JP2000173969A - Rinsing method and photovoltaic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rinsing method for forming high-performance zinc oxide thin films excellent in mass productivity and board adhesion, at a low cost stably. SOLUTION: This is a method for rinsing a zinc oxide thin film formed in a process of depositing zinc oxide thin film on a board, by dipping a board composed of a conductive substrate in an aqueous solution containing at least nitrate ions and zinc ions, and causing a minus current to flow into an opposed electrode dipped in the aqueous solution. The electric conductivity of a rinse bath to be used in rinsing is controlled to 150 μS/cm or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an electrodeposition method,
The present invention relates to a rinsing method for cleaning a zinc oxide thin film in a step of forming a zinc oxide thin film having irregularities having a light confinement effect applied to a solar cell undercoat layer. Further, the present invention relates to a photovoltaic device manufactured by a manufacturing process including the rinsing method.

[0002]

2. Description of the Related Art Conventionally, a photovoltaic element made of hydrogenated amorphous silicon, hydrogenated amorphous silicon germanium, hydrogenated amorphous silicon carbide, microcrystalline silicon, polycrystalline silicon, or the like has been used at a long wavelength. Backside reflective layers have been used to improve collection efficiency. Such a backside reflective layer preferably exhibits effective reflection characteristics at a wavelength near the band edge of the semiconductor material where its absorption is reduced, that is, from 800 nm to 1200 nm. It is metals such as gold, silver, copper, and aluminum that sufficiently satisfy such conditions.

[0003] An optically transparent uneven layer is also provided in a predetermined wavelength range known as an optical confinement effect. Generally, a transparent layer is provided between the back reflection layer and the semiconductor layer. An uneven layer may be provided to improve the short-circuit current density Jsc by effectively using reflected light.

Further, in order to prevent deterioration in characteristics due to a shunt path, a layer made of a light-transmitting material having conductivity, that is, a transparent conductive layer is provided between the back metal layer and the semiconductor layer.

Generally, each of the above-described layers is deposited by a method such as vacuum deposition or sputtering, and shows an improvement of 1 mA / cm ² or more in short-circuit current density Jsc.

As an example of this, “Light confinement effect in a-SiGe solar cell on 29p-MF-22 stainless steel substrate” (Autumn 1990), Proceedings of the 51st Annual Conference of the Japan Society of Applied Physics, p747, Prior Art 2: "P-IA-
15a-SiC / a-Si / a-SiGe Multi
-Bandgap Stacked Solar Ce
lls With Bandgap Profilin
g, "Sannomiya et al., Techn.
ical Digest of the Intern
ational PVSEC-5, Kyoto, Japan
an, p381, 1990, etc., have studied the reflectance and texture structure of a reflective layer composed of silver atoms.

In these prior art examples, the back reflection layer is formed by depositing two layers of silver at different substrate temperatures to form effective concavities and convexities, and light confinement is achieved by the combination of the concavities and convexities and the zinc oxide thin film. It is said that the effect has increased the short-circuit current.

[0008]

The transparent conductive layer used as the light confinement layer described above is deposited by a vacuum deposition method using a resistance heating or an electron beam, a sputtering method, an ion plating method, a CVD method, or the like.

[0009] However, in these methods, the labor for producing the target material and the like is high, the depreciation cost of the vacuum apparatus is large, and the utilization efficiency of the material is poor. For this reason, the cost of the photovoltaic element manufactured by using these methods becomes extremely high, which has been a major obstacle to industrial application of the solar cell.

To cope with these obstacles, a method of combining a back metal layer formed by a sputtering method and a transparent conductive layer formed by an electrodeposition method can be considered.

By using such a method, an expensive vacuum apparatus and an expensive target are not required.
The manufacturing cost of the transparent conductive layer made of a zinc oxide thin film can be reduced drastically. Further, since a transparent conductive layer made of a zinc oxide thin film can be deposited on a large-area substrate, it is promising for a large-area photovoltaic element such as a solar cell.

However, the method of electrochemically depositing a transparent conductive layer composed of a zinc oxide thin film has the following problems.

[0013] The first problem is that the electrolyte solution, which is an electrodeposition bath, is an aqueous solution in which nitrate is very easily precipitated. Therefore, when the substrate is dried, white streak-like stains appear on the zinc oxide thin film. This caused the reliability (adhesion) of the film to decrease and caused poor appearance.

When this zinc oxide thin film is used as a part of a photovoltaic element, these spots cause a decrease in the current value due to a decrease in optical characteristics, and further reduce the adhesion to the photovoltaic element. Let me do it.

As a second problem, a roll for forming a transparent conductive layer composed of a zinc oxide thin film by electrolytic deposition is used.
In the two-roll format, an optimal rinsing method has not been established.

The present invention has been made in view of the above circumstances, and has excellent mass productivity, high performance and low cost.
An object of the present invention is to provide a method for rinsing a zinc oxide thin film for stably forming a zinc oxide thin film having excellent substrate adhesion. In addition, the present invention incorporates a photovoltaic element formed with such a zinc oxide thin film into a solar cell,
The purpose is to contribute to the full-fledged spread of solar power generation.

[0017]

According to the rinsing method of the present invention, in order to achieve the above-mentioned object, a substrate consisting of a conductive substrate is immersed in an aqueous solution containing at least nitrate ions and zinc ions. A method for rinsing the zinc oxide thin film formed in the step of depositing the zinc oxide thin film on the substrate by applying a negative current to the counter electrode immersed in the aqueous solution, comprising: The electrical conductivity of the rinsing bath used for the above is controlled to 150 μS / cm or less.

It is preferable that the electrical conductivity of the rinsing bath used for rinsing is controlled to 1 μS / cm or less.

Further, it is preferable to deposit the zinc oxide thin film in a roll-to-roll manner.

Further, it is preferable to provide a shower tub, a first rinsing bath, and a second rinsing bath, and to perform cleaning in this order.

Further, the photovoltaic element used for the solar cell is preferably manufactured by a manufacturing process including the above-described rinsing method of the zinc oxide thin film formed by electrolytic deposition.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Photovoltaic device A photovoltaic device manufactured by a manufacturing process including a rinsing method according to the present invention will be described with reference to FIG.

FIG. 1 is a schematic view showing a cross section of a photovoltaic element manufactured by a manufacturing process including a rinsing method according to the present invention.

As shown in FIG. 1, the photovoltaic element is an SU
Gold, silver, and the like on a support 101 made of a conductive substrate such as S
A back reflection layer 102 made of a metal such as copper or aluminum;
Transparent conductive layer 10 composed of electrolytically deposited zinc oxide thin film
3. Semiconductor layer 10 made of hydrogenated amorphous silicon, hydrogenated amorphous silicon germanium, hydrogenated amorphous silicon carbide, microcrystalline silicon, polycrystalline silicon, or the like
4. A transparent electrode layer 105 made of ITO or the like and a current collecting electrode layer 106 made of a silver paste or the like are formed in this order. Among the layers, the support 101 and the back reflection layer 102
This forms the light-reflective metal substrate according to the present invention. Note that in the case where a transparent substrate is used and light enters from the substrate side, the support 101 and the back reflection layer 102 are used.
Except for, each layer is formed in reverse order.

Electrodeposition apparatus FIG. 10 shows a conductive substrate 303 (support 10 shown in FIG. 1).
FIG. 1 is a schematic structural view of an apparatus for forming a zinc oxide thin film (the transparent conductive layer shown in FIG. 1) on 1).

As shown in FIG. 10, the apparatus for forming a zinc oxide thin film includes a corrosion-resistant container 301 filled with an electrolytic deposition aqueous solution 302 (electrodeposition bath). A water inlet 308 and an outlet 307 are provided on the side surface, one end of a suction solution pipe 309 is connected to the water inlet 308, and one end of an injection solution pipe 310 is connected to the outlet 307. 309 and a solution circulation pump 311 at the other end of the injection solution pipe 310.
Are connected so that the electrolytic deposition aqueous solution 302 in the corrosion-resistant container 301 circulates.

A heater 312 for heating the electrolytic deposition aqueous solution 302 and a thermometer 313 for measuring the temperature of the electrolytic deposition aqueous solution 302 are provided in the corrosion-resistant container 301.
Is provided.

Then, the conductive substrate 303 and the counter electrode 304 are arranged in the aqueous electrolytic deposition solution 302 so as to face each other.
The load resistance 3 is applied to the conductive base 303 and the counter electrode 304.
By connecting a power supply 305 via the reference numeral 06, a zinc oxide thin film is formed on the surface of the conductive substrate 303.

The concentration of nitrate ion and zinc ion in the aqueous electrolytic deposition solution 302 is preferably 0.002 mol / l to 3.0 mol / l.
0 mol / l, more preferably 0.0 mol / l
1.5 mol / l, optimally 0.05 mol / l to 0.1 mol / l.
7 mol / l. Also, to prevent abnormal growth,
When using an aqueous solution of electrolytic deposition 302 containing saccharose or dextrin, the concentration of saccharose is preferably 500 g / l to 1 g / l, more preferably 10 g / l.
The texture suitable for the light confinement effect is adjusted to 0 g / l to 3 g / l and the dextrin concentration is preferably 10 g / l to 0.01 g / l, more preferably 1 g / l to 0.025 g / l. A zinc oxide thin film having a structure can be efficiently formed.

The temperature of the electrolytic deposition aqueous solution 302 is set to 60
By setting the temperature to not less than ° C., a uniform zinc oxide thin film with little abnormal growth can be efficiently formed.

The current density between the conductive substrate 303 and the counter electrode 304 is preferably 0.1 mA / cm ^{2 to} 100 mA.
/ Cm ² , more preferably 1 mA / cm ^{2 to} 30 mA /
cm ^2, and optimally ^{4mA / cm 2 ~20mA / cm 2} .

In the case of a small-scale apparatus, a magnetic stirrer can be used instead of the circulation system using the solution circulation pump 311 described above.

[Rinse Step] The electrodeposition bath used for electrolytic deposition tends to precipitate as a nitrate during drying, and when the concentration of the solution is high, it looks like a white stain visually. As a countermeasure, a sufficient rinsing step is indispensable. In addition, hot water may be used to improve the rinsing property. Note that, as a synonym for rinsing, rinsing water washing, washing, and the like are sometimes used.

The present invention forms a highly reliable zinc oxide thin film which is excellent in mass productivity, effective in improving solar cell characteristics, has a high light confinement effect, and increases light collection current and reliability. It will contribute. In addition, this is achieved stably at low cost industrially.

For this purpose, after depositing the zinc oxide thin film by electrolytic deposition, a rinsing step is provided, and the rinsing bath used for this rinsing is 150 μS / cm or less, preferably 1 μS / cm.
By controlling in the following manner, it is possible to prevent the occurrence of spots due to precipitation of nitrate and to produce a highly reliable zinc oxide thin film.

Electrodeposition apparatus on long substrate [Main structure of electrodeposition apparatus] An embodiment of an electrodeposition apparatus according to the present invention will be described below.

First, the main structure of the electrodeposition apparatus according to the present invention will be described.

The electrodeposition apparatus according to the present invention comprises, as main devices, an electrodeposition tank for holding an electrodeposition bath for electrochemically depositing zinc oxide, and a respective electrodeposition bath (electrolyte) for the electrodeposition tank. Solution) is heated to a predetermined temperature and fed, and two sets of an independent drainage tank capable of storing all the electrodeposition baths held in the electrodeposition tank and the circulation tank at one time. .

The electrodeposition tank used in the electrodeposition apparatus according to the present invention is made of corrosion-resistant stainless steel, heat-resistant vinyl chloride, FRP, or the like, and has a double structure in which a heat insulating material is interposed to improve heat insulation. There is also. Since the electrodeposition tank has two electrodes inside for electrodeposition of the anode and the long substrate, metal parts such as the tank wall are not exposed to prevent current stray from both electrodes. When a metal bath is used, it is preferable to provide an insulating lining inside and further to set the electrodeposition bath itself at a float potential.

It is also possible to use different electrodeposition baths for a plurality of electrodeposition tanks.

The circulation tank used in the electrodeposition apparatus according to the present invention is made of stainless steel having excellent corrosion resistance and heat resistance, and has a built-in heater for heating the electrodeposition bath. In order to improve the heating efficiency, a double structure can be used similarly to the electrodeposition tank. Further, in order to improve the heating efficiency, it is preferable that the electrodeposition bath circulating in the circulation tank forms a flow flowing around the heater. For this purpose, it is generally preferable to adopt a structure in which the electrodeposition bath is returned from the upper part of the circulation tank, and the heated electrodeposition bath is sent to the electrodeposition tank from the lower part. Further, by providing a plurality of paths for sending the electrodeposition bath to the electrodeposition tank, the heating efficiency can be further improved.

The drainage tank used in the electrodeposition apparatus according to the present invention has an internal capacity capable of holding at least all of the electrodeposition bath of the electrodeposition tank, and the capacity of the electrodeposition bath including the electrodeposition tank and the circulation tank is adjusted. More preferably, it is configured to be able to hold.
The drainage tank does not necessarily need to be heat-resistant, but is preferably made of a heat-resistant material such as an electrodeposition tank for the purpose of holding all the electrodeposition baths in an emergency.

The air stirring means used in the electrodeposition apparatus according to the present invention is such that the electrodeposition bath moves the electrodeposition bath so that the surface of the long substrate can be exchanged in the electrodeposition bath. When a substrate is used, it is configured such that an air pocket is not formed on the long substrate surface. As a specific air stirring means, for example, the air stirring means can be formed such that bubbles come into contact with the long substrate film formation surface from the orifice formed in the tube by buoyancy. This stirring is important particularly when the deposition rate is high, so that the electrodeposition bath is always fresh and touches the surface of the long substrate.

[Specific Configuration of Electrodeposition Apparatus] The specific configuration of the electrodeposition apparatus used when forming a transparent conductive layer made of a zinc oxide film or the like on a long substrate will be described in detail below with reference to the drawings. explain.

FIG. 2 is a configuration diagram showing a specific configuration of an electrodeposition apparatus used for forming a transparent conductive layer on a long substrate. 3 to 9 are enlarged views of each device constituting the electrodeposition apparatus shown in FIG. 2, FIG. 3 is an enlarged view of the unwinding apparatus, and FIG. 4 is a first electrodeposition tank and a first circulation unit. FIG. 5 is an enlarged view of a second electrodeposition tank and a second circulation tank, FIG. 6 is an enlarged view of a first drainage tank and a second drainage tank, and FIG. 7 is a pure water shower tank. , A first hot water tank, a second hot water tank, a drying unit, an enlarged view of a winding device, FIG. 8 is an enlarged view of a pure water heating tank, and FIG. 9 is an enlarged view of the vicinity of an exhaust duct.

As shown in FIG. 2, the electrodeposition apparatus according to one embodiment of the present invention is roughly divided into an unwinding device 2012 for feeding a long substrate 2006 wound in a coil shape, and a first electrodeposition device. First electrodeposition tank 206 for depositing or processing an deposited film
6, a second electrodeposition tank 2116 for depositing or processing a second electrodeposited film, a first circulation tank 2120 for circulating and supplying a heated electrodeposition bath to the first electrodeposition tank 2066, a second electrodeposition tank 21
A second circulating tank 2222 for circulating and supplying the electrodepositing bath heated to 16; a first drain tank 2172 for temporarily storing the electrodepositing bath in the first electrodepositing tank 2066; A second drainage tank 2274 for temporarily storing the electrodeposition bath when the electrodeposition bath of the electrodeposition bath 2116 is drained, and a powder for purifying the electrodeposition bath by removing powder in the electrodeposition bath in the first electrodeposition tank 2066. Filter circulation system (first electrodeposition tank filter circulation filter 216
1 (shown in detail in FIG. 4), a filter circulation system for removing powder in the electrodeposition bath in the second electrodeposition tank 2116 and cleaning the electrodeposition bath (second electrodeposition tank filter). A piping system using a circulation filter 2263 (shown in detail in FIG. 5), a piping system for sending compressed air for bath stirring to the first electrodeposition tank 2066 and the second electrodeposition tank 2116 (a pipe starting from the compressed air inlet 2182) System (shown in detail in FIGS. 4, 5, and 6), a pure water shower tank 2360 for cleaning the long substrate 2006 on which the electrodeposited film is deposited with a pure water shower, and first pure water rinse cleaning. First hot water tank 2361 for
Second hot water tank 236 for performing second pure water rinsing cleaning
2. A pure water heating tank 2339 for supplying hot water required for the hot water tanks 2361 and 2362, a drying unit 2363 for drying the washed long substrate 2006, and a long substrate on which film deposition has been completed. Winding device 2296 for winding coil 2006 again into a coil shape, an exhaust system for water vapor generated in a heating stage or a drying stage of an electrodeposition bath or pure water (electrodeposition washing exhaust duct 2020 or drying exhaust duct 237)
Exhaust system composed of 0 (shown in detail in FIGS. 4, 5, and 7)
It consists of

It should be noted that the long substrate 2006 is unrolled from left to right in FIG.
6, second electrodeposition tank 2116, pure water shower tank 2360, first hot water tank 2361, second hot water tank 2362, drying unit 236
3. Flowing in the order of the winding device 2296, a predetermined electrodeposited film is deposited.

[Unwinding Device] As shown in FIG. 3, the unwinding device 2012 is set with a coil-shaped long substrate 2006 wound on an unwinding device long substrate bobbin 2001.
The long substrate 2006 is sent out through the unwinding device feeding adjustment roller 2003, the unwinding device direction change roller 2004, and the unwinding device discharge roller 2005 in this order.

The coil-shaped long substrate 2006 is used especially when an undercoat layer is previously deposited.
Alternatively, in order to protect the layers, interleaf (interleaf paper) is supplied in a entangled form. For this reason, the unwinding device 2
012, the unwinding bobbin 20
02 is provided. Therefore, the long substrate 2006
When the interleaf is wound around the interleaf 2007, the interleaf 2007 is wound around the unwinding interleaf take-up bobbin 2002 with the unwinding of the long substrate 2006. The transport direction of the long substrate 2006 is indicated by an arrow 2010, the rotation direction of the unwinding device long substrate bobbin 2001 is indicated by an arrow 2009, and the winding direction of the unwinding device interleaf winding bobbin 2002 is This is indicated by arrow 2008.

The long substrate 2006 discharged from the unwinding device long substrate bobbin 2001 and the interleaf wound on the unwinding device interleaf winding bobbin 2002 are located at the position at the start of the transfer and the position at the end of the transfer, respectively. Interference does not occur. Also, the unwinding device 201
The entire structure 2 is covered with an unwinder clean booth 2011 using a hepa filter and a down flow for dust prevention.

[First Electrodeposition Tank] As shown in FIG. 4, the first electrodeposition tank 2066 is provided in a first electrodeposition bath holding tank 2065 capable of keeping the electrodeposition bath warm without corroding the electrodeposition bath. The temperature-controlled electrodeposition bath is held so as to be the first electrodeposition bath surface 2025.

The position of the first electrodeposition bath surface 2025 is realized by an overflow by a partition plate (not shown) provided in the first electrodeposition bath holding tank 2065. The partition plate is installed so as to drop the electrodeposition bath toward the back side in the entire first electrodeposition bath holding tank 2065, and the gutter structure collects and overflows the electrodeposition bath at the first electrodeposition tank overflow return port 2024. The deposition bath is the first electrodeposition tank overflow return path 2117
Through the first circulation tank 2120, where it is heated,
The first electrodeposition bath holding tank 2065 is again formed from the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe 2064.
To form an inflow of electrodeposition bath sufficient to promote overflow.

The long substrate 2006 passes through an electrodeposition tank turn-back roller 2013 (shown in FIG. 3), a first electrodeposition tank entrance roller 2014, a first electrodeposition tank exit roller 2015, and an electrodeposition tank turnover roller 2016. , First electrodeposition tank 2066
Pass through. A lower surface of the long substrate 2006 which is at least a film forming surface (hereinafter, referred to as a “front surface”) is provided between a first electrodeposition tank entrance roller 2014 and a first electrodeposition tank exit roller 2015. ) Are in the electrodeposition bath and face the 28 anodes 2026-2053. In actual deposition, while applying a negative potential to the long substrate 2006 and applying a positive potential to the anodes 2026 to 2053,
It is carried out by flowing an electrodeposition current involving an electrochemical reaction between the two in the electrodeposition bath.

The anode 20 in the first electrodeposition tank 2066
Reference numerals 26 to 2053 denote seven anode mounting tables 2054-2.
060 are placed on each of them. Each of the anode mounting tables 2054 to 2060 has a structure in which the respective anodes 2026 to 2053 are placed via an insulating plate, and a unique electric potential is applied from an independent power supply. Further, the anode mounting tables 2054 to 2060 are connected to the long substrate 2006 and the anodes 2026 to 2053 in the electrodeposition bath.
It also has the function of maintaining the interval between the two. Therefore, it is preferable that the anode mounting tables 2054 to 2060 are designed and manufactured so that the height can be adjusted so as to maintain a predetermined interval.

Immediately before the first electrodeposition roller 2015, a back electrode 2061 of the first electrodeposition tank is provided. The electrode 2061 on the back side of the first electrodeposition bath is
06 is for electrochemically removing the film deposited on the surface opposite to the film-forming surface (hereinafter referred to as “back surface (uramen)”). This is realized by setting the electrode 2061 on the back of the deposition tank to a negative potential. The fact that the back electrode 2061 of the first electrodeposition tank is actually effective is a film that electrochemically adheres to the back surface opposite to the film formation surface of the long substrate 2006 due to the wraparound of the electric field. It is confirmed that the film of the same material as that formed on the film forming surface is visually and visually removed.

The long substrate 2006 that passed through the first electrodeposition tank exit roller 2015 and exited from the electrodeposition bath was subjected to the electrodeposition bath from the first electrodeposition tank outlet shower 2067, and the film deposition surface was dried. To prevent unevenness. In addition, the cover 2019 between electrodeposition tanks provided at a transition portion between the first electrodeposition tank 2066 and the second electrodeposition tank 2116 also traps vapor generated from the electrodeposition bath, and the film formation surface of the long substrate 2006 is dried. Is prevented from doing so. Further, the second electrodeposition tank entrance shower 208
6 works similarly.

[First Circulation Tank] As shown in FIG. 4, the first circulation tank 2120 is responsible for heating and keeping the temperature of the electrodeposition bath in the first electrodeposition tank 2066 and for circulating the jet. As described above, the electrodeposition bath that overflowed in the first electrodeposition tank 2066 is collected at the first electrodeposition tank overflow return port 2024 and passed through the first electrodeposition tank overflow return path 2117,
First electrodeposition tank overflow return path insulation flange 2118
, And reaches the first circulation tank heating storage tank 2121. Eight first circulating tank heaters 2122 to 2129 are provided in the first circulating tank heating storage tank 2121, and are used for initial heating of the electrodeposition bath at room temperature or for the electrodeposition bath in which the bath temperature is reduced by circulation. Reheats to maintain the electrodeposition bath at a predetermined temperature.

Two circulation systems are connected to the first circulation tank heating storage tank 2121. That is, the first circulation tank electrodeposition bath upstream circulation source valve 2130, the first circulation tank electrodeposition bath upstream circulation pump 2132, the first circulation tank electrodeposition bath upstream circulation valve 21
35, first circulation tank electrodeposition bath upstream circulation flexible pipe 2
136, first circulation tank electrodeposition bath upstream circulation flange insulation pipe 2
137, a first electrodeposition tank upstream circulation recirculation system returning from the first electrodeposition tank upstream circulation jet pipe 2063 to the first electrodeposition bath holding tank 2065, a first circulation tank electrodeposition bath downstream circulation source valve 2139,
First circulation tank electrodeposition bath downstream circulation pump 2142, first circulation tank electrodeposition bath downstream circulation valve 2145, first circulation tank electrodeposition bath downstream circulation flexible pipe 2148, first circulation tank electrodeposition bath downstream circulation flange insulation pipe 2149 Through the first electrodeposition tank downstream circulation jet pipe 2064 to return to the first electrodeposition bath holding tank 2065.

The first electrodeposition tank 206 is circulated from the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe 2064.
The electrodeposition bath returned to 6 is upstream of the first electrodeposition tank provided below the first electrodeposition bath holding tank 2065 so as to make the exchange of the electrodeposition bath in the first electrodeposition bath holding tank 2065 effective. Circulating jet 2
063 and the circulating jet pipe 2064 downstream of the first electrodeposition tank are returned as jets through orifices formed in the respective jet pipes.

The amount of reflux in each circulation reflux system is mainly controlled by the degree of opening and closing of the first circulation tank electrodeposition bath upstream circulation valve 2135 or the first circulation tank electrodeposition bath downstream circulation valve 2145. A first circulation tank electrodeposition bath upstream circulation pump 2132 or a first circulation tank electrodeposition bath upstream circulation pump provided in a bypass system in which the outlet and the inlet of the first circulation tank electrodeposition bath downstream circulation pump 2142 are short-circuited and connected. The bypass valve 2133 or the first circulation tank electrodeposition bath downstream circulation pump bypass valve 2141 is controlled.

The bypass system also serves to prevent cavitation in the pump when the amount of reflux is reduced or when the bath temperature is very close to the boiling point. In other words, the cavitation in which the bath liquid evaporates and the liquid cannot be sent due to boiling vaporization shortens the life of the pump remarkably, and is prevented by the bypass system.

When an orifice is formed in the upstream circulation jet pipe 2063 of the first electrodeposition tank and the downstream circulation jet pipe 2064 of the first electrodeposition tank, the amount of reflux is determined by the upstream circulation jet pipe 2063 of the first electrodeposition tank. And the pressure of the bath solution returned to the circulation jet pipe 2064 downstream of the first electrodeposition tank. To know this,
A first circulation tank electrodeposition bath upstream circulation pressure gauge 2134 and a first circulation tank electrodeposition bath downstream circulation pressure gauge 2143 are provided, and the balance of the reflux amount is determined by these pressure gauges 213.
4,2143.

The amount of the reflux bath discharged from the orifice exactly follows Bernoulli's theorem.
In the case where the orifice bored in 064 has a diameter of several millimeters or less, the jet flow rate may be substantially constant over the entirety of the first electrodeposition tank upstream circulation jet pipe 2063 or the first electrodeposition tank downstream circulation jet pipe 2064. it can. Further, when the reflux amount is sufficiently large, the exchange of the electrodeposition bath is performed extremely smoothly. Therefore, even if the first electrodeposition tank 2066 is considerably long, it is necessary to make the concentration of the electrodeposition bath uniform and the temperature uniform. It can be achieved effectively. The first electrodeposition tank overflow return path 211
7 has a thickness that allows a sufficient reflux amount to flow.

The first circulation tank electrodeposition bath upstream circulation flexible pipe 2136 and the first circulation tank electrodeposition bath downstream circulation flexible pipe 2148 provided in each circulation reflux system are:
It absorbs distortion in the piping system, and is particularly effective when using flange-insulated piping or the like, which tends to have insufficient mechanical strength against distortion.

The first circulating tank electrodeposition bath upstream circulating flange insulating pipe 2137 and the first circulating tank electrodepositing bath downstream circulating flange insulating pipe 2149 provided in each circulating reflux system are connected to the first electrodeposition tank overflow return path 2117. Of the first electrodeposition tank overflow return path insulating flange 211 provided in the middle of
8, the first circulation tank 2120 and the first electrodeposition tank 2066 are electrically floated. This is based on the knowledge of the present inventors that by preventing formation of unnecessary current paths, stray current can be prevented and most of the deposited current can be used for an electrochemical film formation reaction. is there.

One of the circulation recirculation systems is a bypass recirculation system comprising a first circulation tank electrodeposition bath bypass circulation flexible pipe 2146 and a first circulation tank electrodeposition bath bypass circulation valve 2147 which return directly to the first circulation tank heating storage tank 2121. Is provided. This bypass recirculation system is provided with a first electrodeposition tank 2066.
When it is desired to circulate the electrodeposition bath without refluxing the bath solution, it is used, for example, when the temperature is raised from room temperature to a predetermined temperature.

The electrodeposition bath is applied to one of the circulation reflux systems from the first circulation tank 2066 to the long substrate 2006 that has passed through the first electrodeposition tank exit roller 2015 and exited from the electrodeposition bath. Liquid supply system to the first electrodeposition tank outlet shower 2067 for the purpose of the present invention is provided. This liquid feed system is connected to the first electrodeposition tank outlet shower 2067 via the first electrodeposition tank outlet shower valve 2150. First electrodeposition bath outlet shower 2
The amount of the electrodeposition liquid sprayed from 067 is adjusted by adjusting the degree of opening and closing of the first electrodeposition bath outlet shower valve 2150.

The first circulating tank heating storage tank 2121 is provided with a lid (not shown), and has a structure for preventing loss of water as steam. When the bath temperature is high, the temperature of the lid also increases. Therefore, it is necessary to consider, for example, attaching a heat insulating material to the surface of the lid from the viewpoint of work safety.

A filter circulation system is provided to remove the powder in the electrodeposition bath of the first electrodeposition tank. First electrodeposition tank 2
066, the first electrodeposition tank filter circulation return flexible pipe 2151, the first electrodeposition tank filter circulation return flange insulating pipe 2152, the first electrodeposition tank filter circulation source valve 2154, the first electrodeposition tank filter circulation. Suction filter 2156, first electrodeposition tank filter circulation pump 2157, first electrodeposition tank filter circulation pump bypass valve 2158, first electrodeposition tank filter circulation pressure switch 2159, first electrodeposition tank filter circulation pressure gauge 2160, first electrodeposition tank filter Electrodeposition tank filter circulation filter 2161, first electrodeposition tank filter circulation flexible pipe 2164, first electrodeposition tank filter circulation flange insulating pipe 2165, first electrodeposition tank filter circulation valve 2166, first electrodeposition tank filter circulation system Precipitation bath upstream return valve 2167, First electrodeposition tank filter circulation system electrodeposition bath midstream return valve 2168, which is from the first electrodeposition vessel filter circulation system electrodeposition bath downstream return valve 2169,.

The electrodeposition bath flows along this path in the direction of the first electrodeposition tank filter circulation 2155, 2162 and 2163. The powder to be removed may jump in from outside the machine, or may be formed on the electrode surface or in a bath depending on the electrodeposition reaction. The minimum size of the powder to be removed is determined by the first electrodeposition tank filter circulation filter 216.
It is determined by the filter size of 1.

The first electrodeposition tank filter circulation return flexible pipe 2151 and the first electrodeposition tank filter circulation flexible pipe 2164 absorb the distortion of the piping,
The purpose is to minimize liquid leakage from the pipe connection portion, protect insulating pipes having poor mechanical strength, and increase the degree of freedom in arranging components of a circulation system such as a pump.

The first electrodeposition tank filter circulation return flange insulating pipe 2152 and the first electrodeposition tank filter circulation flange insulation pipe 2165 are used to prevent the first electrodeposition bath holding tank 2065, which has been floated from the earth ground, to fall to the earth ground. It is intended to float electrically to prevent it.

The first electrodeposition tank filter circulating suction filter 2156 is a wire mesh such as a so-called “tea strainer” for removing large debris, and following the first electrodeposition tank filter circulation pump 2157 and the first electrodeposition tank filter. This is for protecting the circulation filter 2161.

First electrodeposition tank filter circulation filter 21
Numeral 61 is a main part of this circulation system, and is for removing powder mixed or generated in the electrodeposition bath.

The circulation flow rate of the electrodeposition bath of the present circulation system is finely adjusted mainly by the first electrodeposition tank filter circulation valve 2166, and is provided in parallel with the first electrodeposition tank filter circulation pump 2157. Fine adjustment is made by the first electrodeposition tank filter circulation pump bypass valve 2158. A first electrodeposition tank filter circulating pressure gauge 2160 is provided to grasp the circulating flow rate due to these valve adjustments. Also, the first electrodeposition tank filter circulation pump bypass valve 2158 prevents fine adjustment of the flow rate as well as damage to the first electrodeposition tank filter circulation pump 2157 due to cavitation when the entire filter circulation flow rate is reduced. Preventing.

[First drainage tank] As shown in FIGS. 4 and 6, the first electrodeposition tank filter circulation return flange insulating pipe 2152
, The electrodeposition bath can be transferred from the first electrodeposition tank drain valve 2153 to the first liquid drainage tank 2172. This transfer is performed for electrodeposition bath replacement, maintenance of the electrodeposition apparatus, and in an emergency. The electrodeposition bath as the drainage to be transferred is dropped to the first drainage drainage storage tank 2144 by gravity drop. For maintenance and emergency purposes, it is preferable that the first drainage tank drainage storage tank 2144 has a capacity sufficient to store the total bath capacity of the first electrodeposition tank 2066 and the first circulation tank 2120. First drainage tank drainage storage tank 2144
Is provided with a first drainage tank drainage tank upper lid 2277, and a first drainage tank air vent 2171 and a first drainage tank air vent valve in order to make the gravity drop transfer of the electrodeposition bath effective. 2170 are provided.

As shown in FIG. 6, after the temperature of the electrodeposition bath once dropped into the first drainage tank drainage storage tank 2144 is lowered, the wastewater treatment on the building side is performed by the first drainage tank drainage valve 2173. It is sent to a facility or is collected in a drum (not shown) via a first drainage tank drainage recovery valve 2174, a drainage recovery source valve 2175, a drainage recovery suction filter 2176, and a drainage recovery pump 2177. Disposition takes place. Prior to collection and disposal, dilution with water, treatment with a chemical solution, and the like may be performed in the first drainage tank drainage storage tank 2144.

[Agitating Air Introducing Means] As shown in FIG.
In order to stir the electrodeposition bath and equalize the film deposition, a plurality of orifices drilled in the first electrodeposition tank stirring air introduction pipe 2062 installed at the bottom of the first electrodeposition bath holding tank 2065,
Air bubbles are blown out.

The air serving as the air bubble takes compressed air supplied to the factory through a compressed air inlet 2182 (shown in FIG. 6) and presses the compressed air pressure switch 218 for stirring the electrodeposition bath.
3 and in the direction indicated by the first electrodeposition tank compressed air introduction direction 2184 in the order shown in FIG.
5, first electrodeposition tank compressed air flow meter 2186, first electrodeposition tank compressed air regulator 2187, first electrodeposition tank compressed air mist separator 2188, first electrodeposition tank compressed air introduction valve 2189, first electrodeposition tank The first electrodeposition tank passes through a compressed air flexible pipe 2190, a first electrodeposition tank compressed air insulation pipe 2191, and a first electrodeposition tank compressed air upstream control valve 2193 or a first electrodeposition tank compressed air downstream control valve 2192. It reaches the stirring air introduction pipe 2062.

The long substrate 2006 conveyed to the second electrodeposition tank 2116 through the inter-electrodeposition tank return roller 2016 is deposited or treated with a second electrodeposition film. The second electrodeposition film is the same as the first electrodeposition film, but the first electrodeposition film and the second electrodeposition film may form one film, or the same material It may be a two-layer laminate with different properties (for example, a layer of zinc oxide with different particle sizes) or a two-layer laminate with the same properties but different materials. In some cases, for example, the transparent conductive film may be a stack of indium oxide and zinc oxide, or may be a completely different stack of two layers.

Further, a low oxide is deposited in the first electrodeposition tank 2066, an oxidation progressing treatment is performed in the second electrodeposition tank 2116, or a low oxide is deposited in the first electrodeposition tank 2066, and a second electrodeposition is performed. It is possible to perform a combination such as performing an etching process in the analysis tank 2116.

Therefore, electrodeposition or treatment conditions such as an electrodeposition bath or treatment bath, bath temperature, bath circulation amount, current density, and stirring amount are selected according to each purpose. For example,
When it is necessary to change the electrodeposition or processing time between the first electrodeposition tank 2066 and the second electrodeposition tank 2116, the long substrate 20
06 was passed through the first electrodeposition tank 2066 and the second electrodeposition tank 21.
You can change it with 16. For this purpose, the first electrodeposition tank 20
The length is adjusted by changing the length of the tank between the first electrode 66 and the second electrodeposition tank 2116 or by turning the long substrate 2006 back.

[Second electrodeposition bath] As shown in FIG. 5, the second electrodeposition bath 2116 has a second electrodeposition bath holding tank 2115 which can keep the electrodeposition bath warm without corroding the electrodeposition bath. In addition, the temperature-controlled electrodeposition bath is held so as to be the second electrodeposition bath surface 2025.

The position of the second electrodeposition bath surface 2025 is realized by an overflow by a partition plate (not shown) provided in the second electrodeposition bath holding tank 2115. The partition plate is installed so as to drop the electrodeposition bath toward the back side in the entire second electrodeposition bath holding tank 2115, and the gutter structure collects and overflows the electrodeposition bath at the second electrodeposition tank overflow return port 2075. The deposition bath is provided with a second electrodeposition tank overflow return path 2219.
To reach the second circulation tank 2222, where it is heated,
The second electrodeposition bath holding tank 2115 is again formed from the second electrodeposition tank upstream circulation jet pipe 2113 and the second electrodeposition tank downstream circulation jet pipe 2114.
To form an inflow of electrodeposition bath sufficient to promote overflow.

The long substrate 2006 is provided with a folding roller 2016 (shown in FIG. 4) between the electrodeposition tanks, a second electrodeposition tank entry roller 2069, a second electrodeposition tank exit roller 2070, and a pure water shower tank return entry roller 2279. After that, it passes through the inside of the second electrodeposition tank 2116.

The long substrate 2006 is inserted between the second electrode 2069 and the second electrode 2070.
Is located in the electrodeposition bath and faces the 28 second electrodeposition tank anodes 2076 to 2103. The actual deposition is performed by applying a negative potential to the long substrate 2006 and applying a positive potential to the anode, and flowing an electrodeposition current involving an electrochemical reaction between the two in the electrodeposition bath. .

The anode 20 in the second electrodeposition tank 2116
76 to 2103 are the seven second electrodeposition tank anode mounting tables 2
Four pieces are placed on each of 104 to 2110. Each of the anode mounting tables 2104 to 2110 has a structure in which the respective anodes 2076 to 2103 are placed via an insulating plate, and a unique electric potential is applied from an independent power supply. In addition, anode mounting tables 2104 to 2110
Is a long substrate 2006 and an anode 2076 ~ in an electrodeposition bath.
It also has the function of maintaining the interval with the reference numeral 2103. For this reason, it is preferable that the anode mounting tables 2104 to 2110 are designed and manufactured so that the height can be adjusted so as to maintain a predetermined interval.

The second electrode on the back side of the second electrodeposition tank 2111 provided immediately before the second electrodeposition roller 2070 electrochemically removes the film deposited on the backside of the long substrate 2006 in the electrodeposition bath. This is realized by setting the back electrode 2111 of the second electrodeposition tank to a negative potential with respect to the long substrate 2006. The fact that the back electrode 2111 of the second electrodeposition tank is actually effective is that the long substrate 20
A film that is electrochemically attached to the back surface opposite to the film-forming surface of the substrate 06 and is formed of the same material as that formed on the film-forming surface of the long substrate 2006 is visually removed. It is confirmed by

The long substrate 2006 that has passed through the second electrodeposition tank exit roller 2070 and exited from the electrodeposition bath is subjected to an electrodeposition bath from the second electrodeposition tank outlet shower 2297 to dry the film forming surface. To prevent unevenness. In addition, a pure water shower tank folded entry roller cover 23 provided at a transition portion between the second electrodeposition tank 2116 and the pure water shower tank 2360.
18 also traps the vapor generated from the electrodeposition bath and prevents the deposition surface of the long substrate 2006 from drying. Further, the pure water shower tank entrance surface pure water shower 2299 and the pure water shower tank entrance rear pure water shower 2300 (shown in FIG. 7) not only wash and remove the electrodeposition bath but also perform the same function.

[Second Circulation Tank] As shown in FIG. 5, the second circulation tank 2222 serves to heat and keep the electrodeposition bath in the second electrodeposition tank 2116 and to circulate the jet. As described above, the electrodeposition bath overflowed in the second electrodeposition tank 2116 is collected at the second electrodeposition tank overflow return port 2075, passes through the second electrodeposition tank overflow return path 2219, and
Second electrodeposition tank overflow return path insulation flange 2220
, And reaches the second circulation tank heating storage tank 2223. Eight second circulating tank heaters 2224 to 2231 are provided in the second circulating tank heating storage tank 2223, and are used when initially heating the electrodeposition bath at room temperature or when the bath temperature is reduced by circulation. Reheats to maintain the electrodeposition bath at a predetermined temperature.

The second circulation tank heating storage tank 2223 is connected with two circulation systems. That is, the second circulation tank electrodeposition bath upstream circulation source valve 2232, the second circulation tank electrodeposition bath upstream circulation pump 2234, the second circulation tank electrodeposition bath upstream circulation valve 22
37, Flexible pipe 2 circulating upstream of the electrodeposition bath in the second circulation tank
238, 2nd circulation tank electrodeposition bath upstream circulation flange insulation pipe 2
239, a second electrodeposition tank upstream circulation recirculation system returning from the second electrodeposition tank upstream circulation jet pipe 2113 to the second electrodeposition bath holding tank 2115, a second circulation tank electrodeposition bath downstream circulation source valve 2242,
Second circulation tank electrodeposition bath downstream circulation pump 2245, second circulation tank electrodeposition bath downstream circulation valve 2247, second circulation tank electrodeposition bath downstream circulation flexible pipe 2248, second circulation tank electrodeposition bath downstream circulation flange insulation pipe 2249 Through the second electrodeposition tank downstream circulation circulation jet pipe 2114 to return to the second electrodeposition bath holding tank 2115.

The second electrodeposition tank 211 is formed from the upstream circulation jet pipe 2113 and the downstream circulation jet pipe 2114 of the second electrodeposition tank.
The electrodeposition bath returning to 6 is provided upstream of the second electrodeposition bath provided below the second electrodeposition bath holding tank 2115 so that the exchange of the electrodeposition bath in the second electrodeposition bath holding tank 2115 can be effectively performed. Circulating jet 2
From the 113 and the second electrodeposition tank downstream circulating jet pipe 2114, it is recirculated as a jet via orifices formed in each jet pipe.

The amount of reflux in each circulation reflux system is controlled mainly by the opening / closing degree of the second circulation tank electrodeposition bath upstream circulation valve 2237 or the second circulation tank electrodeposition bath downstream circulation valve 2247. A second circulation tank electrodeposition bath upstream circulation pump 2234 or a second circulation tank electrodeposition bath upstream circulation pump provided in a bypass system in which the outlet and the inlet of the second circulation tank electrodeposition bath downstream circulation pump 2245 are short-circuited and connected. The bypass valve 2235 or the second circulation tank electrodeposition bath downstream circulation pump bypass valve 2244 is controlled.

The bypass system also serves to prevent cavitation in the pump when the amount of reflux is reduced or when the bath temperature is very close to the boiling point. As described in the description of the first electrodeposition tank 2066, the cavitation in which the bath liquid evaporates and the liquid cannot be sent due to the evaporation of the bath liquid is remarkably shortened in the service life of the pump. .

When an orifice is formed in the upstream circulation jet pipe 2113 of the second electrodeposition tank and the downstream circulation jet pipe 2114 of the second electrodeposition tank to form a jet, the amount of recirculation is equal to that of the upstream circulation jet pipe 2113 of the second electrodeposition tank. It is almost determined by the pressure of the bath liquid returned to the downstream circulation jet pipe 2114 of the second electrodeposition tank. In order to know this, a second circulation tank electrodeposition bath upstream circulation pressure gauge 2236 and a second circulation tank electrodeposition bath downstream circulation pressure gauge 2246 are provided.
2246.

The amount of the reflux bath blown out from the orifice exactly follows Bernoulli's theorem.
When the orifice drilled in 114 has a diameter of several millimeters or less,
The jet flow rate can be made substantially constant over the whole of the second electrodeposition tank upstream circulation jet pipe 2113 to the second electrodeposition tank downstream circulation jet pipe 2114. Further, when the reflux amount is sufficiently large, the exchange of the electrodeposition bath is performed extremely smoothly. Therefore, even if the second electrodeposition tank 2116 is considerably long, it is necessary to make the concentration of the electrodeposition bath uniform and the temperature uniform. It can be achieved effectively. The second electrodeposition tank overflow return path 2219
Has a thickness that allows a sufficient reflux amount to flow.

The second circulation tank electrodeposition bath upstream circulation flexible pipe 2238 and the second circulation tank electrodeposition bath downstream circulation flexible pipe 2248 provided in each circulation reflux system are
It absorbs distortion in the piping system, and is particularly effective when using flange-insulated piping or the like, which tends to have insufficient mechanical strength against distortion.

The second circulation tank electrodeposition bath upstream circulation flange insulation pipe 2239 and the second circulation tank electrodeposition bath downstream circulation flange insulation pipe 2249 provided in each circulation reflux system are connected to the second electrodeposition tank overflow return path 2219. Second electrodeposition tank overflow return path insulating flange 222 provided in the middle of
In addition to 0, the second circulation tank 2222 and the second electrodeposition tank 2116 are electrically floated. This is based on the knowledge of the present inventors that by preventing formation of unnecessary current paths, stray current can be prevented and most of the deposited current can be used for an electrochemical film formation reaction. is there.

One of the circulation recirculation systems is a bypass recirculation system comprising a second circulation tank electrodeposition bath bypass circulation flexible pipe 2250 and a second circulation tank electrodeposition bath bypass circulation valve 2251 which returns directly to the second circulation tank heating storage tank 2223. Is provided. This bypass reflux system is provided in the second electrodeposition tank 2116.
When it is desired to circulate the electrodeposition bath without refluxing the bath solution, it is used, for example, when the temperature is raised from room temperature to a predetermined temperature.

In addition, the two circulation circulation system from the second circulation tank 2166 has a second electrodeposition tank entrance shower for applying an electrodeposition bath to the long substrate 2006 immediately before reaching the second electrodeposition tank entrance roller 2069. And a long substrate 20 that has passed through the second electrodeposition tank exit roller 2070 and exited from the electrodeposition bath.
Electrodeposition bath outlet shower 2 for applying an electrodeposition bath to 06
297 are provided. The former liquid feeding system is connected to a second electrodeposition tank inlet shower 2068 via a second electrodeposition tank inlet shower valve 2241, and the latter liquid feeding system is connected to a second electrodeposition tank outlet shower valve 2252.
Through the second electrodeposition tank outlet shower 2297.

The spray amount of the electrodeposition liquid from the second electrodeposition tank inlet shower 2068 is equal to the second electrodeposition tank inlet shower valve 2241.
And the amount of the deposited liquid sprayed from the second electrodeposition tank outlet shower 2297 is adjusted by adjusting the degree of opening and closing of the second electrodeposition tank outlet shower valve 2252.

The second circulating tank heating storage tank 2223 is provided with a lid (not shown), and has a structure for preventing loss of water as steam. When the bath temperature is high, the temperature of the lid also increases. Therefore, it is necessary to consider, for example, attaching a heat insulating material to the surface of the lid from the viewpoint of work safety.

A filter circulation system is provided for removing powder in the electrodeposition bath of the second electrodeposition tank. Second electrodeposition tank 2
The filter circulation system for 116 includes a second electrodeposition tank filter circulation return flexible pipe 2253, a second electrodeposition tank filter circulation return flange insulating pipe 2254, a second electrodeposition tank filter circulation source valve 2256, and a second electrodeposition tank filter circulation. Suction filter 2258, second electrodeposition tank filter circulation pump 2260, second electrodeposition tank filter circulation pump bypass valve 2259, second electrodeposition tank filter circulation pressure switch 2261, second electrodeposition tank filter circulation pressure gauge 2262, second electrode Electrodeposition tank filter circulation filter 2263, second electrodeposition tank filter circulation flexible pipe 2266, second electrodeposition tank filter circulation flange insulation pipe 2267, second electrodeposition tank filter circulation valve 2268, second electrodeposition tank filter circulation system Precipitation bath upstream return valve 2269, Second electrodeposition vessel filter circulation system electrodeposition bath midstream return valve 2270, which is from the second electrodeposition vessel filter circulation system electrodeposition bath downstream return valve 2271.

The electrodeposition bath flows in this path in the direction of circulation in the second electrodeposition tank filter 2257, 2264 and 2265. The powder to be removed may jump in from outside the machine, or may be formed on the electrode surface or in a bath depending on the electrodeposition reaction. The minimum size of the powder to be removed is the second electrodeposition tank filter circulation filter 226.
It is determined by the filter size of 3.

The second electrodeposition tank filter circulation return flexible pipe 2253 and the second electrodeposition tank filter circulation flexible pipe 2266 absorb the distortion of the piping,
The purpose is to minimize liquid leakage from the pipe connection portion, protect insulating pipes having poor mechanical strength, and increase the degree of freedom in arranging components of a circulation system such as a pump.

The second electrodeposition tank filter circulating return flange insulating pipe 2254 and the second electrodeposition tank filter circulating flange insulating pipe 2267 are used to prevent the second electrodeposition bath holding tank 2115, which has been floated from earth ground, to fall to earth ground. It is intended to float electrically to prevent it.

The second electrodeposition tank filter circulating suction filter 2258 is a wire mesh such as a so-called “tea strainer” for removing large debris, and following the second electrodeposition tank filter circulation pump 2260 and the second electrodeposition tank filter. This is for protecting the circulation filter 2263.

Second Electrodeposition Tank Filter Circulation Filter 22
Numeral 63 is a main part of this circulation system, and is for removing powder mixed or generated in the electrodeposition bath.

The circulation flow rate of the electrodeposition bath in this circulation system is finely adjusted mainly by the second electrodeposition tank filter circulation valve 2268, and is provided in parallel with the second electrodeposition tank filter circulation pump 2260. Fine adjustment is made by the second electrodeposition tank filter circulation pump bypass valve 2259. A second electrodeposition tank filter circulating pressure gauge 2262 is provided to grasp the circulating flow rate by adjusting these valves. Also, the second electrodeposition tank filter circulation pump bypass valve 2259 can be used for fine adjustment of the flow rate and for preventing the second electrodeposition tank filter circulation pump 2260 from being damaged due to cavitation when the entire filter circulation flow rate is reduced. Preventing.

[Second drainage tank] As shown in FIGS. 5 and 6, the second electrodeposition tank filter circulation return flange insulating pipe 2254
, The electrodeposition bath can be transferred from the second electrodeposition tank drain valve 2255 to the second liquid drainage tank 2274. This transfer is performed for electrodeposition bath replacement, maintenance of the electrodeposition apparatus, and in an emergency. The electrodeposition bath as the drainage to be transferred is dropped into the second drainage drainage storage tank 2273 by gravity drop. For maintenance and emergency purposes,
It is preferable that the second drainage tank 2273 has a capacity enough to store the total bath capacity of the second electrodeposition tank 2116 and the second circulation tank 2222. Second drain tank drain storage tank 227
3 is provided with a second drainage tank drainage tank upper lid 2278, and a second drainage tank air vent 2276 and a second drainage tank air vent in order to make the gravity drop transfer of the electrodeposition bath effective. A valve 2275 is provided.

As shown in FIG. 6, after the temperature of the electrodepositing bath once dropped in the second drainage tank drainage storage tank 2273 is lowered, the wastewater treatment on the building side from the second drainage tank drainage valve 2180 is performed. It is sent to a facility or is collected in a drum (not shown) via a second drainage tank drainage recovery valve 2181, a drainage recovery source valve 2175, a drainage recovery suction filter 2176, and a drainage recovery pump 2177, and Disposition takes place. Prior to collection and disposal, dilution with water, treatment with a chemical solution, and the like may be performed in the second drainage tank 2273.

[Agitating Air Introducing Means] As shown in FIG.
In order to stir the electrodeposition bath and to make the film deposition uniform, air bubbles are blown out from a plurality of orifices formed in the second electrodeposition tank stirring air introduction pipe 2112 installed at the bottom of the second electrodeposition bath holding tank 2115. Squirt.

The air serving as an air bubble takes in compressed air supplied to the factory from a compressed air inlet 2182 (shown in FIG. 6), and presses a compressed air pressure switch 218 for stirring the electrodeposition bath.
3, the second electrodeposition tank compressed air source valve 219 in the direction indicated by the second electrodeposition tank compressed air introduction direction 2194.
5, second electrodeposition tank compressed air flow meter 2196, second electrodeposition tank compressed air regulator 2197, second electrodeposition tank compressed air mist separator 2198, second electrodeposition tank compressed air introduction valve 2199, second electrodeposition tank The second electrodeposition tank passes through the compressed air flexible pipe 2220, the second electrodeposition tank compressed air insulation pipe 2201, and the second electrodeposition tank compressed air upstream control valve 2202 or the second electrodeposition tank compressed air downstream control valve 2272. It reaches the stirring air introduction pipe 2112.

[Preliminary Introducing System] As shown in FIGS. 4, 5, and 6, a preliminary introducing system is provided in the first electrodeposition tank 2066 and the second electrodeposition tank 2116 so that a preliminary liquid or gas can be introduced. is set up. The liquid or gas from the electrodeposition tank pre-introduction port 2213 passes through the electrodeposition tank pre-introduction valve 2214, passes through the first electrodeposition tank pre-introduction valve 2215, passes through the first electrodeposition tank pre-introduction insulation pipe 2216, and the first electrode. It is sent to the precipitation tank 2066. Similarly, the liquid or gas from the electrodeposition tank preliminary introduction port 2213 passes through the electrodeposition tank preliminary introduction valve 2214, the second electrodeposition tank preliminary introduction valve 2217, and the second electrodeposition tank preliminary introduction insulating pipe 2218. It is sent to the second electrodeposition tank 2116.

The most probable pre-introduction system is a holding agent or replenisher for keeping the performance of the electrodeposition bath constant for a long time. In some cases, however, a gas dissolved in the electrodeposition bath may be used. Or an acid that removes powder.

[Rinse] As shown in FIG. 7, the rinse step according to the present invention is performed in three stages: a pure water shower tank 2360, a first hot water tank 2361, and a second hot water tank 2362. In this rinsing step, heated pure water is supplied to the second hot water tank 2362, the drainage thereof is used in the first hot water tank 2361, and the drainage is used in the pure water shower tank 2360. ing. As a result, the long substrate 20
06 is gradually washed with high-purity water after completion of the electrodeposition in the electrodeposition tank. In addition, with such a configuration, the electric conductivity in at least the second hot water tank 2362 is always 150 μS / cm or less, preferably 1 μS / cm.
/ Cm or less, but a pure water shower tank 2360, a first hot water tank 2361, and a second hot water tank 236.
Preferably, all of the two are managed in this way.

This pure water is a pure water shower 2309 at the back surface of the outlet of the second hot water tank immediately before the elongate substrate 2006 exits.
It is supplied to the pure water shower 2310 on the outlet surface of the second hot water tank.

As shown in FIG. 8, pure water to be supplied is supplied from a rinse pure water inlet 2337 to a rinse pure water supply source valve 233.
8 and once stored in a pure water heating tank 2339, heated to a predetermined temperature by pure water heating tank pure water heaters 2340 to 2343, a pure water heating tank pure water delivery valve 2344, a pure water heating tank pure water delivery pump 2346, pure water heating tank pressure switch 2347, pure water heating tank cartridge type filter 234
9, through the pure water heating tank flow meter 2350, one reaches from the second hot water tank outlet backside shower valve 2351 to the second hot water tank outlet backside pure water shower 2309 (shown in FIG. 7), and the other is the second hot water tank outlet From the surface shower valve 2352 to the second hot water tank outlet surface pure water shower 2310 (shown in FIG. 7). The reason why the pure water is heated is to improve the cleaning effect.

[0119] As shown in FIG.
Pure water supplied to 310 and stored in the second hot water tank hot water holding tank 2317 forms a pure water rinsing bath. Here, the long substrate 2006 is washed with still water. In addition, in order to prevent the temperature of the pure water from dropping, the second hot water tank 2361 is used.
Is provided with a second hot water tank warm water keeping heater 2307.

The pure water overflowing from the second hot water tank 2317 is supplied to the first hot water tank 2361.
Is supplied to the first hot water tank hot water holding tank 2362 through the hot water tank connecting pipe 2232 provided in the first hot water tank. In the first hot water tank hot water holding tank 2362, similarly to the second hot water tank 2317, a first hot water tank hot water holding heater 2304 is installed,
It keeps the temperature of pure water. Further, an ultrasonic source 2306 is provided in the first hot water tank 2361, and positively removes dirt on the surface of the long substrate 2006 by using the first hot water tank roller 2282 and the second hot water tank return entry roller 2.
283.

As shown in FIG. 8, the pure water from the first hot water tank hot water holding tank 2316 is supplied to a pure water shower tank pure water shower supply valve 2323, followed by a pure water shower tank pure water shower supply pump 2325, A pure water shower tank pure water shower supply pressure switch 2326, a pure water shower tank pure water shower supply cartridge type filter 2328, a pure water shower tank pure water shower supply flow meter 2329, and a pure water shower tank entrance surface pure water shower valve 2330. To pure water shower tank entrance surface pure water shower 2299 (shown in FIG. 7)
Along with the pure water shower tank inlet back surface pure water shower valve 2331 to the pure water shower tank inlet back surface pure water shower 2300 (shown in FIG. 7).

The pure water is sent from the pure water shower tank outlet back surface pure water shower valve 2332 to the pure water shower tank outlet back surface pure water shower 2302 (shown in FIG. 7), and the pure water shower tank outlet surface pure surface Water shower valve 2
333 to pure water shower tank outlet surface pure water shower 230
3 (shown in FIG. 7).

Then, as shown in FIG. 7, the long substrate 2006
A washing shower flow is applied to the front and back surfaces of the cleaning device.

The water after the shower is received in a pure water shower tank receiving tank 2315, and is directly received in the first hot water tank hot water holding tank 215.
316 and a part of the second hot water tank hot water holding tank 2317 are merged and discarded in the washing system drainage 2336. Normally, since the washed water contains ions and the like, a predetermined treatment is required.

In the pure water shower tank 2360, the first hot water tank 2361, and the second hot water tank 2362 for cleaning, the long substrate 2006
9, pure water shower tank roller 2280, first hot water tank return entry roller 2281, first hot water tank roller 228
2. It is sent to the second hot water tank return entry roller 2283, the second hot water tank roller 2284, and the dry return roller 2285. Immediately after the pure water shower tub turning-back roller 2279, the pure water shower tub back brush 229 is disposed.
8 are provided so as to remove relatively large powders and products having low adhesiveness attached to the back surface of the long substrate 2006.

The long substrate 2006 which reached the drying unit 2363
First, the air knife 23 on the back side of the drying section entrance at the drying section entrance
11. Draining is performed by the air knife 2312 on the drying unit entrance surface. As shown in FIG. 8, the introduction of air into the air knife is performed by a drying system compressed air inlet 2353, a drying system compressed air pressure switch 2354, a drying system compressed air filter regulator 2355, a drying system compressed air mist separator 2356, and a drying system compressed air. Supply valve 2357
Through the path of the drying section inlet back surface air knife valve 2358 or the drying section inlet front surface air knife valve 2359.

Since the air supplied to the drying unit 2363 is inconvenient if it particularly contains water droplets, the role of the drying system compressed air mist separator 2356 is important. That is, water supplied to the drying unit 2363 is removed by the drying system compressed air mist separator 2356.

As shown in FIG. 7, the long substrate 2006
Subsequently, in the process of being conveyed from the drying turn-back roller 2285 to the take-up device entry roller 2286, the I
Drying is performed by the radiant heat of the R lamp 2313. I
If the radiant heat of the R lamp 2313 is sufficient, there is no inconvenience even if the long substrate 2006 is put into a vacuum device such as a CVD device after forming the electrodeposited film. At the time of drying the long substrate 2006, since there is generation of fog due to draining and generation of water vapor due to IR lamp radiation, the drying section exhaust port 2314 connected to the exhaust duct is indispensable.

[0129] As shown in FIG.
Most of the water vapor collected in 70 is returned to water in the drying condenser 2371, and the drying condenser drainage drain 23
It is discarded to 73 and a part is discarded to drying system exhaust 2374. When the vapor contains a harmful gas, the exhaust gas should be subjected to a predetermined treatment.

[Winding device] As shown in FIG. 7, the winding device 2296 includes a winding device entering roller 2286, a winding device direction changing roller 2287, and a winding adjusting roller 22.
The long substrate 2006 is wound in a coil shape on the long substrate winding bobbin 2289 in this order. Further, the take-up device 2296 is provided with an inter-leaf feeding bobbin 2290. When protection of the deposited layer is required, the inter-leaf feeding bobbin 229 is provided.
The interleaf is extended from 0 and is wound around the long substrate 2006.

The transport direction of the long substrate 2006 is indicated by an arrow 22.
The rotation direction of the long substrate winding bobbin 2289 is indicated by an arrow 2293, and the winding direction of the interleaf feeding bobbin 2290 is indicated by an arrow 2294. In FIG. 7, a long substrate winding bobbin 2289 is provided.
The long substrate 2006 that is wound up and the interleaf that is fed out from the interleaf feeding bobbin 2290 do not interfere with each other at the position at the start of conveyance and the position at the end of conveyance. Also, the winding device 229
6 is covered with a take-up device clean booth 2295 using a hepa filter and a down flow for dust prevention.

The winding device direction changing roller 2287 provided in the winding device 2296 has a function of correcting the meandering of the long substrate 2006. That is, based on a signal from a meandering detector (not shown) provided between the winding device direction changing roller 2287 and the winding adjustment roller 2288, the winding device direction changing roller 2 is controlled by hydraulic servo.
By waving 287 about the axis set on the winding device entrance roller 2286 side, the meandering can be corrected.

The control of the winding device direction change roller 2287 is approximately the movement of the roller to the near side or the back side in FIG. 7, and the direction of the movement is determined by detecting the long board meandering from the meandering detector. The direction is opposite. The servo gain depends on the transport speed of the long substrate 2006, but generally does not need to be large. Even when a long substrate 2006 having a length of several hundred meters is wound up, its end faces are aligned with sub-millimeter accuracy.

[Exhaust Duct] When an electrodeposition bath or hot water is used at a temperature higher than room temperature, steam is inevitably generated. Especially 80
At temperatures above ℃, the evolution of water vapor is considerable. The water vapor generated from the bath surface of the tank accumulates on the bath surface of the bath and blows out vigorously from the gap of the electrodeposition device,
When the lid is opened and closed, a large amount of discharge is seen, and water drops from gaps in the electrodeposition apparatus to flow down, thereby deteriorating the operating environment of the electrodeposition apparatus. Therefore, the electrodeposition water washing system exhaust duct 20
It is preferable to forcibly suck and exhaust the air through the exhaust pipe 20.

As shown in FIG. 4, the first electrodeposition tank 2066 has a first electrodeposition tank upstream exhaust port 2021, a first electrodeposition tank midstream exhaust port 2022, and a first electrodeposition tank downstream exhaust port 2023. An effluent duct 2020 is connected to the rinsing water washing system.

Further, as shown in FIG.
16 second electrodeposition tank upstream exhaust port 2071, second electrodeposition tank midstream exhaust port 2072, and second electrodeposition tank downstream exhaust port 2073,
An electrodeposition water washing system exhaust duct 2020 is connected in communication.

Further, as shown in FIG. 9, a pure water shower tank exhaust port 2301 of the pure water shower tank 2360, a first hot water tank exhaust port 2305 of the first hot water tank 2361, and a second hot water tank 2
The second hot water tank exhaust port 2308 362 is connected to an electrodeposition water washing system exhaust duct 2020.

As shown in FIG. 9, the water vapor collected in the electrodeposition water washing system exhaust duct 2020 is supplied to the insulating flange 2365.
Most of the water returns to the water in the electrodeposition washing system exhaust duct condenser 2366, and is discarded to the electrodeposition washing system exhaust duct condenser drainage drain 2368, and part of the electrodeposition washing system exhaust system 23
It is thrown away to 69. When the vapor contains a harmful gas, the exhaust gas should be subjected to a predetermined treatment.

In the electrodeposition apparatus according to this embodiment, since the exhaust duct 2020 is made of stainless steel, the first electrodeposition bath holding tank 2065 of the first electrodeposition tank 2066 and the second electrodeposition tank of the second electrodeposition tank 2116 are formed of stainless steel. In order to make the electrodeposition bath holding tank 2115 have a float potential from the earth ground, an electrodeposition washing system exhaust duct main insulating flange 2365 and an electrodeposition washing system exhaust duct washing side insulating flange 2364 were provided and electrically separated.

[Substrate] The substrate material used in the electrodeposition apparatus according to the present embodiment may be any material as long as it is electrically conductive on the film deposition surface and is not affected by the electrodeposition bath. For example, metals such as SUS, Al, Cu, and Fe are used. Further, a PET film with a metal coating can be used. Among them, SUS is excellent as the long substrate 2006 for performing the element formation process in a later step.

As SUS, either non-magnetic SUS or magnetic SUS can be applied. A typical non-magnetic SUS is SUS304, which has excellent polishing properties and can have a mirror surface of about 0.1 s. A typical magnetic SUS is a ferrite-based SUS 430, which is effectively used in conveyance using magnetic force.

The surface of the substrate may be smooth or rough. The surface properties of SUS can be changed by changing the type of rolling roller in the rolling process. For example, SUS called BA
Is close to a mirror surface, and SUS called 2D has noticeable unevenness. In any case, when observed under an SEM (electron microscope), pleasure on the order of microns may be conspicuous. As a solar cell substrate, a micron-scale structure has a greater effect on the characteristics of the solar cell in both good and bad directions than large undulating irregularities.

Further, these substrates may be formed of another conductive material, and are selected according to the purpose of electrodeposition.
In some cases, it is preferable to form a very thin layer of zinc oxide in advance by another method since the deposition rate in the electrodeposition method can be stably improved. Certainly, the electrodeposition method is advantageous in that the cost is low. However, even if a somewhat expensive method is additionally employed, if the cost can be reduced comprehensively, the combination of the two methods is advantageous.

[Interleaf] As an interleaf for protecting the deposited film, a nonwoven fabric represented by Nomex, a resin film represented by PET, or the like can be used. As a resin film such as PET, it is also possible to use a thin film coated with a softer Cu or Al metal. Of course, the resin film
If the temperature is too high, melting or fusion may occur, so it is necessary to confirm in advance that the long substrate 2006 has cooled to a sufficient temperature. Since the interleaf is eventually discarded, it is preferable to avoid expensive materials as much as possible from the viewpoint of cost reduction technology.

[Tension] Elongating substrate 2006 unwinding device Long substrate bobbin 2001 and long substrate winding bobbin 22
89 and the width of the long substrate 2006 is 1 cm in width.
0.05-50 kg per unit. If the tension is too weak, the long substrate 2006 may inadvertently hang down, deviate from a predetermined transport path, rub off the end portion off the rollers, or significantly deteriorate the controllability of meandering correction. Conversely, if the tension is too strong, the long substrate 200
If the sheet 6 itself is stretched or the conveyance is uneven, the sheet 6 may be stretched only at the end in the width direction to form a so-called "wakame", which may distort the entire apparatus.

The tension is applied to the long substrate winding bobbin 22.
89 and the unwinding device long substrate bobbin 200
It can be generated from slippage with a clutch (a powder clutch or the like is used) attached to one shaft. In this case, the transport path hardly changes irrespective of the size of the tension, and all the intermediate rollers can be driven rollers, so that the degree of freedom in designing the layout of the transport components including the rollers is extremely high. On the other hand, since tension is not generated during non-transportation, another locking means is required to prevent the long substrate 2006 from hanging down at rest.

The tension can also be generated by using a tension roller capable of moving its axis. In this case, control and monitoring of the tension are easy, but the position of the tension roller changes, so that a design for taking the stroke is necessary, and the parallelism of the roller is deviated, and meandering is likely to occur.

Further, the tension can also be generated by positively moving the intermediate roller in a direction in which friction occurs with the long substrate 2006. This method has the advantage that the transport path does not change and that the tension works even when the apparatus is stationary. On the other hand, for a material in which the dynamic friction and the static friction are significantly different, the design is troublesome.

Naturally, the tension exerts its effect on the roller which is conveyed in such a manner as to cover the circumference thereof more than the roller which comes into contact with the horizontal. In order to expect the effect, not only a winding roller but also a feeding roller and a meandering correction roller can be cited.

[Transport Speed] The transport speed of the long substrate 2006 is determined solely based on the balance between the required film thickness of the electrodeposited film and the film deposition speed. In practice, the first electrodeposition tank 2066
And the second electrodeposition tank 2116 has a total of 56 anodes,
The transport speed of the long substrate 2006 is determined by the sum of the respective film deposition rates.

In the electrodeposition apparatus according to this embodiment, the transport speed of the long substrate 2006 is set to 0.5 m / min to 5 m / mi.
n. In experiments, even at the lowest design speed or the highest design speed, 500 m
It has been demonstrated that zinc oxide can be deposited on the long substrate 2006 with good transport at a temperature rise of 85 ° C.

[Roller] The roller used in the electrodeposition apparatus according to the present embodiment not only determines the transport path of the long substrate 2006, but also applies a necessary potential to the long substrate 2006, and Functions such as not forming a large current stray path.

It is particularly important to determine the transport route, and not only that the parallelism is firmly obtained at the beginning, but also that the temperature of the electrodeposition bath rises to a high temperature (for example, 90 ° C.), and that a large bathtub causes thermal expansion. If so, displacement of the position should be kept to a minimum. Actually, sub-milli play is acceptable, but it is preferable that the accuracy of the parallelism is on the order of 100 minutes when the temperature rises. The deviation of the parallelism and the twist cause the long substrate 2006 to be shifted particularly in the electrodeposition tank. In this case, the edge portion is rubbed very often, and so-called “wakame” is generated. I will.

If the long substrate 2006 has a stiffness,
It is not necessary to consider the surface processing using parallel rollers, but in the case of a soft substrate such as Al foil, the rollers can be expanded into a drum shape called a crown,
It is preferable to provide a drainage groove. In such a case, it is effective to drive the rollers synchronously, since there is no tension required to make the rollers driven.

In order to electrically float the roller, the roller may be formed of a resin such as nylon or polyethylene, or the shaft of the metal roller may be formed of a resin. Further, a resin member may be interposed between the bearing installation portions to provide insulation.

Unless power is supplied directly to the long substrate 2006 with a brush or the like, or power is supplied via a bath,
It is preferable to provide at least one roller that applies a potential called a power supply roller. If the roller close to the electrodeposition part can be used as the power supply roller, the design of the electric path for the electrodeposition current is the simplest.

If the power supply roller cannot be placed near the anode because the chemical substance in the electrodeposition bath reacts by touching the electrodeposition bath, alternative or combined use of other methods such as brush power supply or bath power supply should be considered. is there. This is because the long substrate 2006 has a resistance of about 0.01 Ω per meter, and an extremely large heat loss occurs when an electrodeposition current of several tens of amperes is used.

In the meandering correction, as a concept, it is preferable to establish a transport system that hardly shifts by giving the parallelism of the rollers, and to correct a slight shift just before winding. In this case, the correction amount may be detected, and the correction amount may be returned to the meandering correction roller by a feed forward or feedback system. Feed-forward systems are suitable for high-speed systems that are computationally tedious but exceed a few meters per second. On the other hand, the feedback system is not suitable for high-speed conveyance, but can have a simple configuration.

In any case, it is preferable to have a meandering correction roller for moving the long substrate 2006 in the direction to be corrected. In the electrodeposition apparatus according to this embodiment, the winding device direction change roller 2287 also serves as a meandering correction roller. In order to move the long substrate 2006 in the direction to be corrected, it is preferable that the friction with the long substrate 2006 is large. On the other hand, in order to absorb the distortion of the long substrate 2006 due to the correction movement, the long substrate 20 is required.
06 preferably slides on a meandering correction roller. The magnitude of the friction actually used is experimentally determined, including the tension. In some cases, the long substrate 2006
It is effective to select a material that optimizes the friction between the two and to roughen the surface. In order to move the long substrate 2006 in the direction to be corrected, the entire roller may be configured to move in parallel, or a shape that makes a swinging motion about an axis at a certain distance (tangent)・
Roller). The translation roller is effective for large displacement. On the other hand, the tangent roller simplifies the device configuration.

[Electrical configuration of bath, pipe, and other bath holding material]
In order to reduce the stray current and contribute almost all of the flowing current to the electrodeposition and make it a current flowing between the long substrate 2006 and the anode, the electrodeposition tank, the piping connected thereto, and the components in the bath holding tank, etc. It is preferable to perform insulation treatment. Basically, almost all the flowing current can contribute to the electrodeposition by minimizing the metal part in contact with the anode and the long substrate 2006 directly or through a bath.

In addition, since the stray current can be reduced by setting the float potential, the electrodeposition apparatus according to the present embodiment has a structure in which the metal part constituting the electrodeposition tank and the substrate transport roller is floated from the ground. And Insulated piping, large diameter flanged insulated piping, insulating flanges made in overflow return systems, insulating flanges provided in exhaust ducts, etc. are all for this purpose.

[Insulating Flange] It is preferable to use a flanged pipe made of an insulator such as vinyl chloride or heat-resistant vinyl chloride for a pipe portion to be electrically disconnected. The first electrodeposition tank overflow return path insulating flange 2118 provided on the first electrodeposition tank overflow return path 2117 and the second electrode provided on the second electrodeposition tank overflow return path 2219 of the electrodeposition apparatus according to this embodiment. The deposition tank overflow return path insulation flange 2220, the electrodeposition water washing system exhaust duct provided in the electrodeposition water washing system exhaust duct 2020, the washing side insulation flange 2364, the electrodeposition water washing system exhaust duct main insulation flange 2365, and the like have square cross sections. It is provided on the conduit, and the bases are manufactured at the end of the conduit, and they are fastened with insulating bolts with insulating rubber therebetween. The insulating rubber can be used at a high temperature, for example, Viton (trade name), but when it is compressed, some of them suddenly show conductivity, so care must be taken in the selection.

[Electrodeposition bath] As the electrodeposition bath, a bath confirmed by a small experimental device such as a beaker can be basically used. For the deposition of zinc oxide having a light confinement effect applied to a solar cell undercoat layer and having irregularities, for example,
An aqueous solution containing at least nitrate ions and zinc ions can be preferably used. The nitrate ion and zinc ion concentrations are preferably 0.002 mol / l to 3.0 mol.
/ L, more preferably 0.0 mol / l to 1.5 mo
l / l, optimally 0.05 mol / l to 0.7 mol /
l. When using an electrodeposition bath containing saccharose or dextrin to prevent abnormal growth,
The concentration of saccharose is preferably between 500 g / l and 1 g
/ L, more preferably 100 g / l to 3 g / l,
The concentration of dextrin is preferably between 10 g / l and 0.0
1 g / l, more preferably 1 g / l to 0.025 g / l
By setting l, a zinc oxide thin film having a texture structure suitable for the light confinement effect can be efficiently formed.

By setting the temperature of the electrodeposition bath to 60 ° C. or higher, a uniform zinc oxide thin film with little abnormal growth can be efficiently formed.

When the temperature of the electrodeposition bath is high and the generation of steam is remarkable, it is preferable to provide an exhaust duct to suck the steam. By providing the exhaust duct, it is possible to prevent the vapor and the condensed water droplets from coming out of the gap of the electrodeposition apparatus.

When a lid is provided in the tank,
Water vapor blows out when the lid is opened, which is dangerous. Therefore, also in this case, it is preferable to provide an exhaust duct.

When the amount of liquid is reduced due to the generation of steam from the electrodeposition bath and the exhaust suction, pure water may be supplied periodically.

[Heat insulation structure of bath / pipe] It is preferable that the bath / pipe for holding / supplying / draining the heated bath or pure water has a heat insulation structure from the viewpoint of energy saving and prevention of danger. The heat insulating structure of the tank can be realized by a double wall structure sandwiching a heat insulating material such as glass wool, or by providing a heat insulating material on the outside. In general, the heat insulating structure of the pipe can be realized by covering with a heat insulating material.

[Electrodeposition Conditions] In performing the electrodeposition, a negative potential is applied to the long substrate 2006 and a positive potential is applied to the anode to drive an electrochemical reaction. In order to control the film thickness, it is appropriate to perform electrodeposition by current control. The current is preferably defined by the current density, and is set in the range of 0.3 to 100 mA / cm ² .

[Anode] As the anode, a zinc plate having a purity of 2N to 4N can be used as a soluble anode. If the surface of the long substrate 2006 is dirty, it may be washed lightly with diluted nitric acid. It is preferable that the power supply line to the anode be configured to be tightened with SUS bolts, since reliable electrical contact can be guaranteed for a long period of time. SUS or Pt can be used as the insoluble anode.

In particular, when a soluble anode is used, it is preferable that the soluble anode be wrapped in an anode bag in order to prevent the generated zinc oxide powder from generating dust in the electrodeposition bath. As the material of the anode bag,
Cotton or amide resin fibers that are not attacked in the bath can be used, and it is preferable to form an appropriate mesh. The size of the mesh is determined by defining the maximum size of the powder that the electrodeposition bath surely touches the surface and generates dust. For example, the size of a general mesh is selected from 0.5 mm to several mm.

[Electrodeposition power source] Each power source for performing electrodeposition is as follows.
It is preferable to have a float output. As voltage control, when a predetermined potential is applied and a current may flow in a suction direction, a power supply of a suction type should be used.

Each power supply applies a potential to a single anode or a plurality of combined anodes to flow a current. In order to prevent interference between the power sources, it is preferable that a current path connecting the anodes should not appear as much as possible. For this purpose, it is effective to install an insulating plate such as Teflon or vinyl chloride in the bath.

[Pump] The pump basically needs to obtain a sufficient flow rate, but at the same time, should be arranged so as to prevent cavitation. In particular,
At a temperature exceeding 90 ° C., the water evaporates at a stretch due to the negative pressure to be sucked, and the gas tends to idle around the liquid sending fins inside the pump, which tends to cause a cavitation phenomenon. Once cavitation occurs, the pump idles, often causing seizure or breaking fins, resulting in damage to the pump. In order to prevent the pump from being damaged due to the occurrence of cavitation, it is preferable to arrange the pump at a position as low as possible so that the bath liquid is pushed in, that is, a structure in which negative pressure is hardly generated.

[Valve] The valve may be a manual one or an automatic one. In order to reduce malfunction, an automatic valve and a manual valve may be arranged in series.

Some of the valves of the electrodeposition apparatus according to this embodiment are adjusted based on predetermined conditions to control the flow rate. Representatives are the first circulation tank electrodeposition bath upstream circulation valve 2135 and the first circulation tank electrodeposition bath downstream circulation valve 21
45, a first electrodeposition tank filter circulation system electrodeposition bath upstream return valve 2167, a first electrodeposition tank filter circulation system electrodeposition bath middle flow return valve 2168, a first electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2169, First electrodeposition tank filter circulation valve 2166, first electrodeposition tank compressed air introduction valve 218
9. First electrodeposition tank stirring air upstream control valve 2193, first electrodeposition tank stirring air downstream control valve 2192 or
Second circulation tank electrodeposition bath upstream circulation valve 2237, second circulation tank electrodeposition bath downstream circulation valve 2247, second electrodeposition tank filter circulation system electrodeposition bath upstream return valve 2269, second electrodeposition tank filter circulation system electrodeposition In-bath flow return valve 2270, second electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2271, second electrodeposition tank filter circulation valve 2268, second electrodeposition tank compressed air introduction valve 2199, second electrodeposition tank stirring air An upstream control valve 2202, a downstream control valve 2272 for the second electrodeposition tank stirring air, and the like. Also, the valves leading to the shower and the air knife are adjusted based on predetermined conditions to control the flow rate.

[Filter] A filter used in the bath solution system is a filter for removing particles of submicron to about 10 microns represented by a cartridge type filter, and a filter for removing dust having a size of several mm or more. However, they are roughly classified into suction filters that basically consist of wire mesh.

The particle removing filter is required to positively remove powder generated inside from the bath liquid system.
The size of the dust remaining on the film formed on the long substrate 2006 that is finally rolled up is determined by the filter size. Therefore, the required filter size is determined based on the required properties of the membrane.

The suction filter is used for preventing damage to the pump and the valve.

The filter used in the air system is mainly for removing oil mist and moisture mixed in the compressed air.

[Piping] The thickness of the pipe is determined based on the required flow rate in the pipe. In a portion where a large flow rate is required, the diameter is preferably 40 A or more. In the electrodeposition apparatus according to the present embodiment, in FIG. 2, a portion shown as a thick tube uses a nominal diameter of 40A, and a portion shown as a thin tube uses a nominal diameter of 25A.

As the material of the tube, stainless steel is used under extremely favorable conditions, but when electric connection is not preferable, it is also possible to use only a part of a tube such as heat-resistant vinyl chloride. In addition, for the connection with the joint, a thin pipe or the same material is sufficient with the insert, but for the connection of the thick pipe of vinyl chloride and stainless steel, in order to prevent the occurrence of liquid leakage due to repeated thermal expansion and contraction, It is preferred to use a flange joint.

[Circulation Amount] The circulation amount of the bath solution should be sufficient to make the temperature uniform and to make the concentration of the electrodeposition bath used uniform. For example, it may be several tens of l / min or more for an electrodeposition bath of several hundred liters. It is preferable that the circulating bath liquid moves on the anode surface and the long substrate 2006 surface to always form a flow for replenishing a new electrodeposition bath.

[Agitated Air Volume] In the electrodeposition apparatus according to the present embodiment, air agitation is a very effective means for agitating the bath liquid. For example, for several hundred liters of electrodeposition bath, several meters
The flow rate is preferably about ³ / hr or more. In order to perform air stirring, it is preferable to discharge air as small bubbles in order to enhance the stirring effect. For this purpose, for example, a configuration may be adopted in which agitated air is blown from the orifice into the electrodeposition bath.

Further, if an air pocket is formed under the long substrate 2006, the electrodeposition reaction does not proceed, so that the film formation does not proceed. For this reason, it is necessary for the blown-out air to rise without stagnating.

[Backside Electrode] Unnecessary electrodeposited film formed on the backside of the long substrate 2006 is removed by the backside electrode. A negative potential is applied to the back electrode with respect to the long substrate 2006. For this reason, especially in order to prevent interference with the power source for electrodeposition, the two need to have a floating output from each other. A current of 1 A to 30 A is used per back electrode installed in one electrodeposition tank.

The material of the back electrode is Ti having a high hydrogen overvoltage.
And SUS are preferred. Electrodeposits such as zinc oxide that are peeled off from the back surface of the long substrate 2006 and accumulate in the back electrode portion may be mechanically peeled outside the apparatus for repeated use, or the back electrode may be disposable. It may be discarded for each electrode.

[0188]

EXAMPLES Specific experimental results of the rinsing method according to the present invention will be described below with reference to Examples 1 to 5.

[Example 1] In the experiment of Example 1, FIG.
As a negative electrode (conductive substrate 303), a stainless steel 430BA having a thickness of 0.2 mm
000 ° sputtered, and the positive counter electrode 30
As 4, 1-mm thick 4-N zinc was used. Further, the aqueous solution of electrolytic deposition 302 is 80 ° C., 0.2 mol /
1 zinc nitrate solution was used.

Then, 5.0 mA / cm ^{2 is} applied between the positive electrode 304 and the negative electrode (conductive substrate 303).
(0.5 A / dm ² ) for 5 minutes.
A sample on which a μm zinc oxide thin film was deposited was prepared. After that, no rinse, pure water 100cc, 400cc, 10cc
00cc, 20000cc, running water (60sec at 20cc / sec), running water (300sec at 20cc / sec)
Rinsing was performed under the rinsing conditions of c).

Next, the electrical conductivity (Yokokawa Electric SC-82) of the rinsing bath immediately after taking out the sample was measured, and the surface of the sample was visually observed. Further, the sample was placed in an environment at a temperature of 85 ° C. and a humidity of 85% for 1000
After leaving it for a time, the cross-cut tape method (JIS K540008.
5.2) was performed.

Table 1 shows the experimental results.

[0193]

[Table 1]

Table 1 shows the following.

In a visual check, white spots were not observed by controlling the rinsing bath to 150 μS / cm or less as rinsing conditions.

According to the grid tape method, a more reliable zinc oxide thin film can be obtained by controlling the rinsing bath to 1 μS / cm or less as a rinsing condition.

Example 2 In the experiment of Example 2, FIG.
Using the apparatus described above, silver was applied to 0.12 m thick stainless steel 430BA as the negative electrode (conductive base 303).
000 ° sputtered, and the positive counter electrode 30
As 4, 1-mm thick 4-N zinc was used. Further, the aqueous solution of electrolytic deposition 302 is 80 ° C., 0.2 mol /
1 zinc nitrate solution was used.

Then, 5.0 mA / cm ^{2 is} applied between the positive side counter electrode 304 and the negative side electrode (conductive substrate 303).
(0.5 A / dm ² ) for 5 minutes.
A sample on which a μm zinc oxide thin film was deposited was prepared. Thereafter, rinsing was performed under the rinsing conditions of the presence or absence of a shower (5 sec at 20 cc / sec), no rinsing bath replacement, and one rinsing bath of 300 cc.

Next, the electrical conductivity (Yokokawa Electric SC-82) of the rinsing bath immediately after taking out the sample was measured, and the surface of the sample was visually observed. From the waveform of the optical characteristics (J-Spectrum Co., Ltd., V-570), 800 nm
Was determined.

The experimental results are shown in Table 2.

Example 3 In the experiment of Example 3, a sample was prepared under the same conditions as in Example 2 except that an 800 cc rinsing bath was used as a rinsing condition.

The electrical conductivity (Yokokawa Electric SC-82) of the rinsing bath immediately after taking out the sample was measured, and the surface of the sample was visually observed.

Table 2 shows the experimental results.

[0204]

[Table 2]

Table 2 shows the following.

By replacing the rinsing bath, rinsing properties can be effectively improved. That is, the conductivity can be reduced with a small amount of pure water.

Further, by adding a shower to the rinsing step, rinsing properties can be effectively improved.

Further, by replacing the rinsing bath,
Rinsing can be more effectively improved.

[Embodiment 4] In the experiment of Embodiment 4, FIG.
Using the apparatus described in (1), a negative electrode (conductive substrate 303) was prepared by sputtering 2,000 ° of silver on stainless steel 430BA having a thickness of 0.12 mm.
As 04, 4-N zinc having a thickness of 1 mm was used. Further, the aqueous solution of electrolytic deposition 302 is 80 ° C., 0.2 mol /
1 zinc nitrate solution was used.

Then, 5.0 mA / cm ² between the positive counter electrode 304 and the negative electrode (conductive substrate 303).
(0.5 A / dm ² ) for 5 minutes.
A sample on which a μm zinc oxide thin film was deposited was prepared. After that, no rinse, pure water 100cc, 400cc, 10cc
00cc, 20000cc, running water (60sec at 20cc / sec), running water (300sec at 20cc / sec)
Rinsing was performed under the rinsing conditions of c).

Then, as the semiconductor layer 104, n-type amorphous silicon (a-Si) was deposited at 200.degree., Non-doped amorphous silicon (a-Si) was deposited at 2000.degree.
Type microcrystalline silicon (mc-Si) was deposited in the order of 140 °.

Further, 1T0 was deposited at 650 ° by heating in an oxygen atmosphere to form a transparent electrode layer 105 as an upper electrode having an antireflection effect. Further, a grid made of silver was deposited on the transparent electrode layer 105 by heating and vapor deposition to form a current collecting electrode layer 106, thereby forming a photovoltaic element.

This photovoltaic element was used in a solar simulator (AM 1.5, 100 mW / cm ² , surface temperature 25
° C), the short-circuit current density and the conversion efficiency were measured.

Further, this photovoltaic element was heated at a temperature of 85 ° C.
It was left for 1000 hours in an environment with a humidity of 85%, and the conversion efficiency deterioration rate was measured.

Table 3 shows the test results.

[0216]

[Table 3]

Table 3 shows the following.

By rinsing the zinc oxide thin film using the rinsing method according to the present invention, a photovoltaic device having high reliability, excellent short-circuit current density and excellent conversion efficiency can be manufactured. That is, a rinsing bath is used as a rinsing condition.
By controlling it to 50 μS / cm or less, it is possible to manufacture an element having excellent short-circuit current density and conversion efficiency,
Further, by controlling the rinsing bath to 1 μS / cm or less as a rinsing condition, a more reliable photovoltaic element can be manufactured.

[Embodiment 5] In the experiment of Embodiment 5, FIG.
The negative electrode (conductive substrate 303) was prepared by sputtering 2000 mm thick stainless steel 430 · 2D with silver at 2,000 °, and using the positive counter electrode 3 as the negative electrode (conductive substrate 303).
As 04, 4-N zinc having a thickness of 1 mm was used. Further, the aqueous solution of electrolytic deposition 302 is 80 ° C., 0.2 mol /
1 zinc nitrate solution was used.

Then, 5.0 mA / cm ² between the positive electrode 304 and the negative electrode (conductive substrate 303).
(0.5 A / dm ² ) for 5 minutes.
A sample on which a μm zinc oxide thin film was deposited was prepared. After that, without shower, with shower (20cc / sec
The rinsing was further performed under the rinsing conditions of 5 seconds), no rinsing bath replacement, and one rinsing bath replacement.

Then, as the semiconductor layer 104, n-type amorphous silicon (a-Si) is 200 °, non-doped amorphous silicon (a-Si) is 2000 °
Type microcrystalline silicon (mc-Si) was deposited in the order of 140 °.

Further, IT0 was deposited at 650 ° by heating deposition in an oxygen atmosphere to form a transparent electrode layer 105 as an upper electrode having an antireflection effect. Further, a grid made of silver was deposited on the transparent electrode layer 105 by heating and vapor deposition to form a current collecting electrode layer 106, thereby forming a photovoltaic element.

The photovoltaic element was used in a solar simulator (AM 1.5, 100 mW / cm ² , surface temperature 25
° C), the short-circuit current density and the conversion efficiency were measured.

Further, this photovoltaic element was heated at a temperature of 85 ° C.
It was left for 1000 hours in an environment with a humidity of 85%, and the conversion efficiency deterioration rate was measured.

Table 4 shows the test results.

[0226]

[Table 4]

Table 4 shows the following.

As a rinsing method of the zinc oxide thin film, replacing the rinsing bath, adding a shower to the rinsing step, and replacing the rinsing bath after showering, provide high reliability, short-circuit current density and A photovoltaic element having excellent conversion efficiency can be manufactured effectively.

Example 6 An experiment was further performed using the electrodeposition apparatus shown in FIG.

In this experiment, a rolled SUS4
On the 30 2D 101, a roll-type DC magnetron sputtering apparatus is used to deposit 2000 ア ル ミ ニ ウ ム of aluminum to form a back reflection layer 102. On the back reflection layer 102, a similar roll-compatible DC magnetron sputtering apparatus is used. A 1000 ° zinc oxide thin film was deposited. A transparent conductive layer 103 made of a zinc oxide thin film was formed on such a long substrate 2006 by using a roll-to-roll type electrodeposition apparatus shown in FIG.

In the electrodeposition apparatus shown in FIG.
6 is transported via a transport roller to a first electrodeposition tank 2066 and a second electrodeposition tank 2116 for forming a zinc oxide layer.

First electrodeposition tank 2066, second electrodeposition tank 2116
As an electrodeposition bath, zinc nitrate hexahydrate 70 g (0.2 mol / l) and dextrin 0.5 g per liter of water were used.
And a liquid circulation treatment is performed to stir the inside of the electrodeposition bath. The liquid temperature of the electrodeposition bath is 8
It is kept at 0 ° C. and the pH is kept between 4.0 and 6.0.

First electrodeposition tank anodes 2026-2053,
A zinc plate (350 cm × 150 cm) is used for the second electrode anodes 2076 to 2103, and the roll-shaped long substrate 2006 is used as a negative electrode, and the first electrode is used as a positive counter electrode. A current of 10.0 mA / cm ² (1.0 A / dm ² ) is passed between the electrodes 2026 to 2053 and the anodes 2076 to 2103 of the second electrodeposition tank, respectively. Was formed.

After the zinc oxide thin film is electrolytically deposited, the long substrate 2006 is washed in the order of a pure water shower tank 2360, a first hot water tank 2361, and a second hot water tank 2362, and a drying step 2363 is performed. After that, it is wound by the winding device 2296.

At this time, the electric conductivity of the first hot water tank 2361 and the second hot water tank 2362 are 3 μS / cm and 0.
It was 8 μS / cm. The transport speed of the long substrate 2006 was 2000 mm / m. In this way,
On the support 101 (elongated substrate 2006), a back reflection layer 102 and a transparent conductive bath 103 (a zinc oxide thin film) were formed, and a triple structure semiconductor layer 104 was formed by a roll-compatible CVD apparatus.

In the formation of the semiconductor layer 104, first, the back reflection layer 102 and the transparent conductive layer 103 formed on the substrate itself 101 are heated to 340 ° C. using a mixed gas of silane, phosphine and hydrogen. An n-type layer is formed by applying an RF power of 400 W. Next, using a mixed gas of silane, germane, and hydrogen, the substrate temperature was set to 450 ° C.
Microwave power is applied to form an i-layer. further,
At a substrate temperature of 250 ° C., a p-type layer was formed from a mixed gas of boron trifluoride, silane and hydrogen to form a bottom pin layer.

Subsequently, the mixture ratio of silane and germane in the i layer was increased, a middle nip layer was formed in the same procedure, and the i layer was deposited from silane and hydrogen in the same procedure to form a top pin layer. Was formed. Thereafter, ITO was deposited as a transparent electrode layer 105 by a roll-compatible sputtering apparatus. Further, the current collecting electrode layer 106 is made of silver paste.
Was formed.

The photovoltaic element thus formed is
Solar simulator (AM1.5, 100mW / c
(m ² , surface temperature 25 ° C.), the short-circuit current density and the conversion efficiency were measured.

Further, this photovoltaic element was subjected to an HH test (1000 hours in an environment test box under an environment of a temperature of 85 ° C. and a humidity of 85%) as an acceleration test,
The conversion efficiency deterioration rate was measured.

The experimental results are shown in Table 5.

Table 5 shows the results of comparison with Examples 4 and 5 described above.

[0242]

[Table 5]

Table 5 shows the following.

By using the rinsing method according to the present invention, even in a roll-to-roll type electrodeposition apparatus,
This has a great effect on improving the short-circuit current density, the conversion efficiency, and the reliability.

[0245]

According to the method for rinsing a zinc oxide thin film formed by electrolytic deposition according to the present invention, the electric conductivity of a rinsing bath used for rinsing is controlled to 150 μS / cm or less.

Therefore, it is possible to prevent the nitrate contained in the aqueous solution used for electrodeposition from forming as white spots on the zinc oxide thin film, thereby improving the reliability (adhesion) of the zinc oxide thin film. As well as
It does not cause poor appearance.

By controlling the electrical conductivity of the rinsing bath used for rinsing to 1 μS / cm or less, a highly reliable zinc oxide thin film having excellent adhesion even under high temperature and high humidity can be obtained. .

In addition, a zinc oxide thin film is deposited in a roll-to-roll format, and a shower bath, a first rinsing bath,
By performing washing in the order of the second rinsing bath, a highly reliable and high-performance zinc oxide thin film can be continuously and efficiently manufactured.

Further, by introducing a technique for forming a zinc oxide thin film free from stains due to nitrate precipitation into the solar cell manufacturing process, the short-circuit current density and conversion efficiency of the solar cell can be improved, and the yield can be improved. Characteristics and durability can be improved.

Further, as compared with the sputtering method and the vapor deposition method, the material cost and the running cost are very advantageous (for example, the cost is reduced to about 1/100).
It can contribute to the full-fledged spread of solar power generation.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of a photovoltaic element manufactured by a manufacturing process including a rinsing method according to the present invention.

FIG. 2 is a configuration diagram showing an embodiment of an electrodeposition apparatus according to the present invention.

FIG. 3 is an enlarged view of the unwinding device shown in FIG. 2;

FIG. 4 is an enlarged view of a first electrodeposition tank and a first circulation tank shown in FIG. 2;

FIG. 5 is an enlarged view of a second electrodeposition tank and a second circulation tank shown in FIG. 2;

FIG. 6 is an enlarged view of a first drainage tank and a second drainage tank shown in FIG. 2;

FIG. 7 is an enlarged view of a pure water shower tank, a first hot water tank, a second hot water tank, a drying unit, and a winding device shown in FIG.

FIG. 8 is an enlarged view of the pure water heating tank shown in FIG.

FIG. 9 is an enlarged view around the exhaust duct shown in FIG. 2;

FIG. 10 is a configuration diagram showing another embodiment of the electrodeposition apparatus according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 101 Support body 102 Back reflection layer 103 Transparent conductive layer 104 Semiconductor layer 105 Transparent electrode layer 106 Current collecting electrode layer 301 Corrosion-resistant container 302 Electrolytic deposition aqueous solution 303 Conductive substrate 304 Counter electrode 305 Power supply 306 Load resistance 307 Injection port 308 Suction port 309 Inhalation solution pipe 310 Injection solution pipe 311 Solution circulation pump 312 Heater 313 Thermometer 2001 Unwinding device Long substrate bobbin 2002 Unwinding device Interleaf winding bobbin 2003 Unwinding device unwinding adjusting roller 2004 Unwinding device direction change roller 2005 Rolling Unloading device discharge roller 2006 Long substrate 2007 Rewinding interleaf 2008 Interleaf rewinding direction 2009 Unwinding device Long substrate bobbin rotation direction 2010 Long substrate unwinding direction 2011 Unwinding device clean booth 012 Unwinding device 2013 Electrodeposition tank entrance turning roller 2014 First electrodeposition tank entry roller 2015 First electrodeposition tank exit roller 2016 Electrodeposition tank interposition tank turning roller 2017 Electrodeposition tank entrance turning roller cover 2018 First electrodeposition bath holding tank Cover 2019 Cover between electrodeposition tanks 2020 Exhaust duct for electrodeposition water washing 2021 Upstream exhaust port for first electrodeposition tank 2022 Exhaust port for middle flow of first electrodeposition tank 2023 Exhaust port for downstream of first electrodeposition tank 2024 Overflow return port for first electrodeposition tank 2025 First electrodeposition bath bath surface 2026-2053 First electrodeposition tank anode 2054-2060 First electrodeposition tank anode mounting table 2061 First electrodeposition tank back surface electrode 2062 First electrodeposition tank stirring air introduction pipe 2063 First electrode Spouting pipe upstream of the deposition tank 2064 Spouting pipe downstream of the first electrodeposition tank 2065 First electrodeposition bath holding tank 2066 Vessel 2067 First electrodeposition tank outlet shower 2068 Second electrodeposition tank inlet shower 2069 Second electrodeposition tank entrance roller 2070 Second electrodeposition tank exit roller 2071 Second electrodeposition tank upstream exhaust port 2072 Second electrodeposition tank middle exhaust Port 2073 second electrodeposition tank downstream exhaust port 2074 second electrodeposition bath surface 2075 second electrodeposition tank overflow return port 2076-2103 second electrodeposition tank anode 2104-2110 second electrodeposition tank anode mounting table 2111 second Electrode on backside of electrodeposition tank 2112 Second electrodeposition tank stirring air introduction pipe 2113 Second electrodeposition tank upstream reflux jet pipe 2114 Second electrodeposition tank downstream reflux jet pipe 2115 Second electrodeposition bath holding tank 2116 Second electrodeposition tank 2117 First electrodeposition tank overflow return path 2118 First electrodeposition tank overflow return path insulating flange 2119 First electrodeposition tank overflow return direction 2 Reference Signs List 120 First circulation tank 2121 First circulation tank heating storage tank 2122 to 2129 First circulation tank heater 2130 First circulation tank electrodeposition bath upstream circulation source valve 2131 First circulation tank electrodeposition bath upstream circulation direction 2132 First circulation tank electrodeposition Bath upstream circulation pump 2133 First circulation tank electrodeposition bath upstream circulation pump bypass valve 2134 First circulation tank electrodeposition bath upstream circulation pressure gauge 2135 First circulation tank electrodeposition bath upstream circulation valve 2136 First circulation tank electrodeposition bath upstream circulation Flexible pipe 2137 First circulation tank electrodeposition bath upstream circulation flange insulation pipe 2138 Second electrodeposition bath holding tank cover 2139 First circulation tank electrodeposition bath downstream circulation source valve 2140 First circulation tank electrodeposition bath downstream circulation direction 2141 First Circulation tank electrodeposition bath downstream circulation pump bypass valve 2142 First circulation tank electrodeposition bath downstream circulation pump 2143 Under first circulation tank electrodeposition bath Circulation pressure gauge 2144 First drainage tank Drainage storage tank 2145 First circulation tank electrodeposition bath downstream circulation valve 2146 First circulation tank electrodeposition bath bypass circulation flexible pipe 2147 First circulation tank electrodeposition bath bypass circulation valve 2148 First circulation Flexible circulation pipe downstream of the electrodeposition bath 2149 First circulation tank downstream circulation flange insulation pipe 2150 First circulation tank outlet shower valve 2151 First electrodeposition tank filter circulation return flexible pipe 2152 First electrodeposition tank filter circulation return flange Insulation pipe 2153 First electrodeposition tank drain valve 2154 First electrodeposition tank filter circulation source valve 2155 First electrodeposition tank filter circulation direction 2156 First electrodeposition tank filter circulation suction filter 2157 First electrodeposition tank filter circulation pump 2158 No. One electrodeposition tank filter circulation pump Bypass valve 2159 First electrodeposition tank filter circulation pressure switch 2160 First electrodeposition tank filter circulation pressure gauge 2161 First electrodeposition tank filter circulation filter 2162 First electrodeposition tank filter circulation direction 2163 First electrodeposition tank filter circulation direction 2164 First electrodeposition tank filter circulation flexible pipe 2165 First electrodeposition tank filter circulation flange insulating pipe 2166 First electrodeposition tank filter circulation valve 2167 First electrodeposition tank filter circulation system electrodeposition bath upstream return valve 2168 First electrodeposition tank Return valve in the electrodeposition bath of the filter circulation system 2169 First return valve in the electrodeposition bath filter circulation system downstream valve 2170 First drainage tank air vent valve 2171 First drainage tank air vent 2172 First drainage tank 2173 First drainage Tank drain valve 2174 First drain tank drain recovery tank 2175 Drainage collection source valve 2176 Drainage collection suction filter 2177 Drainage collection pump 2178 Drainage collection port 2179 Drainage tank common drainage port 2180 Second drainage tank drainage valve 2181 Second drainage tank drainage collection valve 2182 Pressing Air inlet 2183 Compressed air pressure switch for electrodeposition bath stirring 2184 First electrodeposition tank compressed air introduction direction 2185 First electrodeposition tank compressed air main valve 2186 First electrodeposition tank compressed air flow meter 2187 First electrodeposition tank compressed Air regulator 2188 First electrodeposition tank compressed air mist separator 2189 First electrodeposition tank pressed air flexible pipe 2190 First electrodeposition tank compressed air flexible pipe 2191 First electrodeposition tank compressed air insulation pipe 2192 First electrodeposition tank stirring air Downstream control valve 2193 First electrodeposition tank stirring air upstream control valve 2194 Two electrodeposition tank compressed air introduction direction 2195 Second electrodeposition tank compressed air main valve 2196 Second electrodeposition tank compressed air flow meter 2197 Second electrodeposition tank compressed air regulator 2198 Second electrodeposition tank compressed air mist separator 2199 Second Electrodeposition tank compressed air introduction valve 2200 Second electrodeposition tank compressed air flexible pipe 2201 Second electrodeposition tank compressed air insulation pipe 2202 Second electrodeposition tank stirring air upstream control valve 2203 Electrodeposition tank pure water inlet 2204 Deposition tank pure water introduction valve 2205 First heating storage tank pure water introduction flexible pipe 2206 First heating storage tank pure water introduction valve 2207 First electrodeposition tank pure water introduction valve 2208 First electrodeposition tank pure water introduction insulation pipe 2209 Second Heating tank pure water introduction flexible pipe 2210 Second heating tank pure water introduction valve 2211 Second electrodeposition tank pure water introduction valve 2212 second electrodeposition tank pure water introduction insulating pipe 2213 electrodeposition tank preliminary introduction port 2214 electrodeposition tank preliminary introduction valve 2215 first electrodeposition tank preliminary introduction valve 2216 first electrodeposition tank preliminary introduction insulation pipe 2217 second electrodeposition tank Preliminary introduction valve 2218 Second electrodeposition tank preliminary introduction insulating pipe 2219 Second electrodeposition tank overflow return path 2220 Second electrodeposition tank overflow return path insulating flange 2221 Second electrodeposition tank overflow return direction 2222 Second circulation tank 2223 Second Circulating tank heating storage tank 2224 to 2231 Second circulating tank heater 2232 Second circulating tank electrodeposition bath upstream circulation source valve 2233 Second circulating tank electrodeposition bath upstream circulation direction 2234 Second circulating tank electrodeposition bath upstream circulation pump 2235 Second circulation Tank circulation bath upstream circulation pump bypass valve 2236 Second circulation bath electrodeposition bath upstream circulation pressure gauge 223 Second circulation tank electrodeposition bath upstream circulation valve 2238 Second circulation tank electrodeposition bath upstream circulation flexible pipe 2239 Second circulation tank electrodeposition bath upstream circulation flange insulation pipe 2240 Second circulation tank inlet shower flexible pipe 2241 Second circulation tank inlet Shower valve 2242 Second circulation tank electrodeposition bath downstream circulation source valve 2243 Second circulation tank electrodeposition bath downstream circulation pump direction 2244 Second circulation tank electrodeposition bath downstream circulation pump bypass valve 2245 Second circulation tank electrodeposition bath downstream circulation pump 2246 Second circulation tank electrodeposition bath downstream circulation pressure gauge 2247 Second circulation tank electrodeposition bath downstream circulation valve 2248 Second circulation tank electrodeposition bath downstream circulation flexible pipe 2249 Second circulation tank electrodeposition bath downstream circulation flange insulation pipe 2250 Second Circulation tank electrodeposition bath bypass circulation flexible pipe 2251 Second circulation tank electrodeposition bath bypass circulation Valve 2252 Second electrodeposition tank outlet shower valve 2253 Second electrodeposition tank filter circulation return flexible pipe 2254 Second electrodeposition tank filter circulation return flange insulated pipe 2255 Second electrodeposition tank drain valve 2256 Second electrodeposition tank filter circulation source Valve 2257 Second electrodeposition tank filter circulation direction 2258 Second electrodeposition tank filter circulation suction filter 2259 Second electrodeposition tank filter circulation pump bypass valve 2260 Second electrodeposition tank filter circulation pump 2261 Second electrodeposition tank filter circulation pressure switch 2262 Second electrodeposition tank filter circulation pressure gauge 2263 Second electrodeposition tank filter circulation filter 2264 Second electrodeposition tank filter circulation direction 2265 Second electrodeposition tank filter circulation direction 2266 Second electrodeposition tank filter circulation flexible pipe 2 267 Second electrodeposition tank filter circulation flange insulating pipe 2268 Second electrodeposition tank filter circulation valve 2269 Second electrodeposition tank filter circulation system electrodeposition bath upstream return valve 2270 Second electrodeposition tank filter circulation system electrodeposition bath return valve 2271 Second electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2272 Second electrodeposition tank stirring air downstream control valve 2273 Second drainage tank drainage storage tank 2274 Second drainage tank 2275 Second drainage tank air release valve 2276 Second drain tank air vent 2277 First drain tank drain storage tank top lid 2278 Second drain tank drain storage tank top lid 2279 Pure water shower tank return entry roller 2280 Pure water shower tank roller 2281 First hot water tank return entry roller 2282 First hot water tank roller 2283 Second hot water tank turn-back entry roller 2284 Second hot water tank roller 2285 Drying turn-back roller 2286 Take-up device entry roller 2287 Take-up device direction change roller 2288 Take-up adjustment roller 2289 Long substrate winding bobbin 2290 Interleaf feeding bobbin 2292 Long substrate winding direction 2293 Long substrate winding bobbin rotating direction 2294 Interleaf feeding bobbin rotation direction 2295 Take-up device clean booth 2296 Take-up device 2297 Second electrodeposition tank outlet shower 2298 Pure water shower tank back brush 2299 Pure water shower tank inlet surface pure water shower 2300 Pure water shower tank inlet back pure water Shower 2301 Pure water shower tank exhaust port 2302 Pure water shower tank outlet back side pure water shower 2303 Pure water shower tank outlet surface pure water shower 2304 First hot water tank hot water insulated heater 2305 First hot water tank exhaust 2306 First hot water tank ultrasonic source 2307 Second hot water tank warm water heater 2308 Second hot water tank outlet 2309 Second hot water tank outlet back pure water shower 2310 Second hot water tank outlet front pure water shower 2311 Drying section inlet rear air knife 2312 Drying section inlet surface air knife 2313 IR lamp 2314 Drying section exhaust port 2315 Pure water shower tank receiving tank 2316 First hot water tank hot water holding tank 2317 Second hot water tank hot water holding tank 2318 Pure water shower tank folding entry roller cover 2319 First Hot water tank return entry roller cover 2320 Second hot water tank return entry roller cover 2321 Drying section cover 2322 Hot water tank connection pipe 2323 Pure water shower tank pure water shower supply valve 2324 pure water shower tank pure water shower supply pump bypass valve 2325 pure water Shower tank pure water shower supply pump 2326 Pure water shower tank pure water shower supply pressure switch 2327 pure water shower tank pure water shower supply pressure gauge 2328 pure water shower tank pure water shower supply cartridge type filter 2329 pure water shower tank pure water shower supply Flow meter 2330 Pure water shower tub inlet surface pure water shower valve 2331 Pure water shower tub inlet back pure water shower valve 2332 Pure water shower tub outlet back pure water shower valve 2333 Pure water shower tub outlet surface pure water shower valve 2334 First temperature Water tank hot water holding tank drain valve 2335 Second hot water tank hot water holding tank drain valve 2336 Rinse system drainage 2337 Rinse system pure water port 2338 Rinse system pure water supply valve 2339 Pure water heating tank 2340-2343 Pure water heating tank Pure water heater 2344 Pure water Heat tank pure water delivery valve 2345 Pure water heating tank pure water delivery pump bypass valve 2346 pure water heating tank pure water delivery pump 2347 pure water heating tank pressure switch 2348 pure water heating tank pressure gauge 2349 pure water heating cartridge filter 2350 pure Water heating tank flow meter 2351 Second hot water tank outlet back surface shower valve 2352 Second hot water tank outlet front surface shower valve 2353 Drying compressed air inlet 2354 Drying compressed air pressure switch 2355 Drying compressed air filter regulator 2356 Drying compressed air mist Separator 2357 Drying system compressed air supply valve 2358 Drying unit inlet back surface air knife valve 2359 Drying unit inlet surface air knife valve 2360 Pure water shower tank 2361 First hot water tank 2362 Second hot water tank 2363 Drying unit 2364 Electrodeposition rinsing system exhaust duct Rinsing flange 2365 Electrodeposition rinsing system exhaust duct main insulating flange 2366 Electrodeposition rinsing system exhaust duct condenser 2367 Electrodeposition rinsing system exhaust duct heat exchange grid 2368 Electrodeposition rinsing system exhaust duct condenser drain drain 2369 Electrodeposition washing system exhaust 2370 Dry system exhaust duct 2371 Dry system condenser 2372 Dry system heat exchange grid 2373 Dry system condenser drain drain 2374 Dry system exhaust

Continuation of the front page (72) Inventor: Toyama, 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor: Yusuke Miyamoto 3-30-2, Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. F term (reference) 5F051 AA05 BA12 BA14 CB27 CB29 CB30 FA02 GA02 HA06 HA07

Claims (5)

[Claims] 1. A substrate consisting of a conductive substrate is immersed in an aqueous solution containing at least nitrate ions and zinc ions, and a negative current is applied to a counter electrode immersed in the aqueous solution. A method for rinsing the zinc oxide thin film formed in the step of depositing the zinc oxide thin film on the substrate, wherein the electrical conductivity of the rinsing bath used for rinsing is set to 150 μS.
/ Cm / cm or less. 2. The rinsing method according to claim 1, wherein the electrical conductivity of the rinsing bath used for rinsing is controlled to 1 μS / cm or less. 3. The rinsing method according to claim 1, wherein the zinc oxide thin film is deposited by a roll-to-roll method. 4. The rinsing method according to claim 3, wherein a shower tub, a first rinsing tub, and a second rinsing tub are provided, and cleaning is performed in this order. 5. A photovoltaic device manufactured by a manufacturing process including the rinsing method according to claim 1. Description: