JP4147640B2 - Method for manufacturing composite titanium oxide film element unit - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention uses a hydrothermal synthesis method, such as a condenser, a detector such as an infrared ray and an ultrasonic wave, an ink jet recording head, an actuator such as a micropump, a piezoelectric buzzer, a piezoelectric speaker, etc. The present invention relates to a method of manufacturing a composite titanium oxide thin film element unit in which a composite titanium oxide thin film is finely or precisely formed at a desired position.
[0002]
[Prior art]
In recent years, as the performance and miniaturization of communication equipment, information processing equipment, AV, home appliances, etc. have progressed, the miniaturization and weight reduction of electronic components constituting these equipment are being studied. Attempts have been made to improve performance by making it easier.
[0003]
However, although the desired density and composition can be obtained by thinning by the conventional ceramic polishing method, there is a problem that the yield is poor and the cost is extremely increased to form the target thickness (3 to 50 μm). Further, it is not suitable for forming a piezoelectric crystal film in a free shape such as a curved surface.
[0004]
In addition, the film can be thinned using a sputtering method, a physical vapor deposition method such as a CVD method or a vapor deposition method, a sol-gel method, etc., but in the case of these methods, the mass productivity is increased when the film thickness is increased. In addition, there is a problem that the substrate material is limited because it passes through a high temperature of 400 ° C. or higher during the manufacturing process.
[0005]
As means for solving the above problems, recently, a method of forming a composite titanium oxide film by heat treatment in a solution containing an alkali under a low temperature environment of 200 ° C. or less has been actively studied.
[0006]
This method can be found in, for example, “Preparation of PZT crystal film by hydrothermal synthesis and its electrical properties” (published on October 2, 1995) in the 15th electronic materials research discussion proceedings collection of Japan Ceramic Society. In general, the process consists of a seed crystal formation process in which a PZT seed crystal is deposited on the surface of the titanium metal substrate, and a crystal growth process in which a PZT crystal is further deposited and grown on the PZT seed crystal.
[0007]
Japanese Patent Application Laid-Open No. 8-306980 discloses a method for manufacturing a piezoelectric element unit by a hydrothermal synthesis method. In the method disclosed herein, a film containing titanium is formed in a predetermined region on a substrate that does not contain titanium, such as stainless steel, and a piezoelectric film is formed only in that region by a hydrothermal method. is there. On the other hand, a method is also disclosed in which a protective film of gold, platinum, iridium and Teflon is formed on a substrate containing titanium, and a piezoelectric film is formed only on a portion where titanium is exposed.
[0008]
[Problems to be solved by the invention]
However, even if a substrate containing no titanium is used as disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 8-306980, crystals of the composite titanium oxide may be deposited in unnecessary portions, causing various problems. For example, the stainless steel substrate used in the examples of the above publication is inferior in corrosion resistance to the hot alkaline solution used in the present invention, elution of chromium ions is observed, and the surface is deteriorated. Furthermore, if the reaction is repeated for a long time or repeatedly to increase the film thickness of the composite titanium oxide to be formed, the composite titanium oxide adheres and grows over the entire surface of the deteriorated stainless steel substrate, and the desired fine pattern is formed. It cannot be formed.
[0009]
Further, in a method of forming a protective film such as a gold or platinum layer in a predetermined region of a substrate containing titanium, the protective film is expensive and not practical. In addition, if the Teflon protective film is repeatedly heated and lowered in steps such as seed formation and growth film formation, the protective film peels off due to the difference in thermal expansion from the substrate material, and the function as the protective film is impaired and the pattern itself is lost. Disappear.
[0010]
Accordingly, the present invention provides a method for manufacturing a composite titanium oxide thin film element unit in which such a problem is solved and a composite titanium oxide film is formed in a predetermined pattern on a substrate with a fine pattern easily and inexpensively. With the goal.
[0011]
[Means for Solving the Problems]
In the method of selectively forming a composite titanium oxide film on a substrate by a hydrothermal method, the present inventors have intensively studied a substrate and a protective film for preventing the composite titanium oxide film from being formed, and led to the present invention. It was.
[0013]
That is, the present invention is a method for manufacturing an oxide film element unit having a composite titanium oxide layer in a predetermined region on a substrate, the surface of which is Ni-P (phosphorus content is 3 to 16% by weight). A titanium layer is formed in a predetermined region of the substrate, and the substrate is mixed in an alkaline solution of 0.1 mol / l to 8.0 mol / l with a lead-containing raw material compound of 50 mmol / l to 500 mmol / l and a zirconium-containing raw material compound of 10 mmol / l. 1 to 500 mmol / l, a titanium-containing raw material compound is 500 mmol / l or less , and a strontium and / or barium-containing raw material compound is 0.01 mmol / l to 500 mmol / l. The reaction is carried out at ˜200 ° C., and subsequently, the lead-containing raw material compound is 50 mmol in an alkaline solution of 0.1 mol / l to 8.0 mol / l. / L to 500 mmol / l, zirconium-containing raw material compound is 10 mmol / l to 500 mmol / l, and titanium-containing raw material compound is 10 mmol / l to 500 mmol / l. The present invention relates to a method for producing a composite titanium oxide film element unit, wherein a composite titanium oxide layer is formed on the layer.
[0014]
The present invention also relates to a method for manufacturing an oxide film element unit having a composite titanium oxide layer in a predetermined region on a substrate, and protecting Ni—P (phosphorus content is 3 to 16 wt%) on the substrate. A film is formed, a titanium layer is formed in a predetermined region on the protective film, and the substrate is mixed with a lead-containing raw material compound in an alkaline solution of 0.1 mol / l to 8.0 mol / l in an amount of 50 mmol / l to 500 mmol / l. l, the zirconium-containing raw material compound was prepared to be 10 mmol / l to 500 mmol / l, the titanium-containing raw material compound was 500 mmol / l or less , and the strontium and / or barium-containing raw material compound was prepared to be 0.01 mmol / l to 500 mmol / l. Installed and fixed in a mixed solution, reacted at 80 to 200 ° C., and subsequently contained lead in an alkaline solution of 0.1 mol / l to 8.0 mol / l The reaction is carried out at 80 to 200 ° C. under conditions of 50 mmol / l to 500 mmol / l of the starting compound, 10 mmol / l to 500 mmol / l of the zirconium-containing raw material compound, and 10 mmol / l to 500 mmol / l of the titanium-containing raw material compound. The present invention relates to a method for manufacturing a composite titanium oxide film element unit, wherein a composite titanium oxide layer is formed on the titanium layer.
[0015]
The present invention also relates to a method of manufacturing an oxide film element unit having a composite titanium oxide layer in a predetermined region on a substrate. The rate is 3 to 16% by weight), and the substrate is mixed in an alkaline solution of 0.1 mol / l to 8.0 mol / l with a lead-containing raw material compound of 50 mmol / l to 500 mmol / l and containing zirconium. In a mixed solution prepared such that the raw material compound is 10 mmol / l to 500 mmol / l, the titanium-containing raw material compound is 500 mmol / l or less , and the strontium and / or barium-containing raw material compound is 0.01 mmol / l to 500 mmol / l. Installation and fixation, reaction at 80 to 200 ° C., followed by lead-containing raw material in 0.1 mol / l to 8.0 mol / l alkaline solution By reacting at 80-200 ° C. under conditions of 50 mmol / l to 500 mmol / l of the compound, 10 mmol / l to 500 mmol / l of the zirconium-containing raw material compound, and 10 mmol / l to 500 mmol / l of the titanium-containing raw material compound. The present invention also relates to a method for manufacturing a composite titanium oxide film element unit, wherein a composite titanium oxide film is selectively formed in a region without a protective film on a substrate.
[0016]
In one embodiment of the present invention, the method of forming a protective film of Ni-P (phosphorus content is 3 to 16% by weight) is preferably a plating method.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a film of titanium or a material containing titanium is formed on a predetermined region of the substrate whose main component is at least Ni-P (nickel phosphorus), and the surface of the film of titanium or a material containing titanium is selected. In particular, a method for manufacturing a composite titanium oxide film element unit, characterized in that a composite titanium oxide layer is formed by a hydrothermal method, will be described.
[0018]
As the substrate, it is sufficient that at least the surface is made of a material containing Ni—P (nickel phosphorus) as a main component. On a substrate other than Ni—P (nickel phosphorus) or a substrate other than Ni—P. Further, a film mainly composed of Ni-P may be formed. In that case, an optimum substrate such as a thickness and a material may be selected as the substrate depending on the application to be used. For example, metals such as nickel, titanium, copper and iron, and alloys thereof (stainless steel, etc.) are preferably used. In addition, a polymer, glass, silicon, or the like can be used as the substrate as long as the conductivity can be secured. Further, the substrate is not limited to a planar one. Ni and P should just be contained 80 weight% or more in total.
[0019]
A method for forming a film containing Ni-P as a main component on the surface of the substrate is not particularly limited. For example, a plating method is preferable. When the plating method is used, first, a substrate whose surface has been clarified or pretreated is immersed in a nickel plating bath using sodium hypophosphite as a reducing agent together with a counter electrode, a reaction temperature of 20 ° C. or higher, and a solution pH = Under 4 to 11, a nickel plating protective film containing phosphorus is formed on the entire surface of the substrate until a desired film thickness is obtained. The thickness of this protective film should just be more than the thickness which exhibits the crystal adhesion prevention effect of composite titanium oxide, and although depending on the conditions of a hydrothermal reaction, 50 nm or more is preferable. It is also possible to isolate only the Ni-P film formed in this way and use it as an electroformed nickel phosphorus substrate. The higher the phosphorus content in the Ni-P film, the higher the effect of suppressing the precipitation of the composite titanium oxide film, so the higher the phosphorus content is preferable. The content of phosphorus in Ni—P plating usually formed by a plating method is about 3 to 16% by weight, and more preferably 5% by weight or more.
[0020]
Nickel plating baths that use sodium hypophosphite as the reducing agent include acidic electroless nickel plating baths, alkaline electroless nickel plating baths, and low-temperature electroless nickel plating baths, which are optimal depending on the substrate material and phosphorus content. Various combinations can be selected.
[0021]
Next, a layer containing titanium in a desired shape is patterned on the nickel protective layer containing phosphorus or the Ni-P substrate. The layer containing titanium may contain Ti element, and in addition to metal Ti, titanium oxide, Ti-containing perovskite ceramics, or the like may be used. Examples of the method for forming the titanium layer include film forming methods such as sputtering and vacuum deposition. In addition, as a method for obtaining a desired shape, a method using a shadow mask when forming a titanium layer on the substrate by sputtering or vacuum deposition, or photolithography after forming a titanium layer on the entire surface of the substrate is used. And a method of forming the desired shape. The thickness of the titanium layer is 0.01 to 5 μm, preferably 0.1 to 1.0 μm.
[0022]
A composite titanium oxide crystal is formed on the patterned titanium layer by the hydrothermal method as follows. The composite titanium oxide includes not only ATiO ₃ (where A is at least one of Pb, Ba, Sr, and Ca), but also A (Zr, Ti) O ₃ (where A is Pb, Any perovskite complex oxide containing Ti, such as at least one of Ba, Sr, and Ca, may be used.
[0023]
The hydrothermal method is a method for obtaining a target compound by heating a compound containing an element for forming a film in an alkaline aqueous solution. In the case of a perovskite type complex oxide, the target is obtained by heating at a temperature of about 80 to 300 ° C. practically in an alkaline aqueous solution containing the constituent elements such as Pb, Ba, Sr, Ca, Zr and Ti. A compound can be obtained. Here, an example of forming a film in which PZT (lead zirconate titanate) and a part of Pb are replaced with Sr or Ba in two stages of seed crystal formation and crystal growth will be described. A reaction can also be used.
[0024]
In an alkaline solution of 0.1 mol / l to 8.0 mol / l, the lead-containing raw material compound is 50 mmol / l to 500 mmol / l, the zirconium-containing raw material compound is 10 mmol / l to 500 mmol / l, and the titanium-containing raw material compound is 0 mmol / l. The substrate is placed and fixed in a mixed solution prepared so that the raw material compound containing ~ 500 mmol / l, strontium and / or barium is 0.01 mmol / l to 500 mmol / l, and 80 to 200 ° C, preferably 100 to 160 The initial crystal layer is formed on the patterned titanium layer by reacting at 120 ° C., more preferably 120 to 160 ° C. for 1 minute or longer, preferably 10 minutes or longer. At this time, the nickel plating film containing phosphorus, which is a protective film, has high corrosion resistance to the reaction solution, so that no reaction occurs and a composite titanium oxide seed crystal is formed only on the titanium layer.
[0025]
Next, in an alkaline solution of 0.1 mol / l to 8.0 mol / l, the lead-containing raw material compound is 50 mmol / l to 500 mmol / l, the zirconium-containing raw material compound is 10 mmol / l to 500 mmol / l, and the titanium-containing raw material compound Is reacted at 80 to 200 ° C., preferably 100 to 160 ° C., more preferably 120 to 160 ° C. for 1 minute or more, preferably 10 minutes or more under the condition of 10 mmol / l to 500 mmol / l to form a crystal growth layer A composite titanium oxide crystal film is produced. Also in this reaction, as described above, the nickel-plated film containing phosphorus, which is a substrate protective film, has high corrosion resistance, and thus does not react with the raw material solution, and no crystal growth on the protective film is observed. Therefore, the composite titanium oxide crystal is accurately patterned. Furthermore, the film thickness of the composite titanium oxide can be controlled by repeating the crystal growth reaction.
[0026]
As the compound containing the constituent elements of lead, zirconium, titanium, strontium, and barium used in the hydrothermal reaction in the present invention, chloride, oxychloride, nitrate, hydroxide, oxide and the like are preferable. Examples of the alkali compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
[0027]
Specific examples of the present invention are described in detail below. For example, a nickel substrate is used as a substrate. First, a nickel plating protective layer containing phosphorus by nickel plating using sodium hypophosphite as a reducing agent is formed on the surface of the substrate. A titanium base layer is formed on the protective layer by sputtering, and the titanium layer is patterned into a desired shape by photolithography. Next, an initial composite titanium oxide crystal layer is formed on the patterned titanium layer by hydrothermal reaction in an alkaline solution, and further finely and accurately patterned by hydrothermal reaction in an alkaline solution. A composite titanium oxide crystal film having improved electrical characteristics such as dielectric loss and piezoelectric constant is manufactured.
[0028]
First, a protective film is formed by plating on a substrate, for example, as follows. An acidic electroless nickel plating bath of nickel chloride 30 g / l, sodium citrate 15 g / l, sodium acetate 5 g / l, sodium hypophosphite 10 g / l, Pb ion 2 ppm is prepared, pH = 4.2, 60- A nickel plating protective film is formed on the substrate at 90 ° C. for 10 to 15 minutes. The thickness of the nickel protective film containing phosphorus at this time is about 0.5 to 2.0 μm.
[0029]
Next, after forming a titanium layer by sputtering on the substrate on which the protective film has been formed, it is formed into a desired shape using a photolithography technique. The thickness of this titanium layer is about 0.1 to 1 μm.
[0030]
Next, in order to form an initial crystal layer, a lead-containing raw material compound is 50 mmol / l to 500 mmol / l, and a zirconium-containing raw material compound is 10 mmol / l to 0.1 mol / l to 8.0 mol / l in an alkaline solution. The substrate is placed and fixed in a mixed solution prepared so as to be 500 mmol / l, the titanium-containing raw material compound is 0 mmol / l to 500 mmol / l, and the strontium and / or barium-containing raw material compound is 0.01 mmol / l to 500 mmol / l. And reacting at 80 to 200 ° C., preferably 100 to 160 ° C., more preferably 120 to 160 ° C. for 1 minute or more, preferably 10 minutes or more to form an initial crystalline layer on the patterned titanium layer. The thickness of the initial composite titanium oxide crystal layer at this time is 0.05 to 2.0 μm.
[0031]
Next, in order to grow crystals, in a 0.1 mol / l to 8.0 mol / l alkaline solution, the lead-containing raw material compound is 50 mmol / l to 500 mmol / l, the zirconium-containing raw material compound is 10 mmol / l to 500 mmol / l, And the titanium-containing raw material compound is reacted at 80 to 200 ° C., preferably 100 to 160 ° C., more preferably 120 to 160 ° C. for 1 minute or more, preferably 10 minutes or more, under the conditions of 10 mmol / l to 500 mmol / l. A composite titanium oxide crystal film forming a crystal growth layer is manufactured. The heating method in the hydrothermal reaction is based on a hot water bath or an electric furnace. Thereafter, general cleaning is performed. For example, ultrasonic cleaning is performed in pure water and dried at 100 to 200 ° C. for 2 hours or more. For washing, an organic acid such as acetic acid, nitric acid, sulfuric acid or the like can be used.
[0032]
The composition of the piezoelectric crystal film thus formed is such that the first layer of the initial crystal layer is a solid solution of lead titanate, lead zirconate, strontium titanate and / or barium titanate, strontium zirconate and / or barium zirconate. A composite oxide. The composition of the PZT-based piezoelectric crystal film grown on the initial crystal layer _{PbZr x Ti 1-x O 3} ( however, 0 <x <1) is made from.
[0033]
The electrode used when the PZT-based piezoelectric crystal film obtained in the present invention is made into an element is not particularly limited, but an optimum electrode is selected in consideration of cost and mass productivity. For example, there are nickel by electroless plating and silver of baking type. In addition, aluminum by vapor deposition, platinum, gold, nickel, etc. by sputtering are also used. In addition, when resin is used for the substrate, it is necessary to pay attention to the temperature of the baking type silver electrode because it cannot be heated to a high temperature.
[0034]
Next, a region without a protective film on the substrate is formed by forming a protective film of Ni-P (nickel phosphorus) in a region where a composite titanium oxide film is not formed on the surface of the substrate made of at least titanium or a material containing titanium. A method for selectively forming a composite titanium oxide thin film will be described.
[0035]
The substrate in this case may be a substrate containing Ti as a nucleus for precipitation of seed crystals on the surface, or a Ti metal plate itself. In the region where the composite titanium oxide film is not formed on the substrate, for example, a Ni—P protective film is formed by the plating method described above. As a method for plating a predetermined region, there is a method such as masking. Next, when the seed crystal of the composite titanium oxide film and the growth layer thereof are formed by the hydrothermal method as described above, no film is formed on the Ni-P protective film, and a predetermined pattern is formed. Thus, the composite titanium oxide film element unit of the present invention can be obtained. In addition, by forming an electrode by the above-described method, it can be used for various applications such as a piezoelectric element and a capacitor.
[0036]
【Example】
Hereinafter, specific examples of the present invention will be described in more detail.
[0037]
Example 1
Prepare an acidic electroless nickel plating bath of nickel chloride 30 g / l, sodium citrate 15 g / l, sodium acetate 5 g / l, sodium hypophosphite 10 g / l, lead nitrate 2 mg / l, pH = 4.2, A nickel plating protective film was formed on the entire surface of the 20 μm stainless steel substrate at 90 ° C. for 10 minutes. At this time, the thickness of the nickel protective film containing phosphorus was a uniform plating film having a thickness of 1.0 μm. As a result of X-ray analysis, the composition of this protective film was 90.6% by weight of Ni, 8.9% by weight of P, and 0.5% by weight of Na.
[0038]
Next, a titanium layer was formed by sputtering on the upper surface of the substrate on which the protective film was formed, and then formed into a desired shape using a photolithography technique. The titanium layer thickness was 0.5 μm.
[0039]
In order to form the initial PZT crystal layer on the titanium layer of the substrate thus patterned, the reaction raw material input amount was 150 mmol / l Pb (NO ₃ ) ₂ aqueous solution, 50 mmol / l Sr (NO ₃ ) ₂ aqueous solution, ZrOCl ₂ aqueous solution. 75 mmol / l, TiCl ₄ aqueous solution 25 mmol / l, and KOH aqueous solution 4.15 mol / l. The substrate with the protective film was placed and fixed in the mixed solution, and heat treatment was performed at 150 ° C. for 4 hours under normal stirring operation. Reaction was performed. The composition of the initial crystal layer generated in this step is Pb _x Sr _{1 over x Zr y Ti 1-y O3} ( provided that 0 <x <1,0 <y < 1.) Was.
[0040]
The reaction raw material input amount for crystal growth in the initial crystalline layer thus obtained was 330 mmol / l Pb (NO ₃ ) ₂ aqueous solution, 150 mmol / l ZrOCl ₂ aqueous solution, 150 mmol / l TiCl ₄ aqueous solution, and 5 KOH aqueous solution 5 The substrate with a protective film based on the initial PZT crystal layer was placed and fixed in the mixed solution, and a heat treatment reaction was performed at 130 ° C. for 4 hours under a normal stirring operation. This process was repeated 3 times to obtain a film thickness of 10 μm. Thereafter, ultrasonic cleaning in pure water was performed twice for 3 minutes, and drying was performed at 100 ° C. for 12 hours.
[0041]
The composition of the obtained PZT-based piezoelectric crystal growth film layer was PbZr _x Ti _1-x O ₃ (where 0 <x <1). The surface state of the obtained composite titanium oxide film element unit is shown in FIG. The portion that appears black in FIG. 1 is a region of the Ni-P protective film, and the portion that appears white is a composite titanium oxide film formed on Ti. It can be seen that no adhered crystal particles are seen on the protective film, and the pattern is finely and accurately formed.
[0042]
Comparative Example 1
In Example 1, a Ti layer was formed in a predetermined region of a 20 μm stainless steel substrate in the same manner as in Example 1 except that nickel phosphorus plating was not performed, and a PZT thin film was formed. The surface state of the obtained composite titanium oxide film element unit is shown in FIG. The target pattern is the same as in Example 1, but the PZT film is formed on the surface of the stainless steel substrate on which Ti is not formed, the composite titanium oxide film is formed on the entire surface, and the precise pattern cannot be formed. I understand.
[0043]
Comparative Example 2
In Example 1, instead of nickel phosphorus plating, nickel plating was performed as follows, and Ti was formed in the same manner as in Example 1 except that a PZT film was formed. Nickel plating was performed as follows. Nickel chloride 0.02 mol / l, sodium tartrate 0.02 mol / l, hydrazine 1 mol / l hydrazine is used as a reducing agent, and a nickel plating bath is prepared. A nickel plating protective film was formed on the entire surface of the stainless steel foil. The thickness of the nickel protective film was a uniform plating film having a thickness of 1.5 μm. As a result of X-ray analysis, the composition of this protective film was 98.4 wt% Ni and 1.6 wt% N. The surface state of the obtained composite titanium oxide film element unit is shown in FIG. Although the amount of PZT crystal deposited on the protective film is smaller than that formed directly on the stainless steel substrate, it can be seen that partial precipitation is observed and a precise pattern cannot be formed.
[0044]
【The invention's effect】
When obtaining a composite titanium oxide thin film element unit by forming a composite titanium oxide film with a fine pattern in a predetermined area on the substrate, without using an expensive protective film such as platinum or gold, Teflon, etc. The composite titanium oxide film can be formed on the substrate with a precise pattern without causing the composite titanium oxide to be deposited on the protective film even under severe conditions.
[Brief description of the drawings]
1 is a photograph replacing a drawing showing the surface state of a composite titanium oxide film element unit in which a PZT thin film is formed on a substrate having a Ni—P protective film obtained in Example 1. FIG.
2 is a photograph replacing a drawing showing the surface state of a composite titanium oxide film element unit in which a PZT thin film is formed on a substrate without a Ni—P protective film obtained in Comparative Example 1. FIG.
3 is a photograph replacing a drawing, showing a surface state of a composite titanium oxide film element unit in which a PZT thin film is formed on a substrate having a Ni protective film obtained in Comparative Example 2. FIG.

Claims (4)

A method for manufacturing an oxide film element unit having a composite titanium oxide layer in a predetermined region on a substrate, wherein the surface is Ni-P (phosphorus content is 3 to 16% by weight). The lead-containing raw material compound is 50 mmol / l to 500 mmol / l, the zirconium-containing raw material compound is 10 mmol / l to 500 mmol / l in an alkaline solution of 0.1 mol / l to 8.0 mol / l, Installed and fixed in a mixed solution prepared so that the titanium-containing raw material compound is 500 mmol / l or less and the strontium and / or barium-containing raw material compound is 0.01 mmol / l to 500 mmol / l, and reacted at 80 to 200 ° C. Subsequently, the lead-containing raw material compound is contained in an alkaline solution of 0.1 mol / l to 8.0 mol / l in an amount of 50 mmol / l to 500 m. ol / l, zirconium-containing raw material compound is 10 mmol / l to 500 mmol / l, and titanium-containing raw material compound is reacted at 80 to 200 ° C. under conditions of 10 mmol / l to 500 mmol / l on the titanium layer. A method for producing a composite titanium oxide film element unit, comprising forming a composite titanium oxide layer. A method of manufacturing an oxide film element unit having a composite titanium oxide layer in a predetermined region on a substrate, wherein a protective film of Ni-P (phosphorus content is 3 to 16% by weight) is formed on the substrate, A titanium layer is formed in a predetermined region on the protective film, and the substrate is mixed in an alkaline solution of 0.1 mol / l to 8.0 mol / l with a lead-containing raw material compound of 50 mmol / l to 500 mmol / l, a zirconium-containing raw material compound Is 10 mmol / l to 500 mmol / l, titanium-containing raw material compound is 500 mmol / l or less , and strontium and / or barium-containing raw material compound is 0.01 mmol / l to 500 mmol / l. Then, the reaction is carried out at 80 to 200 ° C., followed by 50% of the lead-containing raw material compound in the 0.1 mol / l to 8.0 mol / l alkaline solution. By reacting at 80 to 200 ° C. under the conditions of mol / l to 500 mmol / l, zirconium-containing raw material compound of 10 mmol / l to 500 mmol / l, and titanium-containing raw material compound of 10 mmol / l to 500 mmol / l, A method for producing a composite titanium oxide film element unit, comprising forming a composite titanium oxide layer on a titanium layer. A method of manufacturing an oxide film element unit having a composite titanium oxide layer in a predetermined region on a substrate, wherein Ni—P (phosphorus content is 3 to 16 wt. %) Protective film is formed, and the substrate is placed in an alkaline solution of 0.1 mol / l to 8.0 mol / l, the lead-containing raw material compound is 50 mmol / l to 500 mmol / l, and the zirconium-containing raw material compound is 10 mmol / l. -500 mmol / l, titanium-containing raw material compound is 500 mmol / l or less , strontium and / or barium-containing raw material compound is installed and fixed in a mixed solution prepared to be 0.01 mmol / l-500 mmol / l, and 80- The reaction was carried out at 200 ° C., and then the lead-containing raw material compound was 50 m in an alkaline solution of 0.1 mol / l to 8.0 mol / l. By reacting at 80 to 200 ° C. under conditions of ol / l to 500 mmol / l, zirconium-containing raw material compound of 10 mmol / l to 500 mmol / l, and titanium-containing raw material compound of 10 mmol / l to 500 mmol / l, A method of manufacturing a composite titanium oxide film element unit, wherein a composite titanium oxide film is selectively formed in a region having no protective film. The method for producing an oxide film element unit according to claim 2 or 3 , wherein the method of forming a protective film of Ni-P (phosphorus content is 3 to 16% by weight) is a plating method.

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