TWI301626B - Capacitor use electrode foil - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode case for a capacitor, and more particularly to an electrode drop which is excellent in electrostatic capacitance and leakage current characteristics.

L· mT U BACKGROUND ART In general, an aluminum electrode constituting an electrolytic capacitor is subjected to electrolytic etching by applying a direct current or an alternating current to an aluminum foil in an aqueous acid solution, forming a large number of recesses on the surface of the foil 10, and expanding the surface area. Anodizing is carried out in the liquid to form an aluminum film on the surface of the foil and used as an electrode material. The method of increasing the electrostatic capacity is, for example, increasing the surface area of the tank or making the oxide film as a dielectric thin, etc., and various studies on these methods have hitherto been made. In addition, increasing the dielectric constant of the oxide film is also a method of increasing the electrostatic capacity, and the formation of a high-capacity titanium oxide film, a composite film of oxidized Qin and Oxide to achieve high capacity is also continued. In progress, but still can not fully increase the electrostatic capacity. For the method of forming a titanium oxide film, the method of forming a titanium oxide film is exemplified by a CVD method (chemical vapor deposition method), a perchlorination method, a vortex method, and a glutathion electrophoresis electrode deposition. Law, but because of the law or extremely difficult to form a film on (4) after (4), the New Zealand gets a full amount of static electricity and the leakage will increase the leakage current. In addition, the above-mentioned CVD method or mining method requires a large-scale vacuum device, which has low productivity, a manufacturing cost, and the like, and is difficult to form due to the u Na method or the lyotropic gel electrode deposition method 1301626. Since the oxide film is formed, a sufficient electrostatic capacitance cannot be obtained, and the leakage current is also increased. For this reason, JP-A-2003-257796 discloses a valve metal oxide polymer-aromatic compound solvent complex containing a high degree of polymerization to improve the sol gel method. However, in order to form an oxide film, heat treatment is required, and the volatility at this time lowers the fineness of the film, so that a sufficient electrostatic capacity cannot be obtained, and leakage current cannot be sufficiently improved. On the other hand, a method of forming a titanium oxide film at a low cost is known, for example, in which a base material is impregnated with boric acid to ammonium fluorotitanate or the like, or the like. A method of depositing a titanium oxide film on the surface of a substrate in a treatment liquid adjusted with an aqueous solution of fluorotitanic acid. In the liquid phase deposition method, the titanium oxide film can be uniformly formed on the surface of the aluminum foil after etching having a complicated shape, regardless of the unevenness or the type of the substrate, and sufficient capacitance can be expected. However, according to the investigation by the inventors of the present invention, the use of a treatment liquid containing boric acid in ammonium fluorotitanate causes a problem that the titanium oxide film deposited on the surface of the aluminum foil has a large leakage current. < The larger the electrode area is, the thinner the dielectric film thickness is, and the larger the capacitance of the capacitor can be obtained. In order to achieve the electrostatic capacity of the capacitor 増 = 2 ,, the dielectric film is formed into a thin film by a liquid deposition method, and the film thickness of the obtained titanium oxide film is relatively uneven, which is difficult to control. In order to reduce the required film thickness, there are problems such as small holes and the like. In the present invention, the present invention has been made in view of the above problems, and its object is to reduce the electrode case for a capacitor and the capacitor using the electrode, and the electrode has defects. A titanium oxide film with low leakage current and high capacitance. The present inventors have devoted themselves to researching and solving the above-mentioned problems, and the electrode of the titanium oxide film having a crystal size of 2 5 n or a non-crystalline structure is used for capacitors (4). The electrostatic capacity is large' and the leakage current characteristics are excellent. Furthermore, the present inventors have found that the titanium oxide film contains (amount of U atom% or more and 25 atom% or less of aluminum), and the electrostatic capacity can be further increased. The present invention is based on the aforementioned knowledge and is required to be The purpose of the present invention is as follows: (1) An electrode for a capacitor is composed of an aluminum crucible, and the aluminum foil has a titanium oxide film having a crucible size of 2.5 nm or less or an amorphous structure. The electrode foil of the capacitor is made of aluminum foil, and the aluminum foil has a film formed of alumina and a titanium oxide film having a crystal size of 2,511,111 or less or a non-15 crystal structure. (3) An electrode for a capacitor The foil is made of an aluminum foil, and the aluminum foil has a film of a titanium oxide film having a crystal size of 2.5 nm or less or an amorphous structure, and a film of one or both of a composite oxide or a mixed oxide of aluminum and titanium. 20 (4) An electrode foil for a capacitor, which is composed of an aluminum foil, and the aluminum foil has a film formed of oxidized, a composite oxide of aluminum and titanium, or a film of a mixed oxide And the crystal size is below 2.5 nm or not A titanium oxide film having a crystal structure. (5) An electrode foil for a capacitor, which is less than or equal to or less than a percentage of a film formed of titanium oxide in any of the above 7 to 161626 of (!) to (4) Aluminium. 'The electrode box containing 0.1 atom% or more and 25 original "V for capacitors is contained in the m formed by any of the above materials (1) to (4), and the concentration is It is ο·1 ', / or more, 25 atomic% or less, and the concentration is increased from the surface of the film to the inside of the film along the depth direction. () The type of electrode used for the capacitor is in the above (1) to (4). Any of the coated towels formed of the secret titanium contains ?s of qi atom% or more and xenon 10% or less, and the above-mentioned wealth includes a layer of titanium oxide having different degrees of rotation. 8) The various types of electricity are used, and the electrode case for capacitors is used in any of (1) to (none of them). [Positive party package] The best mode for carrying out the invention 15 The electrode for capacitor of the present invention The foil is a foil having at least a titanium oxide film having a crystal size of 2.5 nm or less or an amorphous material. The oxidation rate of the oxidation capacitor used in the Ximing Electrolytic Capacitor is large, so it is presumed that (4) can be coated with titanium oxide (IV) Electrolytic Capacitor||Increase the electrostatic capacity. The film having titanium oxide described herein means that the titanium content is 1〇. The atom contains 2% or more and 35 atom% or less, and the remaining component contains a film of an oxygen atom. The impurity may contain hydrogen (U atom% or more, 5 atom% or less, gas atom% or more, and 5 atomic number) In order to form the above titanium oxide film, for example, a liquid phase deposition method can be used. The reaction of precipitating titanium oxide on aluminum by a liquid deposition method can be represented by the following formula = I301626 (1) The hydrolysis is carried out by an equilibrium reaction, that is, the reaction of strontium fluorotitrate with water molecules produces a reaction of titanium oxide with H+ ions and F_ ions.

TiF62>2H2〇(2)Ti02+4H++6F (I) Here, titanium oxide can be precipitated by adding an equilibrium reaction of the formula (I) to the right side. There is also a method in which boric acid is used as an activator which can carry out the hydrolysis equilibrium reaction of the formula (1) to the right side, as disclosed in JP-A-2003-257036 and JP-A-2003-257796. However, if boric acid is used as the activator, as described in ruthenium, the obtained titanium oxide film has a large leakage current and is a film which is not practical. Therefore, when the film is analyzed, the crystal size of the formed titanium oxide grows more than 25 nm regardless of the processing conditions. Although the reason is not clear, the crystal size of titanium oxide is more than 25 nm, and the leakage is markedly remarkable: the characteristics are significantly deteriorated. Therefore, in order to produce a 15 electrode perforation having excellent leakage current characteristics, it is necessary to coat titanium oxide having a crystal size of 2.5 nm or less or an amorphous structure, and the titanium oxide having the above structure can be produced right, and the film formation method is not Limited to liquid deposition. The present inventors investigated the titanium oxide formed by the financial conditions, and found that the W12_ fluocyanate aqueous solution was prepared at a temperature of 1 () to 健, and the substrate (4) was immersed in the aqueous solution. Titanium oxide is deposited on the surface of the substrate 20 to obtain titanium oxide having the above structure. In the present invention, the activator which is carried out to the side of the titanium oxide precipitation of the formula (I) is dissolved in the oven of the substrate. Namely, the treatment liquid of the present invention is a solution in which a solution of sulphur ions is dissolved in a fluorotitanium-aqueous solution. By the action of the ions in the treatment liquid, an oxide having a crystal size of 25 nm or less or an amorphous substance can be precipitated on the surface of the substrate. 91301626 Titanium 0 The pH of the treatment liquid is preferably 4 to 7 and 5 to 7. 6 is better. The reason is that the pH of the field treatment solution is less than that of the bucket, although a complete film can be produced, but the result

The capacitor may be difficult to obtain the required capacitance; and when the pH value of the treatment liquid is greater than 7 days, the treatment liquid tends to become unstable, and the titanium oxide rotary substance f is precipitated in the treatment liquid. The problem of forming a uniform film on the surface. The adjustment of the pH of the heart fluid can be carried out by a conventional method, and the other conditions of the reaction of the present invention are not specific. Further, as the degree of the treatment liquid or the concentration of the ammonium titanate increases, the film formation rate of titanium oxide increases, and the reaction temperature or reaction time can be appropriately set in order to obtain the thickness of the titanium oxide. Further, another aspect of the electrode case for a capacitor of the present invention is that at least f has a film formed by oxidizing 1 liter, and a core having a crystal size of 2.5 nm or less or titanium oxide having a non-structural k. The coating film having the oxide content described above has a content of 10 atom% or more and 45 atom% or less, and the remaining component contains a film of an oxygen atom. The impurities may contain 0.1 atom% or more and 5 atom% or less of hydrogen, and (10) atomic% or more and 5 atom% or less. In the present invention, it is known that a film having excellent leakage current characteristics can be obtained by combining a titanium oxide film and an oxide film. In order to form the above-mentioned film structure on the name box, the method of forming the former titanium oxide film can be combined with the anodizing treatment of the conventional Ming pig. The relationship between the emulsified titanium film and the oxidized I ru film is not particularly limited. For example, after the oxidation is formed on the surface of the porcine pig by anodizing, the titanium film is formed by liquid deposition on the oxygen brain, followed by heating. deal with. At this time, the film structure is sequentially from the side of the wire material to the name / oxidation Ming / oxidation. The appropriate film thickness of each layer in 1301626 can be set as appropriate in consideration of the leakage current characteristics. Determined by electrostatic capacity 5

The electrolyte for anodizing treatment may, for example, be a sulphuric acid, squaric acid, adipic acid, oxalic acid, sulfuric acid, sebacic acid or a solution containing one or two or more ammonium salts, but is not limited to a solution. The conditions for the cation conversion treatment can be carried out under known conditions, and are not particularly limited. For example, an adipic acid aqueous solution can be used as an electrolytic solution, and an anodic oxidation voltage can be set so that the oxide film thickness Z is increased to about 10 nm. 10 15

Further, another aspect of the electrode foil for a capacitor of the present invention is one having at least a titanium oxide film having a crystal size of 2.5 nm or less or an amorphous structure, and a composite oxide or mixed oxide of aluminum and titanium. The aluminum foil of the film or both. The film having one or both of a composite oxide or a mixed oxide of aluminum and titanium as described herein means that the titanium content is 1 〇 atomic% or more and 35 atomic% or less, and the ur content is It is a film in which the remaining component contains an oxygen atom in the case of 〇1 atom% or more and 25 atom%% or less. The impurities may contain hydroquinone 1 atom% or more and 5 atom% number or less, and fluoroquinone 1 atom% or more and 5 atom% or less. By combining the titanium oxide film with the aluminum-titanium composite oxide or the mixed oxide, it is apparent that a film having a small leakage current can be formed. For example, after a titanium oxide film is formed on the surface of an aluminum foil by a liquid phase deposition method, an aluminum-titanium composite oxide layer is formed by anodizing treatment at an anodization voltage of 3 V followed by heat treatment. The film structure is from the side of the aluminum foil substrate: aluminum/aluminum-titanium composite oxide/titanium oxide. Since the appropriate film thickness of each layer is determined by both the leakage current characteristics and the electrostatic capacitance, it may be appropriately set. Further, the vertical relationship between the layers is not particularly limited. 11 1301626 Further, another aspect of the electrode foil for a capacitor of the present invention is a film having at least one of a film formed of alumina, a composite oxide of aluminum and titanium, or a mixed oxide or both. And an aluminum foil having a crystal size of 2511111 or less or a titanium oxide film having an amorphous structure. It is known that a three-layer structure of a titanium oxide film, an aluminum-titanium complex oxide, a mixed oxide, and an aluminum oxide film can form a film having excellent leakage current characteristics. For example, after a titanium oxide film is formed on the surface of an aluminum foil by a liquid phase deposition method, anodization treatment is performed at an anodization voltage of 60 V, followed by heat treatment. The film structure was formed from the aluminum foil substrate side as aluminum/aluminum oxide/aluminum-titanium composite oxide/titanium oxide. Since the appropriate thickness of each layer is determined by taking into account the leakage current characteristics and the electrostatic capacitance, it is preferable to set it. Further, the vertical relationship between the layers is not particularly limited. The film having one or both of a composite oxide or a mixed oxide of aluminum and titanium can be obtained by subjecting the aluminum foil coated with titanium oxide to anodization and heat treatment. By anodizing conditions or heat treatment conditions, a two-layer structure of a titanium oxide film and a composite or mixed oxide film can be prepared, and a titanium oxide film, a composite or mixed oxide film, and a three-layer aluminum oxide film can be formed. structure. The heat treatment temperature is preferably 650 C or less, more preferably 250 to 600 ° C. Less than 2 〇〇 °c may not fully confirm the heat treatment effect, and greater than 65 (rc will make the electrostatic capacity low. The ambient gas during heat treatment is preferably an inert gas such as vacuum, nitrogen or argon.) In the environment, the pressure can be reduced from the atmosphere, and the atmosphere can be decompressed by replacing the atmosphere with an inert gas. The aluminum foil to be used is not particularly limited, and for example, 1N99 having an aluminum purity of 99.99 or more and 1N90 having an aluminum purity of 99.90 or more can be used. Such high-purity aluminum foil (the above number is the alloy number of the aluminum association), the high-purity aluminum foil can make 12 1301626 5

10 is used for electricity valleys. In addition, it can also be a sintered body. Regarding the face, it is not limited to the degree of roughening. x, the thickness of the thickness used is not particularly limited, and the thickness is preferably about 20 to 15 〇 μπι. This is because if (10) is too thin, the 曰 reduces the nucleus, and the over-phase makes the electrostatic capacity per unit mass lower. Further, the electrode for a capacitor of the present invention has at least a titanium oxide plate and contains an additive element hungry! The atomic number is more than %, and the atomic number is 25%. Here, the film having a titanium oxide content of titanium oxide is 10 or more, 35 atom% or less, and the remaining component contains an oxygen atom. The impurities may contain 0.1 atom% or more and 5 atom% or less of hydrogen. 15

Since the titanium oxide is a high dielectric material, it is formed on the surface of the capacitor electrode, and when the titanium film is formed, the titanium oxide acts as a high dielectric, and a high capacitance in the valley is obtained. The thinner the thickness of the titanium oxide film is, the higher the capacity of the capacitor can be obtained, but the defects such as voids are also increased. Therefore, the thickness is preferably 帅1 or more, 〇.5_ or less, and more preferably 0.bm or more, 〇.3_ The following is better. Further, by containing from 0.1 atomic% to 25 atomic % of barium oxide in the titanium oxide film, a film having a higher dielectric constant can be obtained. The present inventors have found that the inclusion of A1 in the titanium oxide film improves the dielectric constant by the molecular orbital calculation described below, and thus completed the present invention. In the present invention, in order to investigate the influence of various additive elements on the titanium oxide film "electricity", the electron polarizability and vibration pole of the model molecule were calculated using the Gaussian 98 program Hartre 20 e-Focl ° as shown in Table 1. Rate. The basic functions used are described in "Gussian basis sets for molecular calculations, S. Hujinaga (eds.), Elsevier (1984). The results of the calculations shown in Table 1 are known from the electronics. The dielectric constant of polarization is almost independent of the additive element type 13 1301626 studied here. On the other hand, it can be seen that the dielectric constant from vibration polarization is the type of -Al(OH)2 of A1 atom. When present in the titanium oxide film, the dielectric constant is greatly increased. That is, if the A1 atom is present in the network structure in which the oxygen atom and the titanium atom are formed in the titanium oxide in the state of -Al(OH)2, Compared with the other five elements, the vibrational polarizability will become larger. This is the reason why the addition of A1 to the titanium oxide film can improve the dielectric constant effect. 1301626 Electron Polarization and Vibration Polarization of the No. 1 Molecular Conducting Method Calculated value of the rate (the value normalized by the number of atoms)

Model Molecular Electron Polarizens / Atomic Number (xlO'3nm3) Vibrational Polarizability / Atomic Number (xlO'3 nm3) OH OH 11 H HO-Ti- 0 -Si-OH II II OH OH 0.71 5.9 OH OH II II HO-Ti- 0-Zr-OH ll II OH OH 0.60 4.1 OH OH II / HO-Ti- 0 - B II \ OH OH 0.72 4.4 OH OH 1 1 / HO-Ti- 0 - A1 II \ OH OH 0.59 4.5 OH F 1 1 / HO-Ti- 0 -A1 II \ OH F 0.64 10.6 OH OH 1 1 ll HO-Ti- 0 -Si-OH 1 1 ll OH OH 0.66 4.8 15 1301626 Since A1 is added as described above Since the dielectric constant of the obtained titanium oxide film can be increased, the required capacitor capacity can be obtained without making the thickness of the film thin. Therefore, when the titanium oxide film is formed by the liquid phase deposition method, it is possible to solve the problems that the thickness of the titanium oxide film obtained by the film thickness is small, the thickness of the titanium oxide film is large, and the defects such as small holes are large. In order to form the above film, a titanium oxide film can be formed on the surface of the gossip foil by liquid deposition. The reaction of depositing titanium oxide on the aluminum foil by the liquid phase deposition method is carried out in accordance with the hydrolysis equilibrium reaction shown by the following formula (I). That is, the reaction of fluorotitanate with water molecules produces a reaction between titanium oxide and H+ ions and ions. 0 TiF62 + 2H2 〇 (2) Ti 〇 2+ 4H + + 6F (I) Here, titanium oxide can be precipitated by adding an A1 ion as an activator which can carry out the equilibrium reaction of the formula (1) to the right side. 15

In the present invention, the aqueous solution of ammonium fluorotitanate is preferably 0.01 mol/l or more and 〇.5 mol/l or less. Although the titanium oxide film can be formed even if the concentration of the aqueous ammonium fluoroantimonate solution is less than 0.1 mol/bu, the film formation speed of the film is later, and the production is low. On the other hand, when the concentration of the aqueous solution of ammonium niobate is more than 0.5 mol A, the titanium oxide particles are easily precipitated in a powder form in an aqueous solution, and it is difficult to obtain an oxide film having a uniform thickness on the A1 foil substrate. The pH of the I treatment solution is preferably 3 to 8 and more preferably 5 to 6. The reason is that when the pH value of the liquid in the field is less than 3, although a complete film can be produced, it is difficult to obtain the required electric capacity; and when the liquid value of the treatment liquid is large, π ' The treatment liquid tends to be unstable, and oxygen is precipitated in the treatment liquid. The wood material f has a problem that it is difficult to form a uniform film on the surface of the substrate. At night pH. The conditioning can be carried out by a conventionally known method, and the other conditions of the precipitation reaction of the 161301626 of the present invention are not particularly limited. The AUI substrate is immersed in the above-mentioned fluorinated titanic acid water-soluble surface to precipitate ~ thickness of the oxidized mulch soil = 5 to _ can be used, for example, the purity of 99.99 or more is more than 1N90 special purity box (the above The number is the alloy number of the New Zealand Association. These high purity inscriptions can be used for capacitors. In addition, it can also be used to burn the knot. Regarding the surname, it is not limited to the extent of the roughening process. The temperature or the immersion time of the above treatment liquid may be appropriately set, but the temperature of the treatment liquid is preferably between normal temperature and thief, and the immersion time (four) minutes to (10) ! A method of adding A1 to a film-formed titanium oxide film is defined. It is also possible to add A1 to the titanium oxide film by a method of injecting a person from the surface of the oxide by an ion implantation method or the like. According to the ion implantation method, according to the ion implantation amount of the A1 ion implanted into the 15th, a desired concentration of ai can be added to the oxide sharp film, and the depth direction distribution of the ai concentration in the titanium oxide film can be controlled by the control of the implantation energy. For the desired distribution state. The method which can be produced at a low cost can also be applied to the titanium oxide film by a method of diffusing atoms from the substrate to the titanium oxide film by anodizing. Namely, an anodizing treatment was carried out by the method described below by forming a surface of an oxidized celite using a liquid deposition method. The electrolytic solution for anodizing treatment may be, for example, a solution of ammonium borate, scalylic acid, adipic acid, oxalic acid, sulfuric acid or hydrazine m, or a solution of two or more kinds of money salts, but is not limited to such solutions. 17 1301626 ” In the anodizing treatment, an aluminum oxide layer can be formed between the A1 box substrate and the titanium oxide film by applying an electric enthalpy to the eight! box substrate in the anodizing treatment electrolyte. The set temperature, the applied voltage, and the like of the anodizing treatment are processed by a known condition without special regulation. For example, the temperature of the anodizing treatment liquid is determined to be sot~sail, and the gas is applied to the A1. 2. The current density of the circulating gossip foil is 〇·ΐηΑ/^2~# corpse/CI11 constant, and the anode is grown between the A1 foil substrate and the above titanium oxide film. Density, the amount of A1 ions eluted from the substrate can be adjusted, and the ai concentration in the titanium oxide film can be adjusted. As the anodized film grows, the voltage and the energization time increase, but due to the thickness of the anodized film and the voltage There is a proportional relationship, so it can be known that the required anodic oxide film thickness can be obtained by monitoring the voltage. The value of the applied voltage reaches the value corresponding to the thickness of the anodized film of 1 〇 nm to 5 〇〇 leg, and the control voltage is 15 £.疋 'Asia keeps a certain time. Borrow The retention time can be obtained. • The A1 concentration distribution in the film of the titanium oxide film is high on the anodic oxide side and low on the surface side of the titanium oxide film, and from the surface of the titanium oxide film to oxidation reduction and anodization. At the interface of the layer, the concentration of A1 is distributed in an inclined state. The above holding time can be set so that the concentration of the titanium oxide can be distributed to a desired fraction of 20 cloth, although it is not particularly specified, but can be kept, for example, aged to aged. By changing the current density in the anodization, the titanium oxide layer becomes a film structure composed of two layers of titanium oxide layers having different wavelengths of g. The concentration of the titanium oxide film is distributed from the substrate. The closer the side is, the higher the rolling degree is, the higher the adhesion between the titanium oxide film and the substrate can be improved. For example, the current density of the anodization is set to lmA/cm2 to 10 mA/cm2 by 18 1301626, which is based on the titanium oxide film. A high A1 concentration layer having an erbium concentration of 1 〇 atomic % to 25 atomic % is prepared in the vicinity of the material side interface, and then the current density of the anodizing is set to 1 OmA/cm 2 to 3 OmA/cm 2 , and the remaining A region of 5 on the surface of the titanium oxide film forms A1 thick It is a low A1 concentration layer of 原子1 atom% to 10 atom%. The thickness of the above 13⁄4 A1 concentration layer is 1〇5~5〇nm, preferably i〇nm~3〇nm. After the anodization, the aluminum foil with titanium oxide is heat-treated to obtain an electrode foil. The heat treatment temperature after the anodization is preferably 4 〇〇〇c, preferably 10 Å to 400 ° C, and less than 200 ° C. There may be cases where the heat treatment effect cannot be confirmed, which is greater than 4 〇〇. When it is 〇, the static capacitance ϊ may be lowered. The ambient gas during heat treatment is preferably in a vacuum or an inert gas such as nitrogen or argon. To create a vacuum environment, The pressure can be reduced from the atmospheric environment, or the ambient gas can be replaced with an inert gas and then decompressed. By the heating, the A1 concentration in the titanium oxide film and its distribution state can be unchanged. An aluminum foil having a titanium oxide film containing A1 as an additive as the anode can be used as a capacitor. Further, the electrolyte or the cathode is not particularly limited and may be appropriately selected and used. Example 1 20 After forming a film using various treatment liquids, the electrostatic capacity, the leak current, and the crystal size were evaluated. The treatment liquid, the treatment conditions, and the results are shown in Tables 2 to 4. The substrate used untreated AU|(1N99) which was not subjected to the finishing process. The treatment solution of the oxidized crystallization film is prepared by (1) county plus (2) adding two kinds of strontium fluorotitanate aqueous solution 19 1301626 liquid. In the case of (1), the treatment liquid was adjusted to pH 3, 4, 5, 6, 7, and 8 by adding ammonia water to an aqueous solution of 01 M (m 〇 1 / 1) of ammonium hexanoate. In the case of (2), the treatment liquid is prepared by disregarding the aqueous solution of fluotitanic acid, adding lanthanum 1 lanthanum borate, and adding ammonia water to adjust the pH to 3, 4, 5, 6, 7, and 8 to produce a substrate. The treatment liquid prepared under the conditions of (1) and (2) was allowed to stand for 5 minutes. For anodization, a 12% aqueous solution of ammonium adipate was used at a temperature of 8 Torr. . A predetermined voltage of 60 minutes is applied. After anodization, heat treatment was carried out in a vacuum at φ 9 〇 ° C, 3 ° C, and 650 ° C for 3 hours. The electrostatic capacity was measured using a 12% aqueous solution of ammonium adipate and a ffiLCR meter at 120 Hz. The leakage current is measured by applying 5^^. The experiment Νο·91 which is described later as a comparative example is compared by the following criteria. The electrostatic capacitance X is equal to Νο·91 or worse 〇 more than Νο·91 is increased by 1 times ~ι ·5 times 15 ◎ ι··91 is increased by ι·5 times or more Leakage current X is greater than No.91 • 〇 is equivalent to No.91 ◎ Less than No. 91 For the crystal size of the film, the full-width half-value of the maximum value obtained by X-ray refraction measurement is obtained by substituting Xie Le formula. Further, the cross-sectional structure of the film was observed by an electron microscope. [Experiment Νο·1~18] ΜUse 0.1Μ/, Qiqin acid aqueous solution as the treatment liquid, and adjust the ammonia to 3, 4, 5, 6, 7, and 8. The substrate was immersed in the treatment liquid at normal temperature for 5 minutes to form a film, and after the film formation, it was washed with water and air-dried. This was followed by maintaining 9 〇t, 300 in a heat treatment at a vacuum of 20 ^ 10 26 650 ° C for 3 hours. ^, [Experiment Νο·19~36 ]: The soil material is anodized with anodizing voltage, and then ammonia solution: _, 4, 5, 6, 7, 8 followed by an aqueous solution of ammonium hexanoate as a treatment liquid Forming a titanium oxide film. The substrate was immersed at room temperature for 5 knives in the night to form a film, and after film formation, it was washed with water and air-dried. Then, heat treatment was carried out in the air at a temperature of 9 ° C, 300 ° C, and 650 ° C for 3 hours. The results are shown in Table 2. Table 2

Heat treatment conditions Titanium oxide Crystal size Film structure (狖 Aluminum foil substrate side) Capacity

〇◎ ◎ ©〇0〇◎◎◎ 0〇0◎© ◎〇ο©©© ◎◎◎◎ ◎◎I ◎◎®l〇j @01 Leakage current test example ΌΜ σ 21 10 1301626 [Experiment Νο· 37 to 54] A 0.1% aqueous solution of ammonium hexafluorotitanate was used as a treatment liquid, and pH was adjusted to 3, 4, 5, 6, 7, and 8 with ammonia water. The substrate was immersed in the treatment liquid at normal temperature for 5 minutes to form a film, and after the film formation, it was washed with water and air-dried. After anodization was carried out by anodizing 5 voltage 3 ¥, heat treatment was carried out in a vacuum at 90 ° C, 300 ° C, and 650 ° C for 3 hours. The results are shown in Table 3. [Experiment Νο·55~72) A 0.1% aqueous solution of ammonium hexafluorotitanate was used as a treatment liquid, and the pH was adjusted to 3, 4, 5, 6, 7, and 8 with ammonia water. The substrate was immersed in the treatment liquid at normal temperature for 5 minutes to form a film, and after the film formation, it was washed with water and air-dried. After anodization was carried out by anodizing at a pressure of 6 Torr, heat treatment was carried out in a vacuum at 90 ° C, 300 ° C, and C 3 j. The results are shown in Table 3. % 22 1301626 Table 3 [War] 2 concentration BO, concentration anodic oxidation voltage heat treatment conditions

Titanium oxide I crystal size I film structure (from the side of Luyeye substrate) change the leakage current

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650〇C 1.8nm 2.5nm 2.4nm 2.2nm 2.2nm 2.2nm 2.3nm 7 children 5 夕 铝 aluminum / alumina / Syrian titanium composite oxide / titanium oxide 〇 1 mutual

© ] 〇 Μ Μ I 〇 L (Comparative Example) [Experiment N0.73 to 90] A 0.1 M aqueous solution of hexafluorotitanate was used as a treatment liquid, and 〇 lM oleic acid was added as a titanium oxide precipitation activator. The substrate was immersed in the treatment liquid at normal temperature for 5 minutes to form a film. After the film formation, the film was washed with water and air-dried. After anodization was carried out at an anodic oxidation voltage of 60 V, heat treatment was carried out in a vacuum for 3 hours, 3 〇〇 C, and 650 C for 3 hours. The results are shown in Table 4. 10 23 1301626 Table 4 Experiment No. Treatment liquid conditions Anode heat treatment conditions Titanium oxide crystal size Film structure characteristics Evaluation Substrate (NH4)2TiF6 Concentration h3 bo3 Concentration Liquid temperature pH Oxidation voltage (from aluminum foil substrate side) Capacity change leakage current Change Preparation 73 3 3.0nm 〇X 74 4 3.1nm 〇X 75 5 90°C 3.2nm 〇X 76 6 3.9nm 〇X 77 7 4.7nm 〇X 78 8 3.8nm 〇X 79 3 4.4nm 〇X 80 4 4.3 Nm S two aluminum / titanium oxide ◎ X 81 A1 foil 0.1M 0.1M hanging 5 60V 300 ° C 4.6nm ◎ X 82 flat 6 4.1nm ◎ X 83 7 4.5nm ◎ X than 84 8 4.8nm 〇X than 85 3 6.2nm 〇X Example 86 4 6.0nm 〇X 87 5 650〇C 6.3nm 〇X 88 6 5.3nm 〇X 89 7 6.5nm 〇X 90 8 6.0nm 〇X 91 A1 foil flat — - - - 60V 300° C — Tri-Aluminum/Alumina $2 ク厶 benchmark [Experiment Νο·91] The substrate was anodized at an anodizing voltage of 60 V, and then kept at 300 ° C for 3 hours in a true 5 air. The heat treatment. The results are shown in Table 4. The electrode foil of the present invention shown in the second and third tables has characteristics superior to those of the comparative examples, and the effects thereof can be confirmed. On the other hand, it was confirmed that the aluminum foil obtained by adding boric acid to the treatment liquid as shown in the fourth table was inferior in leakage current characteristics as compared with the comparative example. 10 Example 2 A1 foil substrate using untreated A1 foil (1N99) which was not subjected to etching processing 〇 The ammonium fluorotitanate concentration in the liquid phase deposition treatment liquid was set to 0.05 mol/l, and ammonia water was added to the aqueous solution to adjust the pH. Adjust to 5.5. The temperature of the treatment liquid 15 was set to normal temperature, and the A1 foil substrate was immersed in the above aqueous ammonium fluorotitanate solution 241301626 for 20 minutes to deposit a titanium oxide film having a thickness of about 2 Å on the surface of the substrate. In the present embodiment, A1 is diffused from the A1 foil of the substrate to the titanium oxide film by anodizing, and A1 is added to the titanium oxide film, which can be produced at a low cost. 5 Anodizing treatment Using a 10% aqueous solution of ammonium adipate, the liquid temperature was set to 70 C' and the current density was set to 〇 1 mA/cm 2 to 5 〇 mA/cm 2 . When the current density is constantly applied to the A1 foil substrate, an anodized film is grown between the A1 foil substrate and the oxidized φ titanium film. By controlling the current density of the energization, the amount of A1 ions eluted from the substrate can be adjusted, and the A1 concentration in the titanium oxide film can be adjusted. 10 As the anodized film grows, the voltage and the energization time increase. However, since there is a proportional relationship between the thickness of the anodized film and the voltage, it is known that the desired thickness of the anodized film can be obtained by monitoring the voltage. At the stage of reaching a value corresponding to the thickness of the anode oxide film of 50 nm, the control voltage is constant and maintained at a certain ratio of four. By this holding time, the ruthenium film in the titanium oxide film of the film can be obtained, and the distribution is high in the anodic oxide film side, and the surface of the oxidized cerium film is •16 spread' and from the surface of the titanium oxide film to At the interface between the titanium oxide film and the anodized layer, the concentration of A1 increases linearly and is distributed in an inclined state. Further, when the holding time is 6 G or more, the A1 concentration in the titanium oxide film is averaged. The titanium oxide film is made of a high-eight layer and a low-layer A1 layer, and the two layers of the structure are the same as A1; the anodizing current density when the layer is formed and the anodizing current density when the layer is low, and The electric waste holding time was set to the conditions shown in Table 6, and anodizing treatment was performed. The detailed implementation is shown in Tables 5 and 6, for example. After the film formation, the electrostatic concentration, the leakage current, and the Al concentration in the titanium oxide film were evaluated. The A1 concentration distribution in the titanium oxide film was quantitatively evaluated by X-ray photoelectron spectroscopy 25 1301626. After the anodizing treatment, heat treatment was carried out by heating to 250 ° C in a vacuum. The electrostatic capacity was measured at 120 Hz using an LCR meter using a 12% aqueous solution of ammonium adipate. 5 Evaluation is performed by the following criteria. Electrostatic capacity X: 2. (^F/cm2 or less 〇: Greater than 2.0pF/cm2, 10pF/cm2 or less ◎: Greater than 10pF/cm2

26 1301626 Table 5

Anodic current density (mA/cm2) Low voltage state retention time during anodization (minutes) A1 concentration distribution state in the titanium oxide film A1 concentration (atomic%) in the titanium oxide film A1 concentration of the titanium oxide surface layer (atoms Number %) A1 concentration (atomic%) of the cerium oxide layer near the interface of cerium oxide/anodized layer. Electrostatic capacity test 25 60 uniform 1 1 1 〇 Example 20 60 uniform 5 5 5 〇 Example 10 60 Uniform 10 10 10 ◎ Example 10 60 Uniform 12 12 12 ◎ Example 8 60 Uniform 15 15 15 ◎ Example 10 60 Uniform 10 10 10 ◎ Example 18 60 Uniform 6 6 6 〇 Example 6 60 Uniform 20 20 20 ◎ Example 5 60 Uniform 22 22 22 ◎ Example 20 60 Uniform 5 5 5 〇 Example 18 60 Uniform 7 7 7 〇 Example 12 60 均·9 9 9 〇 Example 10 60 Uniform 13 13 13 ◎ Example 10 60 Uniform 11 11 11 ◎ Example 9 60 Uniform 14 14 14 ◎ Example 1 60 Uniform 25 25 25 ◎ Example 0.5 60 Uniform 30 30 30 X Comparative Example 0.7 60 Uniform 28 28 28 X Comparative Example 40 60 Uniform ND ND ND X Comparative Example 50 60 Uniform ND ND ND X Comparative Example 20 10 Tilt 1 25 ◎ Example 25 5 Tilt 0.5 15 ◎ Example 5 40 Tilt 10 25 ◎ Example 8 15 Tilt 5 20 ◎ Example 10 10 Tilt 3 10 ◎ Example 10 30 Tilt 7 20 ◎ Example ND: Undetected 27 1301626 The anodic oxygen 4 匕 current density (mA/cm 2 ) at the time of formation of the high AI concentration layer of the sixth table _ the anode oxygen current density (mA/cm 2 ) at the time of formation of the concentration layer Constant voltage state retention time during anodization (minutes) High Al^>^ Layer Α1 concentration (atomic 娄槐) _ concentration layer Α1 concentration (atomic machine) Α1 concentration layer thickness (nm) lie concentration layer Thickness (nm) Electrostatic capacity test 5 25 ___15 20 1 10 __190 ◎ Example 0.5 ^/τ > ί 40 3* /Λ- ^_ 1-卜 30 ND 10 __190 X Comparative example - --1~— -J__30 30 ND in gentry / min / 1 ~ ' ----- L. 190 X Comparative Examples Some of the electrodes of the present invention have superior capacity characteristics' and can be combined with the effects of the present invention. Industrial Applicability ~ (10) Residual Supply - Excellent in leakage fineness by using the present invention <Electrical_, λ)τ, Τ7Γ 10 High-capacity capacitors for lightning to make capacitors reach a small size Sending k electricity (4), it can be dusted and smashed into a valley, and it can be made into a miniaturized mobile machine such as a container. V makes use of 6 hai [simplified description of the diagram] None [Main component description] None

28

Claims (1)

1301626 X. Patent application scope: 1· - The electrode of the capacitor n is composed of materials, and the domain name is a titanium oxide film having a crystal size of 2.5 nm or less or an amorphous structure. 2. An electrode case for a capacitor, which is composed of a material, and which has a film formed of alumina and a titanium oxide film having a crystal size of 2.5 nm or less or an amorphous structure. 3· - Detecting the capacitance of the capacitor H, which is made up of a titanium oxide film having a crystal size of 2.5 mn or less or an amorphous structure, and a composite oxide or mixed oxide of aluminum and titanium. One or both (7) laminator. 4. An electrode foil for a capacitor, which is composed of an aluminum foil, and the aluminum foil has a film formed of alumina, a composite oxide of aluminum and titanium, or a film of a mixed oxide, or both, and A titanium oxide film having a crystal size of 2511111 or less or an amorphous structure. I5 5· An electrode pig for use in an electric grid, which is a film formed of titanium oxide according to any one of the above-mentioned claims 1 to 4, which contains 〇1 atom% or more and 25 atom%%. The following aluminum. An electrode foil for a capacitor, which is contained in a film formed of titanium oxide according to any one of the above-mentioned claims, and wherein the aluminum concentration is 〇·1 atom It is several % or more and 25 atomic % or less, and the said density increases from the surface of a film to the inside of a film along a depth direction. An electrode foil for a capacitor, which is a film formed of titanium oxide according to any one of items 1-4 to 4 of the above-mentioned application, which contains 〇1 atom% or more and 25 atom%% or less. Aluminum, and the above-mentioned film contains 29 1301626 which has two layers of titanium oxide having different aluminum concentrations. 8. A capacitor for use in an electrode foil for a capacitor according to any one of claims 1 to 7. 30