JP6638792B2 - Mist film formation method - Google Patents

Description

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

  In a large-screen display device (display panel) such as a liquid crystal display device, 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 formed on a flat glass substrate. A circuit pattern is transferred by applying a photoresist on the deposited layer, and after the transfer, the photoresist is developed and then etched to form a circuit pattern and the like. However, there is a problem that the size of the glass substrate increases with an increase in the screen size of the display element, so that the substrate transfer device and the processing device also increase in size, and the production line (factory) becomes large. Therefore, a roll-to-roll method (hereinafter simply referred to as a "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 ultra-thin glass sheet material). ) Has been proposed (for example, see Patent Document 1).

  When a flexible film member is processed by a roll method, compared to the conventional production method, the amount of various materials used in production and the amount of various utilities (electric power, pneumatic pressure, refrigerant, etc.) are reduced. Therefore, an additive manufacturing method with less environmental load is desired. The manufacturing method disclosed in Patent Document 1 also applies a necessary material to only a necessary portion at the time of fine patterning of a TFT (thin film transistor) and wiring without using a conventional lithography method using a photoresist. The main method is a manufacturing method using an inkjet method or the like.

  Further, Patent Document 2 discloses a self-assembled monomolecular film (SAM) when an electroconductive ink material is selectively applied on a film material to form an electrode layer or a wiring layer by such an ink jet method. Layer) is uniformly formed, and then the surface of the SAM layer is irradiated with patterned ultraviolet rays corresponding to the shapes of the electrodes and wirings to improve the wettability (lyophobic property) of the surface of the SAM layer. A method of applying 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. Patent Document 3 discloses that a pattern is formed by applying a lyophilic property and a lyophobic contrast to the surface of a substrate in advance and then overlaying a shadow mask on the substrate in the same manner 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 in the same size on the substrate.

International Publication WO2008 / 129819 Pamphlet International Publication WO2010 / 001537 Pamphlet Patent No. 4377775

  However, in the inkjet method, since a functional material such as a conductive material in the form of nano-ink is selectively applied as a small droplet from an ink ejection head to a specified area on a substrate, the pattern size (line width or If the size of the dot is as small as 20 μm or less, for example, the ink droplet landing accuracy from the head is poor, so that the substrate is provided with a contrast by lyophilicity and lyophobic property on the substrate in advance. However, there is a problem that it is difficult to perform a beautiful patterning even if a process in which the ink is concentrated is performed. Of course, it is conceivable to further reduce the number of ink droplets ejected from the nozzles of the head at one time by devising the ink ejection head and the ink material, but there is a problem that productivity is significantly reduced.

  On the other hand, in the method disclosed in Patent Literature 3, since the shadow mask is arranged at a distance from the substrate, the size of the pattern 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, there is little effect. 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 the problem of saying that it will.

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

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

  In the first aspect of the present invention, a carrier gas containing mist is sprayed on the surface of a flexible long substrate to deposit molecules or particles of a material substance contained in the mist on the surface of the substrate. A film forming method using a mist for forming a thin film layer made of the material, wherein a first region to which the mist can be attached by spraying the carrier gas on a surface of the substrate; A first step of forming a second region, and the substrate having undergone the first step is moved in a longitudinal direction at a predetermined transfer speed in a chamber provided at a predetermined length along the longitudinal direction. A transporting step of moving the substrate so as to pass, the carrier gas containing a mist generated from a solution containing molecules or particles of the material substance at a predetermined concentration, along the surface of the substrate moving in the chamber. Said carrying By spraying to flow at a flow rate corresponding to the speed, the film forming method according mist comprising a second step, the to attach the mist to the first region of the substrate.

  According to the present invention, a fine pattern can be formed on a substrate with higher precision than a printing method or an ink jet method, and a thin film layer of a substance to be selectively patterned with a uniform thickness can be easily formed. Can be formed.

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

(1st Embodiment)
Hereinafter, a first embodiment of the substrate processing apparatus of the present invention will be described 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 sequentially sent to four processing units U1, U2, U3, and U4. After that, the structure is wound up by the collection roll FR2, and a fine pattern of a functional material is precisely formed on the substrate P while the substrate P is sent from the supply roll RF1 to the collection roll RF2.

  The processing unit (functional layer forming unit) U1 includes, for example, a transfer drum Gpa for printing and the like, and a photosensitive lyophilic / repellent coupling agent, for example, silane coupling having a fluorine group having liquid repellency to nitrobenzyl. The agent is uniformly applied to at least the entire pattern forming 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 coated on the back surface of the substrate P by a transfer drum Gpb so that unnecessary deposition does not occur in mist deposition in a later process. You may leave it.

  The photosensitive silane coupling agent (photosensitive SAM) used in the present embodiment is constituted by a chemical formula as shown in FIG. 2 as an example, and the details thereof are described on, for example, June 19, 2009 by an independent administrative agency. Paper 1: "Cell patterning technology using near-ultraviolet light using a surface modifier" published at "New Technology Briefing" held by Japan Science and Technology Agency, or JP-A-2003-321479, JP-A-2008-050321 No. 6,086,045.

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

  The substrate P to which the coupling agent has been applied is sufficiently dried (heated at 200 ° C. or lower) in the next processing unit U2, and then sent to the processing unit U3 (patterning unit). The layer (functional layer) of the coupling agent on the surface of the substrate P is irradiated with a predetermined amount of the converted ultraviolet light energy. The processing unit U3 includes a drum mask DM on which a mask for a fine pattern is formed, an illumination system IU that includes a light source in the ultraviolet region (wavelength of 400 nm or less) and irradiates the drum mask DM with ultraviolet illumination light, and a drum mask DM. There is provided a projection optical system PL and the like for imaging the ultraviolet light 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 a 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, a nitrobenzyl-bonded fluorine group is bonded to the nitrobenzyl, and that portion is formed in a lyophobic region. Although it is HPB, when the ultraviolet ray UV is irradiated with a predetermined energy amount, the nitrobenzyl group in the irradiated portion reacts, the bond of the fluorine group is released, and the liquid repellency of the portion is reduced, and the lyophilicity is reduced. Region HPR. That is, the light pattern generated by the drum mask DM is transferred onto the substrate P as a pattern that forms a contrast due to the difference in lyophilicity.

  The substrate P exposed in the processing unit U3 is washed with TMAH as disclosed in JP-A-2008-050321 and then dried in order to remove the bonded fluorine group from the surface of the substrate P. It is desirable to make it. For this purpose, a cleaning tank using TMAH, a cleaning tank using pure water, a drying unit, and the like are provided between the processing units U3 and U4.

  The substrate P that has been subjected to the exposure processing (or the cleaning / drying processing) is then sent to a processing unit (mist deposition section) U4. In the processing unit U4, a so-called mist deposition method is applied. The principle apparatus configuration for that is disclosed in, for example, JP-A-2005-307238. An experimental example of depositing a thin film of zinc oxide (ZnO) was described in Paper 2: Kyoto University Press, "Study on Mist CVD and Its Application to the Growth of Zinc Oxide Thin Film" (issued March 24, 2008) [ URI: http://hdl.handle.net/2433/57270], page 35, pages 43-65.

In the processing unit U4, a liquid (functional solution) containing molecules and particles of a raw material to be deposited on the lyophilic region HPR of the substrate P is atomized by an ultrasonic vibrator into a mist. GS1, a gas supply unit GS2 for supplying a carrier gas such as nitrogen (N ₂ ), argon (Ar) or air (O ₂ ) at a predetermined flow rate, and a mist of a functional solution 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 De for recovering the gas in the chamber TC are provided.

As the raw material, a solution containing molecules or carbon nanotubes which become an oxide semiconductor or an organic semiconductor, a solution for electrodes or wiring containing metal nanoparticles, or a solution having a molecular structure which becomes an insulating film is selected. When zinc oxide (ZnO) is selected as a raw material, as disclosed in the above-mentioned article 2, the atomizer GS1 is supplied with a ZnAc ₂ , 98% H ₂ O solution, and the internal 2.0. The 4 MHz ultrasonic vibrator converts the ZnAc ₂ solution into mist. The mist is sent into the reaction chamber TC together with the carrier gas, and the raw material (mist) is selectively captured in the lyophilic region HPR on the surface of the substrate P that travels at a constant speed in the chamber TC.

  The substrate P subjected to the mist deposition processing in the processing unit U4 is sent to a drying (heating) unit or the like (not shown) to remove a solvent component or the like from the raw material deposited on 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, is taken up by a recovery roll FR2. In this manner, a thin film layer of a raw material is deposited on the substrate P that has passed through the processing unit U4 as a pattern having a shape following the lyophilic region HPR.

  By the way, in general, in an active matrix type display panel (AMOLED) using an organic EL as a light-emitting body, a pixel circuit including a thin film transistor (TFT) as shown in FIG. 3 is provided for each pixel (sub-pixel). . 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 is applied to the gate electrode G2 of the transistor TR2. Transistor TR2 performs voltage / current conversion such that a drive current corresponding to the voltage applied to gate electrode G2 flows from drain electrode D2 to 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, for example, as shown in FIGS. 4A and 4B. FIG. 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 the line 4B-4B in FIG. 4A. The transistors shown in FIGS. 4A and 4B are of a bottom gate type. First, a printing method using a conductive ink or an electroless plating method is used in a recess formed on the upper surface of a substrate P by an imprint method or the like. Thus, gate electrodes G1 and G2 are formed. As shown in FIG. 4B, a gate insulating film Is is stacked thereon, but here, the source electrode S1 of the transistor TR1 and the gate electrode G2 of the transistor TR2 are electrically connected instead of the entire surface of the substrate P. An opening HA for connection is formed by a selective deposition method such as a printing method or an ink-jet method so as to be formed between the transistors TR1 and TR2. Note that the layer of the gate electrode may be formed by a mist deposition method.

  On the insulating film Is, a semiconductor layer MS formed of an organic, oxide, or carbon nanotube provided as a solution is selectively formed by a printing method, an inkjet method, or the like in accordance with a region where each transistor is formed. Is deposited. After the low-temperature annealing (200 ° C. or less) for crystallization (orientation) of the semiconductor layer MS is completed, patterns corresponding to the drain electrodes D1 and D2 and the source electrodes S1 and S2 are applied using conductive ink or the like. You. At this time, in the opening HA of the insulating film Is, the gate electrode G2 of the transistor TR2 is exposed, 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 is formed. Inside, 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 process of forming the gate electrodes G1 and G2, a process of forming the semiconductor layer MS, or a process of forming the drain electrodes D1 and D2 and the source electrodes S1 and S2. In the step of forming However, in the thin film formation by the mist deposition method, the mist size when the solution containing the raw material is converted into a 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 mist concentration) It is desirable to optimize the flow rate of the carrier gas, the temperature in the reaction chamber TC, and the like in the size of the pattern to be formed.

  In the present embodiment, in order to efficiently form a fine pattern similar to the conventional photolithographic method by the mist deposition method, a material (silane coupling) that changes lyophilic and lyophobic by photosensitivity on the substrate P is used. ) And irradiates the substrate P with fine patterned light to form a high-definition pattern having a hydrophilic / hydrophobic contrast. Therefore, since the surface energy of the region HPR having high lyophilicity on the surface of the substrate P is higher than that of the region HPB having high lyophobic property, mist easily adheres to the region HPR. Deposition becomes possible.

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

  If 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). It may grow into a large mist due to the surface energy, and may flow out of the high lyophilic region HPR. Therefore, it is not preferable that the mist diameter is larger than the pattern dimension (ΔDp) to be formed. On the other hand, if it is too small, it takes too much deposition time to form a pattern, which lowers productivity.

  As an example, in the pixel circuits 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. Has a mist size of 6 μm <φm <30 μm. Note that the electrode (wiring) layer, semiconductor layer, insulating film, and the like for forming the TFT have different optimum thicknesses in terms of electrical performance. Therefore, the thickness in the reaction chamber TC depends on the thickness of the pattern to be deposited. Adjustments such as changing the mist concentration, changing the transfer 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 the mist deposition method. To form several layers of a device having a multi-layer structure by the mist deposition method, 1, the sets of processing units U1 to U4 may be serially connected by the number of layers, and the substrates P may be sequentially transferred.

(2nd Embodiment)
Next, a device manufacturing system embodying the above 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). The flexible substrate P (sheet, film, etc.) drawn from the supply roll FR1 is sequentially wound up on the collection roll FR2 via the n units of processing devices U1, U2, U3, U4, U5,. Examples up to this point are shown. The higher-level control device 5 performs overall control of each of the processing devices U1 to Un configuring the manufacturing line.

  In FIG. 5, the orthogonal coordinate system XYZ is set such that the front surface (or the 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 in the Y direction. Shall be performed. The substrate P is subjected to a predetermined pre-treatment in advance to perform a surface modification for strengthening the adhesion of the photosensitive silane coupling agent, or a fine surface for precise patterning on the surface. What formed the partition structure (concavo-convex structure) may be used.

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

  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 by a printing method in the transport direction (long direction) of the substrate P. . In the processing apparatus U1, an impression roller DR2 around which the substrate P is wound, an application roller for uniformly applying the photosensitive functional liquid to the surface of the substrate P on the impression roller 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 a solvent or moisture contained in the photosensitive functional liquid applied to the substrate P, and the like are provided. Have been.

  The processing apparatus U2 heats the substrate P transported from the processing apparatus U1 to a predetermined temperature (for example, about several tens to 120 ° C.) to stabilize 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 transporting the substrate P, a heating chamber section HA1 for heating the loaded substrate P, and a temperature of the heated substrate P in a post-process ( A cooling chamber HA2 for lowering the temperature of the processing apparatus U3) so as to be equal to the environmental temperature of the processing apparatus U3, a driving roller DR3 nipped, and the like are provided.

  The processing apparatus U3 that performs patterning is an exposure apparatus that irradiates the photosensitive functional layer of the substrate P transferred from the processing apparatus U2 with ultraviolet patterning light corresponding to a circuit pattern and a wiring pattern for display. In the processing device U3, an edge position controller EPC that controls the center of the substrate P in the Y direction (width direction) at a fixed position, a nip-driven drive roller DR4, and the substrate P are partially wound with a predetermined tension, and A rotary drum DR5 (press body) for supporting a portion of the pattern P on which pattern exposure is performed in a uniform cylindrical surface, and two sets of drive 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 (illumination mechanism) provided in the cylindrical mask DM and illuminating a mask pattern formed on an outer peripheral surface of the cylindrical mask DM with ultraviolet rays. In order to relatively align (align) an image of a part of the mask pattern of the cylindrical mask DM and the substrate P with the illuminating unit 10) and a part of the substrate P supported in a cylindrical shape by the rotating drum DR5, Alignment microscopes AM1 and AM2 for detecting alignment marks and 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 transferred from the processing device U3, and supplies the atomizer GS1 and the carrier gas illustrated in FIG. In addition to the unit GS2, the mixer ULW, the reaction chamber TC, and the recovery port De, the differential exhaust chambers DE1 and DE2 provided at the front and rear stages of the reaction chamber TC, and the mist-converted raw material passing through the reaction chamber TC A temperature control mechanism HP for adjusting the temperature of the substance gas and the temperature of the substrate P to be conveyed, and a dust collection mechanism RT for capturing molecules and particles of the raw material substance contained in the gas recovered via the recovery port De. , A unit control unit CUC that controls the operation of the processing device U4 in a centralized manner.

  In mist deposition, solutions of various raw materials can be atomized. Among these materials, carbon nanotubes (hereinafter referred to as CNTs) may be harmful to the human body if scattered in the atmosphere. There is also. For this reason, the reaction chamber TC has a highly airtight structure. The front and rear stages of the reaction chamber TC are configured to seal the mist-containing gas containing the raw material so as not to leak out of the apparatus while allowing the transfer of the substrate P. Dynamic exhaust chambers DE1 and DE2 are provided. In addition, about the structure of the atomizer GS1, the supply part GS2 of a carrier gas, etc., what is disclosed by the said paper 2 can be used, and the ultrasonic oscillator is provided in the atomizer GS1, The oscillation frequency and oscillation intensity are adjusted according to the required mist size.

  The processing apparatus U5 warms the substrate P transported from the processing apparatus U4, dries the raw material deposited on the lyophilic region HPR of the substrate P by the mist deposition method, and adjusts the water content to a predetermined value. The heating and drying device is adjusted to a value, but 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 at the time of the winding, the edge position controller EPC2 uses the edge position controller EPC2 so that the center of the substrate P in the Y direction (width direction) or the substrate end in the Y direction does not vary in the Y direction. The relative position in the direction is sequentially corrected and controlled.

  The host control device 5 controls the respective processing devices U1 to Un in FIG. 5 in an integrated manner, and various measurement sensors for measuring the state of the pattern formed on the substrate P, and the transfer state of the substrate P In response to signals from various sensors to be monitored, feedback control and feed forward control in the process are performed at important points. In the above-described device manufacturing system, since an exposure apparatus capable of precisely patterning a fine pattern is used as the processing apparatus U3, the boundary of the liquid-repellent portion formed on the substrate P is extremely sharp, and Since the mist-forming raw material substance is deposited on the lyophilic region HPR, a fine pattern can be formed with high precision.

  According to the manufacturing method using the manufacturing system as described above, the patterning applies the same exposure method as the photolithographic method to the photosensitive functional material, so that the printing method, the inkjet method, and the metal mask (shadow mask) are used. Compared with the method, fine patterning with high accuracy is possible. In addition, unnecessary materials used in conventional photolithography processes such as vacuum film forming equipment and etching equipment are not used, and raw materials can be deposited only on the parts where they are to be deposited, so unnecessary parts are removed by etching. There is no need to do so, and the advantage that the environmental load is small is obtained.

(Third embodiment)
The mist deposition processing apparatus U4 shown in FIG. 5 satisfies the above relation I or relation II, and sets the mist concentration, gas flow rate, temperature, substrate P transfer speed and the like in the reaction chamber TC. Preferably, it is set as an adjustment parameter. This is for controlling the film thickness and denseness of the raw material deposited on the region HPR having high lyophilicity on the substrate P. Furthermore, a function is provided to measure the film thickness of the raw material deposited in the highly lyophilic region HPR, and the mist deposition processing time and conditions (adjustment parameters) are dynamically changed according to the measured value. 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 pattern to be deposited. For the configuration of the same function as the members in FIG. The same reference numerals are given. In FIG. 6, the substrate P is driven by a drive roller DR8 provided in the differential exhaust chamber DE1 and a drive roller DR9 provided in the differential exhaust chamber DE2 to maintain a predetermined tension in the reaction chamber TC. Sent in the direction.

  In the present embodiment, a first nozzle NZ1 for ejecting a mist gas 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. Further, a second nozzle NZ2 for ejecting a mist gas of a solution containing a raw material substance is connected downstream from the mixer ULW2. The two mixers ULW1 and ULW2 are appropriately controlled by the unit control unit CUC so as to make the mist concentration contained in the gas ejected from each of the nozzles NZ1 and NZ2 equal or different. The mist concentration is obtained by changing the mixing ratio between the carrier gas supplied from the supply unit GS2 (see FIG. 5) to each of the mixers ULW1 and ULW2 and the mist gas supplied from the atomizer GS1 (see FIG. 5). Can be realized.

  A nozzle VT for sucking and recovering gas ejected from the nozzles NZ1 and NZ2 is provided downstream of the reaction chamber TC and near the differential exhaust chamber DE2, and the gas in the chamber TC is exhausted by an exhaust unit. It is sent to the recovery port De at a flow rate controlled by Exo. 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 is formed in the chamber TC in the transport direction (X direction) of the substrate P. be able to. The flow can be made slower, faster, 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. However, the mist concentration adjustment range is large, and the gas flow rate is reduced. Since the adjustment can be made in accordance with the transport speed of P, a pattern can be formed (deposited) to have a desired film thickness.

  In the present embodiment, in the reaction chamber TC, the layer thickness of the solution containing the raw material deposited as a mist on the substrate P is located at the most downstream position on the downstream side 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 values. When changing the transfer speed of the substrate P as adjustment of the processing conditions, the unit control unit CUC outputs a 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 device, a spectroscopic ellipsometer, or the like is used. Even at the most downstream position of the reaction chamber TC, the mist deposited on the substrate P contains a solvent (moisture). In some cases, it is not possible to accurately determine the thickness of a pattern that is densely formed of a raw material. Therefore, as shown in FIG. 6, after the processing device U4 for heating and drying the substrate P after the processing device U4 for mist deposition (after the differential evacuation chamber DE2), a pair of nip drive rollers NR1 and NR2 is provided. It is preferable to provide a pool portion of the substrate P constituted by the dancer rollers DSR, and immediately after that, provide a film thickness measurement sensor TMS.

  In this way, immediately after the pool 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 stopped for a fixed 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 from the processing apparatus U5 and the swing stroke Ld of the dancer roller DSR in the Z direction. For example, assuming that the speed Vo of the substrate P is 5 cm / s and the stroke Ld is 50 cm, the substrate P can be kept still 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 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 both preferably capable of measuring a film thickness of a fine pattern (for example, a line width of 20 μm or less). For example, the product names ST2000-DLXn and ST4000-DLX of the optical interference type film thickness meter sold by K-MAC of Korea are microscope type, so they can be easily incorporated, and the diameter of the light spot for measurement is several μm. The measurement time is within a few seconds. In addition, Dainippon Screen Mfg. Co., Ltd.'s optical interference type film thickness measuring device, such as Lambda Ace VM-1020 / 1030, product name RE-8000 equipped with a spectroscopic ellipsometer, etc. are used as the measuring sensor TMS after the processing device U5. Can also be used.

  When measuring the thickness of the pattern of the raw material deposited on the substrate P with the measurement sensor TMS as described above, a specific layer of a TFT portion or a wiring portion of a device (display panel) formed on the substrate P is measured. Although a direct measurement may be performed, 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 deposited thereon is measured. Is also good. An example in which such a test pattern is provided 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, it is assumed that 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 long direction (X direction) of the substrate P. Each panel area 100 is arranged with a predetermined margin in the longitudinal direction of the substrate P, and a constant width margin is set on both sides of the substrate P in the width direction (Y direction). Three marker areas MK1, MK2, and MK3 are provided in the margin between the panel areas 100 in the Y direction, and two marker areas MK4 and MK4 are provided on both sides of each panel area 100 in the Y direction. MK5 is provided.

  Here, three measurement sensors TMS shown in FIG. 6 are provided at a distance in the width direction of the substrate P corresponding 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. A similar test pattern is formed in each of the three marker regions MK1 to MK3 arranged in the Y direction among the marker regions MK1 to MK5.

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

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

  The marker areas MK4 and MK5 arranged on both sides of the panel area 100 in the Y direction have a width of about several mm in the Y direction and a length of several tens of mm in the X direction. May be formed. As described above, when the test pattern is elongated in the longitudinal direction of the substrate P, for example, the test pattern is formed in the marker areas MK4 and MK5 by the measurement sensor TMS in the reaction chamber TC shown in FIG. It is easy to measure the thickness of the test pattern to be performed.

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

  Since there is no other underlying pattern layer in the marker areas MK1 to MK5 as described above, it is necessary to accurately measure the thickness of various test patterns formed by the processing apparatus U4 (mist deposition). Can be. 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), the film thickness condition can be precisely controlled. Become. Further, by comparing the film thicknesses of the same type of test patterns in each of the three marker regions MK1 to MK3 between the panel regions 100, differences in film formation conditions (uneven mist concentration, etc.) in the width direction of the substrate P can be determined. It can be checked and corrected. The measurement sensor TMS may be provided with a sensor for measuring not only the thickness of the formed pattern but also its line width and the like.

(Fourth embodiment)
FIG. 8 shows a mist deposition processing apparatus U4 shown in FIG. 5 integrated with a processing apparatus U5 for performing a heating and drying process, and a substrate P wound around a rotary drum and transported. 1 shows an example of an apparatus for performing the above.

  In FIG. 8, the loaded flexible substrate P is wrapped around the rotary drum RD rotating around the axis AX1 over half a turn or more via the nip drive roller NDR and the tension roller DR10, and the processing is performed. It is folded back by an air turn bar ATB in the heating / drying unit 20 as the device U5, and is carried out via a roller DR11, a tension roller DR12, and a nip drive roller NDR. A cylindrical partition forming the reaction chamber TC is provided in a circumferential range around the rotary drum RD around which the substrate P is wound, and mist gas in the chamber TC is provided at both circumferential ends of the partition. An air seal bearing Pd that does not flow into the environment is provided. Needless to say, an air seal bearing for closing a gap with the rotary drum RD is also provided at an end of the cylindrical partition constituting the chamber TC in the direction of the axis AX1 (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 by the mixer ULW to form a mist-containing gas. Is supplied to one end side of the reaction chamber TC (a portion where the substrate P is in contact with the rotating drum RD). The mist-containing gas travels along a narrow cylindrical space along the surface of the substrate P wound around the rotary drum RD, and the other end of the cylindrical reaction chamber TC (the part where the substrate P separates from the rotary drum RD) Then, the gas is exhausted from the recovery port De.

  In the present embodiment, the rear surface of the substrate P is brought into close contact with the outer peripheral surface of the rotary drum RD and is conveyed. Therefore, unnecessary mist does not flow around the rear surface of the substrate P, so that the rear surface can be kept clean. Further, when a temperature control mechanism is provided along the outer circumference in the rotary drum RD, temperature control with high responsiveness of the substrate P can be performed.

  The substrate P on which the mist is deposited on the lyophilic portion HPR on the surface with the rotation of the rotating drum RD is linearly sent to the first space AT1 of the heating and drying unit 20, and is supplied with an electric heater, a hot air heater, or the like. The pattern by 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, linearly advances in the third space AT3, and reaches the roller DR11. A partition is partitioned between the spaces AT1, AT2, and AT3, and the partition is provided with a slit-shaped opening through which the substrate P passes. Then, a recovery port 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 for substantially a half 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 its surface (the surface on which the raw material is deposited) coming into contact with the surface of the air turn bar ATB. The gas ejected from the air turn bar ATB has a function of further drying the pattern of the raw material deposited on the surface of the substrate P.

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

  As described above, when the substrate P is transported using the rotary drum RD as shown in FIG. 8, if the diameter of the rotary 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 rotary 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 reduced as compared with the case where the reaction chamber TC is linear 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 transport, 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 it is needless to say that the present invention is not limited to the examples. The shapes, combinations, and the like of the respective constituent members shown in the above-described examples are merely examples, and can be variously changed 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 plastic substrate or a resin substrate in addition to a glass substrate or a silicon wafer. Further, the substrate P need not be processed by a roll-to-roll method for a long one wound on a roll, but may be a method of processing a single sheet cut to 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 forming method such as a dip coating method can be used. The spray method is a method in which a spray-like material solution sprayed from a nozzle is applied onto a substrate P, similarly to the mist deposition method. The dip coating method is a method in which the substrate P is placed in a material solution tank for a predetermined time. It is immersed and pulled up.

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

  Furthermore, when using a conventional photolithography process in which a photoresist layer is subjected to photo-patterning (exposure processing) and then developed, and the resist layer is etched according to the pattern, the surface of the substrate P (when there is a base layer) Is made to have a high lyophilic property, and a photoresist material having a high lyophobic property is applied to the surface of the substrate P with a uniform thickness. After that, by performing a development process, 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 surface having high lyophilicity, so that the mist deposition method (or the spray method) , A dip coating method), a precise pattern is formed by the material solution.

FR1: supply roll, FR2: collection roll, P: substrate, U1, U2, U3, U4, U5, Un: processing unit (processing apparatus), Gpa: rotating drum for coating a photosensitive silane coupling agent, Gp1: coating Mechanism, IU: UV illumination system, DM: drum mask,
PL: Projection optical system, DE1, DE2: Differential exhaust chamber, TC: Reaction chamber, GS1: Atomizer for material, GS2: Carrier gas supply unit, ULW: Mixer, HPB: Liquid repellent unit, HPR: Parent Liquid part, RD: rotating drum, MK1 to MK5: marker area, 20: heating and drying unit, 100: display panel area

Claims (11)

A carrier gas containing mist is sprayed on the surface of a long substrate having flexibility, and molecules or particles of a material contained in the mist are deposited on the surface of the substrate to form a thin film layer of the material. A mist forming method,
A first region in which lyophilicity is increased by having a surface energy greater than that of the mist on a surface of the substrate, and a second region in which lyophobic property is enhanced by having a surface energy smaller than that of the mist. A first step of forming a region of
A transfer step of moving the substrate so that the substrate that has passed through the first step passes in a long direction at a predetermined transfer speed in a chamber provided at a predetermined length along the long direction;
Wherein the carrier gas containing the mist is generated from a solution containing molecules or particles of the material at a predetermined concentration, to flow at a flow rate corresponding to the conveying speed along the surface of the substrate to move within said chamber A second step of depositing the mist in the first area of the substrate by spraying;
A film forming method using a mist containing. A film forming method using a mist according to claim 1,
The carrier gas sprayed into the chamber is ejected through an ejection nozzle arranged on the upstream side in the moving direction of the substrate, and the carrier gas sprayed into the chamber is downstream in the moving direction of the substrate. Discharged through a collecting nozzle located on the side,
Film formation method by mist. A film forming method using a mist according to claim 2,
The carrier gas is ejected from the ejection nozzle and is discharged from the recovery nozzle through the chamber so that the flow rate of the carrier gas in the chamber is equal to or faster than the transfer speed of the substrate. The flow rate of the carrier gas to be adjusted is adjusted,
Film formation method by mist. A film forming method using a mist according to claim 3,
In order to adjust the processing conditions of the thin film layer formed on the substrate,
The concentration of the mist contained in the carrier gas sprayed into the chamber from the nozzle for ejection, the concentration of molecules or particles of the material substance contained in the mist, the temperature in the chamber, or the transfer of the substrate One of the speed is adjusted,
Film formation method by mist. A film forming method using a mist according to claim 4,
In order to adjust the concentration of the mist contained in the carrier gas ejected from the ejection nozzle, the mist generated from the solution containing molecules or particles of the material substance by an atomizer is mixed. Mixed with the carrier gas at a predetermined concentration,
Film formation method by mist. A film forming method using a mist according to claim 5,
The carrier gas is any of nitrogen (N ₂ ), argon (Ar), and air (O ₂ ).
Film formation method by mist. A film forming method using a mist according to any one of claims 1 to 6,
The solution containing molecules or particles of the material is any of a solution containing molecules to be a semiconductor, a solution containing carbon nanotubes, a solution containing metal nanoparticles, and a solution having a molecular structure to be an insulating film. ,
Film formation method by mist. A film forming method using a mist according to any one of claims 2 to 6,
The jet nozzle includes a first nozzle and a second nozzle that are arranged side by side along the transport direction of the substrate,
The mist concentration in the carrier gas ejected from the first nozzle is equal to or different from the mist concentration in the carrier gas ejected from the second nozzle,
Film formation method by mist. A film forming method using a mist according to any one of claims 1 to 8,
In the transporting step, the substrate is moved in the longitudinal direction by rotating a rotary drum that winds a part of the substrate in the longitudinal direction into a cylindrical shape,
The chamber has a cylindrical partition wall that forms a cylindrical space along the surface of the substrate over a circumferential range around which the substrate is wound around the rotating drum,
In the second step, the carrier gas containing the mist is sprayed so as to flow along the circumferential direction in the cylindrical space in the chamber,
Film formation method by mist. A film forming method using a mist according to any one of claims 4 to 6,
After drying the liquid component adhered to the surface of the substrate after the second step, further comprising a measurement step of measuring the thickness of the thin film layer deposited on the substrate,
Adjusting the processing conditions according to the thickness of the thin film layer measured in the measurement step,
Film formation method by mist.   A film forming method using a mist according to any one of claims 1 to 6,
  The first step includes:
  After making the surface of the substrate highly lyophilic, a photoresist layer having a high lyophobic property is formed on the surface of the substrate, and the photoresist layer is subjected to photo-patterning and development processing, whereby the Forming a portion from which a photoresist layer has been removed as the first region in which the lyophilicity is enhanced;
Film formation method by mist.

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