JP2008184651A - Plating system and plating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce a cost for manufacturing a pigment sensitized solar battery, by forming a photoelectric layer containing zinc oxide and a template agent, and to shorten a period of time required for the manufacture as well. <P>SOLUTION: A plating system 1 has a unit 3 for forming an electro-conductive layer, in which each part of a resin film 9 that is continuously drawn from a roll 90 is subjected to electroless plating in an electroless plating tank 32, and is subsequently subjected to electrolytic plating in an electrolytic plating tank 34 to have a transparent electro-conductive layer containing zinc oxide formed thereon; and has a unit for forming the photoelectric layer, in which each part of the resin film that is continuously discharged from the unit 3 for forming the electro-conductive layer is subjected to electrolytic plating to have the photoelectric layer containing zinc oxide and the template agent formed thereon. Then, the resin film 9 after having been treated is wound into a roll form. Thus, the cost for forming the pigment sensitized solar battery is reduced by forming the photoelectric layer containing zinc oxide and the template agent, and the period of time required for the manufacture can also be shortened. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a plating system and a plating method used for manufacturing a dye-sensitized solar cell.

  In recent years, attention has been focused on dye-sensitized solar cells that can be used as a power source without impairing the design of various products. The dye-sensitized solar cell has a structure in which a photoelectric layer, a charge transport layer, and a counter electrode substrate having a counter electrode conductive layer are sequentially laminated on a glass substrate having a transparent conductive layer. As a method for forming a transparent conductive layer such as ITO (indium tin oxide) on a substrate, for example, sputtering, PLD (Pulsed Laser Deposition) (also called pulsed laser ablation), CVD (Chemical Vapor Deposition), Alternatively, a spray method or the like is known, and as a method for forming a photoelectric layer, a porous semiconductor layer is formed by applying semiconductor fine particles such as titanium dioxide on a substrate and firing at a high temperature, and then a semiconductor. A technique for adsorbing the dye to the layer is employed.

  In addition, it has also been proposed to manufacture a dye-sensitized solar cell at a low cost using a transparent substrate such as an inexpensive plastic. However, in this case, the above-described method involving a baking treatment cannot be employed when forming the photoelectric layer. Therefore, in Patent Document 1, a dye as a template compound is mixed in an electrolytic bath containing a zinc salt, and the cathode is electrodeposited on the substrate in this electrolytic bath, whereby the dye is adsorbed on the inner surface. A technique for forming a zinc thin film on a substrate has been proposed. Patent Document 1 further discloses a dye-sensitized type in which a high photoelectric exchange rate can be obtained by desorbing a dye after desorbing the dye from the zinc oxide thin film. A technique for manufacturing a solar cell is also disclosed.

In Patent Document 2, a non-conductive substrate is immersed in a zinc oxide deposition solution to form a zinc oxide film on the substrate by an electroless method, and electrolysis is performed using the zinc oxide film as a cathode in the solution. Thus, a technique for forming a transparent zinc oxide coating is disclosed. Moreover, in patent document 3, the electrode layer previously formed in the film board | substrate is immersed in the solution in which each part of the elongate film board | substrate conveyed continuously from a roll was disperse | distributed to the metal oxide semiconductor fine particle. A technique is disclosed in which a photoelectric layer is formed by applying a voltage between the electrode and the electrode plate in the solution and electrodepositing semiconductor fine particles on a film substrate by electrophoresis.
JP 2004-6235 A JP 2000-8180 A JP 2006-5055 A

  By the way, for full-scale practical use of dye-sensitized solar cells, it is required to reduce the manufacturing cost of the dye-sensitized solar cells and to shorten the time required for the manufacturing. Thus, when a substrate is immersed in a plating solution containing zinc ions and a template agent (template compound) by a single wafer processing, a photoelectric layer containing zinc oxide and a template agent is formed on the substrate. It is not easy to reduce costs and manufacturing time.

  This invention is made | formed in view of the said subject, and reduces the manufacturing cost while shortening the manufacturing cost of the dye-sensitized solar cell manufactured by forming the photoelectric layer containing a zinc oxide and a template agent. The purpose is that.

  The invention according to claim 1 is a plating system used for manufacturing a dye-sensitized solar cell, wherein electroless plating is applied to each part of a resin film continuously drawn from a roll, and the surface of each part. Forming an electroless plating layer formed of zinc oxide, and further immersing each of the parts in a plating solution containing at least zinc ions, between the electroless plating layer and the electrode in the plating solution. By applying voltage to each part by applying a voltage, a conductive layer forming part for forming a transparent conductive layer containing zinc oxide on each part, and the conductive layer forming part continuously discharging from the conductive layer forming part While each part is immersed in a plating solution containing zinc ions and a template agent, a voltage is applied between the transparent conductive layer and the electrode in the plating solution to perform electrolytic plating on each of the parts. Position and a photoelectric layer forming section for forming a photoelectric layer containing zinc oxide and the templating agent on.

  Invention of Claim 2 is a plating system of Claim 1, Comprising: While the said electroconductive layer formation part stores the plating solution containing a zinc ion at least, the said electroless plating is performed inside An electroless plating tank and an electrolytic plating tank in which a plating solution containing at least zinc ions is stored and in which the electrolytic plating for forming the transparent conductive layer is performed are provided.

  Invention of Claim 3 is a plating system of Claim 2, Comprising: The said electroless plating is performed before the said electroconductive plating part performs the said electroplating which concerns on formation of the said transparent conductive layer. An intermediate cleaning unit is further provided for cleaning each of the parts that have been performed.

  Invention of Claim 4 is the plating system in any one of Claim 1 thru | or 3, Comprising: Before the said electroplating which concerns on formation of the said photoelectric layer is performed, the said photoelectric layer formation part is the said A pre-cleaning unit for cleaning each part is provided.

  Invention of Claim 5 is a plating system in any one of Claim 1 thru | or 4, Comprising: The said conductive layer formation part and / or the said photoelectric layer formation part convey each said site | part and each said each A conductive roller for applying a potential to the region is provided.

  Invention of Claim 6 is a plating system in any one of Claim 1 thru | or 5, Comprising: The plating solution containing the said at least zinc ion in the said electrolytic plating which concerns on formation of the said transparent conductive layer is other Contains metal ions.

  The invention according to claim 7 is a plating method used for manufacturing a dye-sensitized solar cell, wherein a) electroless plating is applied to each part of a resin film continuously drawn from a roll, and each of the parts Forming an electroless plating layer formed of zinc oxide on the surface of the electrode, and b) immersing each of the parts in a plating solution containing at least zinc ions, while the electroless plating layer and the electrode in the plating solution A step of forming a transparent conductive layer containing zinc oxide on each of the parts by applying a voltage between and applying electrolytic plating to each of the parts, and c) continuously discharging from the plating solution By immersing each of the parts in a plating solution containing zinc ions and a template agent, applying a voltage between the transparent conductive layer and the electrode in the plating solution to perform electrolytic plating on the parts, Each part And forming a photoelectric layer containing zinc oxide and the template agent.

  Invention of Claim 8 is the plating method of Claim 7, Comprising: In said a process and said b) process, the said electroplating concerning formation of the said electroless plating and the said transparent conductive layer mutually Performed in different plating tanks.

  The invention according to claim 9 is the plating method according to claim 8, wherein the respective portions where the electroless plating has been performed are washed between the step a) and the step b). The process of performing is further provided.

  A tenth aspect of the present invention is the plating method according to any one of the seventh to ninth aspects, wherein each of the transparent conductive layers is formed between the step b) and the step c). The method further includes a step of cleaning the site.

  The invention according to claim 11 is the plating method according to any one of claims 7 to 10, wherein the plating solution containing at least zinc ions in the electrolytic plating according to formation of the transparent conductive layer is other than Contains metal ions.

  ADVANTAGE OF THE INVENTION According to this invention, while reducing the manufacturing cost of the dye-sensitized solar cell manufactured by forming the photoelectric layer containing a zinc oxide and a template agent, the time which manufacture can be shortened.

  In the inventions of claims 3 and 9, it is possible to prevent the plating solution in the plating tank in which the electroless plating is performed from being mixed with the plating solution in the plating tank in which the electrolytic plating for forming the transparent conductive layer is performed. In the inventions according to claims 4 and 10, it is possible to prevent the plating solution in the plating tank relating to the formation of the transparent conductive layer from being mixed with the plating solution in the plating tank relating to the formation of the photoelectric layer.

  In the invention of claim 5, a potential can be easily applied to each part of the resin film, and in the inventions of claims 6 and 11, the characteristics of the transparent conductive layer can be variously adjusted.

  FIG. A and FIG. B is a diagram showing a plating system 1 according to an embodiment of the present invention. The plating system 1 is for forming a transparent conductive layer and a photoelectric layer on a transparent resin film 9 (plastic film) by plating. A substrate cut in the process and having a counter electrode conductive layer is provided to face each other with a spacer interposed therebetween. Thereafter, an electrolyte is injected between the rectangular resin film and the counter electrode substrate to form a charge transport layer, whereby a dye-sensitized solar cell is manufactured. Thus, the plating system 1 is used for manufacturing a dye-sensitized solar cell.

  FIG. A and FIG. As shown in B, the plating system 1 includes a plurality of resin film rolls 90 (also referred to as a web (WEB)) before processing to each portion of the resin film 9 (that is, a plurality of belt films continuously present on the belt-shaped resin film). Each of the parts), a drawing part 2 for continuously drawing out, a conductive layer forming part 3 for forming a transparent conductive layer on each part of the resin film 9 drawn continuously, and a photoelectric layer forming for forming a photoelectric layer on the transparent conductive layer The winding part 5 which winds up the site | part 4 and the site | part continuously discharged | emitted from the photoelectric layer formation part 4 in roll shape is provided. In the plating system 1, the lead-out part 2, the conductive layer forming part 3, the photoelectric layer forming part 4 and the winding part 5 are arranged in a line in a predetermined direction, and a plurality of rollers extending in a direction perpendicular to the direction and in a horizontal direction. 61 (in FIG. 1.A and FIG. 1.B, reference numerals 61a and 61b are attached to some of the rollers.) By being arranged over the entire plating system 1, it is pulled out from the lead-out portion 2. Each part of the resin film 9 is continuously conveyed to the winding unit 5. The roller 61 is formed of a material having corrosion resistance against a liquid (processing liquid or plating liquid described later) used in the plating system 1. In addition, FIG. A and FIG. In B, only some of the many rollers actually provided in the plating system 1 are illustrated.

  The conductive layer forming unit 3 includes a pretreatment unit 31 that performs a predetermined pretreatment on the resin film 9, an electroless plating tank 32 that stores the plating solution 321, and in which electroless plating is performed on the resin film 9, and electroless An intermediate cleaning unit 33 for cleaning the resin film 9 immediately after plating, and an electrolytic plating tank 34 for storing the plating solution 341 and for electrolytically plating the resin film 9 therein are provided. In the conductive layer forming unit 3, the pretreatment unit 31, the electroless plating tank 32, the intermediate cleaning unit 33, and the electrolytic plating tank 34 are arranged in a line in order from the drawing unit 2 side toward the photoelectric layer forming unit 4.

  A roller 61a is provided above the electrolytic plating tank 34 and on the intermediate cleaning unit 33 side. As shown in FIG. 2, the roller 61a is rotatably supported by two support plates 614 via a shaft 613, and a slip ring 611 that rotates around the shaft 613 together with the roller 61a is provided at one end of the roller 61a. It is done. A fixed brush 612 that contacts the surface of the rotating slip ring 611 is provided in the vicinity of the slip ring 611, and the conductive fixed brush 612 (formed of conductive carbon or the like) is connected to a power source via a conductor 615. Connected to the unit 342 (see FIG. 1A). The roller 61a, the slip ring 611, and the fixed brush 612 are formed of a conductive material, and the potential supplied from the power supply unit 342 to the fixed brush 612 is applied to the resin film 9 via the slip ring 611 and the roller 61a. In addition, FIG. As shown in A, an electrode 343 is provided in the plating solution 341 of the electrolytic plating tank 34, and the electrode 343 is also connected to the power supply unit 342.

  FIG. The photoelectric layer forming section 4 shown in B is a pre-cleaning section 41 for cleaning the resin film 9 immediately before the electroplating described later relating to the formation of the photoelectric layer, stores the plating solution 421, and electrolyzes the resin film 9 inside. An electroplating bath 42 in which plating is performed and a post-cleaning unit 43 that cleans the resin film 9 immediately after electroplating are provided. The pre-cleaning unit 41, the electroplating bath 42, and the post-cleaning unit 43 include the conductive layer forming unit 3. They are arranged in a line in order from the side toward the winding unit 5. A roller 61b having the same configuration as the roller 61a of FIG. 2 is provided above the electrolytic plating tank 42 and on the side of the pre-cleaning portion 41. Further, an electrode 423 is provided in the plating solution 421 of the electrolytic plating tank 42, and the roller 61 b and the electrode 423 are connected to the power supply unit 422.

  3 is a diagram showing a flow of processing in which the plating system 1 forms the transparent conductive layer and the photoelectric layer on the resin film 9 by plating. A thru | or FIG. C is a cross-sectional view showing the resin film 9 being processed. FIG. 3 shows a flow of processing focusing attention on a part of the resin film 9. In practice, all the processing in FIG. .

  In the plating system 1, the tip of the resin film 9 of the roll 90 is previously attached to the winding unit 5 via the plurality of rollers 61, and a part of the plurality of rollers 61 connected to the motor rotates in the same direction. As a result, the respective portions of the resin film 9 are sequentially pulled out from the roll 90 by the pull-out unit 2 (step S11). Hereinafter, the subsequent processing will be described by paying attention to a part of the resin film 9 drawn out by the drawing portion 2, and this portion will be referred to as a “target portion”.

  The target part pulled out from the roll 90 is immersed in the treatment liquid 311 held by the pretreatment unit 31, and a predetermined pretreatment is performed before the electroless plating is performed (step S12). The pretreatment performed in the pretreatment unit 31 is for making the surface of the target part suitable for electroless plating. For example, depending on the activation treatment of the surface of the target part or the conditions of the electroless plating It is only a cleaning process. In addition, when performing the activation process of the surface of an object site | part, the activator containing a silver ion may be used like the method of patent document 2. FIG.

The target portion drawn from the treatment liquid 311 moves into the electroless plating tank 32 that stores the plating liquid 321. The plating solution 321 contains, for example, zinc nitrate (Zn (NO ₃ ) ₂ ) as a main component (that is, contains nitrate ions and zinc ions as main components), and the target site is immersed in the plating solution 321. As a result, electroless plating is applied to the target part, and FIG. As shown to A, the electroless-plating layer 911 (it shows with a thick line in FIG. 4.A thru | or 4.C) formed with a zinc oxide (ZnO) is formed in the surface of the object site | part of the resin film 9. FIG. (Step S13). Note that FIG. In A, only the electroless plating layer 911 on one main surface is illustrated, but in actuality, the electroless plating layer 911 is formed on the entire surface of the target portion of the resin film 9 (that is, both main surfaces and side surfaces). Is done. FIG. In the electroless plating tank 32 of A, the paths of the resin film 9 are folded back more internally than in the later-described electrolytic plating tank 34, and the resin film 9 can be immersed in the plating solution 321 for a long time. It is said.

  The target part pulled up from the electroless plating tank 32 moves to the intermediate cleaning unit 33, and a cleaning liquid such as pure water is sprayed from the cleaning spray group 331 toward the surface of the target part, and then air is supplied from the air knife 332. Drying is performed (step S14). The target portion after cleaning moves into the electrolytic plating tank 34 via the roller 61a above the electrolytic plating tank 34, and is immersed in a plating solution 341 containing, for example, zinc nitrate as a main component.

  In the power supply unit 342, a negative potential is applied to the electroless plating layer 911 (see FIG. 4.A) of the target portion via the roller 61a, and a positive potential is applied to the electrode 343 (that is, the target portion). Is the cathode, and the electrode 343 is the anode, which is the same in the electrolytic plating tank 42 of the photoelectric layer forming section 4 described later). In this way, by applying a voltage (potential difference) between the electroless plating layer 911 and the electrode 343, electrolytic plating is performed on the target portion (electrodeposition is performed), and FIG. As shown in B, an electrolytic plating layer 912 containing zinc oxide is formed on the target site (step S15). The electroless plating layer 911 and the electrolytic plating layer 912 have high conductivity and high translucency, and the transparent conductive layer 91 is configured by the electroless plating layer 911 and the electrolytic plating layer 912.

After the target portion where the transparent conductive layer 91 is formed is pulled up from the electrolytic plating tank 34, FIG. It moves to the pre-cleaning part 41 as shown to B. In the pre-cleaning unit 41, a cleaning liquid such as pure water is sprayed from the cleaning spray group 411 toward the surface of the target portion, and then hot air is applied in the drying chamber 412 to perform drying (step S16). The target portion after cleaning moves into the electrolytic plating tank 42 via the roller 61b above the electrolytic plating tank 42, and contains, for example, zinc chloride (ZnCl ₂ ) and a template agent as main components (that is, chloride ions). And zinc ions and a template agent as main components.) It is immersed in the plating solution 421. Actually, oxygen is supplied to the plating solution 421 through a supply pipe (that is, oxygen bubbling is performed). The template agent will be described later.

  In the power supply unit 422, a negative potential is applied to the transparent conductive layer 91 at the target portion through the roller 61b (more precisely, through the electroless plating layer 911 on the back surface in contact with the roller 61b and the roller 61b). A positive potential is applied to the electrode 423. In this way, by applying a voltage between the transparent conductive layer 91 and the electrode 423, the target portion is subjected to electrolytic plating (electrodeposition (cathode electrodeposition) is performed), and FIG. As shown in C, a photoelectric layer 92 containing zinc oxide and a template agent is formed on the target site (step S17). Here, the template agent, like the template compound in Patent Document 1, forms a complex with zinc ions in the plating solution 421, so that the inside of the zinc oxide film formed on the transparent conductive layer 91 by electrolytic plating. It is adsorbed on the surface and is typically a dye.

  The target portion where the photoelectric layer 92 is formed is lifted from the electrolytic plating tank 42 and then moved to the post-cleaning unit 43. In the post-cleaning unit 43, a cleaning liquid such as pure water is sprayed from the cleaning spray group 431 toward the surface of the target portion, and then hot air is applied in the drying chamber 432 to perform drying (step S18). And the target site | part after drying is wound up by the winding part 5 in roll shape (step S19).

  In the resin film 9 on which the transparent conductive layer 91 and the photoelectric layer 92 are formed, the template agent is desorbed from the photoelectric layer 92 as necessary to form a porous zinc oxide layer, and then the dye is adsorbed again. (See Patent Document 1 above). And the resin film 9 is cut | disconnected in a subsequent process, and the board | substrate which has a counter electrode conductive layer is provided facing through a spacer. Thereafter, an electrolyte is injected between the rectangular resin film and the counter electrode substrate to form a charge transport layer, whereby a dye-sensitized solar cell is manufactured. When the template agent is desorbed and the dye is re-adsorbed, the template agent is not necessarily a dye. When the charge transport layer is solid, a substrate having a charge transport layer and a counter electrode conductive layer may be laminated without cutting the resin film 9.

  By the way, when forming a photoelectric layer continuously in a resin film, the roll of the resin film in which the transparent conductive layer was previously formed is usually prepared, but the roll of the resin film having such a transparent conductive layer is processed. Each part of the resin film is sequentially drawn from the previous roll, and a transparent conductive layer is formed on the part by sputtering, and then wound into a roll. In this case, a large-scale sputtering apparatus is required, and in general, it takes a long time to form a transparent conductive layer by sputtering. Therefore, the manufacturing cost of the dye-sensitized solar cell is reduced and the manufacturing time is reduced. The limit will occur.

  In contrast, FIG. A and FIG. In the plating system 1 of B, the transparent conductive layer 91 containing zinc oxide is formed by plating in each portion of the resin film 9 continuously drawn out from the roll 90 by the conductive layer forming unit 3. A photoelectric layer 92 containing zinc oxide and a template agent is formed by plating in the photoelectric layer forming unit 4 for the portion continuously discharged from the substrate. As described above, in the plating system 1, the transparent conductive layer 91 and the photoelectric layer 92 are formed by plating between the drawing of the resin film from the roll and the winding of the resin film (ie, the photoelectric layer 92). The transparent conductive layer 91 and the photoelectric layer 92 are formed by plating in a roll-to-roll manner.) The transparent conductive layer 91 and the photoelectric layer 92 can be efficiently formed on the resin film 9 and oxidized. While reducing the manufacturing cost of the dye-sensitized solar cell manufactured by forming the photoelectric layer 92 containing zinc and a template agent, the time required for manufacturing can be shortened.

  In the conductive layer forming unit 3, the portion subjected to the electroless plating in the intermediate cleaning unit 33 is cleaned before the electrolytic plating related to the formation of the transparent conductive layer 91 is performed, so that the electrolytic plating tank It is possible to prevent the plating solution 321 in the electroless plating tank 32 from being mixed with the plating solution 341 in 34, and the high-quality transparent conductive layer 91 can be formed. Moreover, in the photoelectric layer formation part 4, before the electrolytic plating which concerns on formation of the photoelectric layer 92 is performed, the plating liquid in the electrolytic plating tank 42 is wash | cleaned with respect to the object site | part by the pre-cleaning part 41. It is possible to prevent the plating solution 341 in the electrolytic plating tank 34 of the conductive layer forming unit 3 from being mixed with 421, and the high-quality photoelectric layer 92 can be formed.

Moreover, in the plating system 1, what contains magnesium ion (Mg ^<2+> ) and zinc nitrate may be used as the plating solution 341 in the electroplating tank 34 of the conductive layer formation part 3, for example. In this case, in the process of step S15 in FIG. 3, an electrolytic plating layer (magnesium-doped zinc oxide film) containing magnesium and zinc oxide is formed on the target portion. The zinc oxide film doped with magnesium has different characteristics from the zinc oxide film formed using the plating solution 341 not containing magnesium ions. As described above, when the plating solution used for the electrolytic plating related to the formation of the transparent conductive layer contains metal ions other than zinc ions, the characteristics of the transparent conductive layer can be variously adjusted.

  FIG. 5 is a diagram showing another example of the conductive layer forming portion. In the conductive layer forming portion 3a of FIG. The electroless plating tank 32 and the electrolytic plating tank 34 in A are one plating tank 32a, and a plating solution 321a containing, for example, zinc nitrate is stored in the plating tank 32a. A roller 61c having the same configuration as the roller 61a of FIG. 2 is provided above the plating tank 32a and on the side opposite to the pretreatment unit 31, and the roller 61c is connected to the power supply unit 342a. An electrode 343a connected to the power supply unit 342a is disposed in the plating solution 321a of the plating tank 32a. The intermediate cleaning unit 33 is omitted from the conductive layer forming unit 3a.

  In the plating system having the conductive layer forming portion 3a of FIG. 5, the target portion of the resin film 9 pretreated by the pretreatment portion 31 in step S12 of FIG. 3 is in the plating solution 321a in the plating tank 32a. Electroless plating is performed by being immersed, and an electroless plating layer 911 (see FIG. 4.A) is formed on the surface (step S13). The target portion in the plating solution 321a is moved to the opposite side of the pretreatment section 31 by the roller 61 in the plating tank 32a, and a voltage is applied between the electrode 343a and the electroless plating layer 911 by the power supply section 342a. Thus, the electrolytic plating layer 912 is deposited on the electroless plating layer 911 at the target site, and the transparent conductive layer 91 is formed on the target site (step S15). In this operation example, the process of step S14 in FIG. 3 is omitted. Then, FIG. A and FIG. Similar to the plating system 1 of B, the pre-cleaning process, the formation of the photoelectric layer 92, and the post-cleaning process are performed on the target portion (steps S16 to S18), and the transparent conductive layer 91 and the photoelectric layer 92 are formed. The target part is wound up in a roll shape by the winding unit 5 (step S19).

  As described above, in the conductive layer forming part 3a of FIG. 5, the electroless plating and the electrolytic plating are performed in one plating tank 32a, whereby the configuration of the conductive layer forming part 3a that forms the transparent conductive layer is configured. It can be simplified. In addition, FIG. When the electroless plating and the electrolytic plating are performed in separate plating tanks as in the conductive layer forming portion 3 of A, it is possible to reduce the constraint conditions in forming the transparent conductive layer.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made.

  FIG. In the conductive layer forming part 3 of A, the main component of the plating solution 321 stored in the electroless plating tank 32 in which electroless plating is performed is zinc nitrate, but zinc oxide is deposited by electroless plating. However, other plating solutions containing at least zinc ions may be used. In addition, in the electrolytic plating tank 34 in which the electrolytic plating related to the formation of the transparent conductive layer 91 is performed, other plating solutions containing at least zinc ions can be stored as long as zinc oxide can be deposited by electrolytic plating. May be. In the plating tank 32a of the conductive layer forming portion 3a of FIG. 5, a plating solution containing at least zinc ions, in which zinc oxide is deposited by electroless plating, and zinc oxide is also deposited by electrolytic plating. Need to be used.

  FIG. In the photoelectric layer forming part 4 of B, the plating solution 421 stored in the electrolytic plating tank 42 related to the formation of the photoelectric layer 92 contains zinc chloride and a template agent. If it is possible to deposit zinc oxide, other plating solutions containing zinc ions and a template agent may be used.

  In the above embodiment, in each of the conductive layer forming portions 3 and 3a and the photoelectric layer forming portion 4, the conductive rollers 61a, 61b, and 61c used for transporting each part of the resin film 9 cause the transparent conductive layer 91 or A potential is easily applied to the portion during the electrolytic plating related to the formation of the photoelectric layer 92. For example, a conductive member that contacts the corresponding portion of the resin film 9 is separately provided, and the potential is applied to the portion. May be. Of course, a conductive roller may be used only in the conductive layer forming portions 3 and 3a or the photoelectric layer forming portion 4.

It is a figure which shows a plating system. It is a figure which shows a plating system. It is a perspective view which shows the vicinity of a roller. It is a figure which shows the flow of the process which forms a transparent conductive layer and a photoelectric layer on a resin film. It is sectional drawing which shows the resin film in the middle of a process. It is sectional drawing which shows the resin film in the middle of a process. It is sectional drawing which shows the resin film in the middle of a process. It is a figure which shows the other example of a conductive layer formation part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plating system 3, 3a Conductive layer formation part 4 Photoelectric layer formation part 9 Resin film 32 Electroless plating tank 32a Plating tank 33 Intermediate cleaning part 34 (Electroconductive layer formation part) Electrolytic plating tank 41 Pre-cleaning part 42 (Photoelectric layer formation) Electroplating bath 61a, 61b, 61c Roller 90 Roll 91 Transparent conductive layer 92 Photoelectric layer 321, 321a, 341, 421 Plating solution 343, 343a, 423 Electrode 911 Electroless plating layer 912 Electrolytic plating layer S13 to S17 Steps

Claims (11)

A plating system used for manufacturing a dye-sensitized solar cell,
Electroless plating is applied to each part of the resin film continuously drawn from the roll to form an electroless plating layer formed of zinc oxide on the surface of each part, and each part is provided with at least zinc ions. A transparent solution containing zinc oxide on each portion by applying a voltage between the electroless plating layer and the electrode in the plating solution while being immersed in the plating solution. A conductive layer forming part for forming a conductive layer;
A voltage is applied between the transparent conductive layer and the electrode in the plating solution while immersing each of the parts continuously discharged from the conductive layer forming portion in a plating solution containing zinc ions and a template agent. A photoelectric layer forming part for forming a photoelectric layer containing zinc oxide and the template agent on each of the parts by performing electroplating on each of the parts;
A plating system comprising: The plating system according to claim 1,
The conductive layer forming part is
An electroless plating tank for storing a plating solution containing at least zinc ions and in which the electroless plating is performed;
An electrolytic plating tank for storing a plating solution containing at least zinc ions and in which the electrolytic plating for forming the transparent conductive layer is performed;
A plating system comprising: The plating system according to claim 2,
The conductive layer forming unit further includes an intermediate cleaning unit that cleans each of the portions subjected to the electroless plating before the electrolytic plating related to the formation of the transparent conductive layer is performed. And plating system. A plating system according to any one of claims 1 to 3,
The plating system, wherein the photoelectric layer forming unit includes a pre-cleaning unit that cleans each of the parts before the electrolytic plating related to the formation of the photoelectric layer is performed. The plating system according to any one of claims 1 to 4,
The plating system, wherein the conductive layer forming part and / or the photoelectric layer forming part includes a conductive roller that conveys the parts and applies a potential to the parts. A plating system according to any one of claims 1 to 5,
The plating system, wherein the plating solution containing at least zinc ions in the electrolytic plating related to the formation of the transparent conductive layer contains other metal ions. A plating method used for manufacturing a dye-sensitized solar cell,
a) performing electroless plating on each part of the resin film continuously drawn from the roll to form an electroless plating layer formed of zinc oxide on the surface of each part;
b) While immersing each of the parts in a plating solution containing at least zinc ions, by applying a voltage between the electroless plating layer and the electrode in the plating solution to perform electrolytic plating on the parts, Forming a transparent conductive layer containing zinc oxide on each site;
c) Applying a voltage between the transparent conductive layer and the electrode in the plating solution while immersing each part continuously discharged from the plating solution in a plating solution containing zinc ions and a template agent. Forming a photoelectric layer containing zinc oxide and the template agent on each of the parts by electrolytic plating on the parts;
A plating method comprising: The plating method according to claim 7,
In the step a) and the step b), the electroless plating and the electrolytic plating relating to the formation of the transparent conductive layer are performed in different plating tanks. The plating method according to claim 8, comprising:
The plating method further comprising a step of cleaning each of the portions where the electroless plating has been performed between the step a) and the step b). The plating method according to any one of claims 7 to 9,
The plating method further comprising a step of cleaning each of the portions where the transparent conductive layer is formed between the step b) and the step c). A plating method according to any one of claims 7 to 10,
The plating method, wherein the plating solution containing at least zinc ions in the electrolytic plating related to the formation of the transparent conductive layer contains other metal ions.

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