KR101127338B1 - Additive removal method, additive removal apparatus and plating system - Google Patents

Abstract

The plating system includes a plating layer forming unit for forming a plating layer on the resin film 9 by immersing the resin film 9 in a plating solution containing a template agent, and removing the template agent from the plating layer on the resin film 9. The apparatus 4 is provided. The removal apparatus 4 includes a removal liquid tank 41 for storing the removal liquid 411 in which the resin film 9 is immersed, and a light irradiation part 42 for irradiating light toward the resin film 9 in the removal liquid 411. Has In the removal apparatus 4, the removal of the template agent from the plating layer is accelerated by the light from the light irradiation part 42, so that the template agent can be efficiently removed from the plating layer.

Resin Film, Template, Dipping, Plating, Removal Device

Description

Additive removal method, additive removal device and plating system {ADDITIVE REMOVAL METHOD, ADDITIVE REMOVAL APPARATUS AND PLATING SYSTEM}

TECHNICAL FIELD This invention relates to the technique of removing an additive from the plating layer on the object formed by immersing an object in the plating liquid containing an additive, and a plating system using this technique.

In recent years, dye-sensitized solar cells that can be used as power sources without compromising the design of various products have attracted attention. In the dye-sensitized solar cell, a counter electrode substrate having a photoelectric layer, a charge transport layer, and a counter electrode conductive layer is sequentially stacked on a glass substrate having a transparent conductive layer. Has a structure. As a method of forming a transparent conductive layer such as ITO (Indium Tin Oxide) on a substrate, for example, a spatter method, a PLD (Pulsed Laser Deposition) method (also called a pulse laser ablation method), and CVD (Chemical Vapor Deposition) The method or the spray method etc. are known, As a method of forming a photoelectric layer, a porous semiconductor layer is formed by apply | coating semiconductor fine particles, such as a titanium dioxide, on a board | substrate and baking at high temperature, Then, the method of making a pigment | dye adsorb | suck to a semiconductor layer is employ | adopted.

Moreover, manufacturing a dye-sensitized solar cell at low cost using transparent substrates, such as inexpensive plastics, is also proposed. In this case, however, the above-described method involving the firing process cannot be employed when forming the photoelectric layer. In Japanese Patent Laid-Open No. 2004-6235 (Patent 1), a dye, which is a template compound (template), is mixed with an electrolytic bath containing zinc salt, and the electrolytic bath is prepared. A method of forming a zinc oxide thin film on a substrate by applying a cathode electrodeposition to the substrate in the form of a dye adsorbed to the inner surface has been proposed. After removal, the technique of manufacturing the dye-sensitized solar cell by which the pigment | dye is resorbed and a high photoelectric exchange rate is obtained is also disclosed.

By the way, although removal of a template agent from a zinc oxide thin film is normally performed by immersing a board | substrate in a weakly alkaline solution (removing liquid), in such a method, it takes a long time to remove a template agent. Moreover, when forming a plating layer on an object using the plating liquid containing an additive other than a template agent, it may be desirable to remove the said additive from the plating layer on the object, and even in such a case, an additive is removed efficiently from a plating layer. It is required.

[Initiation of invention]

This invention aims at the additive removal method which removes an additive from the plating layer on the object formed by immersing an object in the plating liquid containing an additive, and aims at efficiently removing an additive from a plating layer.

The additive removal method according to the present invention comprises the steps of: a) dipping the object in a removal liquid stored in a removal liquid tank, or continuously applying a removal liquid to the plating layer of the object; b) the a And a step of irradiating the object with light that promotes the removal of the additive from the plating layer in parallel to the step). According to this invention, an additive can be removed efficiently from a plating layer.

Preferably, the additive is a template agent, in which case the template agent may be removed from the plating layer to form a porous layer.

In one preferable embodiment of this invention, the said light contains the light of the wavelength contained in the absorption wavelength band of the said additive, or contains the light of the wavelength contained in the absorption wavelength band of the said plating layer. . Thereby, an additive can be removed more efficiently from a plating layer. More preferably, since the light contains ultraviolet rays, the additive of the organic substance in the plating layer can be more efficiently removed.

In another preferable embodiment of this invention, drying of the said plating layer of the said object is prevented after taking out the said object from the said plating liquid and until the said process a) starts. Thereby, an additive can be removed more efficiently from a plating layer.

The present invention is also directed to an additive removing device for removing an additive from a plating layer on an object formed by immersing the object in a plating liquid containing an additive. The additive removal apparatus includes a removal liquid tank for storing a removal liquid in which the object is immersed, or a removal liquid providing part which is a discharge part for continuously applying the removal liquid to the plating layer of the object, and the additive from the plating layer. A light irradiation part irradiates the object in the said removal liquid tank to the object which promotes removal, or the said object to which the said removal liquid is provided from the said discharge part. Thereby, an additive can be removed efficiently from a plating layer.

The present invention is also directed to a plating system for forming a plating layer on an object. The plating system includes a plating layer forming unit for forming a plating layer on the object by immersing the object in a plating solution containing an additive, and the additive removing device for removing the additive from the plating layer of the object, thereby forming a plating layer. The additive can be efficiently removed from the plating layer.

The above and other objects, features, aspects, and advantages will become apparent from the following detailed description of the present invention made with reference to the accompanying drawings.

1 is a view showing a plating system.

2 is a diagram illustrating a configuration of a removal device.

3 is a diagram illustrating a flow of a process of forming a porous layer on an object.

4 is a view showing another example of the removal device.

5 is a diagram illustrating another example of the plating system.

6 is a view showing still another example of the plating system.

7 is a diagram illustrating another example of the plating layer forming unit.

8 is a view showing still another example of the removal device.

9 is a view showing still another example of the removal device.

10 is a view showing still another example of the plating system.

Best Mode for Implementation of the Invention

FIG. 1: is a figure which shows the plating system 1 by one Embodiment of this invention. The plating system 1 is a system which forms a porous layer (film) by plating on the said transparent conductive layer of the transparent resin film 9 (plastic film) in which the transparent conductive layer was previously formed. In the subsequent step, the porous layer is adsorbed with a dye to form a photoelectric layer. The transparent conductive layer and the resin film 9 having the photoelectric layer laminated thereon are cut, and the substrate having the counter electrode conductive layer is opposed through the spacer. Is installed. Thereafter, an electrolyte solution is injected between the rectangular resin film and the substrate of the counter electrode to form a charge transport layer, thereby producing a dye-sensitized solar cell. Thus, the plating system 1 is used for manufacture of a dye-sensitized solar cell. The term "plating" in the present invention is not limited to metal, but means to produce a substance such as a metal oxide on the surface of the electrode by electrolysis (that is, electrodeposition).

As shown in FIG. 1, the plating system 1 is each part (namely, strip | belt-shaped) of the resin film 9 from the roll 90 of the resin film in which the transparent conductive layer was previously formed, also called web (WEB). A drawing layer forming portion (2) for continuously drawing out each of a plurality of portions continuously present in the resin film, and a plating layer forming portion on the transparent conductive layer by immersing the resin film (9) in a plating solution containing a template agent ( 3) The template agent removal apparatus (referred to as "removing apparatus 4" hereinafter) which removes a template agent from the plating layer on the resin film 9, and the whole control of the plating system 1 is performed. The control unit 10 in charge is provided.

In the plating system 1, the lead portion 2, the plating layer forming portion 3, and the removal device 4 are arranged in one direction in one direction, and the plurality of rollers 61 extending in a horizontal direction perpendicular to the direction. In Fig. 1, a part of the roller is attached with a reference sign 61a. The respective portions of the resin film 9 drawn out from the lead-out part 2 are removed by being disposed over the entire plating system 1. It is conveyed continuously to the drying furnace 49 which is mentioned later of (4). In addition, the roller 61 is formed of the material which has corrosion resistance with respect to the liquid (plating liquid and removal liquid mentioned later) used by the plating system 1. In addition, in FIG. 1, only a part of many rollers actually installed in the plating system 1 is shown.

The coating layer (including an other words, a chloride ion, a zinc ion and a template, the main component) forming part 3, zinc chloride (ZnCl ₂₎ and including the template of claim as main components plated for storing a plating solution (311) A potential is applied to each of the bath 31, the counter electrode 32 and the reference electrode (also called a reference electrode) 33 disposed in the plating solution 311, and the counter electrode 32 and the reference electrode 33, respectively. ) Is provided with a power supply unit (34). Moreover, one roller with the code | symbol 61a among the some roller 61 provided in the plating tank 31 is electrically connected to the power supply part 34. As shown in FIG.

Oxygen inlet tube 312 for supplying oxygen to the plating solution 31 (so-called oxygen bubbling) and a dissolved oxygen meter 313 for measuring oxygen concentration in the plating solution 311. And a thermometer 314 for measuring the temperature of the plating liquid 311. In the plating liquid 311, a heater 315 is provided, and the plating liquid 311 is maintained at a constant temperature by the temperature controller 316 controlling the heater 315 based on the output of the thermometer 314. In the coating layer forming portion 3, it is also possible to use a plating solution or the like, other types of plating solution containing a zinc nitrate (Zn (NO _{3) 2)} and the template, the main components. In addition, a template agent is mentioned later.

2 is a diagram illustrating a configuration of the removal device 4. As shown in FIG. 2, the removal apparatus 4 stores the removal liquid tank 41 which stores the weakly alkaline removal liquid 411 (for example, aqueous solution, such as sodium hydroxide or potassium hydroxide) in which the resin film 9 is immersed. The cleaning film 48 storing the light irradiation part 42 disposed above the removal liquid tank 41, the cleaning liquid such as pure water, and the resin film 9 after the cleaning in the cleaning tank 48 are removed. A drying furnace 49 for drying is provided.

The removal liquid tank 41 is provided with the circulation flow path 43 which circulates the removal liquid 411 using the pump 431, and the density | concentration which detects the density | concentration of a template agent in the removal liquid 411 in the circulation flow path 43 The detector 432 is installed. In addition, a removal liquid tank 433 for storing an unused removal liquid is connected to the circulation passage 43. The removal liquid is removed from the temperature detection part 432 at the time of removing the template agent from the plating layer on the resin film 9 described later. When it is confirmed that the concentration of the template agent in 411 exceeds a predetermined value, a part of the removal liquid 411 in the removal liquid tank 41 is discharged to the drainage tank 434 through the circulation passage 43, and the removal liquid tank ( It is possible to replenish the unused removal liquid to the removal liquid tank 41 from 433 (that is, part of the removal liquid 411 in the removal liquid tank 41 is exchanged.). Thereby, the stable process can be continued without stopping the plating system 1 at the time of replacement | exchange of the removal liquid 411, and also the fall of the throughput by formation of a porous layer is prevented.

The light irradiation section 42 has a light source (for example, a light source having a total luminous flux of 7000 lumens or more (preferably 10000 lumens or more)) such as a halogen lamp or a metal halide lamp. (421) makes it possible to detect the amount of light from the light source. When the decrease in the intensity of the light from the light irradiation section 42 is confirmed by the output from the illuminometer 421, the effect is displayed on the display device having the control unit 10 (see FIG. 1), and the operator is notified. As will be described later, in the removal apparatus 4, the light is irradiated to the resin film 9 in the removal liquid 411 from the light irradiation section 42, thereby promoting the removal of the template agent from the plating layer.

3 is a diagram showing a flow of processing in which the plating system 1 forms a porous layer on the resin film 9. In FIG. 3, the flow of the process which paid attention to a part of resin film 9 is shown, In fact, all the processes in FIG. 3 are performed in parallel with respect to the corresponding site | part of the resin film 9, respectively. In addition, step S11a shown with the broken line rectangle in FIG. 3 has shown the content of the operation | movement performed by the plating system 1b of FIG. 6 mentioned later, and is not performed by the following processes in the plating system 1 of FIG. Do not. In addition, since it may form a porous layer on objects other than the resin film 9 as mentioned later, in FIG. 3, the resin film 9 is generalized and shown as the "object."

In the plating system 1 of FIG. 1, a part of the plurality of rollers 61 connected to the motor starts to rotate in the same direction, so that the resin film 9 which is the object of processing from the roller 90 in the lead-out part 2 is processed. Each part of) is drawn out sequentially. Hereinafter, a part of the resin film 9 withdrawn from the lead-out section 2 will be described, and subsequent processing will be described. This site is referred to as a "target site".

The target portion drawn out from the roll 90 is moved into the plating bath 31 and immersed in the plating liquid 311. In the power supply unit 34, a predetermined reference potential is applied to the reference electrode 33, and a potential at which the difference with the reference potential becomes a predetermined value is applied to the counter electrode 32, and the roller 61a is provided. Through this, a potential at which the difference with the reference potential becomes a predetermined value is also applied to the transparent conductive layer (actually formed on almost the entire surface of the resin film 9) at the target portion. As a result, electroplating is performed on the target portion (electroplating is performed), thereby forming a plating layer (electrode film) containing zinc oxide and a template agent on the target portion (step S11). Here, the template agent forms a complex with zinc ions in the plating solution 311 as in the template compound in Japanese Patent Laid-Open No. 2004-6235 (Patent 1), whereby a transparent conductive layer is formed by electroplating. It is adsorb | sucked to the inner surface of the zinc oxide film formed on it, and typically becomes a pigment | dye.

The target portion on which the plating layer is formed is pulled up from the plating tank 31 and then continuously moved to the removal liquid tank 41, and is supported by the roller 61 in the removal liquid tank 41, as shown in FIG. 2. It is immersed in 411 (step S12). In fact, in the removal apparatus 4, the path | route of the resin film 9 is folded many times by the some roller 61 provided in the removal liquid tank 41, and the resin film 9 is removed in the removal liquid 411. It becomes possible to immerse for a long time. In addition, the light irradiation section 42 (for example, disposed within a range of 1.2 meters (more preferably, 0.8 meters) or less from the target site) is arranged near the target site, so that the target site is high. The light of intensity continues to be irradiated (step S13). As a result, the detachment of the template agent from the plating layer is promoted, the template agent is efficiently removed from the plating layer, and a porous plating layer is formed. In addition, when the removal liquid tank 41 becomes large enough (long) compared with the plating tank 31, the path | route of the resin film 9 does not necessarily need to be folded.

The object portion pulled up from the removal liquid tank 41 moves to the cleaning tank 48 and is immersed in the cleaning liquid. Thereafter, a cleaning liquid such as pure water is injected from the cleaning spray group 481 toward the surface of the target site, and the cleaning liquid on the surface of the target site is removed by air from the air knife 482 (step S14). Thereby, the removal liquid 411 used for the removal of the template agent is prevented from remaining on the resin film 9 and affecting subsequent steps. The object portion after washing passes through the drying furnace 49, and the object portion is dried to prevent dry spots or the like from occurring on the plating layer (porous layer) (step S15).

The target portion on which the porous layer is formed is conveyed to another apparatus (of course, may be once wound up), and the dye is again adsorbed to the porous plating layer, and then the resin film 9 is cut and the counter electrode conductive layer is formed through the spacer. The substrate having the opposite side is provided. Then, an electrolyte solution is injected between the rectangular resin film and the substrate of the counter electrode to form a charge transport layer, thereby producing a dye-sensitized solar cell. In the case where the charge transport layer is in a solid state, a substrate having a charge transport layer and a counter electrode conductive layer may be laminated without cutting the resin film 9.

Next, the experimental result which shows that the removal efficiency of a template agent improves by irradiating light to the plating layer in a removal liquid is described. Here, a plating solution containing 5 mmol (mM) of zinc chloride, 0.1 mol (M) of potassium chloride, and 40 micromol (μM) of eosin Y, a template agent, is prepared per liter of one liter. A plating layer, which is a zinc oxide film containing eosin Y, was formed on a substrate having an area of 1 square centimeter (cm 2). Further, a small removal liquid tank for storing the removal liquid is provided in the draft chamber, the same light irradiation part as that of the removal device 4 is also arranged, and then the substrate after being immersed in the removal liquid for 24 hours without being irradiated with light from the light irradiation part. Sample 3 and the substrate which was not immersed in the removal liquid for 8 hours while irradiating light from the sample 1 and the light irradiation part were made into the sample 3, and the board | substrate which does not immerse in the removal liquid (it also does not irradiate light from the light irradiation part). After the samples 1, 2 and 3 were washed with pure water and dried by injection of nitrogen, the absorbances of the samples 1, 2 and 3 were measured.

In addition, the absorption wavelength of zinc oxide is about 367 nanometers (nm) (exactly, the absorption wavelength of zinc oxide of a single crystal is 367 nm, and in fact, the wavelength of 367 nm is affected by the distortion of crystal lattice and the presence of other atoms. The absorption wavelength of eosin Y is around 530 nm, and the plating layer (zinc oxide film containing eosin Y) formed using the said plating liquid is red.

Table 1 shows the measurement results of absorbance of light having a wavelength of 530 nm of Sample 1, Sample 2, and Sample 3. In Table 1, sample 1, sample 2, and sample 3 are shown by listing 1, 2, and 3 in each column of the column described as "sample" at the top.

Table 1

Here, according to Lambert Berg's law, in a layer containing a specific substance, the absorbance of the specific substance is ABS, the absorption coefficient of the specific substance is ε, the concentration of the specific substance in the layer is C, and the optical path length. (ABS = εCL) is satisfied by setting (thickness of the layer) to L. In Sample 1, Sample 2 and Sample 3, all of the specific materials become Eosin Y, so the extinction coefficient [epsilon] becomes the same, and since the layer containing the specific material is a plated layer of the same thickness, the optical path length L is also the same. Therefore, in samples 1, 2, and 3, it is considered that the ratio of absorbance ABS indicates the concentration ratio (adhesion ratio) of eosin Y in the plating layer as it is. Therefore, in Table 1, the removal rate of Eosin Y in Sample 1 or Sample 2 is obtained by dividing the absorbance of Sample 3 by subtracting the absorbance of Sample 1 or Sample 2 by the absorbance of Sample 3.

As shown in Table 1, the removal rate in Sample 2 is about 2.7 times the removal rate in Sample 1. In fact, the immersion time of the sample 2 in the removal liquid is 1 of 3 of the sample 1, so that when the substrate on which the plating layer is formed is immersed in the removal liquid to remove Eosin Y from the plating layer, by irradiating light to the plating layer from the light irradiation part, It can be understood that the removal efficiency is 8 times or more compared with the case of not irradiating light.

By the way, in the above experiment, even for sample 1 immersed in the removal liquid for 24 hours without irradiating light from the light irradiation unit, the light for illumination installed in the draft chamber was exactly irradiated (actually, only 8 hours were irradiated). . Then, the difference between the intensity | strength on the board | substrate of light from the light source for illumination, and the intensity | strength on the board | substrate of light from a light irradiation part is examined.

In the above experiment, the distance between the light source for illumination light (here, a fluorescent lamp) and the substrate is 1.2 meters (m), and the total luminous flux from the light source for illumination light is 2900 lumens (lm). On the other hand, the distance between the light irradiation part and the substrate is 0.4 m, and the total luminous flux from the light irradiation part is 14000 lumens. Here, the lumen, which is a unit of luminous flux, is defined as "a luminous flux in which a point light source having a constant luminous intensity of one candela (cd) is emitted in a solid angle 1 steradian sr '', and is emitted from the light irradiation unit. Since the ratio of the intensity of the emitted light to the intensity of the light emitted from the light source for illumination is obtained as the ratio of the total luminous flux, the intensity of the light emitted from the light irradiation unit is 4.83 times the intensity of the light emitted from the light source for illumination (= 14000 / 2900).

In addition, since the intensity of the light from the light irradiation unit or the light source for illumination is inversely proportional to the square of the distance between the light irradiation unit or the light source for illumination and the substrate, if the intensity of light emitted from the light irradiation unit and the light source for illumination is the same The intensity of the light from the light irradiation section on the substrate is 9.0 times (= (1 / 0.4 ² ) / (1 / 1.2 ² )) of the intensity of the light from the light source for illumination on the substrate. As described above, since the intensity of the actual light emitted from the light irradiation unit is 4.83 times the intensity of the light emitted from the light source for illumination, the intensity on the substrate of the light from the light irradiation unit is that of the intensity on the substrate of the light from the light source for illumination. 43.5 times (= 4.83 x 9.0).

In fact, even when the light irradiation section is disposed 0.8 meters away from the substrate (that is, twice the distance), the intensity on the substrate of the light from the light irradiation section is about 11 of the intensity on the substrate of the light from the light source for illumination. In this case, the removal of the template agent from the plating layer is sufficiently promoted, and even when the light irradiation unit is disposed at a position 1.2 meters away from the substrate (that is, three times the distance), the intensity of the light from the light irradiation unit on the substrate is used for illumination. It becomes about 5 times the intensity | strength on the board | substrate of light from the light source of, and the removal of a template agent from a plating layer is accelerated to some extent. In addition, even when the fluorescent lamp is used as a light irradiation unit and disposed at a position of 0.4 meters from the substrate, the intensity of the light from the fluorescent lamp on the substrate becomes 9 times the intensity on the substrate of the light from the light source for illumination, and the template is made from the plated layer. Acceleration of removal is realized.

As described above, the high intensity light is irradiated to the resin film 9 from the light irradiation part 42 provided in the vicinity of the resin film 9 in the removal liquid 411 while the resin film 9 is immersed in the removal liquid 411. By doing so, it is possible to remove the template agent from the plating layer on the resin film 9 extremely efficiently (in a short time). In addition, in the plating system 1, the resin film 9 is continuously conveyed from the plating layer forming unit 3 to the removal apparatus 4, thereby improving the throughput by the formation of the porous layer and the quality of the porous layer. Can be.

By the way, although light of a wide range of wavelengths from ultraviolet to visible light is emitted from the light irradiation part 42 of the removal apparatus 4 of FIG. 2, the light from the light irradiation part 42 is contained in the absorption wavelength band of a template agent. By containing light of a wavelength, the template agent in the plating layer of the resin film 9 immersed in the removal liquid 411 is activated. Since the template agent is more stable in the state existing in the removal liquid 411 than the state adsorbed in the zinc oxide film, the release of the template agent from the plating layer is further promoted by activation of the template agent. That is, since the light from the light irradiation part 42 contains light of the wavelength contained in the absorption wavelength band of a template agent, a template agent can be removed more efficiently from a plating layer.

In addition, when the light from the light irradiation section 42 includes light having a wavelength included in the absorption wavelength band of the zinc oxide film that is the main body of the plating layer, electrons in the zinc oxide film are excited to supply electrons to the template agent. . As a result, the template agent is ionized and easily dissolved in the removal liquid 411 in a short time, thereby allowing the template agent to be removed from the plating layer more efficiently.

In addition, since the light from the light irradiation part 42 includes ultraviolet rays (light having a wavelength of 10 to 400 nanometers (nm)), the template agent, which is a high molecular weight organic substance, is decomposed to lower the molecular weight, thereby facilitating detachment from the plating layer. That is, the removal from the plating layer of the template agent of an organic substance can be performed more efficiently.

4 is a diagram illustrating another example of the removal apparatus. In the removal apparatus 4a shown in FIG. 4, the removal liquid regeneration part 435 is provided instead of the drainage tank 434 of the removal apparatus 4 of FIG. 2, and the removal liquid regeneration part 435 is connected to the removal liquid tank 433. FIG. do. The other structure is the same as the removal apparatus 4 of FIG. 2, and has attached | subjected the same code | symbol.

The removal liquid regeneration unit 435 is a removal liquid 411 (the removal liquid 411 containing the template agent removed from the plating layer) discharged from the removal liquid tank 41 through the circulation passage 43, hereinafter referred to as "drain removal liquid". The template agent is removed from the discharge removal liquid by adsorbing the template agent in the discharge removal liquid to the activated carbon filter installed therein. The removal of the template agent from the discharge removal liquid may be realized by decomposing the template agent in the discharge removal liquid by irradiation of ultraviolet rays to the discharge removal liquid and / or photocatalytic action of titanium oxide provided therein. The discharge removal liquid from which the template agent is removed is stored in the removal liquid tank 433 and used for replenishment or replacement of the removal liquid 411 in the removal liquid tank 41.

By the way, in the manufacture of a dye-sensitized solar cell, since the removal liquid is used in large quantities (for example, even if the template agent is removed from the plating layer on a small substrate having an area of 1 cm 2 of one main surface used in the above-described experiments). At least several hundred millimeters (ml) of removal liquid is required.) The manufacturing cost of the solar cell increases, and the method of disposing of the removal liquid creates a load on the environment. On the other hand, in the removal apparatus 4a of FIG. 4, by providing the removal liquid regeneration part 435 which removes the template agent contained in the removal liquid 411 in the removal liquid tank 41, reduction of the manufacturing cost of a solar cell, and It is possible to stably remove the additive from the plating layer while reducing the load on the environment.

5 is a diagram illustrating another example of the plating system. In the plating system 1a of FIG. 5, the spray part 51 which sprays pure water (other liquid may be sufficient) toward the resin film 9 between the plating layer forming part 3 and the removal apparatus 4 is It is provided and pure water is supplied to a plating layer in the middle of conveyance of the resin film 9 from the plating layer forming part 3 to the removal apparatus 4.

Here, in the plating layer formed in the present embodiment, the template agent and the main body (zinc oxide film) of the plating layer are firmly bonded to each other by drying. Therefore, in the plating system 1a of FIG. 5, pure water is supplied to the resin film 9 in the middle of conveyance of the resin film 9 from the plating layer forming part 3 to the removal apparatus 4, and drying of the plating layer is prevented. This prevents the template agent and the main body of the plating layer from firmly bonding (i.e., the adsorption force of the template agent to the zinc oxide film is kept weak), and the template agent is further removed from the plating layer in the removal apparatus 4. Efficient (short time) removal is realized. As a result, while improving the throughput by forming the porous layer, the energy required for removal of the template agent from the plating layer (for example, energy consumed by the light irradiation section 42) is reduced, and the manufacturing cost of the solar cell is reduced. We can plan reduction.

By the way, after taking out the resin film 9 from the plating liquid 311, it is said that drying of the plating layer of the resin film 9 is prevented until the immersion to the removal liquid 411 of the resin film 9 starts. From the viewpoint, for example, a dedicated tank for storing pure water is provided, and the resin film 9 is immersed in the pure water tank until immediately before being immersed in the removal liquid 411 (from the plating layer forming unit 3, the removal device ( It may be said that the conveyance path | route up to 4) is pure water.) By drying the resin film 9 may be prevented. In this case, since the plating liquid 311 remaining on the resin film 9 taken out from the plating tank 31 is reliably removed from the tank of pure water (it can also be called washing of the resin film 9), plating liquid 311 ) Is mixed with the removal liquid 411 to prevent the influence of removing the template agent from the removal apparatus 4.

As mentioned above, the liquid supply part which supplies a liquid to the resin film 9 during conveyance of the resin film 9 from the plating layer forming part 3 to the removal apparatus 4 (for example, the spray part 51 which sprays liquid) ) Or a tank for storing the liquid) is realized to prevent drying of the plating layer before removing the template agent. Moreover, it is also possible to prevent drying of the resin film 9 by speeding up the conveyance from the plating layer forming part 3 to the removal apparatus 4 at high speed.

6 is a diagram illustrating still another example of the plating system. In the plating system 1b of FIG. 6, between the plating layer forming part 3 and the removal apparatus 4, the auxiliary light irradiation part 52 which emits the same light as the light irradiation part 42 of the removal apparatus 4 is Is installed.

In the formation process of the porous layer on the resin film 9 in the plating system 1b of FIG. 6, when a plating layer is formed on the resin film 9 in the plating layer forming part 3 (FIG. 3: step S11), a plating layer In the middle of conveyance of the resin film 9 from the formation part 3 to the removal apparatus 4, light is irradiated to the plating layer of the resin film 9 from the auxiliary light irradiation part 52 (step S11a). Subsequently, the resin film 9 is immersed in the removal liquid 411 in the removal liquid tank 41, and the resin film 9 is irradiated with light from the light irradiation part 42 to remove the template agent from the plating layer (step S12, Step S13). Thereafter, the resin film 9 is taken out of the removal liquid 411 and washed in the washing tank 48 (step S14), and drying is performed in the drying furnace 49, thereby completing the process of forming the porous layer (step) S15).

As described above, in the plating system 1b of FIG. 6, immediately before the resin film 9 is immersed in the removal liquid 411 (that is, after formation of the plating layer and before immersion in the removal liquid 411), the plating layer is removed from the plating layer. By irradiating the resin film 9 with light for promoting the removal of the template agent, the resin film 9 can be immersed in the removal liquid 411 in a state where the template agent is easily separated from the plating layer. As a result, immediately after the resin film 9 is immersed in the removal liquid 411, the detachment of the template agent in the plating layer starts, and the template agent can be more efficiently removed from the plating layer. As a result, the formation process of a porous layer can be performed in a short time (improvement of throughput).

In addition, also in the auxiliary light irradiation part 52, since the emitted light contains an ultraviolet-ray, the organic substance in a plating layer will decompose before immersion, and the removal of the organic substance from the plating layer of the template agent is aimed at. In addition, the light from the auxiliary light irradiation part 52 includes light of the absorption wavelength made of the template or light of the absorption wavelength of the body of the plating layer, thereby activating the template or the body of the plating layer before immersion, thereby allowing the template from the plating layer. It becomes possible to perform removal of an agent more efficiently.

Next, a plating system using the glass substrate as an object of processing will be described. 7 is a diagram illustrating another example of the plating layer forming unit. The plating layer forming part 3a of FIG. 7 is a device of a buried pattern, and the transparent glass substrate 9a which has a transparent conductive layer becomes an object of a process.

The plating layer forming part 3a of FIG. 7 holds the plating bath 31a for storing the plating liquid 311, the substrate holding part 35 and the substrate holding part which are immersed in the plating liquid 311 while holding the glass substrate 9a. A counter electrode disposed in the rotating mechanism 36 and the plating solution 311 that rotate the substrate holding part 35 about the center axis perpendicular to the main surface while passing through the center of the glass substrate 9a held by the 35. (32) and the reference electrode (33), and a power supply unit (34) for applying a potential to each of the transparent conductive layer, the counter electrode (32) and the reference electrode (33) of the glass substrate (9a).

The supply pipe 371 is provided in the plating tank 31a, and the filter 374 is provided in the supply pipe 371. In addition, the supply pipe 371 is connected to the plating liquid tank 373 via the pump 372. In the plating liquid tank 373, the plating liquid returned from the plating tank 31a through the discharge pipe 375 is stored, and the pump 372 drives the pump 372 to remove unneeded substances or bubbles in the plating liquid with the filter 374. The plating liquid is supplied from the 371 to the plating tank 31a, and a predetermined amount of the plating liquid 311 is stored in the plating tank 31a. In reality, the plating liquid 311 from the supply pipe 371 is ejected toward the main surface (main surface on the opposite side to the substrate holding portion 35) of the glass substrate 9a disposed in the plating bath 31a, and the corresponding main surface. The classification of the plating liquid 311 collides with each other. In the plating layer forming portion 3a of FIG. 7, the circulation to circulate the plating liquid 311 between the plating vessel 31a and the plating liquid tank 373 by the supply pipe 371, the pump 372, and the discharge tube 375. The mechanism is built.

The plating bath 31a is provided with a dissolved oxygen meter 313 for measuring the oxygen concentration in the plating liquid 311 and a thermometer 314 for measuring the temperature of the plating liquid 311. A heater 315a is provided in the plating liquid tank 373, and the temperature controller 316 controls the heater 315a based on the output of the thermometer 314, thereby between the plating bath 31a and the plating liquid tank 373. The plating solution 311 circulating is maintained at a constant temperature.

In the supply pipe 371, a gas dissolving unit 376 is provided between the filter 374 and the pump 372, and oxygen is dissolved in the plating liquid 311 according to the measured value of the dissolved oxygen meter 313. In addition, between the filter 374 and the gas dissolving unit 376, an analysis device 377 for analyzing the components of the plating solution 311 is connected, and according to the result of the analysis device 377, the component adjustment unit 373 ), Only the required amount of each component (for example, a high concentration of zinc chloride solution or template agent) contained in the plating solution 311 is supplied to the plating solution tank 373. In addition, the result in the analyzer 377 can be displayed on the display part of the control part 10 (refer FIG. 1).

When forming the porous layer on the glass substrate 9a, first, the substrate holding portion 35 holding the glass substrate 9a in the plating layer forming portion 3a of FIG. 7 is immersed in the plating liquid 311, thereby rotating mechanism. The substrate holding part 35 rotates by 36. In the power supply unit 34, a predetermined reference potential is applied to the reference electrode 33, and a potential at which the difference with the reference potential becomes a predetermined value is applied to the counter electrode 32, and the glass substrate 9a is provided. The transparent conductive layer is also provided with a potential at which the difference from the reference potential becomes a predetermined value. As a result, electroplating is performed on the glass substrate 9a (precursored) to form a high quality (or high purity) plating layer containing zinc oxide and a template agent on the glass substrate 9a (Fig. 3: Step S11).

In reality, in the plating layer forming part 3a, the rotating mechanism 36 is supported by the support arm not shown, and the rotating mechanism 36 in the horizontal direction, the up-down direction, or the direction perpendicular | vertical to the paper surface in FIG. It is possible to oscillate, and after formation of the plating layer, the support arm raises the rotary mechanism 36, and the glass substrate 9a can be taken out. In addition, a mechanism for agitating the plating liquid 311 may be provided in the plating tank 31a as necessary, and a mechanism for removing gas dissolved in the plating liquid is provided in the supply pipe 371, and a gas dissolving unit is provided. In cooperation with 376, the oxygen concentration in the plating solution 311 may be increased.

The glass substrate 9a in which the plating layer was formed is conveyed to the removal apparatus 4b shown in FIG. In the removal apparatus 4b for the glass substrate 9a, the removal liquid tank 41 is formed with a light transmitting member, and the light irradiation part 42 is provided facing one side of the removal liquid tank 41. Subsequently, the substrate cassette 91 for supporting the plurality of glass substrates 9a in a state of being parallel to each other and standing upright is immersed in the removal liquid 411, and the light irradiation part 42 facing the main surface of the glass substrate 9a is provided. By irradiating the plated layer with light from the platen, it is possible to efficiently remove the template agent from the plated layers of the plurality of glass substrates 9a (step S12, step S13). Then, the plurality of glass substrates 9a are taken out from the removal liquid 411 together with the substrate cassette 91 to wash the plurality of glass substrates 9a, and thereafter, the glass substrates 9a are dried (step S14). , Step S15). As described above, in the plating system for the glass substrate 9a, the porous layer can be efficiently formed on the glass substrate 9a.

In addition, in the removal apparatus 4b of FIG. 8 in which the plurality of glass substrates 9a are immersed in a stopped state, the concentration of the template agent removed in the removal liquid 411 in the removal liquid tank 41 is near the portion of the plating layer. In this case, the concentration of the template agent with the removal liquid 411 is lowered in the corresponding portion of the plating layer, so that the amount of release of the template agent is lowered, and the uniformity of removal of the template agent in the entire plating layer is lowered. There is. Therefore, in such a case, it is preferable to provide the mechanism for stirring the removal liquid 411 in the removal liquid tank 41. In addition, depending on the design of the removal apparatus, the removal liquid 411 in the removal liquid tank 41 may be stirred by the flow of the removal liquid 411 ejected from the circulation passage 43 (see FIG. 2).

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, A various deformation | transformation is possible.

In the above embodiment, the template agent is removed from the plating layer by immersing the resin film 9 or the glass substrate 9a (hereinafter referred to as "object") in the removal liquid 411, but as shown in FIG. Similarly, the discharge part 41a which continuously applies a removal liquid to the plating layer of the object (FIG. 9, the glass substrate 9a) in the removal apparatus 4c may be provided. In this case, in the formation process of the porous layer of FIG. 3, the continuous application of the removal liquid from the discharge part 41a to the object is started in step S12, and in parallel with the application of the removal solution, the light irradiation part 42 is released from step S13. Light is irradiated to the plating layer, and the template agent is efficiently removed from the plating layer to which the removal liquid is applied from the discharge part 41a.

As mentioned above, in order to remove a template agent efficiently from a plating layer, the light irradiation part 42 which irradiates the object with the light which promotes removal of a template agent from a plating layer is provided in the removal apparatus 4, 4a-4c. It is important to provide a removal liquid tank 41 for storing the removal liquid in which the object is immersed, or a discharge part 41a for continuously applying the removal liquid to the plating layer of the object as the removal liquid applying part.

In the plating system for which the resin film 9 is the object of treatment, the resin film 9 is removed from the plating liquid 311 and then until the immersion of the resin film 9 into the removal liquid 411 starts. If the removal of the template agent from the plating layer is not affected even when the plating layer of the film 9 is dry, as shown in FIG. 10, the resin film 9 is interposed between the plating layer forming portion 3 and the removal device 4. A drying furnace 54 for drying the film may be provided, and the plating layer on the resin film 9 may be dried. In this case, it is possible to prevent the unnecessary liquid from mixing in the removal liquid 411. In addition, in the plating system 1c of FIG. 10, between the plating layer formation part 3 and the drying furnace 54, the washing part which has the washing tank 531, the cleaning spray group 532, and the air knife 533. 53 is provided, and the resin film 9 immediately after the plating layer is formed is washed, and the plating solution 311 is surely prevented from mixing with the removal liquid 411.

In the case where the glass substrate 9a is to be treated, a firing furnace having a chamber in the plating system, depending on the type of plating layer formed in the plating layer forming portion (plating layer containing an additive other than a template, as described below). May be provided and the plating layer after removal of the additive may be fired. Depending on the plating layer, water, which is a solvent, for example, crystallized water may be blown into the crystal. However, by firing, water in the plating layer can be removed. Further, depending on the type of substrate on which the plating layer is formed, the substrate may be prevented from oxidizing by firing while maintaining the inside of the chamber at a predetermined gas atmosphere (same as in the drying furnace 54 of FIG. 10).

In the said embodiment, although the template agent in a zinc oxide film which is a plating layer is removed, the plating layer formed on the object may be a film other than zinc oxide, and the kind of plating liquid changes also according to the said film. Further, even when the plating layer containing the template agent or the plating layer containing no template agent is formed on the object, the plating liquid used for forming the plating layer is generally used in addition to the components forming the main body of the plating layer. It contains an additive (an additive other than a template agent) which enables adjustment of the etc., and depending on the use of the target object in which a plating layer is formed, the removal of the said additive in a plating layer may be required. Even in such a case, in the removal apparatuses 4 and 4a to 4c which are the additive removal apparatuses, in parallel with the immersion into the removal liquid 411 of the object or the provision of the removal liquid from the discharge part 41a to the object, By irradiating the plating layer with light that promotes the removal of the additive, it is possible to efficiently remove the additive from the plating layer.

In addition to the resin film 9 and the glass substrate 9a, the object to be processed in the plating system may be a semiconductor substrate, a printed wiring board, or various forms other than the substrate.

Although this invention was demonstrated in detail, the above description is illustrative and not restrictive. Accordingly, it is understood that many variations and aspects are possible without departing from the scope of this invention.

Claims (16)

An additive removal method for removing the additive from a plating layer on the object formed by immersing the objects 9 and 9a in a plating solution 311 containing an additive, a) a step (S12) of immersing the object in the removal liquid 411 stored in the removal liquid tank 41, or continuously applying the removal liquid to the plating layer of the object; and b) irradiating light to the object to accelerate the removal of the additive from the plating layer in parallel with the step a). The method of claim 1, The additive removal method of the said light containing the light of the wavelength contained in the absorption wavelength band of the said additive. The method of claim 1, And the light includes light having a wavelength included in an absorption wavelength band of the plating layer. The method of claim 1, The additive removes the light comprises ultraviolet. The method of claim 1, After removing the said object from the said plating liquid, and until the a process starts, drying of the said plating layer of the said object is prevented. The method of claim 1, And a step (S11a) of irradiating the object with light for promoting the removal of the additive from the plating layer before executing the step a). The method according to any one of claims 1 to 6, The additive removal method of the said additive is a template agent. As an additive removing device (4, 4a to 4c) for removing the additive from the plating layer on the object formed by immersing the object (9, 9a) in the plating solution 311 containing the additive, A removal liquid tank 41 for storing the removal liquid 411 in which the object is immersed, or a removal liquid providing part that is a discharge part 41a that continuously applies the removal liquid to the plating layer of the object; Additive removal provided with the light irradiation part 42 which irradiates the object in the said removal liquid tank to the said object in the said removal liquid tank, or the said object to which the removal liquid is provided from the said discharge part by the light which promotes removal of the said additive from the said plating layer. Device. The method of claim 8, The additive removal apparatus which the light from the said light irradiation part contains the light of the wavelength contained in the absorption wavelength band of the said additive. The method of claim 8, The additive removal apparatus which the light from the said light irradiation part contains the light of the wavelength contained in the absorption wavelength band of the said plating layer. The method of claim 8, The additive removal apparatus the light from the said light irradiation part contains an ultraviolet-ray. The method of claim 8, And a removal liquid regeneration unit (435) for removing the additive contained in the removal liquid in the removal liquid tank which is the removal liquid providing unit. The method according to any one of claims 8 to 12, An additive removing device wherein the additive is a template agent. As the plating system 1, 1a-1c which forms a plating layer on the object 9, 9a, Plating layer forming portions 3 and 3a for forming a plating layer on the object by immersing the object in a plating solution 311 containing an additive; An additive removing device (4, 4a to 4c) for removing the additive from the plating layer of the object, The additive removing device, A removal liquid tank 41 for storing the removal liquid 411 in which the object is immersed, or a removal liquid providing part that is a discharge part 41a that continuously applies the removal liquid to the plating layer of the object; And a light irradiating portion (42) for irradiating the object in the removing liquid tank with the light promoting the removal of the additive from the plating layer or the object to which the removing liquid is applied from the discharge portion. The method of claim 14, And a liquid supply part (51) for supplying liquid to the object to prevent drying of the plating layer during conveyance of the object from the plating layer forming part to the additive removing device. The method according to claim 14 or 15, A plating system further comprising another light irradiation section 52 for irradiating the object with light that promotes the removal of the additive from the plating layer during conveyance of the object from the plating layer forming unit to the additive removing device. .

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