JPH0411491B2 - - Google Patents

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is applicable to, for example, far-infrared emitting films, heat ray reflective films,
The present invention relates to a method of manufacturing a zirconia thin film used as a semiconductor film or the like.

(Prior Art) Conventionally, as methods for manufacturing this type of zirconia thin film, PVD methods such as zirconium oxide sputtering method and ion plating method, organic zirconium compound dip method, etc. are known.

(Problems to be Solved by the Invention) In the case of the conventional sputtering method or ion plating method, the equipment is large-scale, and furthermore, the size of the produced zirconia thin film is limited because it is carried out in a vacuum chamber. In the case of the dip method, it has the disadvantage of significantly increasing costs.
It has disadvantages such as difficult pulling operation, poor film quality, and lack of adhesion.

( _Means for Solving the Problems) An object of the present invention is to provide _a method for manufacturing a zirconia thin film that eliminates the above-mentioned disadvantages _.
A spray solution containing _{butoxyzirconium} acetylacetonate represented by _X Zr(OCH ₄ H ₇ ) It consists of forming a zirconia thin film by spraying onto a substrate kept at ~800°C.

In the general formula of butoxyzirconium acetylacetonate, X is set to 1≦X≦3 because if X is less than 1, the solubility in organic solvents will be poor, and if X exceeds 3, thermal decomposition will occur. This is because it becomes difficult to do so. Moreover, it is more preferable that X is in the range of 1.5≦X≦2.5.

The spray solution is adjusted so that the butoxyzirconium acetylacetonate is contained in an organic solvent, preferably an ethanol solvent, so that the zirconia (ZrO ₂ ) content is about 2 to 10 wt%, preferably about 3 to 5 wt%. Zirconia (ZrO ₂ ) content
If it is less than 2wt%, the film formation efficiency will be poor, and if it is less than 10wt%
This is because if the amount exceeds 100%, the raw material is likely to become powder during thermal decomposition.

For the spray solution, for example, butoxyzirconium acetylacetonate may be directly dissolved in an organic solvent such as ethanol, but even if a mixed solution of tetrabutoxyzirconium, acetylacetone, and ethanol is kept at 20 to 60°C, the resulting An ethanol solution of butoxyzirconium acetylacetonate is obtained.

The base material is not particularly limited, but generally a plate-shaped body made of glass, ceramics, etc. is used,
This is heated to 400-800°C, preferably 400-600°C, and then the spray solution is sprayed. This is because if the temperature of the base material is less than 400°C, the film tends to become a mixture of powder, and if it exceeds 800°C, it tends to become powder without forming a film.

In addition, since the spray solution is sprayed onto the substrate that has been heated to 400-800℃ in advance, the spray solution that adheres to the substrate is sequentially thermally decomposed at the same time as it is attached.
Similar to the CVD method, film formation proceeds in a thermodynamic equilibrium state, forming a uniform and transparent zirconia thin film.

The spray solution is generally maintained at a temperature of 20 to 80°C, and the spray pressure is 0.5 to 1.5 Kg/cm ² , preferably 0.8 to 80°C.
Spray at 1.2Kg/ ^cm2 .

(Example) Next, examples of the present invention will be explained.

Acetylacetone to ethyl alcohol 42wt%
Add 20wt% and further add 38wt% of tetrabutoxyzirconium and reflux to convert butoxyzirconium acetylacetonate to zirconia (ZrO ₂ ).
Prepare a spray solution with a concentration of 5wt% and apply it to 40
℃, spray pressure 1.0Kg/cm ² , spray distance
When 15 ml of the solution was sprayed onto a plate-shaped ceramic substrate heated to 500° C. at a distance of 50 cm, a transparent amorphous zirconia thin film with a thickness of 0.5 μm was obtained. The obtained zirconia thin film has a glossy surface and is scratch resistant.
It had excellent adhesion and was a uniform thin film with no pinholes or the like.

The figure is an emissivity characteristic diagram when the obtained zirconia thin film is heated with a heating element, and curves A, B,
C shows characteristic diagrams when heated at 100°C, 150°C, and 200°C, respectively. The obtained zirconia thin film showed swelling at 1200 to 500 cm ^-1 as shown in the figure.
It was confirmed that it was a far-infrared radiator.

(Effects of the Invention) As described above, according to the present invention, a zirconia thin film is formed by spraying a spray solution containing the specific butoxyzirconium acetylacetonate in an organic solvent onto a substrate kept at 400 to 800°C. This has the effect of making it possible to produce a thin zirconia film with the same uniformity and adhesion as the CVD method using an extremely simple method, and also over a large area.

[Brief explanation of drawings]

The drawing is an emissivity characteristic diagram of a zirconia thin film obtained by the manufacturing method of the present invention.

Claims (1)

[Claims] 1 General formula (CH ₃ COCHCOCH ₃ ) _4-X Zr
A spray solution containing butoxyzirconium acetylacetonate represented by ( _{OCH 4} H ₇ ) A method for producing a zirconia thin film comprising spraying onto a substrate to form a zirconia thin film. 2. The method for producing a zirconia thin film according to claim 1, characterized in that a spray solution containing 2 to 10 wt% of the butoxyzirconium acetylacetonate in terms of zirconia (ZrO ₂ ) is used.