JP5981588B1 - Coating method and coating apparatus - Google Patents

Abstract

An object of the present invention is to provide a coating method capable of accurately coating a coating material on a plurality of divided patterns at low cost. A coating method according to an embodiment includes a long head body 11 having an outer surface, a plurality of coating regions 12 provided on the outer surface of the head body 11, and a direction substantially orthogonal to the longitudinal direction of the head body 11. A coating head 10 including a separation region 13 provided between adjacent coating regions 12 is prepared. The coating head 10 is disposed on the coating surface 2a of the substrate 2 with a predetermined gap. The coating material 3 is supplied between the coating head 10 and the coating surface 2 a, and the meniscus column 4 of the coating material 3 is formed across a plurality of coating regions 12. The substrate 2 is moved, and the meniscus column 4 is applied to the application surface while being separated into a plurality of portions corresponding to the plurality of application regions 12. [Selection] Figure 7

Description

  Embodiments described herein relate generally to a coating method and a coating apparatus.

  An organic thin-film solar cell using an organic semiconductor is expected as a low-cost solar cell because an inexpensive coating method can be applied to form an active layer. The cell constituting the organic thin film solar cell module has a structure in which an organic active layer is sandwiched between a transparent electrode and a counter electrode. Since the transparent electrode generally has low conductivity, the efficiency of extracting generated charges to the outside decreases as the cell area increases. Therefore, it is common to form a plurality of strip-shaped cells side by side and connect the plurality of cells in series.

  In order to realize the above-described organic thin-film solar cell module having a plurality of cells at a low cost, it is required to accurately apply a coating material for forming an organic active layer into a plurality of divided patterns. Furthermore, since the film thickness of the organic active layer is on the order of several tens to several hundreds of nm, it is required to form such a very thin layer with high accuracy. However, conventional coating methods cannot accurately form a plurality of patterned organic active layers at low cost. For example, a meniscus printing method is known as a coating method capable of printing an extremely thin layer on a relatively large area at a low cost. However, the conventional meniscus printing method cannot form a plurality of divided organic active layer patterns with low cost and high accuracy. For these reasons, there is a demand for improvement in technology for applying a coating material to a plurality of divided patterns.

JP 2013-066683 A

  The problem to be solved by the present invention is to provide a coating method and a coating apparatus capable of accurately coating a coating material on a plurality of divided patterns at low cost.

The coating method according to the embodiment includes a long head body having an outer surface, a plurality of coating regions provided on the outer surface of the head body so as to divide the longitudinal direction of the head body into a plurality, and a length of the head body. A step of preparing a coating head including a separation region provided between adjacent coating regions along at least a part of the outer surface in a direction substantially perpendicular to the scale direction, and the separation region as a coating surface of the coating object A coating material is provided between the coating head and the coating surface, and the meniscus column of the coating material is straddled across a plurality of coating regions. forming a, by moving at least one of the coating head and the coating object, corresponding meniscus pillar into a plurality of coated regions comprising a step of applying the coated surface while separated into a plurality, the coating material is supplied Mechanism Is supplied, the number of supply mechanism is set to less than or equal to the number of isolation regions.

It is a front view which shows the coating device of 1st Embodiment. It is a side view of the coating device shown in FIG. It is a figure which shows the 1st structural example of the coating head in the coating device shown in FIG. It is a figure which shows the 2nd structural example of the coating head in the coating device shown in FIG. It is a figure which shows the 3rd structural example of the coating head in the coating device shown in FIG. It is a figure which shows the coating method using the coating device shown in FIG. It is a figure which shows the coating method using the coating device shown in FIG. It is a figure which shows the coating method using the coating device shown in FIG. It is a figure which shows the 1st modification of the coating device shown in FIG. It is a figure which shows the 2nd modification of the coating device shown in FIG. It is a figure which shows the 3rd modification of the coating device shown in FIG. It is a figure for demonstrating the division | segmentation mechanism of the meniscus pillar in the coating device shown in FIG. It is a front view which shows the coating device of 2nd Embodiment. It is sectional drawing which shows the structural example of the organic thin-film solar cell produced using the coating device of embodiment. It is a top view of the organic thin film solar cell shown in FIG.

  Hereinafter, a coating method and a coating apparatus according to an embodiment will be described with reference to the drawings.

(First Embodiment / Coating Device and Coating Method)
FIG. 1 is a front view showing a coating apparatus according to the first embodiment, and FIG. 2 is a side view showing the coating apparatus according to the first embodiment. The coating apparatus 1 shown in FIG. 1 and FIG. 2 forms a coating film of a desired shape on a substrate 2 by applying a liquid coating material 3 to a coating surface (surface) 2a of a substrate 2 that is a coating object. It is a device for. The coating apparatus 1 includes a coating head 10, a supply mechanism 20 that supplies the coating material 3 between the substrate 2 and the coating head 10, and a moving mechanism that moves at least one of the coating head 10 and the substrate 2. 30.

  The coating head 10 includes a head body 11 having a substantially cylindrical shape that is long in the x direction in the drawing. A plurality of application regions 12 are provided on the outer peripheral surface of the substantially cylindrical head body 11 so that the longitudinal direction of the head body 11 is divided into a plurality of parts. A separation region 13 is provided between adjacent coating regions 12 along the circumferential direction of the outer peripheral surface of the head body 11. 1 and 2 show the head main body 11 having a substantially cylindrical shape, the shape of the head main body 11 is not limited to this. The head body 11 may have a polygonal columnar shape such as a hexagonal columnar shape. In such a case, the plurality of application regions 12 are provided so as to divide the outer surface of the head main body 11 into a plurality in the longitudinal direction. The separation region 13 is provided along the outer surface in a direction substantially orthogonal to the longitudinal direction of the head body 11.

  The outer peripheral surface of the head main body 11 has a plurality of application regions 12 that divide the longitudinal direction into a plurality of portions, and a coating film divided into, for example, a multiple strip pattern is formed by these. Each of the plurality of application regions 12 corresponds to each pattern of the divided coating film. The separation region 13 is provided so as to divide the outer peripheral surface of the head main body 11 into a plurality of application regions 12. The separation region 13 shown in FIGS. 1 and 2 is provided along the entire circumference of the outer peripheral surface of the head body 11, but may be provided along only a part of the outer peripheral surface in the circumferential direction. The separation region 13 may be provided along at least a part of the outer peripheral surface of the head body 11 in the circumferential direction (at least a part of the outer surface in a direction substantially orthogonal to the longitudinal direction).

  The separation region 13 has a function of separating a meniscus column of the coating material 3 to be described later into a plurality according to the plurality of coating regions 12. The meniscus column separation operation will be described in detail later. Specific configurations of the separation region 13 include a recess portion 14 shown in FIG. 3, a liquid repellent portion 15 shown in FIG. 4, a structure in which the recess portion 14 and the liquid repellent portion 15 shown in FIG. The recessed portion 14 has a shape recessed from the outer peripheral surface of the head main body 11 toward the inside. 3A is a front view of the coating head 10, and FIG. 3B is a cross-sectional view taken along the line XX of FIG. 3A. The same applies to FIGS. 4 and 5. The specific shape of the recess 14 is not particularly limited, and a V-groove shape, a square groove shape, a round groove shape, or the like can be applied.

  The liquid repellent portion 15 has, for example, a coating of a material having higher liquid repellency than the outer peripheral surface of the head body 11 with respect to the coating material 3. The liquid repellent portion 15 may be formed by connecting a member having higher liquid repellency to the head body 11. The film (liquid repellent film) as the liquid repellent portion 15 is formed using a material selected according to the coating material 3 and the constituent material of the head body 11. Examples of the material for forming the liquid repellent coating include, but are not limited to, a fluororesin such as polytetrafluoroethylene (PTFE), a resin material such as a silicone resin, and a metal plating material containing a fluororesin. . The liquid repellent film is formed by patterning a liquid repellent material on the outer peripheral surface of the head main body 11, or after forming a liquid repellent material on the entire outer peripheral surface of the head main body 11, a film at a portion that does not require liquid repellency. It can form by the method of removing. The shape of the liquid repellent portion 15 may be convex or concave with respect to the application region 12, or may be a flat shape having no step between the two regions.

  The film as the liquid repellent part 15 may be formed in the recessed part 14 as shown in FIG. In this case, the liquid repellent film may be formed so as to fill the entire depth direction of the recessed portion 14 or may be formed so as to fill a part of the recessed portion 14 in the depth direction. Further, the liquid repellent film may be formed so as to protrude from the recessed portion 14. When the recess 14 is formed along only a part of the outer peripheral surface of the head body 11 in the circumferential direction, the coating as the liquid repellent portion 15 is provided only in a minute region at the end of the recess 14 in the circumferential direction. Also good. The shape of the recessed portion 14 forming the liquid repellent film may be any of a V groove shape, a square groove shape, a round groove shape, and the like.

  The film as the liquid repellent portion 15 has a method of selectively embedding a liquid repellent material in the recessed portion 14, and has a liquid repellency after the liquid repellent material is formed on the entire outer peripheral surface of the head body 11 having the recessed portion 14. It can be formed by a method of removing an unnecessary portion of the film. For example, when a liquid repellent film having a thickness t is formed on the entire outer peripheral surface of a columnar head body 11 having a recessed portion 14 having a depth d, and the liquid repellent film is scraped off with a scraping amount a by cutting or the like, By processing so that a satisfies t <a <dt, a desired liquid repellent portion 15 can be obtained. The film forming method of the liquid repellent material is appropriately selected according to the liquid repellent material, and for example, a coating method or a plating method is applied.

  The supply mechanism 20 supplies the coating material 3 between the coating head 10 and the coating surface 2 a of the substrate 2. The supply mechanism 20 includes a syringe pump 21 that can accurately discharge a small amount of material, for example. However, the supply mechanism 20 is not limited to this, and a method suitable for discharging a trace amount material can be used. The moving mechanism 30 includes, for example, a stage 31 on which the substrate 2 that is an application target is placed, and a drive mechanism 32 for the stage 31. The stage 31 is movable by a drive mechanism 32 in the y direction in the figure. The drive mechanism 32 may have a mechanism for moving the stage 31 in the z direction in the figure. The moving mechanism 30 may be configured to move the coating head 10.

  Next, the process of applying the coating material 3 to the substrate 2 using the coating apparatus 1 will be described with reference to FIGS. First, the coating head 10 is disposed on the coating surface 2a of the substrate 2 with a predetermined gap. The coating head 10 is disposed so that the separation region 13 faces the coating surface 2a. In the case where the separation region 13 is provided over the entire circumference of the outer peripheral surface, the coating head 10 may simply be disposed on the coating surface 2a with a predetermined gap. When the separation region 13 is provided along a part of the outer peripheral surface, the region having the separation region 13 is disposed so as to face the application surface 2a. In this state, the coating material 3 is supplied from the supply mechanism 20 between the coating head 10 and the coating surface 2a of the substrate 2 (FIGS. 6A and 7A).

  The coating material 3 supplied from the supply mechanism 20 wets and spreads in the x direction between the outer peripheral surface of the head body 11 and the coating surface 2a, and further gets over the separation region 13 existing between the adjacent coating regions 12. A meniscus column 4 straddling a plurality of application regions 12 is formed. The meniscus column 4 is a columnar body having an arcuate curved surface, the gap between the head body 11 and the coating surface 2a of the substrate 2, the properties of the coating material 3 (viscosity, surface tension, etc.), and the supply of the coating material 3 It has a desired shape according to the amount and the like. A coating film having a desired film thickness is formed according to the shape of the meniscus column 4, properties such as the viscosity and surface tension of the coating material 3, the moving speed of the substrate 2, and the like.

  In forming the meniscus column 4 straddling the plurality of application regions 12, it is preferable to supply the coating material 3 between the plurality of application regions 12 and the application surface 2 a from one supply mechanism 20. The number of application regions 12 to which the coating material 3 is supplied from one supply mechanism 20 is not particularly limited, and may be a plurality. Although one supply mechanism 20 is shown in FIGS. 1 and 7, a plurality of supply mechanisms 20 may be used depending on the number of application regions 12. Even in this case, the number of supply mechanisms 20 is preferably set to be smaller than the number of application regions 12.

  Next, the stage 31 is driven to move the substrate 2 in one direction (y direction), thereby applying the coating material 3 to the coating surface as shown in FIGS. 6B, 7B, and 8. The coating film 5 is formed by applying to 2a. At the beginning of the movement of the substrate 2, as shown in FIG. 8, a solid film is formed by the coating material 3 remaining in the recessed portion 14 or the coating material 3 existing between the liquid repellent portion 15 and the coating surface 2 a of the substrate 2. It becomes a shape. When the transfer of the coating material 3 in the recessed portion 14 or in the vicinity of the liquid repellent portion 15 to the substrate 2 is completed, a divided pattern 5A is formed. In this way, the meniscus column 4 can be applied to the application surface 2 a of the substrate 2 while being separated according to the plurality of application regions 12 by the separation region 13 provided on the outer peripheral surface of the head body 11. Accordingly, it is possible to form the coating film 5 having the multiple strip-shaped pattern 5A corresponding to the plurality of application regions 12.

  Before moving the substrate 2 in order to apply the coating material 3 to the coating surface 2a of the substrate 2, the gap between the head body 11 and the coating surface 2a is widened, or the movement of the substrate 2 is performed simultaneously with the widening of the gap. You may implement. When the coating apparatus 1 has a rotation mechanism for the coating head 10, the head body 11 may be rotated simultaneously with the enlargement of the gap or the movement of the substrate 2, or separately from these. By performing such a process, the separation of the meniscus column 4 can be promoted. The gap between the head body 11 and the coating surface 2a can be enlarged by raising the coating head 10, lowering the stage 31, or rotating the head body 11 eccentrically.

  The indented portion 14 and the liquid repellent portion 15 as the separation region 13 depend on the width between the divided patterns of the coating film, various characteristics of the coating material 3, the gap between the head body 11 and the coating surface 2a, etc. In order to effectively exhibit the separation action of the pillars 4, it is preferable to have a width of 0.1 mm or more with respect to the longitudinal direction of the head body 11. If the width of the recessed portion 14 and the liquid repellent portion 15 is less than 0.1 mm, the separating function of the meniscus column 4 may be insufficient. When it is desired to increase the width between the divided patterns of application (for example, 10 mm), the application head 10 having a large diameter is used, for example, the circumferential shape of the separation region 13 is reduced, and the width of the end portion in the circumferential direction is reduced. This can be dealt with by making the shape gradually wider (for example, 10 mm) toward the center in the circumferential direction (for example, 0.1 mm). Furthermore, it is preferable that the recessed portion 14 has a depth of 0.1 mm or more from the outer peripheral surface of the head main body 11. By applying the depression 14 in this way, the separating action and pattern applicability of the meniscus column 4 can be enhanced.

When the separation region 13 is formed along only a part of the head body 11 in the circumferential direction, the formation region of the partial separation region 13 in the circumferential direction can be set according to the nip length of the meniscus column 4. preferable. When the circumferential length of the outer peripheral surface corresponding to the nip length of the meniscus Column 4 (cross-sectional width of the outer peripheral surface and is in contact portions of the head main body 11 of the meniscus Column 4) was L _n, partial separation region 13 forming region L with respect to the circumferential direction of is preferably set to exceed the circumferential length L _n. When forming region L of the isolation region 13 is not more than the circumferential length L _n, there is a possibility that the separating action of the meniscus column 4 is reduced.

  As described above, the meniscus column 4 straddling the plurality of application regions 12 is separated in the separation region 13 according to the plurality of application regions 12, thereby having a multiple strip-like pattern 5A corresponding to the plurality of application regions 12. The coating film 5 can be formed with high accuracy. Moreover, since the apparatus configuration of the coating apparatus 1 is almost the same as that of a conventional meniscus printing apparatus, there is no increase in apparatus cost. Therefore, it becomes possible to form the coating film 5 having the multiple strip-shaped pattern 5A at low cost and with high accuracy.

  Further, by forming the meniscus column 4 across the plurality of application regions 12 with one supply mechanism 20, adjustment of the supply mechanism 20 and alignment work can be simplified, application unevenness can be suppressed, excess application material can be reduced, and supply can be performed. It is possible to improve the variation due to individual differences of the mechanism 20, reduce the amount of cleaning necessary for cleaning the supply mechanism 20, and the like. That is, when a syringe pump is arranged in each of a plurality of application areas, a large number of syringe pumps are required. For this reason, in order to prevent air bubbles from being mixed into the meniscus column, if a small amount of coating material is left in the syringe pump, the amount of extra coating material increases. Since there are individual differences in syringe pumps, the supply amount tends to vary. When cleaning the syringe pump, the required amount of cleaning liquid increases. When changing the application width and application pitch of pattern application, it is necessary to change the arrangement pitch of the syringe pump. However, when trying to reduce the application pitch, the syringe pumps may interfere with each other and may not line up. This makes it difficult to align the needle. Furthermore, vertical stripe-shaped application unevenness is likely to occur at the position of the needle portion.

  By supplying the application material 3 from the supply mechanism 20 such as one syringe pump 21 to the plurality of application regions 12, the above-described points can be solved. Even when the coating width and the coating pitch are changed, it is not necessary to adjust the supply mechanism 20. There is no need to change the arrangement pitch of the supply mechanism 20. The present invention can also be applied to a fairly narrow coating pitch. The positioning operation of the supply mechanism 20 with respect to the coating head 10 is simplified. In addition, the occurrence of vertical stripe-like coating unevenness is suppressed. Furthermore, the following effects can be obtained by reducing the number of supply mechanisms 20. Even when air bubbles are prevented from entering the meniscus column, the amount of extra coating material can be reduced. Variations in coating film thickness, coating width, coating position, and the like due to individual differences in the supply mechanism 20 are improved. The amount of cleaning liquid required when cleaning the supply mechanism 20 can be reduced.

  The coating apparatus 1 of the first embodiment can be variously modified. As shown in FIG. 9, the supply mechanism 20 for the coating material 3 may include a manifold 22 that divides the discharge port of the coating material 3 discharged from one syringe pump 21 into a plurality of parts, for example. The supply mechanism 20 for the coating material 3 is not limited to the syringe pump method, and for example, a slit die coating method may be applied. FIG. 10 shows a supply mechanism 20 having a slit die 23. The slit die 23 includes a die block 24 having a sharp tip, and a slit portion 25 and a manifold portion 26 provided in the die block 24. A liquid supply nozzle (not shown) is connected to the manifold portion 26. The coating material 3 supplied from the liquid supply nozzle is supplied between the coating head 10 and the coating surface 2 a of the substrate 2 from the tip of the slit portion 25 via the manifold portion 26.

  The coating apparatus 1 according to the embodiment may include a mechanism 40 that divides one meniscus column 4 straddling the plurality of coating regions 12 into a plurality of portions according to the plurality of coating regions 12. FIG. 11 shows an example of a mechanism for dividing one meniscus column 4 into a plurality of parts. A dividing mechanism 40 shown in FIG. 11 includes a dividing member 41 that divides the meniscus column 4 into a plurality of parts. The coating head 10 and the dividing mechanism 40 will be described with reference to FIGS. 11 and 12. 12A is a cross-sectional view of the head main body 11 cut at the separation region 13, FIG. 12B is a cross-sectional view of the split member 41, and FIG. 12C is a state in which the head main body 11 and the split member 41 are overlapped. FIG. 4D is a diagram showing a state in which the dividing member 41 is moved to divide the meniscus column 4.

  The head main body 11 includes a plurality of columnar portions 17 that constitute a plurality of application regions 12 and a shaft portion 18 that connects the columnar portions 17. An outer peripheral portion of the shaft portion 18 constitutes a separation region 13. The dividing member 41 has substantially the same cross-sectional shape as the cylindrical portion 17 and substantially the same width as the shaft portion 18, and connects the dividing portions 42 provided for each separation region 13 to the plurality of dividing portions 42. And a connecting portion 43 that is moved while moving. The dividing portion 42 is provided with an elongated hole through which the shaft portion 18 of the head main body 11 is inserted and the dividing member 41 can be moved away from the application surface 2a from the state where the dividing member 41 is overlapped with the cylindrical portion 17. 44 is provided.

  The dividing process of the meniscus column 4 using the dividing member 41 is as follows. First, as shown in FIGS. 11A and 12C, the dividing member 41 is arranged with respect to the head body 11 so that the cylindrical portion 17 and the dividing portion 42 overlap each other. In such a state, the head main body 11 and the dividing member 41 are arranged on the application surface 2a of the substrate 2 with a predetermined gap. Next, the coating material 3 is supplied between the head body 11 and the dividing member 41 and the coating surface 2 a of the substrate 2. Since the divided portion 42 is arranged in the space that becomes the divided region 13 of the head main body 11, the coating material 3 does not enter the space that becomes the divided region 13, and the coating surface 2 a of the head main body 11 and the substrate 2. The meniscus pillar 4 straddling the plurality of application regions 12 is formed between the two.

  Next, as shown in FIGS. 11B and 12D, the dividing member 41 is moved in a direction away from the application surface 2a (z direction in the drawing). After the dividing unit 42 is moved, a space that becomes the divided region 13 appears. Therefore, the meniscus column 4 is divided into a plurality according to the application region 12 by capillary action or the like based on the appearance of this space. The dividing member 41 is preferably formed of a material having higher liquid repellency than the head body 11 with respect to the coating material 3. In this way, the initial meniscus column 4 is divided into a plurality of meniscus columns 4A corresponding to the plurality of application regions 12. By moving the substrate 2 in one direction in this state, the coating material 3 is coated on the coating surface 2 a of the substrate 2. Since the meniscus column 4 is divided into a plurality of meniscus columns 4A, the coating film 5 having a multiple strip-like pattern 5A can be formed as in FIG.

Second Embodiment / Coating Device and Coating Method
Next, a coating method and a coating apparatus according to the second embodiment will be described with reference to FIG. FIG. 13 is a front view showing a coating apparatus 51 according to the second embodiment. In addition, in the coating apparatus 51 of 2nd Embodiment shown in FIG. 13, the same code | symbol is attached | subjected to the same part as 1st Embodiment, and those description may be abbreviate | omitted partially. Moreover, although illustration of a part of the configuration is omitted in FIG. 13, the basic configuration is the same as that of the first embodiment.

  In the coating apparatus 51 of the second embodiment, the coating head 10 includes a head body 11 in which a flow path (communication hole) 52 for the coating material 3 is provided. Each of the plurality of application regions 12 provided in the head main body 11 is provided with slits 53 connected to the flow paths 52. The slit 53 is opened on the outer surface of the application region 12. The coating head 10 of the second embodiment has the same configuration as the coating head 10 of the first embodiment, except that the head body 11 has a flow path 52 and a slit 53 of the coating material 3. .

  A flow path 52 of the coating material 3 provided inside the head body 11 is connected to a coating material tank 54 that stores the coating material 3 via a supply pipe 55. The coating material tank 54 is movable in the vertical direction along the direction of gravity. The coating material tank 54 and the supply pipe 55 constitute a supply unit for the coating material 3. When the coating material tank 54 is moved upward in a state where the head main body 11 is arranged on the coating surface 2 a of the substrate 2 with a predetermined gap, the coating material 3 is slit through the supply pipe 55 and the flow path 52. It is discharged from the opening. Since the slit 53 is provided for each of the plurality of application regions 12, a meniscus column is formed between each of the plurality of application regions 12 and the application surface 2a. By moving the substrate 2 in one direction in this state, a coating film having a multiple strip pattern can be formed.

In the coating apparatus 51 of the second embodiment, the coating material tank 54 and the supply piping 55 together with the flow path 52 and the slit 53 provided in the head main body 11 constitute the coating material 3 supply mechanism 20. The supply mechanism 20 in the second embodiment has a function of forming a meniscus column of the coating material 3 between the plurality of coating regions 12 and the coating surface 2a.
Also by using such a supply mechanism 20, a coating film having a multiple strip-like pattern corresponding to the plurality of application regions 12 can be formed with high accuracy. Furthermore, as in the first embodiment, adjustment of the supply mechanism 20 and simplification of the alignment operation, reduction of excess coating material, improvement of variation due to individual differences in supply mechanisms such as syringe pumps, and the like can be realized. It becomes possible.

(Third embodiment / organic thin film solar cell)

  The coating apparatus 1 and the coating method using the same according to the embodiment are suitably used for, for example, a process of forming an organic active layer in a method for manufacturing an organic thin film solar cell module. 14 and 15 show an example of an organic thin-film solar cell module 100 to which the coating method of the embodiment is applied in the step of forming an organic active layer. In FIG. 15, the counter electrode is not shown. The organic thin-film solar cell module 100 shown in FIGS. 14 and 15 has a plurality of cell portions 102A and 102B connected in series. A plurality of separated first electrode layers 103A and 103B are formed on the support substrate 101. Photoelectric conversion layers 104A and 104B are formed on the first electrode layers 103A and 103B, respectively. Second electrode layers 105A and 105B are formed on the photoelectric conversion layers 104A and 104B, respectively. The second electrode layer 105A of the cell portion 102A is electrically connected to the first electrode layer 103B of the cell portion 102B.

  In the organic thin film solar cell module 100 shown in FIG. 14, the photoelectric conversion layer 104 is irradiated with light such as sunlight or illumination light from the support substrate 101 side. The photoelectric conversion layer 104 includes, for example, an organic active layer including a p-type semiconductor and an n-type semiconductor, and a first intermediate layer (not shown) (for example, disposed between the first electrode layer 103 and the organic active layer). An electron transport layer) and a second intermediate layer (for example, a hole transport layer) (not shown) disposed between the organic active layer and the second electrode layer 105. When the organic active layer absorbs the light applied to the photoelectric conversion layer 104, charge separation occurs at the phase interface between the p-type semiconductor and the n-type semiconductor, thereby generating electrons and holes that are paired therewith. Of the electrons and holes generated in the organic active layer, for example, electrons are collected by the first electrode layer 103, and holes are collected by the second electrode layer 105.

  The support substrate 101 is made of a light transmissive material. As a constituent material of the support substrate 101, inorganic materials such as alkali-free glass, quartz glass, and sapphire, organic materials such as polyethylene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polyamide, polyamideimide, and liquid crystal polymer Is mentioned.

  The first electrode layer 103 is made of a material having optical transparency and conductivity. Constituent materials of the first electrode layer 103 include indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO), tin oxide doped with fluorine (FTO), indium-zinc oxide (IZO), indium-gallium. -Conductive metal oxides such as zinc oxide (IGZO), metals such as gold, platinum, silver, copper, titanium, zirconium, cobalt, nickel, indium, aluminum, alloys containing these metals, or poly (3,4) -Conductive polymers such as ethylenedioxythiophene) / poly (4-styrenesulfonic acid) (PEDOT / PSS). The first electrode layer 103 is formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a coating method, or the like.

  The organic active layer has a function of performing charge separation by irradiated light and includes a p-type semiconductor and an n-type semiconductor. For the p-type semiconductor, a material having an electron donating property is used. For the n-type semiconductor, an electron-accepting material is used. Both the p-type semiconductor and the n-type semiconductor constituting the organic active layer may be an organic material, or one of them may be an organic material.

  The p-type semiconductor contained in the organic active layer includes polythiophene and derivatives thereof, polypyrrole and derivatives thereof, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane And derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline and derivatives thereof, phthalocyanine derivatives, porphyrin and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, etc. These may be used together.

As the n-type semiconductor contained in the organic active layer, fullerene and fullerene derivatives are preferably used. The fullerene derivative should just have a fullerene skeleton. Fullerenes and fullerene derivatives include fullerenes such as C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ , fullerene oxides in which at least some of the carbon atoms of these fullerenes are oxidized, and some carbon atoms of the fullerene skeleton. Examples thereof include a compound modified with an arbitrary functional group, a compound in which these functional groups are bonded to each other to form a ring, and the like.

  The organic active layer has a bulk heterojunction structure including, for example, a mixture of a p-type semiconductor material and an n-type semiconductor material. The bulk heterojunction organic active layer has a microphase separation structure of a p-type semiconductor material and an n-type semiconductor material. In the organic active layer, the p-type semiconductor phase and the n-type semiconductor phase are phase-separated from each other to form a nano-order pn junction. When the organic active layer absorbs light, positive charges (holes) and negative charges (electrons) are separated at these phase interfaces, and are transported to the electrodes 103 and 105 through each semiconductor.

  The bulk heterojunction organic active layer uses a solution obtained by dissolving a p-type semiconductor and an n-type semiconductor in a solvent as a coating material, and this coating material is used as a support substrate (transparent electrode) having a first electrode layer (transparent electrode) 103 and the like. Substrate) 101 is applied by coating. The coating material constituting the organic active layer is coated on the support substrate (transparent substrate) 101 by applying the coating apparatus 1 of the embodiment and a coating method using the coating apparatus 1. This makes it possible to form the photoelectric conversion layers 103A and 103B having a multiple strip-like pattern as shown in FIG. 15 with high accuracy and low cost. Although the thickness of an organic active layer is not specifically limited, 10 nm-1000 nm are preferable.

  The electron transport layer has a function of blocking holes generated in the organic active layer and selectively and efficiently transporting electrons to the first electrode layer 103. Examples of the constituent material of the electron transport layer include metal oxides such as zinc oxide, titanium oxide, and gallium oxide, and organic materials such as polyethyleneimine. The hole transport layer has a function of blocking electrons generated in the organic active layer and transporting holes to the second electrode layer 105 selectively and efficiently. Examples of the constituent material of the hole transport layer include organic conductive polymers such as PEDOT / PSS, polythiophene, polypyrrole, polyacetylene, triphenylenediamine polypyrrole, and polyaniline, and metal oxides such as molybdenum oxide and vanadium oxide. The electron transport layer and the hole transport layer are formed by, for example, a vacuum film formation method such as a vacuum deposition method or a sputtering method, a sol-gel method, a coating method, or the like.

  The second electrode layer 105 is made of a material having conductivity and, in some cases, light transmission. As the constituent material of the second electrode layer 105, for example, platinum, gold, silver, copper, nickel, cobalt, iron, manganese, tungsten, titanium, zirconium, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, Metals such as rubidium, cesium, calcium, magnesium, barium, samarium and terbium, alloys containing them, conductive metal oxides such as indium-zinc oxide (IZO), conductive polymers such as PEDOT / PSS Or carbon materials such as graphene and carbon nanotubes. The second electrode layer 105 is formed by, for example, a vacuum film formation method such as a vacuum deposition method or a sputtering method, a sol-gel method, a coating method, or the like.

In addition, the coating apparatus 1 of embodiment and the coating method using the same are not restricted to the formation process of the organic active layer of the organic thin-film solar cell module mentioned above, The formation process of an electron carrying layer or a positive hole transport layer, 1st electrode It can be applied to a forming process to which a coating method is applied, such as a forming process of a layer or a second electrode layer. Furthermore, not only the manufacturing process of the organic thin film solar cell module, but also manufacturing of a perovskite solar cell using a perovskite semiconductor thin film having an organic-inorganic hybrid structure in the active layer, a solar cell combining a perovskite semiconductor thin film and an organic semiconductor thin film, etc. It can be applied to the process. For example, as a perovskite semiconductor used in the active layer, (CH ₃ NH ₃ ) BX ₃ (B is a metal atom such as Pb or Sn, and X is a halogen element such as I, Br, or Cl) is known. . Furthermore, not only in the manufacturing process of a solar cell, but also in general techniques in which multiple strip-shaped pattern coating as shown in FIG. 8 is useful, such as organic EL (electroluminescence) type illumination and display. Can be applied.

  Next, examples and evaluation results thereof will be described.

Example 1
By forming 22 indentations with a width of 1.2 mm at equal intervals on the outer peripheral surface of a cylindrical body made of SUS303 having a diameter of 16 mm and a length of 302.4 mm, 23 coating areas (width: 12 mm) An application head having The depth of the recess was 0.5 mm. The recess was formed over the entire circumference of the coating head.

  To 1 ml of monochlorobenzene, 8 mg of PTB7 ([poly {4,8-bis [(2-ethylhexyl) oxy] benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl-1t- alt-3-fluoro-2-[(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophene-4,6-diyl}] / p-type semiconductor) and 12 mg of PC70BM ([6,6] phenyl) (C71 methyl butyrate ester / n-type semiconductor) was dispersed to prepare a coating solution as a material for forming the organic active layer.

  A syringe pump was used for the coating liquid supply mechanism. The barrel is made of glass and the needle is made of stainless steel. As an application target, an alkali-free glass substrate having an ITO electrode was used. As a pretreatment, a glass substrate cleaned with UV ozone and a glass substrate that was not pretreated were used, but there was no difference in the effects described later.

  The coating head described above was placed on a glass substrate as a coating object. The gap between the coating head and the glass substrate was 0.88 mm. Three syringe pumps were used, and these were installed so as to be almost evenly arranged with respect to the entire width of the coating head. A total of 1.4 ml of the coating solution was discharged to form one meniscus column for the entire width of the coating head. Thereafter, when the glass substrate was moved in one direction, a coating film having a multiple strip-like pattern as shown in FIG. 8 could be formed.

  As a result of observing the obtained multiple strip-shaped coating film, the pattern was well divided and the shape accuracy was excellent. Furthermore, when an Ag electrode was formed on the organic active layer (coating film) by a vapor deposition method to produce an organic thin film solar cell, it was confirmed that good characteristics were exhibited. Although not described in detail here, an electron transport layer was formed between the ITO electrode and the organic active layer, and a hole transport layer was formed between the organic active layer and the Ag electrode.

(Example 2)
Twenty-two indentations having a width of 1.2 mm and a depth of 0.25 mm were formed at equal intervals on the outer peripheral surface of a SUS303 cylinder having a diameter of 16.2 mm and a length of 302.4 mm. The recess was formed over the entire circumference of the coating head. The liquid repellent treatment was performed on the entire surface of the cylindrical body having a hollow portion. The liquid repellent treatment was performed by PTFE compound plating (manufactured by Metal Film Laboratory Co., Ltd.). The plating thickness was 10 μm. The liquid repellent part was formed by scraping the outermost surface of the coating head by 0.11 mm by a cutting method. The plating film formed in the 0.25 mm indentation is not scraped. In this way, a coating head having 22 liquid repellent portions and 23 coating areas (width: 12 mm) was manufactured. When the coating liquid was applied under the same conditions as in Example 1 using the resulting coating head, good results were obtained as in Example 1.

  In addition, although several embodiment of this invention was described, these embodiment is shown as an example and is not intending limiting the range of invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  DESCRIPTION OF SYMBOLS 1,51 ... Coating apparatus, 2 ... Board | substrate, 3 ... Coating material, 4 ... Meniscus pillar, 5 ... Coating film, 10 ... Coating head, 11 ... Head main body, 12 ... Coating area | region, 13 ... Separation area | region, 14 ... Indentation part DESCRIPTION OF SYMBOLS 15 ... Liquid-repellent part, 20 ... Supply mechanism, 30 ... Movement mechanism, 31 ... Stage, 32 ... Stage drive mechanism, 41 ... Dividing member, 52 ... Flow path, 53 ... Slit, 54 ... Coating material tank.

Claims (10)

An elongated head body having an outer surface, a plurality of application regions provided on the outer surface of the head body so as to divide the longitudinal direction of the head body into a plurality, and a length direction of the head body. Providing an application head comprising a separation region provided between adjacent application regions along at least a portion of the outer surface in a direction orthogonal to each other;
Placing the application head on the application surface with a predetermined gap while directing the separation region toward the application surface of the application object;
Supplying a coating material between the coating head and the coating surface, and forming a meniscus column of the coating material across the plurality of coating regions;
Moving at least one of the coating head and the coating object, and applying the meniscus column to the coating surface while separating the meniscus column into a plurality corresponding to the plurality of coating regions ,
The coating method, wherein the coating material is supplied from a supply mechanism, and the number of the supply mechanisms is set to be equal to or less than the number of the separation regions . The coating method according to claim 1 , wherein the separation region has at least one of a recessed portion and a liquid repellent portion formed on the outer surface. The coating method according to claim 2 , wherein the liquid repellent portion includes a material having higher liquid repellency than the outer surface of the head main body with respect to the coating material. Further comprising the step of dividing the meniscus pillar into a plurality to correspond to the plurality of coating regions, The coating method according to any one of claims 1 to 3. An elongated head body having an outer surface, a plurality of application regions provided on the outer surface of the head body so as to divide the longitudinal direction of the head body into a plurality, and a length direction of the head body. An application head comprising: a separation region provided between adjacent application regions along at least a portion of the outer surface in a direction orthogonal to each other;
A supply mechanism for supplying a coating material between the coating head and a coating surface of a coating object so as to form a meniscus column of the coating material across the plurality of coating regions;
A moving mechanism that moves at least one of the application head and the application target so as to apply the meniscus column to the application surface while separating the meniscus column in correspondence with the application areas ;
The number of the supply mechanisms is a coating apparatus set to be equal to or less than the number of the separation regions . The coating apparatus according to claim 5 , wherein the separation region has at least one of a recessed portion and a liquid repellent portion formed on the outer surface. The coating apparatus according to claim 6 , wherein the liquid repellent portion includes a material having higher liquid repellency than the outer surface of the head body with respect to the coating material. Further comprises a mechanism for dividing the meniscus pillar into a plurality to correspond to the plurality of coating regions, the coating apparatus according to any one of claims 5 to 7. The coating apparatus according to claim 8 , wherein the split mechanism has a split member that has a cross section at least partially overlapping the head main body and is movable in a direction away from the coating surface. An elongated head body having an outer surface, a plurality of application regions provided on the outer surface of the head body so as to divide the longitudinal direction of the head body into a plurality, and a length direction of the head body. An application head comprising: a separation region provided between adjacent application regions along at least a portion of the outer surface in a direction orthogonal to each other;
A supply mechanism for supplying a coating material between the coating head and the coating surface of the coating object so as to form meniscus columns of the coating material between the plurality of coating regions and the coating surface,
A moving mechanism for moving at least one of the application head and the application object so as to apply the application material from the plurality of meniscus pillars to the application surface according to the application areas ;
The supply mechanism includes a flow path of the coating material provided along the longitudinal direction in the head body, and the plurality of coating areas connected to the flow path and open to an outer surface of the coating area. A coating apparatus comprising: a slit provided for each; and a supply unit that supplies the coating material into the flow path .

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