the surface of the substrate and depositing particles contained in the mist on the surface of the substrate,
A transport mechanism for continuously moving a substrate having a lyophilic portion formed on the surface as the substrate in a predetermined transport direction at a constant transport speed;
The substrate is passed through a predetermined length along the transport direction, and a mist of a functional solution containing molecules or particles of a material substance for an electronic device is transported. A chamber sprayed to flow along the surface of the substrate at a flow rate adjusted according to speed;
A film forming apparatus using mist. A film forming apparatus using the mist according to claim 1,
In the chamber, an ejection nozzle for spraying the mist gas on the surface of the substrate on the upstream side in the transport direction of the substrate, and transporting the gas sprayed in the chamber to the substrate A recovery nozzle for suctioning downstream in the direction is provided,
Mist deposition system. A film forming apparatus using the mist according to claim 2,
The flow rate of the gas in the chamber is adjusted to the transport speed of the substrate by adjusting the flow rate of the gas ejected from the ejection nozzle and the flow rate of the gas sucked by the recovery nozzle. A control unit that controls to be the same as or faster than
Mist deposition system. A film forming apparatus using the mist according to claim 3,
The control unit includes: a concentration of the mist contained in the gas sprayed into the chamber from the ejection nozzle; a concentration of molecules or particles of the material substance contained in the mist; a temperature in the chamber; Adjusting the transport speed of the substrate by the transport mechanism;
Mist deposition system. A film forming apparatus using a mist according to claim 4,
In order to adjust the concentration of the mist contained in the gas sprayed into the chamber from the nozzle for ejection, generated from an H2O solution containing molecules or particles of the material substance by an atomizer using an ultrasonic vibrator A mixer for mixing the mist with a predetermined concentration with the carrier gas to be the gas,
Mist deposition system. A film forming apparatus using a mist according to claim 5,
The carrier gas is any one of nitrogen (N ₂ ), argon (Ar), and air (O ₂ ).
Mist deposition system. It is the film-forming apparatus by the mist as described in any one of Claims 1-6,
The functional solution containing molecules or particles of the material substance is any one of a solution containing molecules serving as a semiconductor, a solution containing carbon nanotubes, a solution containing metal nanoparticles, or a solution having a molecular structure serving as an insulating film. Is,
Mist deposition system. It is the film-forming apparatus by the mist as described in any one of Claims 2-6,
The nozzle for ejection includes a first nozzle and a second nozzle arranged side by side along the transport direction of the substrate,
The mist concentration of the gas ejected from the first nozzle is the same as or different from the mist concentration of the gas ejected from the second nozzle,
Mist deposition system.

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