JP3445203B2 - Zinc oxide electrodeposition method and apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for electrochemically depositing zinc oxide on a substrate from an aqueous solution, and more particularly to a method and apparatus for forming a zinc oxide thin film with improved conductivity. Pertain to. The zinc oxide thin film according to the present invention can be effectively used for a reflective layer of a solar cell, for example. Hereinafter, the method of electrochemically depositing from an aqueous solution may be referred to as electrodeposition, but it has the same meaning as electroplating.

[0002]

2. Description of the Related Art In Japanese Unexamined Patent Publication No. 9-92864,
An example in which a zinc oxide thin film is deposited and deposited on a long substrate from an aqueous solution and applied to a solar cell has been reported. Here, a technique is disclosed in which a transparent conductive film (zinc oxide film) can be deposited from an acidic solution containing zinc nitrate and nitric acid by applying an electric current.

Further, JP-A-10-140373 discloses a technique of electrochemically forming a zinc oxide film having excellent uniformity by adding a carbohydrate to an aqueous solution.

Further, the present applicant has filed Japanese Patent Application No. 10-3770.
No. 05 “Substrate with zinc oxide layer, method for forming zinc oxide layer, photovoltaic element and method for producing the same”, a metal aluminum layer formed by sputtering on a roll substrate, and an aluminum oxide layer whose surface is treated with oxygen plasma Further, a method is proposed in which a zinc oxide layer is formed by sputtering and then a zinc oxide layer is formed by electrodeposition.

The method of electrically depositing zinc oxide from an aqueous solution, as claimed in these publications, can form a film much more easily and cheaply than a vacuum process such as a sputtering method. Is big.

[0006]

However, when the present inventor examined an electrochemical deposition method from an aqueous solution, the electrical resistance value of the zinc oxide film formed was not constant.
That inconvenience was found. In particular, it often showed a high resistance value of two digits or more without knowing the reason, and could not be applied to, for example, a solar cell.

Zinc oxide is deficient in oxygen as described in "Physical Science Selection: Electrically Conductive Oxides" (Tetsuo Tsuda, Heichiro Nasu, Atsushi Fujimori, Kiichi Shiratori, Sokabo, 1993 revised fourth edition). Type n-type semiconductor, and variations in its resistance have been pointed out for some time.

For example, J. O. Barnes et a
l. J. Electrochem. Soc. , 127
(1980), 1636-1640, "Relatio.
nship Between Deposition
Conditions and Physical P
properties of Sputtered Zn
It has been pointed out that in the case of "O", the resistance value of the zinc oxide film sputter-deposited under the condition of different oxygen concentration greatly changes due to the difference in carrier density due to oxygen defects.

In addition, A. P. Roth et al. ，
JAP, 52 (1981), 6685-6692, "P.
properties of zinc oxide f
ilms prepared by the oxid
"ation of diety zinc" states that the resistance of a zinc oxide thin film formed by a CVD method is greatly affected by the amount of oxygen during film formation and the chemical oxygen adsorption at grain boundaries.

S. Major et al. , Thin
Solid Films, 143 (1986), 19
-30, "Thickness-Dependent
Properties of Indium-Dope
In d ZnO Films ”, regarding the zinc oxide thin film formed by the sol-gel method, the thinner the film, the greater the influence of the interfacial barrier due to the chemisorption of oxygen. However, it is possible to avoid the influence by doping indium. There is.

[0011] Also, Baosheng Sang et
al. , JJAP, 37 (1998), L1125-
L1128, "Highly Stable ZnO"
Films by Atomic Layer Dep
position ", it is reported that the resistance value can be lowered even in a thin film by introducing boron into the zinc oxide film formed by the MOCVD method at the atomic layer level and performing doping.

The meaning of these documents is that zinc oxide adsorbs oxygen to grain boundaries regardless of the manufacturing method, thereby forming an acceptor level (that is, a trap for electrons which are n-type carriers), If the carrier can supply enough carriers to fill the level, there is no effect, but if not, an interface barrier is formed and the resistance increases. Therefore, when it is difficult to increase the resistance, a method of absorbing oxygen, securing a film thickness sufficient to supply carriers, or increasing the carrier density in advance by doping is used. Is.

The difficulty encountered by the inventor, however, was that the argument due to oxygen adsorption was inapplicable. That is, in the case of oxygen adsorption, vacuum annealing is extremely effective, whereas the inventor of the present invention was able to reduce the resistance by raising the temperature whether in vacuum or in the atmosphere. It was also found that a temperature of 400 ° C. or higher rather leads to a slight increase in resistance, which is not preferable. Furthermore, as mentioned above, "it shows a resistance value higher than two digits without knowing the reason", but this was measured by applying an electric field in the vertical direction to a zinc oxide thin film with a film thickness of 1000 Å to several microns. At that time, when the potential applied to both ends of the film was about 0.01 V, a substantially predetermined resistance value was exhibited with respect to a potential of about 0.5 V, which was extremely non-ohmic. . Further, additionally, Japanese Patent Laid-Open No. 10-140373.
Electrochemical deposition from an aqueous solution based on Japanese Patent Laid-Open Publication does not form a film on the negative electrode side, so that adsorption of oxygen is rather hindered, and it is not possible to actively supply oxygen also in the subsequent steps. No, if the cause is oxygen adsorption, its source is unknown.

For this reason, although water adsorption is suspected, there is no quantitative treatment of water adsorption and electric resistance in the film thickness direction of zinc oxide thin films in general. Also, for the same film thickness, the initial low resistance value is usually higher in the sputtering method and the electrochemical deposition from an aqueous solution. It is not clear whether it is inevitable due to the process restriction of immersion.

In the industrialization of electrochemical deposition from an aqueous solution based on Japanese Patent Application Laid-Open No. 10-140373, such unclear points have been a major obstacle. In fact, in the process of studying using a roll film forming apparatus to be described later, even if the water was intended to be sufficiently drained by the IR heater, when a solar cell was actually constructed, an abnormally large series resistance R _S was exhibited, and oxidation occurred. The resistance in the film thickness direction of the zinc film sometimes increased unexpectedly.

An object of the present invention is to provide a method and an apparatus capable of stably supplying a low resistance zinc oxide thin film by using electrochemical deposition from an aqueous solution.

[0017]

[Problem Avoidance Means Learned from Prior Art] JP-A-9-9
The drying according to Japanese Patent No. 2864 is that "IR heater heating drying in the air, hot air heating drying using hot oxygen, vacuum drying and the like are used" (page 4, 25 stages), and in the examples, "drying furnace 156 is It consists of a warm air nozzle 157 and an infrared heater 158. The warm air nozzle 157 also performed water repellency at the same time.The temperature of the warm air at the warm air nozzle 157 was 150 ° C. The temperature of the infrared heater 158 was 200 ° C. It was disclosed. ”

A drying system in which electrochemical deposition from an aqueous solution based on Japanese Unexamined Patent Publication No. 10-140373 has actually been attempted to industrialize and a disadvantage has occurred is draining with a room temperature air knife, followed by an IR heater. The temperature of the IR heater itself was heated to several hundred degrees, but the temperature of the hollow thermocouple on the substrate surface was about 180 ° C. Vacuum drying had no effect. In addition, although it was added to the IR heater and warm air was sent by an electric dryer, the improvement effect was hardly seen.

Japanese Unexamined Patent Publication (Kokai) No. 10-140373 discloses detailed contents regarding additives and orientation. Regarding the drying of the zinc oxide film after the film formation, the above-mentioned Japanese Unexamined Patent Publication (Kokai) No. 9-9.
No description is given above.

In Japanese Patent Application No. 10-377005 "Zinc Oxide Layer Substrate, Method for Forming Zinc Oxide Layer, Photovoltaic Element and Manufacturing Method Thereof"
In the stage, “... It is conveyed to the warm air drying furnace 2051. Here, it is dried with the convection air having a temperature sufficient to dry the water. The convection air therefor is the hot air generated in the hot air generating furnace 2055. , The dust is removed through the filter 2054, and is blown out from the warm air introducing pipe 2052. The overflowing air is again collected from the warm air collecting pipe 2053 and mixed with the outside air from the outside air introducing pipe 2056 to generate the hot air generating furnace 2055. It will be sent to ... "

However, as mentioned above, even if hot air was blown by the electric heating dryer, the effect was hardly obtained.

However, it was found that when the piece cut out from the roll was heated to 150 to 300 ° C. in an oven or an electric furnace, the resistance value was significantly lowered, and it became clear that there is a factor that can be adjusted in the subsequent process. It is reasonable to speculate that it may be inevitable due to the process restriction of being immersed in an aqueous solution. Therefore, it is necessary to suppress the conditions in order to stably supply a low resistance zinc oxide thin film by using electrochemical deposition from an aqueous solution. Unfortunately, the prior art does not answer this request.

[0023]

[Experiment for understanding mechanism] [Experiment 1: Quantification of adsorbed moisture and comparison with sputtered film] A zinc oxide film was formed on a SUS430 roll substrate (2D
Surface) 1 by electrochemical deposition from aqueous solution
A film with a thickness of μm was formed, and after drying with an IR heater, a roll with a zinc oxide film was produced in which no moisture was visually observed. A 2 x 4 cm piece cut out from the roll
Similarly, a 2 × 4 cm piece cut out from a zinc oxide roll having a film thickness of 1 μm formed by a sputtering method and a Karl Fischer moisture meter (MKC-51 manufactured by Kyoto Electronics Co., Ltd.
The water content was quantified through 0). The results are about 150 μg for electrochemical deposition and about 15 for sputter.
It was μg. It was found that the one that was electrochemically deposited from the aqueous solution contained approximately 10 times more water.

[Experiment 2: Presence of Crystal Water] In order to determine whether water is contained in the form of crystal water or is simply adsorbed, the electrochemically deposited zinc oxide deposited thickly is scraped off. Differential thermal analyzer (EXST manufactured by Seiko Denshi
TGA was measured by AR6000). The measurement was conducted up to 450 ° C, but no moisture release was observed at a specific temperature.
The weight change was always observed at a constant speed. From this, it was found that water was contained in the form of adsorption.

[Experiment 3: Relationship between residual water content and resistance value under some dry conditions] Using a roll with a zinc oxide film prepared in Experiment 1 (IR heater process is passed), part of which is 5 cm square Cut into test pieces and put in a portable electric furnace (AMF-10 manufactured by Asahi Rika Seisakusho Co., Ltd.), and the rest is placed in a roll dryer (in-house manufactured device, referred to as RD here), and in the atmosphere under each drying condition. Dried. After that, the test piece was left as it was, and the roll-dried one was cut into a test piece size, and a vacuum vapor deposition machine was used to vapor-deposit Cr and Au metal using a 0.25 cm ² (5.6φ) mask to deposit the upper electrode. Then, the resistance value between the SUS substrate and the SUS substrate was measured. Further, the test pieces under the same conditions were measured for water content with the above-mentioned Karl Fischer water content measuring device, and the correlation with the resistance value was checked. Table 1 shows a list of the experimental results.

[0026]

[Table 1]

In measuring the electric resistance, since the measuring system itself including the measuring needle has a circuit resistance of about 0.4Ω, it may be considered that the degree includes an error (no correction). The residual water content was expressed as a percentage by normalizing the actual water content of the measured water content to the water content of the product that was not dried (the IR heater process is passing). From Table 1 of this result, the following was found. The resistance value depends on the residual water content. If 30% of water is removed, the resistance value will drop sufficiently. The amount of water removed increases with temperature and time, but the effect of temperature is greater. The set temperature of the system deviates by about 100 ° C., but the tendency is the same.

[Experiment 4: Water adsorption after drying] The test piece dried in Experiment 3 was allowed to stand in a normal environment in a room for 3 days, but no increase in contained water was observed.

[Conclusion of Experiment] It was found that not only oxygen but also water adsorption increases the resistance value. Moisture adsorption is a fatal part of the process using water and contains more water than sputter. However, these waters are released by drying in the air, and the resistance value is lowered. Usually 10%, especially 3
A moisture removal of 0% guarantees a practically preferred resistance value. Once released, the water does not easily adsorb. Drying that promotes the removal of water requires sufficient temperature to be applied to the membrane,
Since the set temperature varies greatly depending on the system, it needs to be experimentally determined.

[0030]

Means for Solving the Problems Based on the above experiments and conclusions, the inventions reached by the present inventor to solve the above problems are as follows.

That is, the present invention is a zinc oxide electrodeposition method in which zinc oxide is electrochemically deposited from an aqueous solution on a substrate, and the deposited film is washed with water and dried. It is characterized in that at least 30% can be released.

Further, according to the present invention, in a zinc oxide electrodeposition apparatus in which zinc oxide is electrochemically deposited from an aqueous solution on a substrate, and the deposited film is washed with water and dried, the water content adsorbed on zinc oxide is contained in a drying section. It is characterized by having a means for releasing at least 30%.

A further feature of the above zinc oxide electrodeposition method and electrodeposition apparatus of the present invention is that "at least 30% of the water content adsorbed on zinc oxide is desorbed by, for example, warm air from a warm air generating circulator.""The temperature of warm air is 2
"It is at least 00 ° C", "the substrate is a roll-shaped metal", "the substrate transportation speed is 1000 mm / min or more", "the aqueous solution contains zinc nitrate, and its concentration is 0.05M. / L or more "," a thin film of zinc oxide is formed on the substrate by sputtering prior to deposition by electrodeposition "," the thickness of the zinc oxide thin film by sputtering is 2000 Å or less ", Is included.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described based on a specific device.

[General Structure and Operation of Electrodeposition Apparatus of the Present Invention] FIG. 2 shows a long substrate electrodeposition apparatus to which the present invention can be applied. Further, enlarged views of the division are shown in FIGS. 2 and 3 to 9, the names and reference numerals of the respective parts are the same. A procedure for forming or depositing an electrodeposition film on a long substrate using this apparatus will be described with reference to these drawings.

The apparatus is roughly divided into an unwinding apparatus 2012 for feeding a long substrate wound in a coil, a first electrodeposition tank 2066 for depositing or processing a first electrodeposited film, and a second electrodeposited film. A second electrodeposition tank 2116 for depositing or treating, a first circulation tank 2120 for circulatingly supplying the heated electrodeposition bath to the first electrodeposition tank, and a cyclic supply of the heated electrodeposition bath for the second electrodeposition tank. Two circulation tank 2222, first depositing bath when draining the electrodeposition bath of first electrodeposition tank 2066; first draining tank 2172, second depositing bath of the second electrodeposition tank 2116 when draining the electrodeposition bath A drainage tank 2274 and a filter circulation system for cleaning the bath by removing powder in the electrodeposition bath in the first electrodeposition tank 2066 (first electrodeposition tank filter circulation filter 2161 (see FIG. 4))
(A piping system connected to the second electrodeposition tank 2116 (see FIG. 5)) which removes powder in the electrodeposition bath in the second electrodeposition tank 2116 to clean the bath. , First electrodeposition tank 2066 and second electrodeposition tank 21
16, a piping system for sending compressed air for bath agitation (a piping system starting from compressed air inlet 2182 (see FIG. 6)),
A pure water shower tank 2360 for cleaning a long substrate on which an electrodeposited film is deposited with a pure water shower, a first warm water tank 2361 for performing a first pure water rinse cleaning, and a second for performing a second pure water rinse cleaning Hot water tank 2362, pure water heating tank 2339 for supplying hot water of necessary pure water to these hot water tanks, drying section 2363 for drying the washed long substrate, long substrate on which film deposition is completed is again coiled. Winding device 2296 for winding up to the above, an exhaust system of vapor generated in a heating step or a drying step of an electrodeposition bath or pure water (electrodeposition washing system exhaust duct 2020 (see FIGS. 4 and 5) or a drying system exhaust duct 2370 (see FIG. 7)).

The long substrate is unwinding device 20 from left to right in the figure.
12, the first electrodeposition tank 2066, the second electrodeposition tank 2116, the pure water shower tank 2360, the first hot water tank 2361, the second hot water tank 2362, the drying section 2363, and the winding device 2296 are carried in this order and predetermined. The electrodeposited film is deposited.

In the unwinding device 2012, as shown in FIG. 3, the coiled long substrate 2006 wound on the unwinding device long substrate bobbin 2001 is set, and the unwinding device feeding adjustment roller 2003 and the unwinding device direction are set. The long substrate 20 is passed through the conversion roller 2004 and the unwinding device discharge roller 2005 in this order.
06 is sent out. An interleaf (interleaving paper) is supplied to the coiled long substrate in the form of being wound in order to protect the substrate or the layer, especially when the undercoat layer is previously deposited. Therefore, when the interleaf is wound, the interleaf 2007 is wound on the unwinding device interleaf winding bobbin 2002 together with the feeding of the long substrate.

The long substrate 2006 is conveyed in the direction of arrow 201.
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 indicated by an arrow 2008.

In the figure, the long substrate discharged from the unwinding device long substrate bobbin 2001 and the interleaf wound up on the unwinding device interleaf take-up bobbin 2002 are located at the start position and at the end of the transfer, respectively. It shows that there is no interference at the position.

The entire unwinding device has a structure covered with a unwinding device clean booth 2011 using a hepa filter and downflow to prevent dust.

As shown in FIG. 4, the first electrodeposition bath 2066 is a temperature controlled electrodeposition bath in a first electrodeposition bath holding tank 2065 which can keep the electrodeposition bath warm without being corroded. Are held so as to become the bath surface 2025 of the first electrodeposition bath. The position of this bath surface is realized by an overflow due to a partition plate provided in the first electrodeposition bath holding tank 2065. A partition plate (not shown) is installed so as to drop the electrodeposition bath toward the inner side of the entire first electrodeposition bath holding tank 2065, and is collected in the first electrodeposition tank overflow return port 2024 in a gutter structure. The overflowed electrodeposition bath is the overflow return path 211 of the first electrodeposition tank.
7 to the first circulation tank 2120, where it is heated, and again heated from the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe 2064 to the first electrodeposition bath holding tank 20.
Reflux to 65 to form enough inflow of the electrodeposition bath to encourage overflow.

The long substrate 2006 is passed through the electrodeposition tank inlet folding roller 2013 (see FIG. 3), the first electrodeposition tank entrance roller 2014, the first electrodeposition tank exit roller 2015, and the electrodeposition tank interfolding roller 2016, It passes through the first electrodeposition tank 2066. Between the first electrodeposition tank entry roller 2014 and the first electrodeposition tank exit roller 2015, at least the lower surface of the long substrate (the surface in the present specification is often referred to as “surface”) which is a film formation surface.
28 anodes 2 in the electrodeposition bath.
It faces 026 to 2053. The actual electrodeposition is performed by applying a negative potential to the long substrate and a positive potential to the anode, and flowing an electrodeposition current accompanied by an electrochemical reaction between them in the electrodeposition bath.

In the present apparatus, four anodes 2026 to 2053 in the first electrodeposition tank 2066 are mounted on seven anode mounting bases 2054 to 2060.
The anode mounting table has a structure in which each anode is placed via an insulating plate, and a unique potential is applied from an independent power source. In addition, the anode mounting table 20
54 to 2060 are long substrates and anodes 202 in the electrodeposition bath
It also has a function of maintaining the distance from 6 to 2053. Therefore, the anode mounting tables 2054 to 2060 are usually designed and manufactured so that the heights thereof can be adjusted so as to maintain a predetermined interval.

The first electrodeposition tank backside electrode 2061 provided immediately before the first electrodeposition tank leaving roller 2015, the surface opposite to the film forming surface of the long substrate in the bath (often referred to as "rear surface" in this specification).
(Hereinafter referred to as ") is electrochemically removed, and this is realized by setting the first electrodepositing tank rear surface electrode 2061 to the negative potential with respect to the long substrate 2006.
The fact that the first electrodepositing tank back surface electrode 2061 is actually effective means that it is formed on the film formation surface of the long substrate, which is electrochemically attached to the back surface on the opposite side of the film formation surface of the long substrate due to the wraparound of the electric field. This is confirmed by the fact that the film made of the same material as that described above is visually removed.

The long substrate that has passed through the first electrodeposition tank exit roller 2015 and exited from the electrodeposition bath is subjected to the electrodeposition bath from the first electrodeposition tank outlet shower 2067, and the film-forming surface is dried. Prevents unevenness. The first electrodeposition tank 2066
The inter-deposition tank cover 2019 provided at the crossing portion between the second electrodeposition tank 2116 and the second electrodeposition tank 2116 also traps the vapor generated from the electrodeposition bath and prevents the film formation surface of the long substrate from drying. Further, the second electrodeposition tank inlet shower 2068 also functions to prevent drying.

The first circulation tank 2120 is the first electrodeposition tank 206.
It is responsible for heating and heat retention of the electrodeposition bath in 6 and jet circulation. As described above, the electrodeposition bath overflowed in the first electrodeposition tank 2066 is the first electrodeposition tank overflow return port 2
Collected in 024, overflow return path 1 of the first electrodeposition tank
117, and reaches the first circulation tank heating storage tank 2121 through the first electrodeposition tank overflow return path insulating flange 2118. Eight first circulation tank heaters 2122 to 2129 are provided in the first circulation tank heating storage tank 2121, and when the room temperature electrodeposition bath is initially heated, or the circulation lowers the bath temperature. Is reheated to function in maintaining 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, and the first circulation tank electrodeposition bath upstream circulation valve 213.
5, first circulation tank electrodeposition bath upstream circulation flexible pipe 21
36, first circulation tank electrodeposition bath upstream circulation flange insulating pipe 21
After passing through 37, the first electrodeposition tank upstream circulation reflux system returns from the first electrodeposition tank upstream circulation jet pipe 2063 to the first electrodeposition bath holding tank 2065, the first circulation tank electrodeposition bath downstream circulation source valve 2139, One 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 insulating pipe 2149. After that, it is a circulating circulation system downstream from the first electrodeposition tank, which returns from the circulating jet pipe 2064 to the first electrodeposition bath holding tank 2065.

The first electrodeposition tank 206 is connected from the first electrodeposition tank upstream circulation jet tube 2063 and the first electrodeposition tank downstream circulation jet tube 2064.
The electrodeposition bath returning to 6 is the first electrodeposition bath holding tank 2 so that the exchange of the electrodeposition bath in the first electrodeposition bath holding tank 2065 can be effectively performed.
First electrodeposition tank upstream circulation jet pipe 20 provided at the lower part of 065
63 and the first circulation tank downstream circulation jet tube 2064 are recirculated as a jet stream through the orifices formed in each jet tube.

The amount of reflux in each circulation reflux system is mainly
It is controlled by the opening / closing degree of the first circulation tank electrodeposition bath upstream circulation valve 2135 or the first circulation tank electrodeposition bath downstream circulation valve 2145, and further fine adjustment is performed by the first circulation tank electrodeposition bath upstream circulation pump 2132 or the first circulation. First circulation tank electrodeposition bath upstream circulation pump bypass valve 2133 or first circulation tank electrodeposition bath downstream circulation pump bypass hull provided in a bypass system in which the outlet and the inlet of the tank electrodeposition bath downstream circulation pump 2142 are short-circuited and connected. Controlled by 2141. The bypass system also plays a role of preventing cavitation in the pump when the amount of reflux is small or when the bath temperature is extremely close to the boiling point. Cavitation, which makes the bath liquid boil to vaporize and cannot pump the liquid, significantly shortens the life of the pump.

When a jet is formed by forming an orifice in the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe 2064, the reflux amount is almost the first electrodeposition tank upstream circulation jet pipe 2063. And the pressure of the solution returned to the circulating 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.
The balance of the reflux amount can be known with these pressure gauges. To be precise, the amount of the reflux bath liquid blown out from the orifice complies with Bernoulli's theorem, but when the orifice bored in the jet tube has a diameter of several millimeters or less, the first electrodeposition tank upstream circulation jet tube 2063 or the first electrodeposition tank downstream circulation is used. The jet flow rate can be made substantially constant over the entire jet pipe 2064.

Further, when the reflux amount is sufficiently large, the bath can be replaced very smoothly, so that the first electrodeposition tank 20
Even if 66 is considerably long, it is possible to effectively make the concentration of the bath uniform and the temperature uniform. Of course, the first electrodeposition tank overflow return path 2117 should have a thickness capable of flowing this sufficient reflux amount.

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 strain in the piping system, and is particularly effective when using flange-insulated piping or the like, which tends to lack mechanical strength against strain.

The first circulation tank electrodeposition bath upstream circulation flange insulating pipe 2137 and the first circulation tank electrodeposition bath downstream circulation flange insulating pipe 2149 provided in each circulation reflux system are the first electrodeposition tank overflow return path 2117. The first circulation tank 2120 and the first electrodeposition tank 2066 are electrically floated together with the first electrodeposition tank overflow return insulating flange 2118 provided on the way. This is because the formation of unnecessary current paths is prevented, that is, the prevention of stray current leads to the stable and effective progress of the electrochemical film formation reaction utilizing the electrodeposition current. It is based on knowledge.

In one circulation / reflux system, a bypass circulation consisting of a first circulation tank electrodeposition bath bypass circulation flexible pipe 2146 directly returning to the first circulation tank heating storage tank 2121 and a first circulation tank electrodeposition bath bypass circulation valve 2147. A system is provided and is used when it is desired to circulate the bath without refluxing the bath liquid in the first electrodeposition tank, for example, when the temperature is raised from room temperature to a predetermined temperature.

Further, in one circulation / reflux system from the first circulation tank 2120, the first electrodeposition is performed in which a long substrate passing through the first electrodeposition tank leaving roller 2015 and discharged from the electrodeposition bath is subjected to the electrodeposition bath. A liquid delivery system is provided to reach the bath outlet shower 2067, and is connected to the first electrodeposition bath outlet shower 2067 via the first electrodeposition bath outlet shower valve 2150. The amount of electrodeposition liquid sprayed from the first electrodeposition tank outlet shower 2067 is
It is adjusted by adjusting the opening / closing degree of the shower valve 2150 at the outlet of the first electrodeposition tank.

The first circulation tank heating storage tank 2121 is actually provided with a lid, and has a structure for preventing water from being lost as steam. When the bath temperature is high, the temperature of the lid is also high, so it is necessary to consider attaching a heat insulating material from the viewpoint of work safety.

A filter circulation system is provided for removing powder from the first electrodeposition tank electrodeposition bath. The filter circulation system for the first electrodeposition tank includes a first electrodeposition tank filter circulation return flexible pipe 2151, a first electrodeposition tank filter circulation return flange insulating pipe 2152, a first electrodeposition tank filter circulation source valve 2154, and a first electrode. Deposition 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 circulation filter 216
1, first electrodeposition tank filter circulation flexible pipe 21
64, first electrodeposition tank filter circulation flange insulating pipe 21
65, first electrodeposition tank filter circulation valve 2166, first electrodeposition tank filter circulation system electrodeposition bath upstream return valve 216
7. The first electrodeposition tank filter circulation system in-bath return valve 2168 and the first electrodeposition tank filter circulation system downstream electrode return bath valve 2169. In this route, the electrodeposition bath is the first electrodeposition tank filter circulation direction 2155, 2162,
It flows in the direction of 2163. The powder to be removed may jump from the outside of the machine or may be formed on the surface of the electrode or in the bath depending on the electrodeposition reaction. The minimum size of the powder to be removed is determined by the filter size of the first electrodeposition tank filter circulation filter 2161.

The first electrodeposition tank filter circulation return flexible pipe 2151 and the first electrodeposition tank filter circulation flexible pipe 2164 absorb the strain of the pipe,
The purpose of this is to minimize the liquid leakage from the pipe connecting portion, protect the insulated pipe having poor mechanical strength, and increase the degree of freedom in arranging the components of the circulation system including the pump.

The first electrodeposition tank filter circulation return flange insulation pipe 2152 and the first electrodeposition tank filter circulation flange insulation pipe 2165 prevent the first electrodeposition bath holding tank 2065 floated from the earth ground to the earth ground. In order to prevent it, it is intended to float electrically.

The first electrodeposition tank filter circulation suction filter 2156 is, so to speak, a wire mesh like "tea strainer", and removes large dust, and the subsequent first electrodeposition tank filter circulation pump 2157 and the first electrodeposition tank filter circulation. This is for protecting the filter 2161.

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

The circulation flow rate of the electrodeposition bath of the present circulation system is mainly the first electrodeposition tank filter circulation valve 2166, and secondly the first electrodeposition tank filter circulation pump 2157 provided in parallel. The tank filter circulation pump bypass valve 2158 is used for fine adjustment. A first electrodeposition tank filter circulation pressure gauge 2160 is provided in order to grasp the circulation flow rate due to the adjustment of these valves. The first electrodeposition tank filter circulation pump bypass valve 2158 prevents fine adjustment of the flow rate, and also prevents cavitation from occurring and damaging the first electrodeposition tank filter circulation pump 2157 when the entire filter circulation flow rate is reduced. There is.

The electrodeposition bath can be transferred from the first electrodeposition tank drain valve 2153 to the first drainage tank 2172 (see FIG. 6) through the first electrodeposition tank filter circulation return flange insulating pipe 2152. This transfer is performed for electrodeposition bath replacement, equipment maintenance, and in an emergency. The electrodeposition bath as the transferred waste liquid is dropped by gravity and the first waste liquid tank waste liquid storage tank 2144.
Be dropped by. For the purpose of maintenance or emergency, it is preferable that the first drainage tank drainage storage tank 2144 has a capacity enough to store the total bath capacity of the first electrodeposition tank 2066 and the first circulation tank 2120.

The first drainage tank drainage storage tank 2144 is provided with a first drainage tank drainage storage tank upper lid 2277, and in order to effectively make the gravity drop transfer of the electrodeposition bath, the first drainage tank An air vent 2171 and a first drainage tank air vent valve 2170 are provided.

The temperature of the electrodeposition bath once dropped into the first drainage tank drainage storage tank 2144 is lowered from the first drainage tank drainage valve 2173 to the waste water treatment on the building side or the first drainage solution. Tank drainage recovery valve 2174, drainage recovery source valve 217
5. Drainage recovery After passing through the suction filter 2176 and the drainage recovery pump 2177, it is collected in a drum can (not shown) and appropriate disposal is performed. It is also possible to perform dilution with water or treatment with a chemical solution in the first drainage tank drainage storage tank 2144 prior to the recovery or treatment.

In order to stir the electrodeposition bath and make the electrodeposition film uniform, a first electrodeposition tank stirring air introduction pipe 2062 (see FIG. 4) installed at the bottom of the first electrodeposition bath holding tank 2065. Air bubbles are ejected from a plurality of orifices drilled. As for the air, the compressed air supplied to the factory is taken in through the compressed air introduction port 2182 (see FIG. 6), passes through the compressed air pressure switch 2183 for electrodeposition bath stirring, and is shown in the first electrodeposition tank compressed air introduction direction 2184. Direction, in order, the first electrodeposition tank compressed air source valve 2185, the first electrodeposition tank compressed air flow meter 2186, the first electrodeposition tank compressed air regulator 2187, and the first electrodeposition tank compressed air mist separator 21.
88, the first electrodeposition tank compressed air introduction valve 2189, the first electrodeposition tank compressed air flexible pipe 2190, the first electrodeposition tank compressed air insulating pipe 2191, and the first electrodeposition tank compressed air upstream side control valve 2193 or It passes through the control valve 2192 on the downstream side of the compressed air in one electrodeposition tank and reaches the agitating air introduction pipe 2062 in the first electrodeposition tank.

The long substrate conveyed to the second electrodeposition tank 2116 (see FIG. 5) through the inter-electrodeposition tank folding roller 2016 has a second electrodeposition film deposited or processed. Depending on how to use this device, the second electrodeposition film is the same as the first electrodeposition film, and the first electrodeposition film and the second electrodeposition film may form one film. Also, it may be a stack of two layers that are made of the same material but have different characteristics (for example, a stack of layers having different particle sizes made of zinc oxide), and two layers made of different materials while having the same characteristics. May be a laminated layer (for example, a laminated layer of indium oxide and zinc oxide as the transparent conductive film) or a completely different two layered layer. The second electrodeposition tank 21 is formed by depositing a substance and performing an oxidation process in the second electrodeposition tank 2116, or by depositing a low oxide in the first electrodeposition tank 2066.
It is possible to perform a combination such as performing an etching process at 16. Therefore, the electrodeposition bath or treatment bath, bath temperature, bath circulation amount, current density, agitation amount and other electrodeposition or treatment conditions are selected according to each purpose. When it is necessary to change the electrodeposition or treatment time between the first electrodeposition tank 2066 and the second electrodeposition tank 2116, the passage time of the long substrate 2006 is set to the first electrodeposition tank 2066 and the second electrodeposition tank 2116. For this purpose, the length of the first electrodeposition tank 2066 and the second electrodeposition tank 2116 may be changed, or the long substrate may be folded back for adjustment.

As shown in FIG. 5, the second electrodeposition bath 2116 is a temperature controlled electrodeposition bath in a second electrodeposition bath holding tank 2115 capable of keeping the electrodeposition bath warm without being corroded. Are held so as to become the second electrodeposition bath surface 2074. The position of this bath surface is realized by an overflow due to a partition plate provided in the second electrodeposition bath holding tank 2115. The partition plate (not shown) is installed so as to drop the electrodeposition bath toward the inner side of the entire second electrodeposition bath holding tank 2115, and is collected in the second electrodeposition tank overflow return port 2075 in a gutter structure. The overflowed electrodeposition bath is the second electrodeposition tank overflow return path 221.
9 to the second circulation tank 2222, where it is heated, and again heated from the second electrodeposition tank upstream circulation jet pipe 2113 and the second electrodeposition tank downstream circulation jet pipe 2114 to the second electrodeposition bath holding tank 21.
Reflux to 15, forming enough inflow of the electrodeposition bath to encourage overflow.

The long substrate 2006 is passed through the electrodeposition tank folding roller 2016, the second electrodeposition tank entry roller 2069, the second electrodeposition tank exit roller 2070, and the pure water shower tank turnover roller 2279, and then the second electrodeposition. It passes through the tank 2116. Between the second electrodeposition tank entry roller 2069 and the second electrodeposition tank exit roller 2070, the surface of the long substrate was in the electrodeposition bath, and 28 second electrodeposition tank anodes 2076
To 2103. The actual electrodeposition is performed by applying a negative potential to the long substrate and a positive potential to the anode, and flowing an electrodeposition current accompanied by an electrochemical reaction between them in the electrodeposition bath.

In the present apparatus, four anodes 2076 to 2103 in the second electrodeposition tank 2116 are mounted on seven anode mounting bases 2104 to 2110.
The anode mounting table has a structure in which each anode is placed via an insulating plate, and a unique potential is applied from an independent power source. In addition, the anode mounting table 21
04-2110 is a long substrate and an anode 207 in the electrodeposition bath.
It also has a function of holding the interval between 6 and 2103. Therefore, the anode mounting bases 2104 to 2110 are usually designed and manufactured so that the heights thereof can be adjusted so as to maintain a predetermined interval.

The second electrodeposition tank backside electrode 2111 provided immediately before the second electrodeposition tank leaving roller 2070 is for electrochemically removing the film deposited on the backside of the long substrate in the bath. As with the first electrodepositing tank backside electrode 2061, this is achieved by setting the second electrodepositing tank backside electrode 2111 to the negative potential with respect to the long substrate 2006.

The long substrate that has passed through the second electrodeposition tank exit roller 2070 and exited from the electrodeposition bath is subjected to the electrodeposition bath from the second electrodeposition tank outlet shower 2297, and the film-forming surface is dried. Prevents unevenness. The second electrodeposition tank 2116
The deionized water shower tank turn-in roller cover 2318, which is provided between the pure water shower tank 2360 and the deionized water shower tank 2360, also traps the vapor generated from the electrodeposition bath and prevents the deposition surface of the long substrate from drying. There is. Further, the pure water shower tank inlet surface pure water shower 2299 and the pure water shower tank inlet rear surface pure water shower 2300 (see FIG. 7) not only wash and drop the electrodeposition bath, but also function similarly.

The second circulation tank 2222 is the second electrodeposition tank 211.
It is responsible for heating and heat retention of the electrodeposition bath in 6 and jet circulation. As described above, the electrodeposition bath overflowed in the second electrodeposition tank 2116 is the second electrodeposition tank overflow return port 2
No. 075, 2nd electrodeposition tank overflow return path 2
219, the second electrolytic bath overflow return path insulating flange 2220, and the second circulation tank heating storage tank 2223. Eight second circulation tank heaters 2224 to 2231 are provided in the second circulation tank heating storage tank 2223, and when the room temperature electrodeposition bath is initially heated, or the circulation lowers the bath temperature. Is reheated to function in maintaining the electrodeposition bath at a predetermined temperature.

Two circulation systems are connected to the second circulation tank heating storage tank 2223. 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 223.
7, second circulation tank electrodeposition bath upstream circulation flexible pipe 22
38, second circulation tank electrodeposition bath upstream circulation flange insulating pipe 22
After passing through 39, the second electrodeposition tank upstream circulation reflux system returning from the second electrodeposition tank upstream circulation jet pipe 2113 to the second electrodeposition bath holding tank 2115, the second circulation tank electrodeposition bath downstream circulation source valve 2242, Two 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 insulating pipe 2249. After that, the second circulation tank reflux circulation system returns from the second circulation tank downstream circulation jet pipe 2114 to the second deposition bath holding tank 2115.

The second electrodeposition tank 211 and the second electrodeposition tank downstream circulation jet pipe 2113 and 2114 are connected to each other to form the second electrodeposition tank 211.
The electrodeposition bath returning to No. 6 is the second electrodeposition bath holding tank 2 so as to effectively exchange the electrodeposition bath in the second electrodeposition bath holding tank 2115.
115 a second electrodeposition tank upstream circulation jet pipe 21 provided in the lower part
13 and the second circulation tank downstream circulation jet pipe 2114 are recirculated as a jet flow through the orifices formed in the respective jet pipes.

The amount of reflux in each circulation reflux system is mainly
It is controlled 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, and further fine adjustment is performed by the second circulation tank electrodeposition bath upstream circulation pump 2234 or the second circulation. Second circulation tank electrodeposition bath upstream circulation pump bypass valve 2235 or second circulation tank electrodeposition bath downstream circulation pump bypass hull provided in a bypass system in which the outlet and the inlet of the tank electrodeposition bath downstream circulation pump 2245 are short-circuited and connected. 2244. The bypass system also plays a role of preventing cavitation in the pump when the amount of reflux is small or when the bath temperature is extremely close to the boiling point. As described in the description of the first electrodeposition tank, the cavitation, which causes the bath liquid to boil and vaporize and the liquid cannot be sent, significantly shortens the life of the pump.

When a jet is formed by forming orifices in the second electrodeposition tank upstream circulation jet pipe 2113 and the second electrodeposition tank downstream circulation jet pipe 2114, the reflux amount is almost the same as the second electrodeposition bath upstream circulation jet pipe 2113. And the pressure of the solution returned to the downstream circulation jet pipe 2114 in 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,
The balance of the reflux amount can be known with these pressure gauges. To be precise, the amount of the reflux bath liquid blown out from the orifice complies with Bernoulli's theorem, but when the orifice bored in the jet tube has a diameter of several millimeters or less, the second electrodeposition tank upstream circulation jet tube 2113 or the second electrodeposition tank downstream circulation is used. The jet flow rate can be made substantially constant over the entire jet pipe 2114.

Further, when the reflux amount is sufficiently large, the bath can be replaced very smoothly, so that the second electrodeposition tank 21
Even if 16 is considerably long, the concentration of the bath and the temperature can be effectively equalized. It goes without saying that the second electrodeposition tank overflow return path 2219 should have a thickness capable of flowing this sufficient reflux amount.

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 strain in the piping system, and is particularly effective when using flange-insulated piping or the like, which tends to lack mechanical strength against strain.

The second circulation tank electrodeposition bath upstream circulation flange insulating pipe 2239 and the second circulation tank electrodeposition bath downstream circulation flange insulating pipe 2249 provided in each circulation reflux system are the second electrodeposition tank overflow return path 2219. The second circulation tank 2222 and the second electrodeposition tank 2116 are electrically floated together with the second electrodeposition tank overflow return insulating flange 2220 provided on the way. This is because the formation of unnecessary current paths is prevented, that is, the prevention of stray current leads to the stable and effective progress of the electrochemical film formation reaction utilizing the electrodeposition current. It is based on knowledge.

In one circulation / reflux system, the bypass circulation consisting of the second circulation tank electrodeposition bath bypass circulation flexible pipe 2250 and the second circulation tank electrodeposition bath bypass circulation valve 2251 directly returning to the second circulation tank heating storage tank 2223. A system is provided, which is used when it is desired to circulate the bath without refluxing the bath liquid in the second electrodeposition tank, for example, when raising the temperature from room temperature to a predetermined temperature.

Further, both circulation reflux systems from the second circulation tank 2222 are sent to a second electrodeposition tank inlet shower 2068 where an electrodeposition bath is placed just before reaching the second electrodeposition tank entrance roller 2069. Two liquid feeding systems are provided, one for passing the second substrate to the second electrodeposition tank outlet shower 2297, which passes the second electrodeposition tank exit roller 2070 and elongates the substrate that has come out of the electrodeposition bath. , The former to the second electrodeposition tank inlet shower 2068 via the second electrodeposition tank inlet shower valve 2241, and the latter to the second electrodeposition tank outlet shower 2297 via the second electrodeposition tank outlet shower valve 2252. Is connected. The amount of the electrodeposition liquid sprayed from the second electrodeposition tank inlet shower 2068 is controlled by adjusting the opening / closing degree of the second electrodeposition tank inlet shower valve 2241, and the electrodeposition from the second electrodeposition tank outlet shower 2297. The amount of liquid spray is adjusted by adjusting the opening / closing degree of the shower valve 2252 at the outlet of the second electrodeposition tank.

The second circulation tank heating storage tank 2223 is actually provided with a lid and has a structure for preventing water from being lost as steam. When the bath temperature is high, the temperature of the lid is also high, so it is necessary to consider attaching a heat insulating material from the viewpoint of work safety.

The second electrodeposition tank A filter circulation system is provided for removing powder from the electrodeposition bath. The filter circulation system for the second electrodeposition tank 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 electrode. Deposition 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 electrodeposition tank filter circulation filter 226
3, second electrodeposition tank filter circulation flexible pipe 22
66, second electrodeposition tank filter circulation flange insulating pipe 22
67, second electrodeposition tank filter circulation valve 2268, second electrodeposition tank filter circulation system electrodeposition bath upstream return valve 226
9. The second electrodeposition tank filter circulation system in-flow return valve 2270 and the second electrodeposition tank filter circulation system downstream electrode return bath valve 2271. In this route, the electrodeposition bath is the second electrodeposition tank filter circulation direction 2257, 2264,
It flows in the direction of 2265. The powder to be removed may jump from the outside of the machine or may be formed on the surface of the electrode or in the bath depending on the electrodeposition reaction. The minimum size of the powder to be removed is determined by the filter size of the second electrodeposition tank filter circulation filter 2263.

The second electrodeposition tank filter circulation return flexible pipe 2253 and the second electrodeposition tank filter circulation flexible pipe 2266 absorb strain of the pipe,
The purpose of this is to minimize the liquid leakage from the pipe connecting portion, protect the insulated pipe having poor mechanical strength, and increase the degree of freedom in arranging the components of the circulation system including the pump.

The second electrodeposition tank filter circulation return flange insulation pipe 2254 and the second electrodeposition tank filter circulation flange insulation pipe 2267 prevent the second electrodeposition bath holding tank 2115 floated from the earth ground to the earth ground. In order to prevent it, it is intended to float electrically.

The second electrodeposition tank filter circulation suction filter 2258 is, so to speak, a wire mesh like a "tea strainer", and removes large dust, followed by a second electrodeposition tank filter circulation pump 2260 and a second electrodeposition tank filter circulation. This is for protecting the filter 2263.

Second electrodeposition tank filter circulation filter 22
63 is the main part of this circulation system, and is for removing the powder mixed or generated in the electrodeposition bath.

The circulation flow rate of the electrodeposition bath of the present circulation system is mainly the second electrodeposition tank filter circulation valve 2268, and secondly the second electrodeposition tank filter circulation pump 2260 which is provided in parallel. The tank filter circulation pump bypass valve 2259 is used for fine adjustment. A second electrodeposition tank filter circulation pressure gauge 2262 is provided in order to grasp the circulation flow rate due to the adjustment of these valves. The second electrodeposition tank filter circulation pump bypass valve 2259 prevents fine adjustment of the flow rate and also prevents the second electrodeposition tank filter circulation pump 2260 from being damaged when cavitation occurs when the entire filter circulation flow rate is reduced. There is.

The electrodeposition bath can be transferred from the second electrodeposition tank drain valve 2255 to the second drainage tank 2274 (see FIG. 6) through the second electrodeposition tank filter circulation return flange insulating pipe 2254. This transfer is performed for electrodeposition bath replacement, equipment maintenance, and in an emergency. The electrodeposition bath as the transferred waste liquid is dropped by gravity and the second waste liquid storage tank 2273
Be dropped by. For the purpose of maintenance or emergency, it is preferable that the second drainage tank drainage storage tank 2273 has a capacity to store the total bath capacity of the second electrodeposition tank 2116 and the second circulation tank 2222.

The second drainage tank drainage storage tank 2273 is provided with a second drainage tank drainage storage tank upper lid 2278. In order to effectively make the gravity drop transfer of the electrodeposition bath, the second drainage tank An air vent 2276 and a second drainage tank air vent valve 2275 are provided.

After the temperature of the electrodeposition bath dropped in the second drainage tank drainage storage tank 2273 is lowered, the second drainage tank drainage valve 2180 is used for wastewater treatment on the building side or the second drainage solution is used. Tank drainage recovery valve 2181, drainage recovery source valve 217
5. Drainage recovery After passing through the suction filter 2176 and the drainage recovery pump 2177, it is collected in a drum can (not shown) and appropriate disposal is performed. It is also possible to perform dilution with water or treatment with a chemical solution in the second drainage tank drainage storage tank 2273 prior to recovery or treatment.

In order to stir the electrodeposition bath and make the electrodeposition film uniform, a second electrodeposition tank stirring air introduction pipe 2112 (see FIG. 5) installed at the bottom of the second electrodeposition bath holding tank 2115 is used. Air bubbles are ejected from a plurality of orifices drilled. The air takes in the compressed air supplied to the factory from the compressed air introduction port 2182 (see FIG. 6), passes through the compressed air pressure switch 2183 for stirring the electrodeposition bath, and is shown in the second electrodeposition tank compressed air introduction direction 2194. In the direction, the second electrodeposition tank compressed air source valve 2195, the second electrodeposition tank compressed air flow meter 2196, the second electrodeposition tank compressed air regulator 2197, and the second electrodeposition tank compressed air mist separator 21.
98, the second electrodeposition tank compressed air introduction valve 2199, the second electrodeposition tank compressed air flexible pipe 2220, the second electrodeposition tank compressed air insulating pipe 2201, and the second electrodeposition tank compressed air upstream side control valve 2202 or the second. It passes through the second electrodeposition tank compressed air downstream side control valve 2272 and reaches the second electrodeposition tank stirred air introduction pipe 2112.

First electrodeposition tank 2066 and second electrodeposition tank 2116
As shown in FIG.
A preliminary introduction system is installed as shown in. The liquid or gas from the electrodeposition tank preliminary introduction port 2213 passes through the electrodeposition tank preliminary introduction valve 2214, the first electrodeposition tank preliminary introduction valve 2215, the first electrodeposition tank preliminary introduction insulating pipe 2216, and the first electrode. It is introduced into the deposition tank 2066 and into the second deposition tank 2116 via the second deposition tank preliminary introduction valve 2217 and the second deposition tank preliminary introduction insulating pipe 2218. The most likely pre-introduction system is a retentive agent or replenisher to keep the bath capacity constant for a long time, but in some cases it is a gas that dissolves in the bath or an acid that removes powder. It is.

The cleaning is performed by the pure water shower tank 2 shown in FIG.
360, first hot water tank 2361, second hot water tank 2362 3
Done in steps. The heated pure water is supplied to the second warm water tank 2362, and the drained liquid is used in the first warm water tank 2361.
Further, the drained liquid is used in the pure water shower tank 2360. As a result, the long substrate is gradually washed with highly pure water after completion of the electrodeposition in the electrodeposition tank.

The second warm water tank 2362 uses pure water of the highest purity. This pure water is supplied to the second hot water tank outlet back surface pure water shower 2309 and the second hot water tank exit surface pure water shower 2310 immediately before the long substrate exits. As shown in FIG. 8, the deionized water to be supplied is once passed through the deionized water deionization port 2337, the deionized water deionization source valve 2338, and the deionized water heating tank 2 once.
Stored in 339, pure water heating tank pure water heating heater 234
It is heated to a predetermined temperature from 0 to 2343, and a pure water heating tank pure water delivery valve 2344, a pure water heating tank pure water delivery pump 234.
6, pure water heating tank pressure switch 2347, pure water heating tank cartridge type filter 2349, pure water heating tank flow meter 23
50 through the second hot water tank outlet rear surface shower valve 2351 from the second hot water tank outlet rear surface pure water shower 2309.
(FIG. 7), the other is from the second hot water tank outlet surface shower valve 2352 to the second hot water tank outlet surface pure water shower 2310.
(Fig. 7). The heating is for improving the cleaning effect.

The pure water supplied to the shower and accumulated in the second warm water tank warm water holding tank 2317 forms a pure water rinse bath, where the long substrate is washed with still water. The second warm water tank 2362 is provided with a second warm water tank warm water keeping heater 2307 so that the temperature of the pure water does not decrease.

Pure water overflowing from the second hot water tank hot water holding tank 2317 is supplied to the first hot water tank 2361 from the second hot water tank 2362 through the hot water tank connecting pipe 2232. Similar to the second warm water tank 2362, the first warm water tank 2361 is provided with a first warm water tank warm water keeping heater 2304 to hold the temperature of pure water. Further first hot water tank 2361
An ultrasonic wave source 2306 is installed in it to positively remove dirt on the surface of the long substrate between the first hot water tank roller 2282 and the second hot water tank turn-in roller 2283.

Pure water from the first warm water tank warm water holding tank 2316 is pure water shower tank pure water shower source valve 2323.
Then, as shown in FIG. 8, pure water shower tank pure water shower supply pump 2325, pure water shower tank pure water shower supply pressure switch 2326, pure water shower tank pure water shower supply cartridge type filter 2328, pure water shower tank From the pure water shower tank inlet surface pure water shower valve 2330 to the pure water shower tank inlet back surface pure water shower 2299 (FIG. 7) through the pure water shower supply flow meter 2329, and from the pure water shower tank entrance rear surface pure water shower valve 2331. Pure water shower tank inlet Back surface Pure water shower 2300 (Fig. 7)
To the back of the pure water shower tank outlet Pure water shower valve 233
2 to pure water shower tank outlet back surface pure water shower 2302
(FIG. 7), from the pure water shower tank outlet surface pure water shower valve 2333 to the pure water shower tank outlet surface pure water shower 2
303 (FIG. 7), and a shower flow for cleaning is applied to the back surface of the long substrate and the front surface of the long substrate at the inlet and the outlet of the pure water shower tank 2360, respectively.

The water that has been showered is received by the pure water shower tank receiving tank 2315, merges with the first hot water tank hot water holding tank 2316 and a part of the second hot water tank hot water holding tank 2317 as it is, and then becomes the flush system drainage 2336. Be thrown away. Usually, the washed water contains ions and the like, and thus requires a predetermined treatment.

In the pure water shower tank 2360, the first warm water tank 2361, and the second warm water tank 2362 for cleaning, the long substrate is the pure water shower tank turn-in roller 2279, the pure water shower tank roller 2280, and the first warm water tank. Turn-back entry roller 2281, first hot water tank roller 2282, second hot water tank turn-in roller 2283, second hot water tank roller 2
284, it is sent to the drying section folding roller 2285.

Pure water shower tank turn-in roller 227
Immediately after 9, a back surface brush 2298 of a pure water shower tank is provided so as to remove relatively large powder adhering to the back surface of the long substrate and a product having weak adhesion.

Long substrate 2006 reaching the drying section 2363
First, at the inlet of the drying section, the air knife 23
11. The water is drained by the air knife 2312 on the inlet surface of the drying section. As shown in FIG. 8, the introduction of air into the air knife is performed by the dry system compressed air inlet 2353, the dry system compressed air pressure switch 2354, the dry system compressed air filter regulator 2355, the dry system compressed air mist separator 2356, and the dry system compressed air supply. Valve 2357,
After that, it is done by a path of the drying section inlet back surface air knife valve 2358 or the drying section entrance front surface air knife valve 2359. Since the air supplied to the drying unit 2363 is inconvenient especially when it contains water droplets, the role of the dry-type compressed air mist separator 2356 is important.

Subsequently, in the process of being conveyed from the drying folding roller 2285 to the winding device advancing roller 2286, the IR lamps 2313 arranged side by side are dried by the radiant heat.
If the radiant heat of the IR lamp 2313 is sufficient, there will be no inconvenience even if the long substrate 2006 is placed in a vacuum device such as a CVD device after forming an electrodeposition film. At the time of drying, there is generation of fog due to draining of water and generation of water vapor due to IR lamp radiation, and therefore the drying unit exhaust port 2314 connected to the exhaust duct is indispensable.

Most of the water vapor collected in the drying system exhaust duct 2370 returns to water in the drying system condenser 2371 as shown in FIG.
And part of it is discharged to the dry system exhaust 2374. If the water vapor contains harmful gases, the exhaust should be treated as prescribed.

The winding device 2296 (see FIG. 7) includes a winding device advancing roller 2286 and a winding device direction changing roller 2.
The long substrate 2006 is wound on the long substrate winding bobbin 2289 in a coil shape through the 287 and the winding adjustment roller 2288 in that order. If deposited layer protection is needed,
The interleaf is delivered from the interleaf delivery bobbin 2290 and wound on the long substrate. Long board 2
The transport direction of 006 is indicated by an arrow 2292, 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, the long substrate wound on the long substrate winding bobbin 2289 and the interleaf delivered from the interleaf delivery bobbin 2290 do not interfere with each other at the transport start position and the transport end position, respectively. Shows. The entire winding device has a structure covered with a winding device clean booth 2295 that uses a hepa filter and downflow to prevent dust.

In this winding device, the winding device direction changing roller 2287 has a function of correcting the meandering of the long substrate. Based on a signal from a meandering detector installed between the winding device direction changing roller 2287 and the winding adjusting roller 2288, the winding device direction changing roller 2287 is moved to the winding device advancing roller 2286 by hydraulic servo.
By swinging around the axis set on the side, the meandering can be corrected. Winding device direction change roller 22
Control of 87 is approximately the movement of the roller toward the front side or the back side in FIG. 7, and the direction of the movement is opposite to the long substrate meandering detection direction from the meandering detector. The servo gain depends on the transport speed of the long substrate, but generally does not require a large object. Even if a long substrate with a length of several hundred meters is rolled up, its end faces can be aligned with sub-millimeter accuracy.

When the electrodeposition bath or hot water is used at a temperature higher than room temperature, water vapor is inevitably generated. Especially when a temperature above 80 ° C. is used, steam generation becomes considerable. The water vapor generated from the bath surface of the tank accumulates on the bath surface of the tank, vigorously blows out from the gap of the device, sees a large amount of release when opening and closing the lid, and drops as water droplets from the gap of the device, It deteriorates the operating environment of the device. For this reason, it is preferable to forcibly suck and exhaust air through the exhaust duct.

The first electrodeposition tank upstream exhaust port 2021 of the first electrodeposition tank 2066, the first electrodeposition tank midstream exhaust port 2022, the first electrodeposition tank downstream exhaust port 2023, and the second electrodeposition tank 2116 second Exhaust port 2071 upstream of electrodeposition tank, middle-flow exhaust port 20 of second electrodeposition tank
72, a second electrodeposition tank downstream exhaust port 2073, 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 23.
The exhaust duct 2 through the second hot water tank exhaust port 2308 of 62.
The steam collected in 020 passes through the insulating flange as shown in FIG. 9, and most of it returns to water in the electrodeposition flushing system exhaust duct condenser 2366 and is discarded to the electrodeposition flushing system exhaust duct condenser drain drain 2368. , Part of which is thrown away to the exhaust system 2369 of the electrodeposition water washing system. If the water vapor contains harmful gases, the exhaust should be treated as prescribed.

In this apparatus, 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 bath holding tank 2115 of the second electrodeposition tank 2116 are grounded. In order to change the potential from the ground to the float potential, the electrodeposition flushing system exhaust duct basic insulating flange 2365 and the electrodeposition flushing system exhaust duct flushing side insulating flange 2364 were provided and electrically separated.

[Substrate] The substrate material used in this device is
It can be used as long as it has electrical continuity on the film formation surface and is not attacked by the electrodeposition bath, and metal such as SUS, Al, Cu, Fe is used. A PET film having a metal coating, etc. can also be used. Among these, SUS is excellent as a long substrate for performing the element formation process in a later step.

As the SUS, both non-magnetic SUS and magnetic SUS can be applied. A representative of the former is SUS304, which has excellent polishability and can be made into a mirror surface for about 0.1 s. The representative of the latter is ferrite type SUS430,
It is effectively used for transportation using magnetic force.

The surface of the substrate may be smooth or rough. The surface property is changed by changing the type of rolling roller in the SUS rolling process. What is called BA is close to a mirror surface, and the unevenness is remarkable in 2D. When observed under an SEM (electron microscope) on both surfaces, a twist in the unit of micron may be noticeable. As a battery board, rather than a large wavy unevenness,
The structure of the micron unit greatly affects the characteristics of the solar cell in both good and bad directions.

Further, these substrates may be formed with another conductive material and are selected depending on the purpose of electrodeposition.
In some cases, it is preferable to previously form a very thin layer of zinc oxide by another method because the deposition rate in the electrodeposition method can be stably improved. In that case, a thin film formed by sputtering can be used. As described above, 1000 to 2000
If the film is less than Å, the resistance value may increase due to adsorption of oxygen and water in the air. Alternatively, when immersed in a high temperature electrodeposition bath, water adsorption occurs and the resistance increases.

However, according to the experiments conducted by the present inventor, when zinc oxide is electrochemically deposited from an aqueous solution on the thin film zinc oxide for sputtering, for example, 1 μm or more, a large resistance value is obtained if the subsequent drying is sufficient. Is not observed. It is considered that this is because the trap sites could be replenished with sufficient carriers from the zinc oxide electrochemically deposited from the aqueous solution. Therefore, the thin film of zinc oxide formed in advance is sufficient even if it is a thin film whose resistance increases when it is a single film. Of course, referring to the above-mentioned paper proposed to prevent the influence of oxygen adsorption, elements such as B, Al, In, and Ga are mixed in the sputtering target in an amount of several% or less to increase the resistance from the beginning. It is also possible to form a film that does not.

[Interleaf] As an interleaf for protecting the deposited film, a non-woven fabric typified by Nomex, a resin film typified by PET, or the like can be used. A resin film such as PET is a softer Cu
It is also possible to use a thinly coated metal such as Al or Al. Needless to say, it is necessary to confirm in advance that the substrate has cooled to a sufficient temperature, because the resin film melts or fuses if the temperature is too high. When using non-woven fabric or paper, attention should be paid to their moisture absorption amount in advance. As already pointed out, once released, it takes time for the water to re-adsorb on the zinc oxide layer.
If the product is stored as rolled in a moistened interleaf, it may cause instability in production. When long-term storage is expected by using an interleaf such as a nonwoven fabric or paper, it is preferable to dry the interleaf such as a nonwoven fabric or paper before winding.

[Warm Air Drying] In the present invention, at least 30% of the water content adsorbed on zinc oxide is released when the deposited film is dried. This makes it possible to provide a stable low-resistance zinc oxide thin film without adding a secondary additive to the aqueous solution that causes electrochemical deposition.

It is preferable to use warm air for drying the deposited film, because the heat from the heat source can be effectively transferred to the formed zinc oxide layer. In fact, when the equipment is dried, the total heat of the IR lamp 2313 is about 10 kW.
However, it was not dried sufficiently. This is because the reflectance of the surface on which zinc oxide is formed is 70% or more, and the SU on the back is
It was considered that this was due to the fact that the S-plane was 50% or more. When a material that can reduce the reflectance can be used, or when the back surface blackening treatment can be performed, sufficient thermal efficiency can be expected even with the radiation drying method.

The hot air drying used in the present invention is applicable as long as the hot air is made to flow along the surface of the substrate. Since SUS has poor heat conduction among metals, it is preferable to make the surface that comes in contact with warm air large, and to increase the length of the drying section, make the hot air blowing surface large, or use the hot air blowing nozzle. It is good to increase the number.

It is inconvenient if the warm air for drying contains dust. Normally, this device does not have to be installed in a clean room, but it is better to remove dust from the wind when it is directly exposed to the wind. To do that, HEPA
It is advisable to install a filter etc. in a part of the hot air duct.

The temperature of the warm air is preferably set to 200 ° C. or higher, whereby the temperature of the drying member, that is, the substrate here, can be effectively raised to a temperature at which water can be removed. Further, it is possible to reliably secure low resistance over the entire area even for a long substrate.

[Conveyance Speed] For the film formation, the substrate conveyance speed is determined in consideration of the required film thickness of the electrodeposited film and the film formation speed. In reality, the first electrodeposition tank 2066 and the second electrodeposition tank 2116 have a total of 56 anodes, and the transport speed of the long substrate is determined by the sum of the film deposition speeds of the respective anodes.

In this device, 0.5 m / min to 5 m / m
It was designed within the range of in, and it is possible to experimentally deposit zinc oxide on a long substrate of 500 m or more at a temperature of 85 ° C. under good transportation at a minimum speed and a maximum speed. Proved that there is.

The transport speed is also determined in consideration of the degree of drying. That is, if the conveying speed is too fast, the drying is insufficient, which is not preferable, and even if the conveying speed is lowered, it is not enough. The apparatus preferably has a drying capacity commensurate with the transport speed at which deposition is possible, but if it is difficult due to cost and space constraints, a transport speed suitable for the drying capacity should be selected.

This apparatus uses an IR lamp of about 10 kW in total, but it is almost impossible to reduce the resistance value to several Ωcm ² or less at a conveying speed of 1 m / min or more only by using the IR lamp. The resistance value was finally reduced by dropping it to 0.2 m / min.

On the other hand, in the present invention, as shown in the embodiments described later, by incorporating the warm air dryer as shown in FIG. The amount of heat does not stay in a part of the substrate,
It can promote moisture removal evenly and reduce the overall resistance value to several Ωcm ^2.
It can be:

[0128]

EXAMPLES Examples according to the present invention will be described below.

[Example 1] An IR lamp 2313 of the electrodeposition apparatus shown in Figs. 2 to 9 which constitutes the warm air drying section shown in Fig. 1.
It was incorporated immediately after (see FIG. 7).

In the figure, reference numeral 1002 denotes a roll substrate, which is conveyed in the direction of the arrow. Reference numeral 1003 is a heat insulating wall whose outer shape is made of a SUS plate and glass wool is filled therein. Insulation wall 1
003 minimizes the amount of contact of the hot air with the outside air to prevent the temperature of the hot air from decreasing, and also prevents the hot air from leaking and heating the electrodeposition apparatus unnecessarily and causing damage. is there.

The warm air nozzles 1004a to 1004h are
The US tube is formed by forming an orifice, and hot air is blown into the heat retaining wall 1003 in the form of an air knife from both sides of the roll substrate 1002.

The hot air is obtained by mixing the recovered hot air from the hot air recovery duct 1005 for recovering the hot air blown into the heat retaining wall with the outside air from the outside air introduction duct 1006 for introducing the outside air and controlling the temperature. It becomes hot air in the generation furnace 1008 and is sent to the hot air supply path 1011. The rate of introduction of outside air is controlled by the outside air control valve 1007. By constantly introducing a fixed amount of outside air, it is possible to prevent abnormal heating in the hot air generating furnace 1008. The warm air sent to the hot air supply path 1011 passes through the HEPA filter 1012 and the dust contained therein is removed. The hot air from which dust has been removed is further introduced into the hot air nozzles through the hot air introduction duct 1013, a manifold (not shown), and the hot air nozzles.

The path of hot air, that is, the hot air recovery duct 100.
5, hot air generating furnace 1008, hot air passage 1011, HEPA
The filter 1012, the warm air introduction duct 1013, and the manifold are preferably surrounded by a heat insulating material in order to prevent unnecessary heat radiation and increase the efficiency of the heat source. This is also preferable for preventing accidents due to unnecessary contact with the operator.

The hot air generating furnace 1008 has a blower fan 100.
9 and an electric heater 1010. The heater capacity of the hot air generator 1008 used was 10 kW, and the air circulation rate was 2 m ³ / min. The diameter of the orifice formed in the SUS tube of each warm air nozzle was 0.5 mm, and 7 orifices were arranged per one. The length of the substrate transfer path inside the heat retaining wall was set to about 2 m.

The thickness of the rolled SUS substrate is 0.12 mm.
And the width is 355 mm. This roll substrate is 100
When transported at 0 mm / min, the substrate temperature at the heat insulating wall outlet was 150 ° C. by a contact thermometer. On the other hand, the atmospheric temperature inside the heat retaining wall was 250 ° C. When the thickness of zinc oxide electrochemically deposited from the aqueous solution is set to 1 μm and the water content is measured in the same manner as the above-mentioned experiment, the electrode is formed and the electric resistance is measured, the residual water content is 55%, and the resistance value is Is 0.5 Ωcm ^2, which is a significant improvement over the resistance value of about 90 Ωcm ² when the present hot air fan is not used.

Whether the IR lamp is operated or not, the resistance value thereof largely depends on the presence or absence of the hot air dryer,
While it can be seen that the IR lamp only serves to drain the surface, the effect of the hot air dryer was quite clear.

[Example 2] The dryer of Example 1 (Fig. 1) was incorporated in the electrodeposition apparatus of Figs. 2 to 9 in the same manner as in Example 1.

The same roll substrate as in Example 1 is set to 1500 mm.
The residual moisture and electric resistance of the same zinc oxide film were measured at a transport speed of / min. The residual water content was 70%, and the resistance value was 3.4 Ωcm ² , which was close to the upper limit but sufficient for use in applications such as solar cells.

[Example 3] The dryer of Example 1 (Fig. 1) was incorporated in the electrodeposition apparatus of Figs. 2 to 9 in the same manner as in Example 1. However, the heat capacity of the hot air generating furnace was increased to 30 kW. As a result, the ambient temperature was 350 ° C., and the exit temperature of the roll substrate was 1000 mm / min.
It reached 0 ° C.

The same roll substrate as in Example 1 was set to 3000 mm.
The residual moisture and electric resistance of the same zinc oxide film were measured at a transport speed of / min. The residual water content was 40% and the resistance value was 0.4 Ωcm ² , and a sufficiently low resistance could be achieved.
However, with the same parameters, 100 roll substrate
When it was sent at a transport speed of 0 mm / min, the substrate temperature at the exit exceeded 300 ° C., and a cooling fan was required at the subsequent stage.

[0141]

INDUSTRIAL APPLICABILITY The present invention is an electrodeposition method in which zinc oxide is electrochemically deposited on a substrate from an aqueous solution and the deposited film is washed with water and dried. % Is a zinc oxide electrodeposition method characterized by releasing it, so that a secondary additive is not added to the aqueous solution for causing electrochemical deposition,
It is possible to provide a stable low resistance zinc oxide thin film without changing the state of film formation. When a secondary additive is used, it can be used not only for chemical treatment for drainage, but also for changes in hydrogen overvoltage and the like, which may cause electrochemical deposition of zinc oxide and accompanying morphological changes. is there.

When at least 30% of the water content adsorbed on zinc oxide is released by hot air, the temperature difference in the drying section can be made small, and a high temperature section is created in a part of the device to design. There is no restriction such as making it difficult or taking an extra space for arrangement.
For example, when a radiant heat source such as an IR heater is used, the temperature of the heat source is extremely high, but the actual temperature rise of the drying member is not so large.

When the temperature of the warm air is 200 ° C. or higher, the temperature of the drying member, that is, the substrate here, can be effectively raised to a temperature at which water can be removed.
Further, it is possible to reliably secure low resistance over the entire area even for a long substrate.

Further, when the substrate is a roll-shaped metal, it is easy to rapidly cool the temperature of the substrate that has once risen due to hot air drying or the like, and a temperature rise in a short time can be realized. By doing so, unnecessary moisture removal can be promoted, while not requiring extra heating time,
No unnecessary heat is applied to the formed film.

The substrate transfer speed is 1000 mm / m.
When it is not less than in, the amount of heat of the drying means does not stay in a part of the substrate, the moisture can be uniformly promoted to be removed, and the overall resistance can be easily reduced.

Further, when the aqueous solution contains zinc nitrate and the concentration thereof is 0.05 M / l or more, the unevenness of the zinc oxide surface is remarkably developed, and even in such a case, 30% of the water desorption is extremely high. It is effective and has a great heating effect by means such as warm air.

When a zinc oxide thin film is formed on the substrate by sputtering prior to deposition by electrodeposition, the number of zinc oxide carriers electrochemically formed from the aqueous solution formed above is sufficiently large. As a result, even if a thin sputtered film, which is easily affected by moisture adsorption and has a high resistance, is attached, the overall resistance can be sufficiently reduced.

When the thickness of the zinc oxide thin film formed by the sputtering is 2000 liters or less, the number of zinc oxide carriers electrochemically formed from the aqueous solution formed on the upper portion can be sufficiently increased as in the above case. Therefore, the zinc oxide film can be effectively formed.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a warm air dryer preferably used in the present invention.

FIG. 2 is an overall configuration diagram showing an example of a zinc oxide electrodeposition apparatus of the present invention.

FIG. 3 is a schematic view showing an example of an unwinding device in the zinc oxide electrodeposition device of the present invention.

FIG. 4 is a schematic view showing an example of a first electrodeposition tank in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 5 is a schematic diagram showing an example of a second electrodeposition tank in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 6 is a schematic diagram showing an example of the area around a drainage tank in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 7 is a schematic diagram showing an example from a pure water shower tank to a winding device in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 8 is a schematic view showing an example of a pure water heating tank, a compressed air system and a drainage system in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 9 is a schematic diagram showing an example of an exhaust duct system in the zinc oxide electrodeposition apparatus of the present invention.

[Explanation of symbols]

1002 Roll substrate 1003 Heat insulation wall 1004a to 1004h Warm air nozzle 1005 Hot air recovery duct 1006 Outside air introduction duct 1007 Outside air control valve 1008 Hot air generating furnace 1009 Blower fan 1010 Electric heater 1011 Hot air duct 1012 HEPA filter 1013 Hot air inlet duct 2001 Unwinding device Long substrate bobbin 2002 Unwinding device interleaf Winding bobbin 2003 Unwinding device Unwinding adjustment roller 2004 Unwinding device direction changing roller 2005 Unwinding device discharge roller 2006 Long substrate 2007 Winding interleaf 2008 Interleaf winding direction 2009 Winding Unwinding device Long substrate bobbin rotating direction 2010 Long substrate unwinding direction 2011 Unwinding device Clean booth 2012 Unwinding device 2013 Electrodeposition tank inlet folding roller 2014 First electrodeposition tank Input roller 2015 First electrodeposition tank exit roller 2016 Electrodeposition tank turnback roller 2017 Electrodeposition tank entrance turnover roller cover 2018 First electrodeposition bath holding tank cover 2019 Electrodeposition tank cover 2020 Electrodeposition washing system exhaust duct 2021 1st Electrodeposition tank upstream exhaust port 2022 First electrodeposition tank midstream exhaust port 2023 First electrodeposition tank downstream exhaust port 2024 First electrodeposition tank overflow return port 2025 First electrodeposition bath surface 2026 to 2053 First electrodeposition tank anode 2054-2060 1st electrodeposition tank anode mounting table 2061 1st electrodeposition tank back electrode 2062 1st electrodeposition tank stirring air introduction pipe 2063 1st electrodeposition tank upstream circulation jet pipe 2064 1st electrodeposition tank downstream circulation jet pipe 2065 First electrodeposition bath holding tank 2066 First electrodeposition tank 2067 First electrodeposition tank outlet shower 2068 Second electrodeposition tank inlet shower 2069 Second electrodeposition Ingress roller 2070 Second electrodeposition tank exit roller 2071 Second electrodeposition tank upstream exhaust port 2072 Second electrodeposition tank midstream exhaust port 2073 Second electrodeposition tank downstream exhaust port 2074 Second electrodeposition bath surface 2075 Second electrodeposition Tank overflow return port 2076 to 2103 Second electrodeposition tank anode 2104 to 2110 Second electrodeposition tank anode mounting table 2111 Second electrodeposition tank rear surface electrode 2112 Second electrodeposition tank stirred air introduction pipe 2113 Second electrodeposition tank upstream reflux Jet pipe 2114 2nd electrodeposition tank downstream reflux jet pipe 2115 2nd electrodeposition bath holding tank 2116 2nd electrodeposition tank 2117 1st electrodeposition tank overflow return path 2118 1st electrodeposition tank overflow return path Insulation flange 2119 1st electrode Crystallization tank overflow return direction 2120 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 First Circulation tank electrodeposition bath downstream 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 bar Ipas circulation flexible pipe 2147 First circulation tank electrodeposition bath bypass circulation valve 2148 First circulation tank electrodeposition bath downstream circulation flexible pipe 2149 First circulation tank electrodeposition bath downstream circulation flange Insulation pipe 2150 First circulation tank outlet shower valve 2151 1st electrodeposition tank filter circulation return flexible pipe 2152 1st electrodeposition tank filter circulation return flange insulating pipe 2153 1st electrodeposition tank drain valve 2154 1st electrodeposition tank filter circulation source valve 2155 1st electrodeposition tank filter circulation direction 2156 First electrodeposition tank filter circulation suction filter 2157 First electrodeposition tank filter circulation pump 2158 First electrodeposition tank filter circulation pump bypass valve 2159 First electrodeposition tank filter circulation pressure switch 2160 First electrodeposition tank filter circulation pressure gauge 2161 Daiden 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 Insulation pipe 2166 First electrodeposition tank filter Circulation valve 2167 1st electrodeposition tank filter circulation system electrodeposition bath upstream return valve 2168 1st electrodeposition tank filter circulation system electrodeposition bath midstream return valve 2169 1st electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2170 1st Drainage tank air vent valve 2171 1st drainage tank air vent 2172 1st drainage tank 2173 1st drainage tank drainage valve 2174 1st drainage tank drainage recovery valve 2175 drainage recovery source valve 2176 drainage suction suction filter 2177 drain Liquid recovery pump 2178 Drainage recovery port 2179 Drainage tank common drain Port 2180 Second drainage tank drainage valve 2181 Second drainage tank drainage recovery valve 2182 Compressed air introduction port 2183 Compressed air pressure switch 2184 for stirring electrodeposition bath 2184 First electrodeposition tank compressed air introduction direction 2185 First electrodeposition tank Compressed air source 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 compressed air introduction valve 2190 First electrodeposition tank compressed air Air flexible pipe 2191 First electrodeposition tank compressed air insulating piping 2192 First electrodeposition tank stirred air downstream side control valve 2193 First electrodeposition tank stirred air upstream side control valve 2194 Second electrodeposition tank compressed air introduction direction 2195 Second Electrodeposition tank compressed air source 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 insulating pipe 2202 Second electrodeposition tank stirred air upstream side control Valve 2203 Electrodeposition system pure water introduction port 2204 Electrodeposition system pure water introduction valve 2205 First heating storage water pure water introduction flexible pipe 2206 First heating storage water pure water introduction valve 2207 First electrodeposition tank pure water introduction valve 2208 1 electrodeposition tank pure water introduction insulation pipe 2209 second heating storage water pure water introduction flexible pipe 2210 second heating storage water pure water introduction valve 2211 second electrodeposition tank pure water introduction valve 2212 second electrodeposition tank pure water introduction insulation pipe 2213 Preliminary introduction port for electrodeposition tank 2214 Preliminary introduction valve for electrodeposition tank 2215 Preliminary introduction valve for second electrodeposition tank 2216 Preliminary introduction insulation for first electrodeposition tank 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 Insulation flange 2221 Second electrodeposition tank overflow return direction 2222 Second circulation tank 2223 Second circulation tank heating storage tanks 2224 to 2231 Second circulation tank heater 2232 Second circulation tank electrodeposition bath upstream circulation source valve 2233 Second circulation tank electrodeposition bath upstream circulation direction 2234 Second circulation tank electrodeposition bath Upstream circulation pump 2235 Second circulation tank electrodeposition bath upstream circulation pump bypass valve 2236 Second circulation tank electrodeposition bath upstream circulation pressure gauge 2237 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 containing shower head Kisible 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 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 Insulation pipe 2255 Second electrodeposition tank drain bar Lube 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 2nd electrodeposition tank filter circulation pressure switch 2262 2nd electrodeposition tank filter circulation pressure gauge 2263 2nd electrodeposition tank filter circulation filter 2264 2nd electrodeposition tank filter circulation direction 2265 2nd electrodeposition tank filter circulation direction 2266 2nd Electrodeposition tank filter circulation flexible pipe 2267 Second electrodeposition tank filter circulation flange Insulation 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 Ri valve 2271 2nd electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2272 2nd electrodeposition tank stirred air downstream side control valve 2273 2nd drainage tank drainage storage tank 2274 2nd drainage tank 2275 2nd drainage tank Air vent valve 2276 Second drainage tank air vent 2277 First drainage tank drainage storage tank top lid 2278 Second drainage tank drainage storage tank top lid 2279 Pure water shower tank turn-in roller 2280 Pure water shower tank roller 2281 First hot water tank turn-back entry Roller 2182 First hot water tank roller 2283 Second hot water tank turn-in roller 2284 Second hot water tank roller 2285 Dry turn-back roller 2286 Winding device entrance roller 2287 Winding device direction changing roller 2288 Winding adjusting roller 2289 Long substrate winding bobbin 2290 Interleaf feeding bobbin 2292 long board Taking-up direction 2293 Long substrate take-up bobbin rotating direction 2294 Interleaf feeding bobbin rotating direction 2295 Take-up device Clean booth 2296 Take-up device 2297 Second electrodeposition tank outlet shower 2298 Pure water shower tank backside brush 2299 Pure water shower tank inlet surface Pure water shower 2300 Pure water shower tank inlet back surface Pure water shower 2301 Pure water shower tank exhaust port 2302 Pure water shower tank outlet back surface Pure water shower 2303 Pure water shower tank outlet surface Pure water shower 2304 1st warm water tank warm water heater 2305 First hot water tank exhaust port 2306 First hot water tank ultrasonic source 2307 Second hot water tank hot water heat retaining heater 2308 Second hot water tank exhaust port 2309 Second hot water tank outlet back surface pure water shower 2310 Second hot water tank outlet surface pure water shower 2311 Dry Part entrance back air knife 2312 dry Part inlet surface Air knife 2313 IR lamp 2314 Drying part 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 turn-in 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 source 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 tank Work flow meter 2330 Pure water shower tank inlet surface Pure water shower valve 2331 Pure water shower tank inlet back surface Pure water shower valve 2332 Pure water shower tank outlet back surface Pure water shower valve 2333 Pure water shower tank outlet surface Pure water shower valve 2334 1 hot water tank hot water holding tank drain valve 2335 2nd hot water tank hot water holding tank drain valve 2336 water washing system drain 2337 water washing system pure water port 2338 water washing system pure water source valve 2339 pure water heating tanks 2340 to 2343 pure water heating tank pure water heating Heater 2344 Pure water heating 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 tank cartridge Type filter 2350 Pure water heating tank flow meter 2351 Second warm water tank outlet back side shower valve 2352 Second warm water tank outlet front side shower valve 2353 Dry system compressed air inlet 2354 Dry system compressed air pressure switch 2355 Dry system compressed air filter regulator 2356 Dry system compressed air mist separator 2357 Dry system compressed air Supply valve 2358 Drying part inlet back side air knife valve 2359 Drying part inlet surface air knife valve 2360 Pure water shower tank 2361 First hot water tank 2362 Second hot water tank 2363 Drying part 2364 Electrodeposition rinsing system Exhaust duct Water rinsing side insulating flange 2365 Electrodeposition rinsing system Exhaust duct Main insulation flange 2366 Electrodeposition washing system exhaust duct condenser 2367 Electrodeposition washing system exhaust duct heat exchange grid 2368 Electrodeposition washing system exhaust duct condenser drainage drain 2369 Electrodeposition washing system exhaust 2370 Drying system exhaust duct 2371 Drying system condenser 2372 Drying system heat exchange grid 2373 Drying system condenser drainage drain 2374 Drying system exhaust

Front Page Continuation (72) Inventor Yusuke Miyamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-11-229193 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) C25D 9/08 C23C 14/08 H01L 31/04

Claims (16)

(57) [Claims] 1. In an electrodeposition method in which zinc oxide is electrochemically deposited on a substrate from an aqueous solution, and the deposited film is washed with water and dried, at least 30% of water adsorbed on zinc oxide is released during drying. A zinc oxide electrodeposition method characterized by the above. 2. At least 3 of water adsorbed on zinc oxide
The zinc oxide electrodeposition method according to claim 1, wherein 0% is removed by hot air. 3. The zinc oxide electrodeposition method according to claim 2, wherein the temperature of the hot air is 200 ° C. or higher. 4. The zinc oxide electrodeposition method according to claim 1, wherein the substrate is a roll-shaped metal. 5. The substrate transfer speed is 1000 mm / min.
It is above, The zinc oxide electrodeposition method in any one of the Claims 1 thru | or 4 characterized by the above-mentioned. 6. The zinc oxide electrodeposition method according to claim 1, wherein the aqueous solution contains zinc nitrate and the concentration thereof is 0.05 M / l or more. 7. The zinc oxide electrodeposition method according to claim 1, wherein a zinc oxide thin film is formed on the substrate by sputtering prior to deposition by electrodeposition. 8. The zinc oxide thin film formed by sputtering has a thickness of 2
The zinc oxide electrodeposition method according to claim 7, wherein the zinc oxide electrodeposition is 000Å or less. 9. In an electrodeposition apparatus in which zinc oxide is electrochemically deposited on a substrate from an aqueous solution, and the deposited film is washed with water and dried, at least 30% of water adsorbed on zinc oxide is separated in a drying section. A zinc oxide electrodeposition apparatus comprising means. 10. The zinc oxide electrodeposition apparatus according to claim 9, wherein the means for removing at least 30% of the water content adsorbed on the zinc oxide is a warm air generating circulator. 11. The zinc oxide electrodeposition apparatus according to claim 10, wherein the temperature of the warm air generated by the warm air generating circulator is 200 ° C. or higher. 12. The zinc oxide electrodeposition apparatus according to claim 9, wherein the substrate used is a roll-shaped metal. 13. The substrate transfer speed is 1000 mm / mi.
It is n or more, The zinc oxide electrodeposition apparatus in any one of Claim 9 thru | or 12 characterized by the above-mentioned. 14. The aqueous solution contains zinc nitrate, and the concentration thereof is 0.05 M / l or more.
14. The zinc oxide electrodeposition apparatus according to any one of 1 to 13. 15. The zinc oxide electrodeposition apparatus according to claim 9, wherein a zinc oxide thin film is formed on the substrate by sputtering prior to deposition by electrodeposition. 16. The zinc oxide electrodeposition apparatus according to claim 15, wherein the thickness of the zinc oxide thin film formed by sputtering is 2000 Å or less.