JP3949045B2 - Functional element sheet and manufacturing method thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a functional element sheet formed by forming a film of a functional material using a discharge device and a method for manufacturing the functional element sheet.
[0002]
[Prior art]
In recent years, the development of light-emitting elements using organic substances has been accelerated as a self-luminous display that replaces a liquid crystal display.
Such element formation is performed by patterning a functional material, and is generally performed by a photolithography method. For example, as an organic electroluminescence (hereinafter referred to as organic EL) element using an organic substance, Appl. Phys. Lett. 51 (12), 21 September 1987 (Non-Patent Document 1, page 913), a method for forming a film of low molecules by vapor deposition has been reported. Further, in the organic EL element, as a means for coloring, a method in which a different light emitting material is deposited on a desired pixel through a mask is performed. However, such a method by vacuum film formation and a method by photolithography have the disadvantages that the number of steps is large and the production cost is high in order to form elements over a large area.
[0003]
In response to such a problem, the present inventor, in forming and patterning a functional material film for forming a functional element represented by such an organic EL element, disclosed US Pat. No. 3,060,429 (patent) Document 1), US Pat. No. 3,298,030 (Patent Document 2), US Pat. No. 3,596,275 (Patent Document 3), US Pat. No. 3,416,153 (Patent Document 4), US Pat. No. 3,747,120 (Patent Document 5), US Patent No. 5729257 (Patent Document 6) or the like can be used to apply a functional material at a stable yield and low cost, regardless of the vacuum film forming method and the photolithography / etching method. We thought that it could be applied to a desired position.
[0004]
For example, when an organic EL element is considered as an example of a functional element, a composition in which a hole injecting / transporting material and a light emitting material constituting such an organic EL element are dissolved or dispersed in a solvent is discharged from an inkjet head. It was thought that this could be realized by patterning and coating on the transparent electrode substrate and patterning the hole injection / transport layer and the light emitting material layer.
[0005]
As prior arts that disclose the same idea, for example, JP 2000-323276 A (Patent Document 7), JP 2001-60493 A (Patent Document 8), and the like are known. For these, although the concept of forming an organic EL element by the ink jet method or a detailed study from the material side has been made, the structure of the entire functional element substrate manufactured by such means has not been studied much. Absent.
[0006]
[Patent Document 1]
U.S. Pat. No. 3,060,429
[Patent Document 2]
US Pat. No. 3,298,030
[Patent Document 3]
US Pat. No. 3,596,275
[Patent Document 4]
U.S. Pat. No. 3,416,153
[Patent Document 5]
U.S. Pat. No. 3,747,120
[Patent Document 6]
US Pat. No. 5,729,257
[Patent Document 7]
JP 2000-323276 A
[Patent Document 8]
JP 2001-60493 A
[Non-Patent Document 1]
Appl. Phys. Lett. 51 (12), 21 September 1987, pages 913
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation,
The first object is to propose a functional element sheet having a novel configuration in which a functional element group is formed.
The second object is to prevent the functional element from being damaged in various situations where the functional element sheet having such a novel configuration is used.
The third object is to propose a self-luminous element sheet having a novel configuration.
The fourth object is to propose a method for manufacturing a functional element sheet having such a novel configuration.
[0008]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides:
First, droplets of a solution containing a functional material are sprayed on a flexible resin sheet serving as a base, volatilizing components in the solution are volatilized, and solid content is applied to the flexible resin sheet serving as the base. The functional component group is formed by remaining in the substrate, and the solid component is mainly composed of an organic material, and the functional component follows the flexibility of the flexible resin sheet serving as the base. In the functional element sheet that is possible, the functional material is a plurality of different types of materials, and the functional element formed thereby is organic EL A light emitting element; Organic EL Organic driving light-emitting elements Semiconductor materials, insulating film materials and electrodes Depending on the material Organic A driving element including a transistor was formed on the same sheet.
[0009]
Second The above 1 In the functional element sheet described above, another flexible sheet or a protective organic material is provided on the functional element.
[0010]
First 3 A functional element sheet manufacturing method comprising a functional element group formed on a flexible resin sheet, wherein the flexible resin sheet serving as a base is a substrate having a higher rigidity than the flexible resin sheet serving as a base. On the flexible resin sheet of the composite substrate formed in close contact, a droplet of a solution containing a functional material is sprayed and applied to volatilize a volatile component in the solution, so that the solid content becomes the base of the flexible resin sheet. A functional element group is formed by allowing it to remain on top, and the solid component is mainly composed of an organic material, and the functional element can follow the flexibility of the flexible resin sheet serving as the base. In the method for producing a functional element sheet, the functional material is a plurality of different materials, and the functional element formed thereby is an organic material. EL A light emitting element; Organic EL Organic driving light-emitting elements Semiconductor materials, insulating film materials and electrodes Depending on the material Organic A driving element including a transistor is formed on the same sheet, and then formed by peeling the flexible resin sheet serving as the base from the highly rigid substrate.
[0011]
First 4 A functional element sheet manufacturing method comprising a functional element group formed on a flexible resin sheet, wherein the flexible resin sheet serving as a base is a substrate having a higher rigidity than the flexible resin sheet serving as a base. On the flexible resin sheet of the composite substrate formed in close contact, a droplet of a solution containing a functional material is sprayed and applied to volatilize a volatile component in the solution, so that the solid content becomes the base of the flexible resin sheet. A functional element group is formed by allowing it to remain on top, and the solid component is mainly composed of an organic material, and the functional element can follow the flexibility of the flexible resin sheet serving as the base. In the method for producing a functional element sheet, the functional material is a plurality of different materials, and the functional element formed thereby is an organic material. EL A light emitting element; Organic EL Organic driving light-emitting elements Semiconductor materials, insulating film materials and electrodes Depending on the material Organic It is a driving element including a transistor, and after forming them on the same sheet, another flexible sheet is laminated on the functional element or a protective organic material is provided, and then the base flexibility The resin sheet was formed by peeling from the rigid substrate.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a case where an organic EL element is considered as an example of a functional element. Here, on the flexible sheet 5 adhered to the glass substrate 6, an ITO (indium tin oxide) transparent electrode pattern 4 divided in a mosaic shape and a barrier 3 surrounding the transparent electrode portion are formed. In the above example, the solution 2 in which the organic EL material that develops red, green, and blue is dissolved is sprayed from the nozzle 1 by the ink jet principle so as to be arranged in each color mosaic. Details of the providing method will be described later. The composition of the solution is, for example, as follows.
[0013]
Solution composition
Solvent: dodecylbenzene / dichlorobenzene (1/1, volume ratio)
Red ... Polyfluorene / perylene dye (98/2, weight ratio)
Green ... Polyfluorene / coumarin dye (98.5 / 1.5, weight ratio)
Blue ... Polyfluorene
[0014]
The ratio of the solid to the solvent is, for example, 0.4% (weight / volume). Here, the composite substrate composed of the flexible sheet 5 and the glass substrate 6 provided with such a solution is heated at 40 ° C., for example, and after removing the solvent, a suitable metal mask is formed on the substrate, Aluminum is sputtered by 2000 angstrom (not shown), lead wires are drawn from ITO and aluminum, and the device is completed using ITO as an anode and aluminum as a cathode. An element that emits red, green, and blue light in a predetermined shape with an applied voltage of about 15 volts is obtained.
[0015]
An element is formed by previously forming electrodes on the substrate, and then spraying and applying droplets of such a solution to volatilize the volatile components in the solution and leave the solid content on the substrate. Formation may be performed.
Alternatively, fine (0.001 μm to 1 μm) fine metal particles such as Au and Ag are dispersed in a pasty material whose main composition is an organic material, and a solution obtained by diluting it with a solvent is sprayed and applied in the same manner. An electrode pattern may be formed.
And the flexible sheet | seat 5 in which the element was formed is peeled from the composite substrate which comprised such an element, and a flexible functional element sheet | seat is obtained.
[0016]
In addition, although it is a case where an organic EL element is considered here as an example of a functional element, it is not necessarily limited to such an element and material. For example, when an electron-emitting device is considered, a solution containing a palladium-based compound is used. In this case, the final form is an electron-emitting display that is packaged by opposingly arranging a face plate having a phosphor on the electron-emitting element sheet. Moreover, an organic transistor etc. can be suitably manufactured as a functional element. In any case, the various functional elements of the present invention are formed on a flexible sheet, and the final functional element sheet has flexibility and does not break even when bent.
[0017]
Here, as a means for applying a solution containing such a functional material, the principle of inkjet ejection is applied in the present invention. The specific method will be described below.
[0018]
FIG. 2 is a view for explaining one embodiment of the functional element sheet manufacturing apparatus of the present invention. In the figure, 11 is an ejection head unit (jet head), 12 is a carriage, 13 is a substrate holder, 14 Is the composite substrate before peeling the flexible sheet forming the functional element, 15 the supply tube of the solution containing the functional material, 16 is the signal supply cable, 17 is the ejection head control box, 18 is the X direction scan motor of the carriage 12 , 19 is a Y-direction scan motor of the carriage 12, 20 is a computer, 21 is a control box, 22 (22X ₁ , 22Y ₁ , 22X ₂ , 22Y ₂ ) Is a substrate positioning / holding means.
[0019]
FIG. 3 is a schematic diagram showing a configuration of a droplet applying device applied to the production of the functional element sheet of the present invention, and FIG. 4 is a schematic configuration diagram of a main part of an ejection head unit of the droplet applying device in FIG. It is. The configuration in FIG. 3 is different from the configuration in FIG. 2 in that the functional element group is formed on the flexible sheet by moving the substrate 14 side. 3 and 4, 31 is a head alignment control mechanism, 32 is a detection optical system, 33 is an ejection head, 34 is a head alignment fine movement mechanism, 35 is a control computer, 36 is an image identification mechanism, 37 is an XY direction scanning mechanism, Reference numeral 38 denotes a position detection mechanism, 39 denotes a position correction control mechanism, 40 denotes an ejection head drive / control mechanism, 41 denotes an optical axis, 42 denotes an element electrode, 43 denotes a droplet, and 44 denotes a droplet landing position. The droplet applying device (ejection head 33) of the discharge head unit 11 may be any mechanism as long as it can discharge a given amount of droplets in a fixed amount, and in particular, an ink jet mechanism that can form droplets of several to several hundred pl. Is desirable.
[0020]
Examples of the ink jet method include a method disclosed in US Pat. No. 3,683,212 (Zoltan method), a method disclosed in US Pat. No. 3,747,120 (Stemme method), and US Pat. No. 3,946,398. As in the disclosed method (Kyser method), an electrical signal is applied to the piezo-vibration element, this electrical signal is converted into mechanical vibration of the piezo-vibration element, and droplets are discharged from a fine nozzle according to the mechanical vibration. Is generally called a drop-on-demand system.
[0021]
As other methods, there are methods (Sweet method) disclosed in US Pat. No. 3,596,275, US Pat. No. 3,298,030, and the like. This generates a recording liquid droplet with a controlled charge amount by a continuous vibration generation method, and the generated charge amount controlled droplet flies between deflection electrodes to which a uniform electric field is applied. Thus, recording is performed on a recording member, which is usually called a continuous flow method or a charge control method.
[0022]
Furthermore, as another method, there is a method disclosed in Japanese Patent Publication No. 56-9429. This is a method in which bubbles are generated in a liquid and droplets are ejected and ejected from fine nozzles by the action force of the bubbles, which is called a thermal ink jet method or a bubble ink jet method.
[0023]
As described above, methods for ejecting droplets include a drop-on-demand method, a continuous flow method, a thermal ink jet method, and the like, and the method may be appropriately selected as necessary.
[0024]
In the present invention, in such a functional element sheet manufacturing apparatus (FIG. 2), the composite substrate 14 is determined by adjusting its holding position by the substrate positioning / holding means 22 of this apparatus. Although simplified in FIG. 2, the substrate positioning / holding means 22 is in contact with each side of the composite substrate 14 and can be finely adjusted in the order of μm in the X direction and the Y direction orthogonal thereto. These are connected to the ejection head control box 17, the computer 20, the control box 21, etc., and the positioning information, fine adjustment displacement information, etc., the position information of the droplet application, the timing, etc. can be constantly fed back.
[0025]
Furthermore, the functional device sheet manufacturing apparatus of the present invention has a rotation position adjustment mechanism (not shown because it is located below the composite substrate 14), in addition to the position adjustment mechanism in the X and Y directions. . In this connection, the shape of the functional element sheet of the present invention and the arrangement of the functional element group to be formed will be described first.
[0026]
As the functional element sheet of the present invention, various resin sheets and polymer films including a flexible polyethylene resin and vinyl resin are preferably used. Further, such a sheet or film may be a single material or a composite material layer in which a plurality of layers are laminated. The main component of the material is the organic material as described above in order to provide flexibility, but it may contain a material other than the organic material as long as the flexibility is not impaired. For example, a composite sheet having an organic material film covered on the upper and lower surfaces of a very thin (several μm to several 100 μm) glass sheet can also be suitably used. Such resin sheets and polymer films are also effective in reducing the weight.
Since such resin sheets and polymer films are not rigid, various functionalities such as glass substrates, ceramic substrates such as alumina, and stainless steel, which are higher in rigidity than these flexible sheet materials, are used when functional element sheets are manufactured. It is brought into close contact with a metal substrate or the like, set in a functional device sheet manufacturing apparatus in the form of a composite substrate 14, and droplets are applied to the flexible sheet surface. That is, a material substrate having higher rigidity than the flexible sheet material is used as the support. After the functional element is formed, as described above, the flexible sheet on which the element is formed is peeled from the substrate that is the support, and a flexible functional element sheet is obtained.
[0027]
The shape of the composite substrate in which various resin sheets and polymer films used for the production of the functional element sheet of the present invention are adhered is the function of economically producing, supplying, or finally producing such a substrate. In consideration of the use of the conductive element sheet, etc., it is rectangular (right-angled quadrilateral). That is, the two vertical and horizontal sides constituting the rectangular shape are substrates in which the two vertical sides are parallel to each other, the two horizontal sides are parallel to each other, and the vertical and horizontal sides form a right angle.
[0028]
With respect to such a composite substrate, in the present invention, the functional element groups to be formed are arranged in a matrix, and two directions orthogonal to each other of the matrix are the vertical side or the horizontal side of the substrate. The functional element group is arranged so as to be parallel to the direction. The reason why the functional element groups are arranged in a matrix and the reason why the vertical and horizontal sides of the substrate are parallel to two orthogonal directions of the matrix will be described below.
[0029]
As shown in FIG. 2 or FIG. 3, in the present invention, after the positional relationship between the composite substrate 14 and the solution ejection port surface of the ejection head unit 11 is first determined, the position control is not particularly performed. That is, the discharge head unit 11 performs relative movement in the X and Y directions in parallel with the flexible sheet surface, which is the surface on which the functional element group is formed, while maintaining a certain distance from the composite substrate 14. (For example, an organic EL material or a solution in which a conductive material is dissolved, an organic semiconductor material, or the like) is sprayed. That is, the X direction and the Y direction are two directions orthogonal to each other. When positioning the composite substrate 14, the vertical or horizontal side of the composite substrate 14 is set to be parallel to the Y direction or the X direction. In this case, since the functional element group to be formed is parallel to the two directions of the matrix arrangement, it is possible to form the element group with high accuracy only by a mechanism that performs ejection while performing relative movement. In other words, if a composite substrate shape, a matrix arrangement of functional element groups, and a relative movement device in two directions of X and Y orthogonal to each other as in the present invention are used, the composite substrate before element formation droplet ejection is performed. If the positioning of 14 is accurately performed, a highly accurate matrix arrangement of functional element groups can be obtained.
[0030]
Here, the description will be returned to the rotational position adjustment mechanism. As described above, in the present invention, the composite substrate 14 is accurately positioned before droplet ejection for element formation is performed, only relative movement in the X and Y directions is performed, and no other control is performed. It is intended to obtain a matrix arrangement of functional elements. In this case, a problem is a shift in the rotation direction (the rotation direction with respect to the axis perpendicular to the plane determined by the two directions X and Y) when the composite substrate 14 is first positioned.
In order to correct this shift in the rotational direction, the present invention has a rotational position adjustment mechanism (not shown) that is not shown (not visible under the composite substrate 14) as described above. Accordingly, when the displacement in the rotational direction is also corrected and the side of the composite substrate 14 is positioned, the apparatus of the present invention can obtain a highly accurate matrix arrangement of functional element groups by relative movement only in the X and Y directions.
[0031]
The rotational position adjusting mechanism is the same as that of the substrate positioning / holding means of FIG. ₁ , 22Y ₁ , 22X ₂ , 22Y ₂ Although it is described as a separate mechanism (not visible under the composite substrate 14), the substrate positioning / holding means 22 may have a rotational position adjusting mechanism. For example, the substrate positioning / holding means 22 is brought into contact with the side of the composite substrate 14 so that the entire position of the substrate positioning / holding means 22 can be adjusted in the X direction or the Y direction. If the two screws provided at a distance are moved independently at the portion of the means 22 that is in contact with the side of the composite substrate 14, the angle can be adjusted. This rotational position control information is also connected to the ejection head control box 17, the computer 20, the control box 21, etc. in the same manner as the positioning information and fine adjustment displacement information in the X and Y directions, and the droplet application position information, The timing can be constantly fed back.
[0032]
Next, other means and configuration of positioning according to the present invention will be described. In the above description, the substrate positioning / holding means 22 is brought into contact with the side of the composite substrate 14 so that the entire position of the substrate positioning / holding means 22 can be adjusted in the X direction or the Y direction. Here, an example in which strip-like patterns are provided in two directions orthogonal to each other on the flexible sheet surface of the composite substrate 14 instead of the sides of the composite substrate 14 will be described. As described above, in the present invention, the functional element groups are formed in a matrix on the flexible sheet surface, but here, the above-described two-direction band-shaped patterns orthogonal to each other are formed on the matrix. It is formed so as to be parallel to two orthogonal directions. Such a pattern can be easily formed on the flexible sheet surface by a photofabrication technique.
[0033]
Alternatively, the pattern as described above is not created only for that purpose, and the element electrode 42 (FIG. 4) and the wiring patterns such as the X-direction wiring and the Y-direction wiring of each element are orthogonal to each other of the present invention. It may be regarded as a two-directional strip pattern. If such a belt-like pattern is provided, pattern detection can be performed by a detection optical system 32 using a CCD camera and a lens as will be described later with reference to FIG.
[0034]
Next, in the Z direction, which is a direction perpendicular to the X and Y directions, in the present invention, after the positional relationship between the composite substrate 14 and the solution ejection surface of the ejection head unit 11 is first determined, There is no particular position control. That is, the ejection head unit 11 ejects a solution containing a functional material while performing a relative movement in the X and Y directions while maintaining a certain distance from the composite substrate 14. 11 position control in the Z direction is not performed. The reason for this is that if the control is performed at the time of injection, not only the mechanism and control system become complicated, but also the formation of functional elements by applying droplets to the flexible sheet surface becomes slow, and the productivity is significantly reduced. Because.
[0035]
Instead, in the present invention, the flatness of the composite substrate 14 and the flatness of the portion of the apparatus that holds the composite substrate 14, and the accuracy of the carriage mechanism that relatively moves the discharge head unit 11 in the X and Y directions are improved. By doing so, the Z direction control at the time of jetting is not performed, and the relative movement of the ejection head unit 11 and the composite substrate 14 in the X and Y directions is performed at high speed, thereby improving the productivity. As an example, the variation in the distance between the composite substrate 14 and the solution ejection port surface of the ejection head unit 11 at the time of application of the solution according to the present invention is suppressed to 5 mm or less (the size of the composite substrate 14 is 200 mm × 200 mm or more and 4000 mm × 4000 mm or less).
[0036]
In addition, although the apparatus is configured so that the plane determined by two directions of X and Y directions is normally maintained in a horizontal direction (a plane perpendicular to the vertical direction), when the composite substrate 14 is small (for example, 500 mm × 500 mm or less) In this case, the plane determined by the two directions of X and Y is not necessarily horizontal, and it is only necessary to make the positional relationship of the arrangement of the composite substrates 14 most efficient for the apparatus.
[0037]
Next, although other examples of the present invention are described, the present invention is not limited to these examples. FIG. 3 is an example in which the side of the composite substrate 14 is moved when the ejection head unit 31 and the composite substrate 14 are moved relative to each other, unlike the case of FIG. 2. FIG. 4 is an enlarged schematic configuration diagram showing the discharge head unit of the apparatus of FIG. First, in FIG. 3, reference numeral 37 denotes an XY direction scanning mechanism, on which the composite substrate 14 is placed. The functional element formed on the flexible sheet surface on the composite substrate 14 has, for example, the same configuration as that of FIG. 1, and as a single element, similar to the configuration shown in FIG. It consists of an ITO transparent electrode 4. Disposed above the composite substrate 14 is an ejection head unit 11 that applies droplets. In the present embodiment, the ejection head unit 11 is fixed, and the composite substrate 14 is moved to an arbitrary position by the XY direction scanning mechanism 37, whereby the relative movement between the ejection head unit 11 and the composite substrate 14 is realized.
[0038]
Next, the configuration of the ejection head unit 11 will be described with reference to FIG. In FIG. 4, reference numeral 32 denotes a detection optical system that captures image information on the flexible sheet 5, close to the inkjet head 33 that ejects the droplet 43, the optical axis 41 and the focal position of the detection optical system 32, and the inkjet head. It is arranged so that the landing position 44 of the droplet 43 by 33 coincides. In this case, the positional relationship between the detection optical system 32 and the inkjet head 33 shown in FIG. 3 can be precisely adjusted by the head alignment fine movement mechanism 34 and the head alignment control mechanism 31. The detection optical system 32 uses a CCD camera and a lens.
[0039]
In FIG. 3, reference numeral 36 denotes an image identification mechanism for identifying image information captured by the previous detection optical system 32, and has a function of binarizing the contrast of the image and calculating the center of gravity position of the binarized specific contrast portion. I have it. Specifically, VX-4210, a high-accuracy image recognition device manufactured by Keyence Corporation can be used. A means for giving position information on the functional element substrate (composite substrate) 14 to the image information thus obtained is a position detection mechanism 38. For this purpose, a length measuring device such as a linear encoder provided in the XY direction scanning mechanism 37 can be used. The position correction control mechanism 39 corrects the position based on the image information and the position information on the flexible sheet 5, and this mechanism corrects the movement of the XY direction scanning mechanism 37. . Further, the inkjet head 33 is driven by the inkjet head control / drive mechanism 40, and droplets are applied onto the flexible sheet 5. Each control mechanism described so far is centrally controlled by the control computer 35.
[0040]
In the above description, the ejection head unit 11 is fixed, and the composite substrate 14 is moved to an arbitrary position by the XY direction scanning mechanism 37 to realize relative movement between the ejection head unit 11 and the composite substrate 14. However, it is needless to say that the composite substrate 14 may be fixed and the ejection head unit 11 may scan in the XY directions as shown in FIG. In particular, when using a medium-sized substrate of about 200 mm × 200 mm to a large composite substrate of 2000 mm × 2000 mm or more, the composite substrate 14 is fixed as in the latter, and the X and Y directions in which the ejection head unit 11 is orthogonal to each other. It is better to adopt a configuration in which the liquid droplets are sequentially applied in such two orthogonal directions.
[0041]
In the present invention, when the size of the composite substrate 14 is a medium-sized substrate of about 200 mm × 200 mm to 400 mm × 400 mm, it is also conceivable to perform paper conveyance of the ink jet printer. That is, the ejection head unit 11 mounted on the carriage 12 is scanned only in the X direction (or only in the Y direction), and the composite substrate 14 is conveyed in the Y direction (or X direction). In that case, productivity is remarkably improved.
[0042]
When the size of the composite substrate 14 is about 200 mm × 200 mm or less, the ejection head unit for applying droplets is a large array multi-nozzle type that can cover the range of 200 mm, and the ejection head unit and the composite substrate 14 are moved relative to each other. It is possible to perform relative movement in only one direction (for example, only in the X direction) without performing in two orthogonal directions (X direction and Y direction), and the mass productivity can be improved. When the size of 14 is 200 mm × 200 mm or more, it is difficult to realize a large array multi-nozzle type discharge head unit capable of covering such a range of 200 mm in terms of technology / cost. In this way, the ejection head unit 11 scans in two directions of X and Y orthogonal to each other, and the application of the liquid droplets in this way It is better to adopt a configuration that sequentially performs in two orthogonal directions.
[0043]
In particular, as a final functional element sheet, even when a sheet having a size smaller than 200 mm × 200 mm is manufactured, when a plurality of large functional sheets are manufactured from a large sheet, the original composite substrate 14 ( Since the functional element sheet) is 400 mm × 400 mm to 2000 mm × 2000 mm or more, the ejection head unit 11 is scanned in two directions of X and Y orthogonal to each other, and the liquid droplets of the solution are used. It is better to adopt a configuration in which the application is sequentially performed in such two orthogonal directions.
[0044]
As the material of the droplet 43, in addition to the organic EL material described above, for example, polyphenylene vinylene (polyparaphenylylene vinylene derivative), polyphenylene derivative, and other low molecular organic EL soluble in benzene derivatives. Materials such as materials, polymer organic EL materials, and polyvinyl carbazole can be used. Specific examples of the organic EL material include rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, Nile red, coumarin 6, quinacridone, polythiophene derivatives, and the like. In addition, electron transporting and hole transporting materials, which are peripheral materials in organic EL display, are also used as a functional material for producing the functional element of the present invention.
[0045]
Other functional materials for producing the functional element of the present invention include organic semiconductor materials. Examples of the organic semiconductor material include a low molecular compound and a high molecular compound, and examples of the low molecular compound include the following.
That is, polycyclic quinone derivatives such as phthalocyanine derivatives, naphthalocyanine derivatives, azo compound derivatives, perylene derivatives, indigo derivatives, quinacridone derivatives, anthraquinones, cyanine derivatives, fullerene derivatives, or indoles, Nitrogen-containing cyclic compound derivatives such as carbazole, oxazole, inoxazole, thiazole, imidazole, pyrazole, oxadiazole, pyrazoline, thiathiazole, triazole, hydrazine derivative, triphenylamine derivative, triphenylmethane derivative, stilbene, anthraquinone di Quinone compound derivatives such as phenoquinone, and polycyclic aromatic compound derivatives such as anthracene, pentacene, pyrene, phenanthrene, and coronene. These low-molecular compounds are preferably in an amorphous state, and preferably have a starburst type molecular shape in which the amorphous state is stable.
[0046]
As the polymer compound, the structure of the low molecular compound described above is in the main chain of a normal electrically inactive polymer chain such as polyethylene chain, polysiloxane chain, polyether chain, polyester chain, polyamide chain, polyimide chain, etc. Alternatively, a pendant bonded as a side chain is used.
[0047]
In addition, as the polymer compound, a conjugated polymer compound as exemplified below can also be used favorably.
That is, aromatic conjugated polymers such as polyparaphenylene, aliphatic conjugated polymers such as polyacetylene, heterocyclic conjugated polymers with polypyrrole and polythiophene ratios, heteroatom-containing conjugates such as polyanilines and polyphenylene sulfide Carbons such as composite conjugated polymers having a structure in which structural units of the above conjugated polymers such as poly (phenylene vinylene), poly (arylene vinylene) and poly (thienylene vinylene) are alternately bonded. A conjugated polymer is preferably used.
In addition, oligosilanes such as polysilanes, disilanylene allylene polymers, (disilanylene) ethenylene polymers, and (disilanylene) ethynylene polymers such as disilanylene-carbon conjugated polymer structures and carbon-based conjugated structures Polymers that are alternately linked are preferably used.
[0048]
Such a main chain type conjugated polymer chain is preferable to the previous pendant type because of its superior carrier transport properties such as carrier mobility.
In addition, polymer chains made of inorganic elements such as phosphorus and nitrogen may be used.
Furthermore, polymers in which an aromatic ligand is coordinated to a polymer chain such as phthalocyanate polysiloxane may be used.
[0049]
Further, a ladder-like polymer obtained by heat-treating perylenes such as perylenetetracarboxylic acid and ring-condensing may be used. Furthermore, a ladder-type polymer obtained by heat-treating a polyethylene derivative having a cyano group such as polyacrylonitrile may be used.
Furthermore, a composite material in which an organic compound is intercalated into perovskites may be used.
[0050]
Other functional materials for producing the functional element of the present invention include silicon glass precursors for interlayer insulating films frequently used for semiconductors and the like, or silica glass forming materials. Examples of the precursor include polysilazane (for example, manufactured by Tonen), organic SOG material, and the like.
[0051]
As the electrode material, an organic conductive material containing a conjugated polymer compound such as polyaniline, polythiophene, or polypyrrole is used.
Another example is a color filter material. Specifically, Sumika Red B (trade name, Sumitomo Chemical dye), Kayaron Fast Yellow GL (trade name, Nippon Kayaku dye), Diaserine Fast Brilliant Blue B (trade name, Mitsubishi Kasei dye), etc. Sublimation dyes and the like can be used.
[0052]
In the solution composition of the present invention, the boiling point of the benzene derivative is preferably 150 ° C. or higher. Specific examples of such a solvent include O-dichlorobenzene, m-dichlorobenzene, 1,2,3-trichlorobenzene, O-chlorotoluene, p-chlorotoluene, 1-chloronaphthalene, bromobenzene, O-dibromo. Examples thereof include benzene and 1-dibromonaphthalene. Use of these solvents is preferable because volatilization of the solvent can be prevented. These solvents are preferable because of their high solubility in aromatic compounds. The solution composition of the present invention preferably contains dodecylbenzene. As dodecylbenzene, n-dodecylbenzene alone may be used, or a mixture of isomers may be used.
[0053]
This solvent has a boiling point of 300 ° C. or more and a viscosity of 6 cp or more (20 ° C.). Of course, this solvent alone may be used, but by adding it to other solvents, it is possible to effectively prevent the solvent from evaporating and is suitable. . Also, since the viscosity of the above solvents other than dodecylbenzene is relatively small, it is very suitable because the viscosity can be adjusted by adding this solvent. According to the present invention, after supplying the solution composition as described above onto a flexible sheet by a discharge device, the composite substrate to which the flexible sheet is adhered is processed at a temperature higher than the discharge temperature to form a film. A functional film forming method is provided. The discharge temperature is room temperature, and it is preferable to heat the substrate after discharge within a range in which the flexible sheet material is not deformed. By performing such a treatment, the content deposited due to the volatilization of the solvent during discharge and the decrease in temperature is redissolved, and a uniform and homogeneous functional film can be obtained.
[0054]
In the above-described functional film manufacturing method, it is preferable to heat the composite substrate after applying the discharge composition onto the flexible sheet by a discharge device and then processing the composite substrate at a temperature higher than the discharge temperature. By treating in this way, volatilization of the solvent during heating can be delayed, and the re-dissolution of the contents is further promoted. As a result, a uniform and homogeneous functional film can be obtained. In the method for producing a functional film, the composite substrate is preferably decompressed immediately after the high temperature treatment to remove the solvent. By treating in this way, phase separation of the contents during the concentration of the solvent can be prevented.
[0055]
In any material or functional element, the present invention performs element formation by volatilizing a volatile component in the solution and leaving a solid content on the substrate. The solvent (volatile component) is a means for ejecting droplets by the ink jet principle. The main constituent material of the solid content (function-expressing material) is made of an organic substance. As a characteristic of the organic material, when a functional element is formed on a flexible sheet, it can be deformed following the deformation without damaging the functional element when the flexible sheet is deformed. Because. Such a flexible functional element sheet realizes a functional element sheet that can be deformed, and opens the way to displays such as paper and transistors.
[0056]
When such a droplet 43 is applied to a desired element electrode portion by the ejection head unit (ejection head) 11, the position to be applied is measured by the detection optical system 32 and the image identification device 36, and the measurement data, ejection Correction coordinates are generated based on the distance between the ejection port surface of the head unit (ejection head) 11 and the composite substrate 14 and the moving speed of the carriage, and the ejection head unit (ejection head) 11 is placed on the front surface of the composite substrate 14 according to the correction coordinates. Droplets are applied while moving in the X and Y directions. As the detection optical system 32, a combination of a CCD camera or the like and a lens can be used. As the image identification device 36, a commercially available one that binarizes an image and obtains its center of gravity can be used.
[0057]
As described above, in the present invention, the ejection head unit (jet head) 11 moves the carriage in the X direction (or Y direction, or two directions of X and Y) in parallel while maintaining a certain distance from the composite substrate 14. While performing, the solution is sprayed to form a functional element group on the flexible sheet. At that time, each time the solution for forming each element is ejected, the carriage movement is stopped and the ejection is performed, so that a highly accurate element group can be formed. However, since the productivity is remarkably lowered, as described above, the solution is sequentially ejected without stopping the carriage movement.
[0058]
Next, a liquid jet head suitably applied to the present invention will be described with reference to FIGS. This example is an example of 7 nozzles. In this liquid ejecting head, a piezo element 46 is provided as an energy acting part in a flow path 45 into which a solution 56 is introduced. When a pulsed signal voltage is applied to the piezo element 46 to distort the piezo element 46 as shown in FIG. 5A, the volume of the flow path 45 is reduced and a pressure wave is generated. A droplet 43 is discharged from 1. FIG. 5B shows a state in which the piezoelectric element 46 is no longer distorted and the volume of the flow path 45 is increased.
[0059]
Here, the solution 56 introduced into the flow path 45 immediately before the nozzle 1 has passed through the filter 57. In the present invention, the filter 57 is thus provided in the ejection head, and the filter removal function is provided in the vicinity of the nozzle 1. Such a filter 57 can be incorporated into the ejection head 11 as shown in FIG. The ejection head 11 itself can also be made compact.
[0060]
As such a filter 57, for example, a stainless mesh filter is preferably used, and the pore diameter (filter mesh size) is set to 0.5 μm to 2 μm.
[0061]
Next, another example of the liquid ejecting head suitably applied to the present invention will be described with reference to FIG. This example is an example of a thermal type (bubble type) liquid jet head.
The liquid ejecting head shown here is of a type in which droplets are ejected from a short channel portion in which a solution flows, and is called an edge shooter type.
Here, an example in which the number of nozzles of the liquid ejecting head is four is shown. This liquid ejecting head is formed by bonding a heating element substrate 66 and a lid substrate 67. The heating element substrate 66 is formed on a silicon substrate 68 by an individual electrode 69, a common electrode 70, and an energy application unit by a wafer process. It is comprised by forming the heat generating body 71 which is.
[0062]
On the other hand, the lid substrate 67 is provided with a groove 74 for forming a channel into which a solution containing a functional material is introduced, and a common liquid chamber for storing the solution introduced into the channel. A recess region 75 is formed, and the heat generating substrate 66 and the lid substrate 67 are joined as shown in FIG. 7A, whereby the flow path and the common liquid chamber are formed. In the state where the heating element substrate 66 and the lid substrate 67 are joined, the heating element 71 is located on the bottom surface of the channel, and the solution introduced into these channels at the end of the channel. The nozzle 65 for ejecting a part of the nozzle as a droplet is formed. Here, the nozzle shape is rectangular, but it may be round. The lid substrate 67 is formed with a solution inlet 76 for supplying a solution into the supply liquid chamber by a supply means (not shown). 7B is a perspective view when the heating element substrate 66 and the lid substrate 67 are disassembled, and FIG. 7C is a perspective view when the lid substrate 67 shown in FIG. 7B is viewed from the back side. FIG.
[0063]
In the present invention, a single functional element is formed by a plurality of liquid droplets, or a pattern for forming a functional element or the like by a plurality of liquid droplets is formed by overlapping or contacting dots. Therefore, when such a multi-nozzle type liquid jet head is used, a functional element can be formed very efficiently. In this example, a four-nozzle liquid ejecting head is shown, but the present invention is not necessarily limited to four nozzles. Needless to say, the larger the number of nozzles, the more efficiently the functional elements are formed. However, this is not simply a matter of increasing the number, and if it increases, the liquid jet head becomes expensive, and the probability of clogging of the jet nozzle increases. The balance of the production efficiency of the conductive element).
[0064]
FIG. 8 shows a view of the multi-nozzle type liquid jet head manufactured as described above, as viewed from the nozzle side. In the present invention, such a multi-nozzle type liquid jet head is provided for each solution to be jetted and mounted on a carriage as shown in FIG. FIG. 10 is a perspective view thereof.
In FIGS. 9 and 10, the multi-nozzle type liquid jet heads are labeled A, B, C, and D, respectively, but each of the liquid jet heads A, B, C, and D has a nozzle portion of each liquid jet head. A solution containing different types of functional materials is ejected for each liquid ejecting head while being configured to be separated for each ejecting head.
[0065]
The present invention uses a multi-nozzle type liquid ejecting head as described above to eject a solution containing a different type of functional material in each liquid ejecting head to produce a functional element sheet. The finally produced functional element sheet exhibits functions such as, for example, an organic EL element or an organic transistor.
[0066]
Next, a composite substrate made of a polyethylene sheet and a Pyrex (registered trademark) glass substrate is set in such a manufacturing apparatus of the present invention, and a solution is actually injected onto the polyethylene sheet, so that an organic EL element is used as a functional element. An example of the conditions when forming is shown below.
The substrate size was 400 mm × 550 mm, the polyethylene sheet thickness was 1 mm, and the Pyrex (registered trademark) glass substrate thickness was 5 mm. The two are in close contact with each other so that an air layer does not enter between them due to a slight adhesive action on the surface of the polyethylene sheet itself.
The used ejection head is a drop-on-demand type liquid ejection head using a piezo element as shown in FIG. 6 and has a nozzle diameter of Φ22 μm and a multi-nozzle type with 32 nozzles. The nozzle arrangement density was 200 dpi in one row. Three of these were stacked and mounted on a carriage.
[0067]
The solutions used were the following three types of solutions. In the mixed solution of O-dichlorobenzene / dodecylbenzene, solution 1 was polyfluorene / perylene dye (98/2, weight ratio), and solution 2 was poly (polyethylene). Fluorene / coumarin dye (98.5 / 1.5, weight ratio), solution 3 is a solution in which 0.1% by weight of polyfluorene is mixed.
[0068]
The input voltage to the piezo element was 24 V, and the drive frequency was 12 kHz. At that time, 8 m / s is obtained as the initial jet velocity, and the mass of one drop is 4 pl. The carriage scanning speed (X direction) was 5 m / s. The distance between the ejection head nozzle and the composite substrate was 2.5 mm.
In addition, the droplet shape at the time of droplet flight is separately ejected and observed under the same conditions as the element formation so that the shape becomes a substantially round droplet immediately before adhering to the substrate surface (2.5 mm in the example of the present invention). The drive waveform was controlled and sprayed. In addition, even when the round spherical shape was not obtained, and the columnar shape was extended in the flight direction, the drive waveform was controlled so that the length was within 3 times the diameter. At that time, a driving condition (driving waveform) that does not involve a plurality of minute droplets behind the flying droplets was selected.
[0069]
Then, after drawing out the lead wire from ITO and aluminum, the polyethylene sheet on which the functional element group (herein, the organic EL light emitting element group) is formed is peeled off from the Pyrex (registered trademark) glass substrate, and the flexible function without rigidity. A functional element sheet (organic EL light-emitting element sheet) was obtained. When a voltage of 10 V was applied to this with ITO as the anode and aluminum as the cathode, red, green and blue light emission was obtained satisfactorily.
The present invention is not limited to an example of a drop-on-demand type ink jet head using such a piezo element, and it goes without saying that a jet head based on a thermal ink jet principle can also be suitably used.
[0070]
Further, in the electrode formation, the organic conductive material containing a conjugated polymer compound such as polyaniline, polythiophene, polypyrrole or the like as described above may be ejected by droplets, and all may be made of an organic material. Needless to say.
[0071]
The flexible functional element sheet (organic EL light-emitting element sheet) manufactured in this way is, for example, a paper-like display that can be bent and carried by taking advantage of its flexibility and the light weight of the resin. It can be used as a device (paper-like display).
Alternatively, it can be handled in the same way as a cloth, and a part or all of the clothes can be used as a functional element sheet (organic EL light emitting element sheet) with flexibility, and can be used as a light emitting garment indicating the presence of workers at night. There is also a method of using it as an effective luminescent (lighting) garment such as an event. Both of these are the works that can be achieved by utilizing the light weight and flexibility of resin, which is an organic material.
Also, it can be used as a large display by being attached to a wall or the like.
Even in that case, since flexibility can be utilized, even if the wall or the like is not a flat plate but a curved surface, it can be attached so as to follow it, and its application is very wide.
[0072]
The above shows an example of using an organic EL light emitting element sheet, but an electronic device such as an organic transistor can also be manufactured with the same manufacturing technique. Such an organic electronic device can be used as a device for driving the organic EL light-emitting element, so that it can be formed on the same sheet as the organic EL element, thereby providing a paper-like display having a drive circuit, a memory, and the like. Is realized.
[0073]
In addition, such an organic electronic device does not necessarily have to be manufactured and used at the same time as such a light emitting element, and it goes without saying that it may be used as a single electronic device. In particular, since the flexible functional element sheet of the present invention can be manufactured as a large sheet using the ink jet principle, an electronic device using a low-cost mass-produced organic material can be realized by making it a small chip. .
[0074]
By the way, the above explanation is only a principle explanation in manufacturing, but in actual use, whether it is a light emitting element or an electronic device, it is exposed as it is (exposed), Because there is a defect, it is protected by laminating a flexible sheet that exhibits the same characteristics as the base flexible sheet, or by applying a solution diluted with a protective organic material in a solvent. Is desirable. Specifically, an epoxy resin, an acrylic resin, or the like is preferably used. Alternatively, a transparent cover plate made of plastic or the like may be disposed facing and casing (packaged).
[0075]
First, FIG. 1 shows an example in which droplets are jetted and applied into the barrier 3, but in forming the functional element group of the present invention, the barrier 3 as shown in FIG. 1 is not necessarily used. It is not necessary, but it should be noted that a functional element is formed directly on a flat substrate by forming an electrode pattern or applying droplets. Further, FIG. 4 shows a diagram in which droplets are ejected obliquely onto the substrate surface. This is because the droplets fly obliquely in this manner in order to illustrate the detection optical system 32 and the ejection head 33 together. It should be noted that, in practice, the spraying is applied so that it is substantially perpendicular to the substrate.
[0076]
Furthermore, by using a resist material or the like as the spray solution, the present invention is also applied to the case where a three-dimensional structure is formed from a resist pattern or a resist material. The functional element in the present invention refers to such a resist material. A film pattern or a three-dimensional structure formed of such a resin material is also included.
[0077]
A solution in which fine metal particles (0.001 μm to 1 μm) such as Au and Ag are dispersed in an organic solvent is also a solution containing a functional material suitably used in the present invention. Such a solution is suitably used for forming an electrode pattern such as the above light emitting element or organic transistor.
[0078]
【The invention's effect】
A functional element group is formed by spraying droplets of a solution containing a functional material on a flexible sheet, volatilizing a volatile component in the solution, and leaving a solid content on the flexible sheet. As a result, a functional element sheet having a new configuration can be manufactured efficiently and at low cost.
[0079]
In the functional element sheet having a novel structure as described above, the solid component is mainly composed of an organic material, and the functional element is capable of following the deformation of the flexibility of the flexible sheet. Therefore, even if it is used in a situation where force is applied to such a functional element sheet and bent, the functional element is not damaged, and a functional element sheet that is strong against external force is obtained. I was able to.
[0080]
In addition, in the functional element sheet having the above-described novel configuration, the organic material is an organic EL material, so that it is possible to realize a completely new self-luminous display that is deformable and strong against external force. It was.
[0081]
A method for producing a functional element sheet formed by forming a functional element group on a flexible sheet, wherein the flexible sheet is in close contact with a substrate having rigidity higher than that of the flexible sheet. After forming a functional element group by spraying a droplet of a solution containing a functional material, volatilizing a volatile component in the solution, and leaving a solid content on the flexible sheet, Since the flexible sheet is formed by peeling, a functional element sheet that is strong against external force can be manufactured efficiently and at a low cost with a completely new configuration that has not been conventionally used.
[Brief description of the drawings]
FIG. 1 is a perspective view schematically showing one process for producing a functional element using a discharge composition according to an example of the present invention.
FIG. 2 is a view for explaining an embodiment of the functional element substrate manufacturing apparatus of the present invention.
FIG. 3 is a schematic configuration diagram showing a droplet applying device applied to manufacture of a functional element substrate of the present invention.
4 is a schematic configuration diagram of a main part of an ejection head unit of the droplet applying device shown in FIG. 3;
FIG. 5 is a diagram illustrating a droplet ejection principle of an ejection head using a piezoelectric element that is preferably used in the present invention.
FIG. 6 is a diagram showing the structure of a jet head using a piezoelectric element that is preferably used in the present invention.
FIG. 7 is an example of a thermal type (bubble type) liquid jet head suitably applied to the present invention.
FIG. 8 is a view of a multi-nozzle type liquid ejecting head as viewed from the nozzle side.
FIG. 9 is a diagram in which a multi-nozzle type liquid jet head is stacked for each solution to be jetted and unitized.
FIG. 10 is a perspective view of the head unitized in this way.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... (Liquid ejecting head) Nozzle, 2 ... Organic EL material discharged by inkjet method, 3 ... Organic substance (polyimide) barrier, 4 ... ITO transparent electrode, 5 ... Plastic substrate, 6 ... Glass substrate, 11 ... Discharge head unit (Jet head), 12 ... carriage, 13 ... substrate holder, 14 ... substrate, 15 ... supply tube for solution containing functional material, 16 ... signal supply cable, 17, 21 ... control box, 18 ... X-direction scan Motor: 19 ... Y-direction scan motor, 20 ... computer, 22 ... substrate positioning / holding means, 31 ... head alignment control mechanism, 32 ... detection optical system, 33 ... ink jet head, 34 ... head alignment fine movement mechanism, 35 ... control computer , 36 ... Image identification mechanism, 37 ... XY direction scanning mechanism, 38 ... Position detection mechanism, 3 ... Position correction control mechanism, 40 ... Inkjet head drive / control mechanism, 41 ... Optical axis, 42 ... Element electrode, 43 ... Droplet, 44 ... Droplet landing position, 45 ... Flow path, 46 ... Piezo element, 56 ... Solution 57 ... Filter, 65 ... Nozzle, 66 ... Heat generating substrate, 67 ... Cover substrate, 68 ... Silicon substrate, 69 ... Individual electrode, 70 ... Common electrode, 71 ... Heat generating member, 74 ... Groove, 75 ... Recessed region, 76 ... solution inlet.

Claims (4)

Injecting and applying droplets of a solution containing a functional material onto a flexible resin sheet serving as a base, volatilizing volatile components in the solution, and leaving solid content on the flexible resin sheet serving as the base A functional element group is formed, and the solid component is mainly composed of an organic material, and the functional element has a function that can follow the flexibility of the flexible resin sheet serving as the base. in sexual element sheet, the functional material is a different type of material, it the functional element formed by an organic EL light emitting element, an organic semiconductor material and an insulating film for driving the organic EL light emitting element a driving device comprising an organic transistor formed me by the material and the electrode material, the functional element sheet characterized by forming them on the same sheet. The functional element sheet according to claim 1, wherein another functional sheet or a protective organic material is provided on the functional element. A method for producing a functional element sheet comprising a functional element group formed on a flexible resin sheet, wherein the flexible resin sheet serving as a base is in close contact with a substrate having higher rigidity than the flexible resin sheet serving as a base. A droplet of a solution containing a functional material is sprayed on the flexible resin sheet of the composite substrate, and the volatile components in the solution are volatilized, and the solid content is applied to the base flexible resin sheet. A functional element group is formed by allowing the solid content to remain, and the solid component is mainly composed of an organic material. The functional element can follow the flexibility of the flexible resin sheet serving as the base. the method of manufacturing a functional element sheet, the functional material is a different type of material, the functional element formed thereby has to drive the organic EL device, the organic EL light emitting element A driving device comprising an organic transistor formed me by the organic semiconductor material and the insulating film material and an electrode material, after forming them on the same sheet, high flexibility resin sheet serving as the base of the rigid substrate A method for producing a functional element sheet, wherein the functional element sheet is formed by peeling from a functional element sheet. A method for producing a functional element sheet comprising a functional element group formed on a flexible resin sheet, wherein the flexible resin sheet serving as a base is in close contact with a substrate having higher rigidity than the flexible resin sheet serving as a base. A droplet of a solution containing a functional material is sprayed on the flexible resin sheet of the composite substrate, and the volatile components in the solution are volatilized, and the solid content is applied to the base flexible resin sheet. A functional element group is formed by allowing the solid content to remain, and the solid component is mainly composed of an organic material. The functional element can follow the flexibility of the flexible resin sheet serving as the base. the method of manufacturing a functional element sheet, the functional material is a different type of material, the functional element formed thereby has to drive the organic EL device, the organic EL light emitting element A driving device comprising an organic transistor formed me by the organic semiconductor material and the insulating film material and an electrode material, after forming them on the same sheet, another flexible sheet over the said functional element A method for producing a functional element sheet, comprising: laminating or providing a protective organic material, and then peeling the flexible resin sheet serving as the base from the highly rigid substrate.

Images