WO2007023881A1

WO2007023881A1 - Method for forming electrode pattern, method for connecting electrode patterns, method for forming dye sensitized semiconductor electrode and photoelectric cell module

Info

Publication number: WO2007023881A1
Application number: PCT/JP2006/316562
Authority: WO
Inventors: Hideo Kogure
Original assignee: Kansai Paint Co., Ltd.
Priority date: 2005-08-26
Filing date: 2006-08-24
Publication date: 2007-03-01

Abstract

Provided is a method for electrically connecting a pair of electrode patterns (22, 83) arranged through an insulating layer. A bonding mask (69) is provided with a wiring section forming hole (68b) penetrating the front and rear planes of a laminated body wherein a base material film (64) is bonded on a hot melt layer (66). The method is provided with a step of bonding the mask on a first substrate (82) whereupon the first electrode pattern (83) is formed on a front plane, by thermocompression so that a wiring section forming hole (68b) is aligned with the first electrode pattern (83). The method is also provided with a step of filling the wiring section forming hole (68b) with a conductive paste (61a); a step of peeling the base material film (64) from the hot melt layer (66); and a step of bonding a second substrate (20) whereupon a second electrode pattern (22) is formed on the front plane, on the exposed hot melt layer (66) by thermocompression so that the second electrode pattern (22) is aligned with the wiring section forming hole (68b).

Description

Specification

Technical field of electrode pattern formation method, electrode pattern connection method, dye-sensitized semiconductor electrode formation method, and photovoltaic module

TECHNICAL FIELD [0001] The present invention relates to a method for forming electrode patterns, a method for connecting electrode patterns, a method for forming dye-sensitized semiconductor electrodes, and a photovoltaic module.

Background art

[0002] A substrate on which an electrode pattern is formed is widely used in photovoltaic cells, displays, and the like that convert light energy such as sunlight into electrical energy. For example, in the case of a photovoltaic cell such as an amorphous silicon photovoltaic cell or a dye-sensitized photovoltaic cell, a plurality of photovoltaic cells having a photoelectric conversion layer between a pair of substrates each formed with an electrode pattern made of a transparent conductive film or the like are connected to a wiring portion. A photovoltaic module is configured by connecting in series or in parallel via

[0003] As a method of forming an electrode pattern on a substrate, a photolithographic method in which a photosensitive resin is applied to the surface of the substrate, then ultraviolet rays are irradiated through a photomask, and etching is performed using a chemical solution. Conventional power is also known (for example, Patent Document 1). However, when the electrode pattern is formed by photolithography, depending on the material of the substrate, there is a risk that it will be damaged by the acid of the chemical solution or the strength of the solution. The amount of chemicals that are produced is also unsuitable for mass production due to environmental pollution problems.

[0004] In addition, as a method for establishing electrical connection between electrode patterns formed on a pair of substrates between two adjacent photovoltaic cells, Patent Document 2 discloses a photovoltaic cell using a connecting member such as a soldered copper ribbon. A solar cell module that is electrically connected to each other is disclosed. However, such an electrode pattern conduction method is not suitable for mass production because it is difficult to perform work efficiently when many photovoltaic cells are connected in series or in parallel.

Further, as a method for forming a dye-sensitized semiconductor electrode on an electrode pattern, for example, a patent As disclosed in Reference 3, after forming a semiconductor electrode by coating a dispersion of titanium oxide fine particles on an electrode substrate and drying it, the electrode substrate is immersed in a dye solution and light is applied to the semiconductor electrode. Conventionally, a method for supporting a sensitizing dye is known. However, such a method cannot efficiently form a dye-sensitized semiconductor electrode and is not suitable for mass production.

Patent Document 1: Japanese Patent Laid-Open No. 8-330692

Patent Document 2: Japanese Patent Laid-Open No. 2005-101519

Patent Document 3: Japanese Patent Laid-Open No. 2002-216861

Disclosure of the invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide an electrode pattern forming method excellent in mass productivity, a connection method between electrode patterns, a dye-sensitized semiconductor electrode forming method, and a photovoltaic module.

Means for solving the problem

[0007] The object of the present invention is to provide an electrode pattern on a substrate using a main electrode forming mask in which a hot melt layer is covered with a coating layer made of a metal material and has a main electrode forming opening penetrating the front and back surfaces. A step of thermocompression bonding the main electrode forming mask to the surface of the substrate through the hot melt layer, and a physical form of the conductive vapor deposition material through the opening for forming the main electrode. This is achieved by an electrode pattern forming method comprising a step of forming a main electrode pattern on the substrate by performing vapor deposition and a step of peeling off the main electrode formation mask.

[0008] The object of the present invention is achieved by a photovoltaic module in which a photoelectric conversion layer and a counter electrode are laminated on a main electrode pattern formed on a substrate by the electrode pattern forming method.

[0009] Further, the object of the present invention is a method of electrically connecting a pair of electrode patterns arranged via an insulating layer, in a laminate in which a base film is bonded to a hot melt layer. A bonding mask having a wiring portion forming hole penetrating the front and back surfaces is connected to the first substrate having the first electrode pattern formed on the front surface with respect to the wiring portion forming hole and the first electrode. A step of thermocompression bonding so as to align with the no-turn, a step of filling the wiring part formation hole with a conductive paste, a step of peeling the base film from the hot melt layer, and the exposed Thermocompression bonding a second substrate having a second electrode pattern formed on the surface thereof to the hot melt layer so that the second electrode pattern and the wiring portion forming hole are aligned. This is achieved by a connection method between the electrode patterns provided.

[0010] Further, the object of the present invention is a photovoltaic module comprising a plurality of photovoltaic cells each having a photovoltaic conversion layer between the first electrode pattern and the second electrode pattern, wherein one photovoltaic cell is provided. And the second electrode pattern and force in the other photovoltaic cell are connected by the connection method between the electrode patterns, and this is achieved by the photovoltaic module.

[0011] Further, the object of the present invention is a method of forming a dye-sensitized semiconductor electrode on an electrode pattern, wherein the hot melt layer is covered with a coating layer made of a metal material and penetrates the front and back surfaces. A step of thermocompression bonding a semiconductor electrode forming mask having an opening to a substrate on which an electrode pattern is formed so that the opening and the electrode pattern are aligned; and a semiconductor electrode in the opening A method of forming a dye-sensitized semiconductor electrode, comprising: a step of filling a material; a step of supporting a photosensitizing dye on a semiconductor electrode material filled in the opening; and a step of peeling off the semiconductor electrode formation mask. Is achieved.

[0012] The object of the present invention is achieved by a photovoltaic module in which a counter electrode is laminated on a semiconductor electrode formed by the method for forming a dye-sensitized semiconductor electrode. The invention's effect

[0013] According to the present invention, it is possible to provide an electrode pattern formation method, a connection method between electrode patterns, a dye-sensitized semiconductor electrode formation method, and a photovoltaic module that are excellent in mass productivity.

[0014] Further, according to the connection method between electrode patterns of the present invention, reliable conduction between electrode patterns can be obtained.

Brief Description of Drawings

FIG. 1 is a process sectional view showing an example of a process of forming a main electrode pattern on a substrate of a front electrode film. FIG. 2 is a process sectional view showing an example of a process for forming an auxiliary electrode pattern on a substrate of a front electrode film.

FIG. 3 is a process perspective view showing an example of a process for continuously forming the main electrode pattern and the auxiliary electrode pattern on a substrate.

FIG. 4 is a process cross-sectional view illustrating an example of a process for forming a semiconductor electrode.

FIG. 5 is a cross-sectional view showing an example of a back electrode film.

FIG. 6 is a process cross-sectional view showing an example of a pre-process for forming a wiring portion and an electrolyte layer.

FIG. 7 is a process cross-sectional view illustrating an example of a process for forming a wiring portion and an electrolyte layer.

FIG. 8 is a cross-sectional view of a photovoltaic module according to an embodiment of the present invention.

FIG. 9 is a process cross-sectional view illustrating an example of an electrolyte layer formation and sealing process.

FIG. 10 is a process sectional view showing another method for forming a main electrode pattern using a main electrode formation mask.

FIG. 11 is a cross-sectional view of a main electrode formation mask used in still another method for forming a main electrode formation pattern.

FIG. 12 is a process cross-sectional view illustrating another method for forming an electrode pattern.

Explanation of symbols

2 Adhesive layer

4 Coating layer

6 Base film

8 Hot menoleto layer

10 Laminate

10a Main electrode formation mask

12a opening

20 substrates

22 Electrode pattern

22a Main electrode pattern

22b Auxiliary electrode pattern 30 Front electrode film

30a Semiconductor electrode formation mask

32a opening

34 Semiconductor electrode

62 Adhesive layer

64 Base film

66 Hot menoleto layer

68 Laminate

68a Electrolyte container

68b Wiring part formation hole

69 Mask for bonding

80 Back electrode film

90 electrolyte layer

91 Sealing part

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, a method for producing a photovoltaic module using an electrode pattern forming method according to an embodiment of the present invention will be described with reference to the accompanying drawings.

1.Formation of front electrode film

The method for producing the front electrode film constituting the photovoltaic module will be described with reference to the process cross-sectional views shown in FIGS. First, as shown in FIG. 1 (a), a base film 6 having an adhesive layer 2 formed on one surface and a coating layer 4 formed on the other surface is prepared, and the adhesive layer 2 is exposed on the exposed surface. The hot melt layer 8 is bonded together to form a laminate 10 as shown in FIG. 1 (b).

[0018] For the pressure-sensitive adhesive layer 2, a heat-resistant strong pressure-sensitive adhesive such as acrylic resin or urethane resin can be used. The thickness of the pressure-sensitive adhesive layer 2 is not particularly limited and is, for example, 1 to 40 / ζ πι.

[0019] The coating layer 4 is made of a metal material such as aluminum or copper, and protects the surface of the base film 6 during a subsequent cleaning process. The thickness of the coating layer 4 is not particularly limited. For example, 1 to 50πι.

[0020] The base film 6 is a hard film formed of force such as polypropylene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, and the thickness is 20

About 100 μm is preferable.

[0021] The hot menoleto layer 8 is, for example, a known polyester resin, polyamide resin, EVA resin, polyolefin resin, or the like in which a rosin or terpene tackifier is added. Things can be used.

Next, the laminate 10 is subjected to die cutting to form an opening 12a as shown in FIG. 1 (c). The opening 12a is an opening for forming a main electrode, and has a shape corresponding to a main electrode pattern formed on a substrate 20 described later. Thus, the opening for forming the main electrode

A main electrode forming mask 10a having 12a is obtained.

Next, as shown in FIG. 1 (d), this main electrode formation mask 10 a is adhered onto the substrate 20.

. As the substrate 20, polyethylene terephthalate (PET), polyethylene naphthalate (PE

Examples thereof include a resin film having high heat resistance and insulation such as N), and a glass substrate. In addition, polymethylol methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyethersulfone, polyolefin, triflate. Examples include cetyl cellulose and acrylic resin.

[0024] The main electrode forming mask 10a can be bonded to the substrate 20 by thermocompression using a thermocompression roller or the like, but the adhesive strength is increased by making the hot melt layer 8 in a semi-molten state. It is preferable to adjust so as not to be too much and to allow easy peeling between the hot melt layer 8 and the substrate 20.

Next, the upper surface side of the substrate 20 is subjected to corona discharge treatment, excimer treatment, and the like to clean the portion exposed from the opening 12a on the substrate 20, and then conductive through the opening 12a. By performing physical vapor deposition of the vapor deposition material, a main electrode pattern 22a is formed on the substrate 20 as shown in FIG. 1 (e). Then, as shown in FIG. 1 (f), the main electrode formation mask 10 a is peeled between the hot melt layer 8 and the substrate 20.

[0026] Examples of physical vapor deposition for forming the main electrode pattern 22a include vacuum vapor deposition, sputtering, and ion plating. Also as a conductive vapor deposition material Illustrative examples include transparent materials such as ITO (indium tin oxide), FTO (fluorine-doped tin oxide), and ΑΤΟ (antimond-type tin oxide). The pattern shape of the main electrode pattern 22a is not particularly limited, and various shapes such as a strip shape, a rectangular shape, and a linear shape are possible, and a plurality of pattern part forces can be configured.

Thus, after forming the main electrode pattern 22a on the substrate 20, the auxiliary electrode pattern 22b is formed on the same substrate 20 using the auxiliary electrode formation mask 10b. The auxiliary electrode pattern 22b can be created by the same procedure as the method for creating the main electrode pattern 22a described above. For the laminate 10, the auxiliary electrode pattern 22b is used for forming the auxiliary electrode instead of the opening 12a for forming the main electrode. It is obtained by forming the opening 12b.

[0028] As shown in FIG. 2 (a), the auxiliary electrode forming mask 10b is aligned with the substrate 20 so that the opening 12b is disposed at a desired position with respect to the main electrode pattern 22a on the substrate 20. Then, the hot melt layer 8 is temporarily bonded to the substrate 20 in the same manner as described above. Then, by performing physical vapor deposition of the conductive vapor deposition material through the opening 12b, the auxiliary electrode pattern 22b is formed along the main electrode pattern 22a on the substrate 20, as shown in FIG. 2 (b). To do. Examples of the material of the auxiliary electrode pattern 22b include metal materials such as platinum, gold, copper, silver, chromium, copper-chromium, and the like, which preferably have a lower resistance than the main electrode pattern 22a.

[0029] In the present embodiment, as long as the auxiliary electrode pattern 22b is formed along the main electrode pattern 22a, the force is formed linearly along both longitudinal edges of the main electrode pattern 22a. The position and shape of the auxiliary electrode pattern 22b are not particularly limited. Thereafter, the auxiliary electrode forming mask 10b is peeled off, whereby the front electrode in which the electrode pattern 22 composed of the main electrode pattern 22a and the auxiliary electrode pattern 22b is formed on the substrate 20 as shown in FIG. 2 (c). Film 30 is obtained.

In the present embodiment, after the main electrode pattern 22a is formed, the auxiliary electrode pattern 22b is formed! /, But the auxiliary electrode pattern 22b is formed first and then the main electrode pattern 22a is formed. It may be formed.

That is, as shown in FIG. 12 (a), after the auxiliary electrode formation mask 10b is adhered on the substrate 20 such as an electrode film and the auxiliary electrode pattern 22b is formed through the opening 12b, As shown in FIG. 12 (b), the auxiliary electrode forming mask 10b is peeled off. And as shown in Fig. 12 (c) As described above, the main electrode formation mask 10a is attached on the substrate 20 on which the auxiliary electrode pattern 22b is formed, and after the cleaning process such as the corona discharge treatment is performed on the substrate 20 through the opening 12a, the opening is formed. A main electrode pattern 22a is formed through the portion 12a. In the present embodiment, the auxiliary electrode pattern 22b is formed along the outer peripheral edge of the main electrode pattern 22a, and the main electrode pattern 22a is formed so as to be filled therebetween.

Next, a semiconductor electrode material is vapor-deposited through the opening 12a, and as shown in FIG. 12 (d), a semiconductor layer 34a is deposited on the upper surface of the main electrode pattern 22a, and then the upper surface of the semiconductor layer 34a. A semiconductor electrode material is applied to the semiconductor electrode 34 with a squeegee or the like to form a semiconductor electrode 34 as shown in FIG. Thereafter, the main electrode forming mask 10a is peeled off.

In this way, by forming the main electrode pattern 22a after the formation of the auxiliary electrode pattern 22b, the semiconductor electrode 34 is formed in addition to the formation of the main electrode pattern 22a by using the main electrode formation mask 10a. Therefore, the main electrode forming mask 10a can also be used as a semiconductor electrode forming mask, thereby improving the manufacturing efficiency. The formation of the semiconductor electrode 34 will be described in detail later.

[0034] The main electrode forming mask 10a can be peeled off by a force that can be performed between the hot melt layer 8 and the substrate 20, or by forming the adhesive layer 2 with a weak adhesive force. The front electrode film 30 in which the hot melt layer 8 remains can also be produced as shown in FIG. 12 (f).

The auxiliary electrode pattern 22b may be provided with only the main electrode pattern 22a on the substrate 20, which is not always necessary. However, when the main electrode pattern 22a is made of, for example, ITO, the power loss increases as the length in the longitudinal direction increases. In this case, the auxiliary electrode pattern along the longitudinal direction of the main electrode pattern 22a. It is preferable to provide 22b. In this case, the surface resistance value of the auxiliary electrode pattern 22b is made smaller than the surface resistance value of the main electrode pattern 22a by forming the auxiliary electrode pattern 22b with a material having a lower resistance than the material of the main electrode pattern 22a. Set as follows. More specifically, when the surface resistance value of the main electrode pattern 22a in use is set to 1, the surface resistance value of the auxiliary electrode pattern 22b is preferably 0.1 or less. The surface resistance of the main electrode pattern 22a is 100 Ω The surface resistance of the auxiliary electrode pattern 22b made of platinum The value can be 3 Ω / mouth.

The formation of the electrode pattern 22 (the main electrode pattern 22a and the auxiliary electrode pattern 22b) on the substrate 20 can be performed continuously as follows, for example. First, as shown in a perspective view in FIG. 3 (a), tl ^ standing holes H are formed on both side edges of the film-like substrate 20 and the laminate 10, respectively. Forms a main electrode forming mask 1 Oa by providing a plurality of openings 12a at regular intervals along the longitudinal direction.

[0037] Then, the substrate 20 and the main electrode formation mask 10a are respectively transported by the transport rolls 42 and 44, and as shown in FIG. By supplying between the rolls 4 6 and 46, the main electrode forming mask 10 a is thermocompression bonded to the substrate 20. For example, it is preferable to set the thermocompression bonding conditions of the thermocompression rolls 46 and 46 so that the hot melt layer 8 is temporarily bonded in a semi-molten state. Pressure is 0.5MPa and pressurization time is 2 seconds.

[0038] The thermocompression-bonding rolls 46, 46 are provided with engagement portions S on both sides, and the alignment holes H of the substrate 20 and the main electrode forming mask 10a are engaged with the engagement portions S. The alignment of the main electrode forming mask 10a in the width direction and the longitudinal direction is performed. The alignment of the substrate 20 and the main electrode forming mask 10a is not limited to such a method. For example, alignment of alignment marks provided in place of the alignment hole H and the engaging portion S is performed. Is possible. In addition, the substrate 20 and the main electrode formation mask 10a may be aligned by a cold roll having sprocket holes before passing through the thermocompression-bonding rolls 46, 46. It is possible to easily redo the case.

[0039] The substrate 20 is wound around a winding roll (not shown) in a state where the main electrode forming mask 10a is temporarily bonded, and then loaded into a physical vapor deposition apparatus such as a vacuum vapor deposition apparatus. Then, the film is drawn out again in the physical vapor deposition apparatus, and after physical vapor deposition is performed through the opening 12a, the main electrode formation mask 10a is peeled off by the adhesive roll 48 as shown in FIG. The main electrode pattern 22a remains.

Next, as shown in FIG. 3 (d), an auxiliary electrode forming mask 10b is laminated on the surface of the substrate 20 on which the main electrode pattern 22a is formed by a transport roll (not shown), Thermocompression bonding The auxiliary electrode forming mask 10b is temporarily bonded to the substrate 20 by supplying between the base plates 52 and 52. Thereafter, the substrate 20 is transported to the physical vapor deposition apparatus in the same manner as described above, and after physical vapor deposition is performed through the opening 12b, the auxiliary electrode formation mask 10b is peeled off, and the auxiliary electrode pattern remains. .

[0041] Thus, according to the electrode pattern forming method of the present embodiment, the electrode pattern can be continuously formed without using a water-soluble chemical solution or an organic solvent as in the prior art. Mass production can be made possible while reducing the load.

In addition, since the hot melt layer is covered with a coating layer made of a metal material cover in the main electrode forming mask 10a (or the auxiliary electrode forming mask 10b), the physical property of the conductive material It is possible to prevent the hot melt layer 8 from sticking to the substrate 20 due to heat during vapor deposition, and the main electrode forming mask 10a (or the auxiliary electrode forming mask 10b) can be easily peeled off from the substrate 20. . Such an effect is particularly remarkable when the base film 6 is interposed between the coating layer 4 and the hot melt layer 8 as in the present embodiment.

[0043] The configuration of the main electrode formation mask 10a (or the auxiliary electrode formation mask 10b) is not necessarily limited to that of the present embodiment, and may be other configurations as long as the hot melt layer 8 is covered with the coating layer 4. For example, it may be performed by rubbing a structure in which the coating layer 4 is directly formed on the surface of the hot melt layer 8.

[0044] The electrode pattern forming method described above is suitable as a method for forming an electrode pattern of a dye-sensitized photovoltaic cell, as will be described later, but is not limited thereto, and is applicable to other types of photovoltaic cells. It can also be used as a method of forming electrode patterns used in other devices such as liquid crystal display devices and EL light emitting devices.

2. Formation of semiconductor electrode (photoelectric conversion layer)

A semiconductor electrode to be a photoelectric conversion layer is formed on the substrate 20 on which the electrode pattern 22 is formed as follows. First, a semiconductor electrode formation mask 30a having an opening 32a, which is configured similarly to the main electrode formation mask 10a (see FIG. 1 (c)), is prepared. As shown in FIG. The semiconductor electrode forming mask 30a is bonded onto the substrate 20 while aligning with the opening 32a. In addition, in the semiconductor electrode formation mask 30a, the same code | symbol is attached | subjected to the component similar to the main electrode formation mask 10a. [0045] The adhesion of the semiconductor electrode forming mask 30a to the substrate 20 may also be a temporary adhesion that can be easily peeled between the hot melt layer 8 and the substrate 20, similarly to the adhesion of the main electrode forming mask 10a. preferable. In this state, the surface of the substrate 20 is subjected to a corona discharge treatment or the like to clean the surface of the electrode pattern 22 exposed from the opening 32a, and then the electrode pattern 22 is formed on the electrode pattern 22 as shown in FIG. The first semiconductor layer 34a that also has a semiconductor electrode material force is formed by physical vapor deposition. Next, as shown in FIG. 4C, a semiconductor electrode material is applied with a squeegee or the like, and a second semiconductor layer 34b is deposited on the first semiconductor layer 34a. In the first semiconductor layer 34a, the second semiconductor layer 34b may be formed directly on the electrode pattern 22 that is not always necessary. Examples of the semiconductor electrode material include oxides such as zinc, niobium, tin, titanium, indium, tandasten, tantalum, molybdenum, manganese, nickel, and copper, and gallium phosphate and indium phosphide.

[0046] The first semiconductor layer 34a is a dense film formed by physical vapor deposition, and prevents a photosensitizing dye and an electrolytic solution described later from coming into contact with the electrode pattern 22. On the other hand, the second semiconductor layer 34b has a diameter of 5ηπ! In order to increase the amount of photosensitizing dye supported later. The desired thickness of the porous film formed by depositing semiconductor fine particles of about 200 nm is usually about 0.1 to 20 m. Further, after the semiconductor fine particles are deposited, water washing may be performed by applying a titanium sol or peroxotitanium sol such as a hydrolyzable titanium compound, a hydrolyzable titanium low condensate, titanium hydroxide, or a titanium hydroxide low condensate. After the above, the second semiconductor layer 34b can be obtained by evaporating water by heating as necessary.

Thereafter, as shown in FIG. 4 (d), the sensitizing dye solution is immersed in the second semiconductor layer 34b, electrophoretic or squeegee-coated, and then dried. As a result, a semiconductor electrode 34 on which is supported is obtained.

[0048] Conventionally known photosensitizing dyes used for dye sensitization in semiconductor electrode 34 can be used, for example, ruthenium-tris, ruthenium-bis, osmium-tris, osmium bis type transitions. Metal complexes, or ruthenium monocis-diaquabibilicil complexes, or so-called metal chelate complexes such as phthalocyanines, porphyrins, dithiolate complexes, and acetylethylacetonate complexes, and organic dyes such as cyanazine dyes, merocyanine dyes, rhodamine dyes, And oxadiazole derivatives, benzothiazole derivatives , Coumarin derivatives, stilbene derivatives, organic compounds having an aromatic ring, etc.

. These dyes have a functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amide group, an amino group, a carboxylic group, and a phosphine group so that they are easily chemically adsorbed on the second semiconductor layer 34b. It preferably has a group. For example, these photosensitizing dyes can be dissolved in an appropriate solvent, and then the dye solution can be adsorbed and supported on the second semiconductor layer 34b.

Thereafter, by removing the semiconductor electrode formation mask 30a, the semiconductor electrode 34 remains on the electrode pattern 22 of the substrate 20 as shown in FIG. 4 (e).

The formation of the semiconductor electrode 34 on the substrate 20 can be performed in the same manner as the formation of the electrode pattern 22. That is, the film-like laminate 10 is also fed with a force such as a roll to form alignment hole alignment marks on both side edges and to provide an opening 32a corresponding to the electrode pattern 22, thereby providing a semiconductor electrode forming mask 30a. Form. Then, the semiconductor electrode forming mask 30a is laminated on the substrate 20, and after thermocompression bonding, it is conveyed to a coating apparatus such as a screen printing machine or a roll coating machine. The alignment between the substrate 20 and the semiconductor electrode forming mask 30a can be performed using alignment holes and alignment marks.

[0051] Then, after the semiconductor electrode material and the dye solution are sequentially applied onto the substrate 20 in the coating apparatus, the substrate 20 is transported to a drying apparatus and subjected to heat drying. Thereby, the formation of the semiconductor electrode 34 on the substrate 20 is completed. Thereafter, the semiconductor electrode forming mask 30a is peeled off by the adhesive force of the adhesive roll, and the semiconductor electrode 34 remains.

As described above, according to the method for forming a semiconductor electrode of the present embodiment, a semiconductor electrode having high photoelectric conversion efficiency can be formed continuously and efficiently.

3. Formation of back electrode film

The back electrode film can be manufactured by forming a main electrode pattern on the substrate in the same procedure as in the case of the front electrode film 30 described above. As the material used for the main electrode pattern of the back electrode film, transparent materials such as ITO (Indium Tin Oxide), FTO (Fluorine-doped Oxidized Tin) and ATO (Antimony Monopoxide) are used. Other examples include metal materials such as gold, silver, copper, platinum, and chromium, and two or more of these may be stacked to form the main electrode pattern. For example, after depositing an ITO film on the substrate through the opening of the main electrode formation mask, further depositing a platinum film through this opening. Thus, the main electrode pattern of the knock electrode film can be formed. Further, before forming a main electrode pattern having a strong force such as metal on the substrate, an undercoat film is applied on the substrate and dried, so that an undercoat layer 81 is interposed on the substrate 82 as shown in FIG. Thus, it is possible to form the back electrode film 80 on which the electrode pattern 83 is formed, whereby the adhesion of the electrode pattern 83 can be enhanced.

[0053] The knock electrode film can also be formed using a main electrode formation mask in which a hot melt layer and a coating layer are laminated via an adhesive layer. That is, as shown in FIG. 10 (a), after the coating layer 4 is bonded to the hot melt layer 8 via the adhesive layer 2, a die cutting process is performed as shown in FIG. 10 (b). By forming the opening 12a, the main electrode formation mask 1OOa can be obtained. In FIG. 10, the same parts as those shown in FIG.

[0054] Thereafter, the main electrode forming mask is adhered onto the substrate in the same procedure as shown in FIGS. 1 (d) to (f), and then the conductive material is physically vapor-deposited to form a hot melt layer. The main electrode pattern can be formed on the substrate by peeling the main electrode forming mask between the substrate and the substrate.

[0055] As shown in FIG. 10 (c), an undercoat layer 81 may be formed on the surface of the substrate 20 to which the main electrode forming mask 100a is adhered by applying an undercoat material and drying it in advance. Good. Also, the hot melt layer 8 and the covering layer 4 can be bonded together by heat-bonding the hot melt layer 8 to the covering layer 4 and firmly adhering them instead of the adhesive layer 2. As shown in FIG. 11, the main electrode forming mask 10 la can be configured such that the hot melt layer 8 is directly bonded to the coating layer 4.

4. Wiring formation

Next, a method for forming a wiring portion for establishing conduction between the above-described front electrode film 30 and back electrode film 80 will be described.

First, as shown in FIG. 6 (a), a base film 64 having an adhesive layer 62 formed on one side is prepared, and a hot-melt layer 66 is bonded to the adhesive layer 62, so that FIG. As shown in (b), a laminate 68 is formed.

[0057] The pressure-sensitive adhesive layer 62 is easily peelable from the hot-melt layer 66. A heat-resistant slight pressure-sensitive adhesive made of a krill resin can be used. The thickness of the pressure-sensitive adhesive layer 62 may be set in consideration of the thickness of the electrolyte layer described later, for example, 1 to 40 / ζ πι.

[0058] The base film 64 is a hard film force formed of polypropylene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, fluorine resin, etc., and has a thickness of about 20 to about LOO m. preferable.

[0059] The hot melt layer 66 is, for example, a publicly known material in which a rosin-based or terpene-based tackifier is added to a polyester-based resin, a polyamide-based resin, an EVA-based resin, a polyolefin-based resin, or the like. Can be used.

[0060] Next, as shown in FIG. 6 (c), only the hot melt layer 66 is cut (half removed) to form an electrolyte solution storage portion 68a and a wiring portion that penetrates the entire laminate. A hole 68b is formed, and a bonding mask 69 is created. At this time, the electrolytic solution flow path for supplying the electrolytic solution to the electrolytic solution storage portion 68a is also formed by half-cutting to remove only the hot melt layer 66.

[0061] Then, as shown in FIG. 6 (d), the bonding mask 69 is placed on the substrate 82 of the back electrode film 80 so that the wiring portion forming hole 68b and the electrode pattern 83 are aligned. The hot melt layer 66 is thermocompression bonded to the substrate 82 using a thermocompression roller or the like. In this thermocompression bonding, it is preferable that the hot melt layer 66 is sufficiently melted and firmly adhered to the substrate 82. Specifically, the adhesive strength between the hot melt layer 66 and the substrate 82 is preferably 2 NZcm or more. On the other hand, the adhesive strength between the adhesive layer 62 and the hot melt layer 66 is smaller than the adhesive strength between the hot melt layer 66 and the substrate 82, which is preferably easily peelable as described above. It is preferable. Specifically, the adhesive strength between the pressure-sensitive adhesive layer 62 and the hot melt layer 66 is preferably 0.01 to 0.2 NZcm.

[0062] In the process up to this point, the film-like laminate 68 is also fed with a force such as a roll to form alignment holes and alignment marks on both side edges, and to provide an electrolyte solution containing portion 68a and a wiring portion forming hole 68b. After forming the bonding mask 69 by forming, it can be continuously performed by placing on the substrate 82 and thermocompression bonding.

[0063] After that, the conductive paste for forming the wiring portion described above is squeezed onto the bonding mask 69, whereby a conductive material is formed in the wiring portion forming hole 68b as shown in FIG. 7 (a). pace Fill with 61a. Then, the bonding mask 69 is peeled between the pressure-sensitive adhesive layer 62 and the hot melt layer 66 by a peeling roller or the like, and the base film 64 is removed while the hot melt layer is removed as shown in FIG. Layer 66 remains.

[0064] The conductive paste 61a is formed by stirring and mixing a solder alloy powder into a resin solution. The solder alloy should preferably be exemplified by a low melting point solder alloy powder such as SnZBi, Sn / Bi / Pb, Sn / Bi / Zn, Bi / Pb, Sn Zln, Sn / Bi / Pb, Sn / Bi / ln, SnZBiZPbZln. The desired melting point can be obtained by appropriately adjusting the composition ratio. The average particle size of the solder alloy powder can be exemplified by about 0.01 to 50 m.

[0065] More specifically, it is more preferable that the liquidus temperature of the solder alloy powder is lower than the heat-resistant limit temperature of the substrate 20 and is 150 ° C or less at the maximum. Here, the “heat-resistant limit temperature” refers to the maximum temperature at which material deterioration and deterioration can be prevented. For example, PET: about 130 ° C, methylmethacrylate acrylic resin: about 70 ° C, silicone Fat: About 180 ° C. On the other hand, considering the use at high temperatures outdoors, the liquidus temperature of the solder alloy powder is preferably 60 ° C or higher, more preferably 70 ° C or higher. Table 1 shows the relationship between the composition ratio and the solidus temperature and liquidus temperature.

[0066] [Table 1]

[0067] The resin solution is made of various organic solvents, water, or a solvent that is a mixture of two or more of these, acrylic resin, acrylic urethane resin, urethane resin, polyester resin, phenol resin. What melt | dissolved thermosetting resin with favorable flexibility and adhesiveness, such as these, can be used preferably. It is preferable that the resin to be dissolved has a degree of heat resistance that does not cause thermal decomposition when the solder alloy powder is heated and melted.

[0068] If the volume ratio (volume fraction) of the solder alloy powder in the volume of the resin solution is too large, adhesion to the substrate will be ensured, whereas if it is too small, good electrical conductivity will be ensured. Furthermore, it is preferable that the power is 50 to 90%, more preferably 70 to 85%.

[0069] Next, the front electrode film 30 with the hot melt layer 8 (see FIG. 12 (f)) is connected to the conductive paste 61a with the electrode pattern 22 on the substrate 20 as shown in FIG. 7 (c). At the same time, alignment is performed so that the semiconductor electrode 34 on the electrode pattern 22 is accommodated in the electrolyte accommodating portion 68a, and the hot melt layers 8 and 66 are bonded together. Thereafter, the hot melt layers 8 and 66 are heated and melted using a thermocompression roller or the like, and the front electrode film 30 and the back electrode film 80 are firmly adhered.

In actual manufacturing, as shown in FIG. 8, a plurality of photovoltaic cells having the semiconductor electrode 34 are formed between the electrode patterns 22 and 83, and the adjacent semiconductor electrodes 34 and 34 are connected to the electrode patterns 22 and 83, respectively. In addition, it is preferable to be configured to be electrically connected in series (or in parallel) via the conductive paste 6 la. The conductive paste 6 la filled in the wiring portion forming hole 68b by heating the hot melt layer 66 melts the resin and adheres to the front electrode film 30 and the back electrode film 80, respectively. As a result of melting and enabling connection between the electrode patterns 22 and 83, reliable conduction between the front electrode film 30 and the back electrode film 80 can be obtained. The heating temperature and calorie heating time of the hot melt layer 66 may be appropriately set in consideration of the material of the hot melt layer 66 and the conductive paste 61a, for example, about 120 to 150 ° C, about 10 to 15 Minutes.

[0071] Thus, according to the method for forming a wiring portion of the present embodiment, in the step of bonding the front electrode film 30 and the knock electrode film 80, the wiring portion is formed at the same time. Efficiency can be increased.

[0072] In the present embodiment, a resin film is used as the base film 64. For example, For example, a film made of another material such as a metal film can be used. In addition, the adhesive layer 62 interposed between the base film 64 and the hot melt layer 66 is not necessarily required. If the base film 64 can be easily peeled from the hot melt layer 66, the hot melt layer 66 is not necessary. The base film 64 can be directly bonded to the substrate.

The above description is an example for achieving three-dimensional conduction between the front electrode film 30 and the back electrode film 80. In the front electrode film 30 or the back electrode film 80, the electrode patterns 22, 83 are used. On the substrate 20, 82 of the front electrode film 30 or the back electrode film 80 in order to connect each electrode part constituting the electrode in series or in parallel, or to form an electrical connection part to the electrode pattern 22, 83. It is also possible to form a wiring portion made of the conductive paste described above. In this case, the wiring part is formed by applying a conductive paste on the substrate with a squeegee or the like through a wiring part forming mask having an opening of a predetermined shape.

[0074] Similar to the above-described main electrode forming mask 10a, the wiring portion forming mask has a hot melt layer on one side of a base film made of PET or the like via an adhesive layer 2 made of a strong adhesive. The formed configuration can be exemplified, and the hot melt layer can be temporarily bonded in a peelable manner by thermocompression bonding in a semi-molten state with a thermocompression-bonding roll or the like. The surface of the base film may be coated with a heat resistant film as necessary. In addition to this, the wiring portion formation mask can be configured to have a weak adhesive layer with adjusted adhesive strength on one surface of the base film, and can be crimped to the substrate by a crimping roll. Furthermore, the above-described wiring part forming mask with a hot melt layer may be laminated on such a wiring part forming mask with a weak adhesive layer.

[0075] According to such a method for forming a wiring portion, a wiring portion having good adhesion and conductivity can be efficiently manufactured.

5. Formation of electrolyte layer

Next, an electrolyte layer is formed between the front electrode film 30 and the back electrode film 80. In the hot melt layer 66 remaining on the substrate 82, an electrolyte solution flow path is formed, which communicates the electrolyte container 68a with the outside.

[0076] As shown in FIG. 9 (a), the electrolyte solution is sucked on the OUT side of the electrolyte channel. The electrolyte solution is supplied from the IN side of the flow path, and the electrolyte solution is injected into the electrolyte storage portion 68a, so that the electrolyte layer 90 is formed. Examples of the electrolytic solution include those obtained by dissolving an electrolyte such as iodine Z iodide, bromine Z bromide, or a transition metal complex in a solvent such as acetonitrile or ethylene carbonate or an ionic liquid such as an imidazolium salt. Note that the flow of the electrolytic solution in FIG. 9 (a) is shown schematically, and actually the electrolytic solution flows in a direction penetrating the drawing.

[0077] In addition to injecting the above-described electrolyte solution, the electrolyte layer is pre-coated with a gel electrolyte, a molten salt electrolyte, a solid electrolyte, or the like on the front electrode film 30 or the back electrode film 80, and then the front electrode film 30 Also, the back electrode film 80 can be bonded together.

6.Ultrasonic welding

After the formation of the electrolyte layer 90, as shown in FIG. 9 (b), the front electrode film 30 and the back electrode film 80 are ultrasonically welded so as to surround the entire electrolyte container 68a. 91 is formed, and the electrolyte solution of the electrolyte layer 90 is sealed. Then, by removing the outside of the sealing portion 91, as shown in FIG. 9C, a photovoltaic module in which the photoelectric conversion layer and the counter electrode are sequentially stacked on the electrode pattern is completed. The output from the photovoltaic module can be taken out from connection terminal holes 92 and 92 formed at two corners.

[0078] Ultrasonic welding can be performed using an ultrasonic welding apparatus including a horn to which vibration energy is transmitted from a vibrator and a pedestal on which an object to be welded is placed. The upper surface of the pedestal is provided with a protrusion (energy director) for concentrating vibration energy. The front electrode film 30 and the back electrode film 80 are pressed between the horn and the pedestal, and the horn force By applying ultrasonic vibration, frictional heat is generated, the resin melts, and the two are joined. In order to reliably seal the electrolyte layer 90 by ultrasonic welding, it is preferable that the substrates 20, 82 of the front electrode film 30 and the back electrode film 80 and the hot melt layer 66 have the same material strength. Here, the “equivalent material” means a material having substantially the same physical property values such as a melting temperature and a thermal expansion coefficient in addition to the case where the materials are completely the same. The specific material is preferably at least one selected from polyethylene terephthalate (PET), silicon-based resin, fluorine-based resin, and acryl-based resin, especially polyethylene terephthalate. Is preferred.

Claims

The scope of the claims

[1] A method in which an electrode pattern is formed on a substrate using a main electrode formation mask in which a hot melt layer is covered with a coating layer made of a metal material and has openings for forming a main electrode penetrating the front and back surfaces. And

Thermally bonding the main electrode formation mask to the surface of the substrate through the hot melt layer;

Forming a main electrode pattern on the substrate by performing physical vapor deposition of a conductive vapor deposition material through the opening for forming the main electrode; and

And a step of peeling the main electrode formation mask.

[2] The main electrode formation mask is formed by laminating the hot melt layer on one side of a base film via an adhesive layer and laminating the coating layer on the other side of the base film. The method for forming an electrode pattern according to claim 1.

[3] After the step of peeling the main electrode formation mask,

A hot electrode layer is covered with a coating layer made of a metal material, and an auxiliary electrode forming mask having an auxiliary electrode forming opening penetrating the front and back surfaces is thermocompression bonded to the surface of the substrate through the hot melt layer. Process,

Forming an auxiliary electrode pattern along the main electrode pattern by performing physical vapor deposition of a conductive vapor deposition material through the auxiliary electrode forming opening;

Peeling the auxiliary electrode forming mask between the hot melt layer and the substrate,

3. The electrode pattern forming method according to claim 1, wherein the auxiliary electrode pattern is formed to have a surface resistance value force S smaller than that of the main electrode pattern.

[4] Before the step of thermocompression bonding the main electrode formation mask to the surface of the substrate,

Forming an auxiliary electrode pattern by performing physical vapor deposition of the conductive vapor deposition material through the opening for forming the auxiliary electrode; Peeling the auxiliary electrode forming mask between the hot melt layer and the substrate,

[5] A photovoltaic cell module in which a photoelectric conversion layer and a counter electrode are sequentially stacked on the main electrode pattern formed on the substrate by the electrode pattern forming method according to any one of claims 1 to 4.

[6] A method of electrically connecting a pair of electrode patterns arranged via an insulating layer,

A laminate mask in which a base film is bonded to a hot-melt layer is used to attach a mask for bonding in which holes for forming wiring parts that penetrate the front and back surfaces are formed on the first substrate on which the first electrode pattern is formed. Thermocompression bonding so that the wiring portion forming hole and the first electrode pattern are aligned, and

Filling the wiring part forming hole with a conductive paste;

Peeling the base film from the hot melt layer;

A process of thermocompression bonding the second substrate on which the second electrode pattern is formed on the exposed hot-melt layer so that the second electrode pattern and the wiring part formation hole are aligned. A connection method between electrode patterns.

[7] The connection method between electrode patterns according to [6], wherein the base material film is laminated on the hot-melt layer via an easily peelable pressure-sensitive adhesive layer.

[8] The conductive paste contains a solder alloy powder,

The method of connecting between electrode patterns according to claim 6 or 7, wherein a liquidus temperature of the solder alloy powder is 60 ° C or higher and lower than a heat resistance limit temperature of the first substrate and the second substrate. Law.

[9] The conductive paste according to any one of claims 6 to 8, wherein a solder alloy powder is mixed with a resin solution, and a volume fraction of the solder alloy powder with respect to the resin solution is 50 to 90%. Connection method between described electrode patterns.

[10] A photovoltaic cell having a photoelectric conversion layer between the first electrode pattern and the second electrode pattern A plurality of photovoltaic cell modules,

The first electrode pattern in one of the photovoltaic cells and the second electrode pattern and force in the other photovoltaic cell are connected by the connection method between the electrode patterns according to any one of claims 6 to 9! Photovoltaic module that is being revived.

[11] A method of forming a dye-sensitized semiconductor electrode on an electrode pattern,

A semiconductor electrode forming mask in which the hot melt layer is covered with a coating layer made of a metal material and has openings that penetrate the front and back surfaces is formed on a substrate on which the electrode pattern is formed on the surface. A step of thermocompression bonding so that alignment is performed, a step of filling the opening with a semiconductor electrode material,

A method of forming a dye-sensitized semiconductor electrode, comprising: supporting a photosensitizing dye on the semiconductor electrode material filled in the opening; and peeling the semiconductor electrode forming mask.

[12] The semiconductor electrode formation mask is formed by laminating the hot melt layer on one side of a base film with an adhesive layer interposed therebetween, and laminating the coating layer on the other side of the base film. The method for forming a dye-sensitized semiconductor electrode according to claim 11.

[13] The step of filling the opening with a semiconductor electrode material includes:

Forming a first semiconductor layer having a semiconductor electrode material force on the electrode pattern by physical vapor deposition;

The method for forming a dye-sensitized semiconductor electrode according to claim 11 or 12, further comprising a step of forming a second semiconductor layer by applying a semiconductor electrode material on the first semiconductor layer.

14. A photovoltaic module in which a counter electrode is laminated on a semiconductor electrode formed by the method for forming a dye-sensitized semiconductor electrode according to any one of claims 11 to 13.