CN110697783A - Composite metal oxide target material and composite metal oxide film formed by composite metal oxide target material - Google Patents

Abstract

A composite metal oxide target material has a chemical formula A_xCs_yWO_zWherein x is more than or equal to 0.2 and less than or equal to 2, y is more than or equal to 0.2 and less than or equal to 0.4, and z is more than or equal to 2.5 and less than or equal to 4, wherein A is selected from Bi, B, Al, Zn, Zr, Si, V and Co. The invention also provides a composite metal oxide film, which is formed by the composite metal oxide target through a dry coating process. The composite metal oxide target has high density and simple process, and the composite metal oxide film has the advantages of UV resistance, visible light penetration resistance,Multiple effects of infrared ray blocking.

Description

Composite metal oxide target and composite metal formed from composite metal oxide target oxide film

【Technical field】

The invention relates to a composite metal oxide target and a composite metal oxide film formed by the composite metal oxide target.

【Background technique】

Due to global warming, the duration of sunshine and high temperature is longer, excessive ultraviolet light exposure is harmful to the human body, and thermal radiation caused by infrared rays has adverse effects on the skin. In addition, infrared rays are transmitted through glass, which increases the indoor temperature in summer In winter, the heat of indoor heating flows to the outdoors, both of which will increase the cooling or heating power of the air conditioner, which indirectly causes energy problems and requires more effective thermal barrier materials.

At present, there are thermal insulation materials prepared by wet method (organic substances such as PET, PVB, etc. are mixed with nano-ceramic powder), but they are not wear-resistant, temperature-resistant, and have poor reliability, especially for high-rise curtains. Short life, poor weather resistance (yellowing), limited application, difficult maintenance, etc. In addition, the optical film is attached to the substrate by an organic film, but because the optical film used contains multi-layer coating, there is a problem of high cost and price, and the organic coating is affected by time or ultraviolet radiation and heat. Deterioration, yellowing, peeling, etc. may occur, which in turn affects the life and reliability.

Therefore, the development of optical materials with simple process, multi-function, long life and high reliability is an important subject in the related technical field at this stage.

[Content of the invention]

The invention provides a composite metal oxide target and a composite metal oxide film.

The composite metal oxide target provided by the present invention has the chemical formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.2≤y≤0.4, 2.5≤z≤4, and A is selected from Bi, B, Al, Zn, Zr, Si, V and Co.

In one embodiment, the density of the composite metal oxide target is greater than 90%.

In one embodiment, the composite metal oxide target has the chemical formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.2≤y≤0.4, 2.5≤z≤4, and A is selected from Bi, B, Al, Zn , Zr, Si, V and Co, and x/y may fall in the range of 2.2 to 8.3.

In another embodiment, the composite metal oxide target has the formula _AxCsyWOz , where 0.63≤x≤1.88, _{0.2≤y≤0.4} , _2.5≤z≤4 , and A is selected from Bi, B, Al , Zn, Zr, Si, V and Co.

In yet another embodiment, the composite metal oxide target has the formula _AxCsyWOz , where 0.2≤x≤2, _{0.23≤y≤0.33} , _2.5≤z≤4 , and A is selected from Bi, B, Al , Zn, Zr, Si, V and Co.

In one embodiment, the composite metal oxide target has the formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.2≤y≤0.4, 2.85≤z≤3.44, and A is selected from Bi, B, Al, Zn, Zr, Si, V and Co.

In one embodiment, the composite metal oxide target has the chemical formula A _x Cs _y WO _z , wherein 0.63≤x≤1.88, 0.23≤y≤0.33, 2.85≤z≤3.44, and A is selected from Bi, B, Al, Zn, Zr, Si, V and Co.

The composite metal oxide film provided by the present invention has the chemical formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.2≤y≤0.4, 2.5≤z≤4, and A is selected from Bi, B, Al, Zn, Zr , Si, V and Co. In one embodiment, the thickness of the composite metal oxide film may be less than 1000 nm.

In one embodiment, the composite metal oxide film has the chemical formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.2≤y≤0.4, 2.5≤z≤4, and A is selected from Bi, B, Al, Zn , Zr, Si, V and Co.

In one embodiment, the composite metal oxide film has the chemical formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.2≤y≤0.4, 2.5≤z≤4, and A is selected from Bi, B, Al, Zn, Zr, Si, V, and Co, and x/y may fall within the range of 2.2 to 8.3.

In one embodiment, the composite metal oxide film has the formula A _x Cs _y WO _z , wherein 0.63≤x≤1.88, 0.2≤y≤0.4, 2.5≤z≤4, and A is selected from Bi, B, Al, Zn , Zr, Si, V and Co.

In one embodiment, the composite metal oxide film has the formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.23≤y≤0.33, 2.5≤z≤4, and A is selected from Bi, B, Al, Zn , Zr, Si, V and Co.

In one embodiment, the composite metal oxide film has the formula A _x Cs _y WO _z , wherein 0.2≤x≤2, 0.2≤y≤0.4, 2.85≤z≤3.44, and A is selected from Bi, B, Al, Zn , Zr, Si, V and Co.

In yet another embodiment, the composite metal oxide film has the formula A _x Cs _y WO _z , wherein 0.63≤x≤1.88, 0.23≤y≤0.33, 2.85≤z≤3.44, and A is selected from Bi, B, Al, Zn, Zr, Si, V and Co.

According to an embodiment of the present invention, the composite metal oxide film has infrared transmittance≤40%, visible light transmittance>50%, visible light reflectance≤25%, and ultraviolet transmittance≤25%, and has the advantages of thermal insulation, resistance to Efficacy of reflection.

【Detailed ways】

The invention achieves its optical transparency, high visible light transmittance and infrared absorption characteristics through the material composition design of the composite metal oxide film, and can be directly coated on the glass surface without additional adhesive layer, so it has the advantage of high reliability . Because common general oxides are easy to react with cesium tungsten, the composition and properties of cesium tungsten are changed; and the more oxides are added, the more reactions with cesium tungsten, and the more difficult it is to control the optical properties; however, the present invention The mixed oxide is sintered with cesium tungsten. Without changing the physical properties of cesium tungsten, the synthesized target and film can have good multiple optical properties.

In one embodiment of the present invention, the composite metal oxide target is prepared by cesium tungsten, such as Cs _0.33 WO ₃ powder and mixed oxide (such as bismuth, boron, aluminum, zinc, silicon, tin, Oxides of vanadium, zirconium, and cobalt) are uniformly mixed and sintered at high temperature (for example, 450°C to 800°C), densified, cooled, and then polished and processed. The mixed oxide can be bismuth oxide (Bi ₂ O ₃ ), boron oxide (B ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ) or aluminum hydroxide (Al(OH) ₃ ) or an aluminum-containing precursor compound, zinc oxide (ZnO), silicon oxide (SiO ₂ ), tin oxide (SnO ₂ ), vanadium oxide (V ₂ O ₅ ), zirconium oxide (ZrO ₂ ), cobalt trioxide (Co ₂ O ₃ ) or containing Cobalt precursors are calcined.

In the embodiment of the present invention, the synthesis of cesium tungsten powder is made by mixing a precursor of tungsten oxide with a salt containing cesium, and then reacting at a high temperature (for example, 100°C-600°C) to form a powder, and then passing through the powder. refined or dispersed.

In an embodiment of the present invention, the composition of the mixed oxide powder (LM-420, Jingming Chemical) is shown in the following table:

In an embodiment of the present invention, the composite metal oxide thin film is obtained by using the composite metal oxide target of the present invention by dry coating, such as sputtering, thermal spraying, etc., and the film thickness can be applied according to the application. Depending on the needs, it can be less than 1000 nm, less than 500 nm, or less than 200 nm, for example. The substrate can be glass, ceramic or metal plate; the coating atmosphere can be hydrogen, argon, oxygen or any combination thereof, for example, a mixed gas of oxygen and argon in a ratio of 1/10 to 1/1 can be used Alternatively use pure oxygen or pure argon. The heat treatment temperature of the coating is 350℃-800℃. If it is higher than this range, the crystal structure will change or volatilize after coating, which will not satisfy the optical properties. If it is lower than this range, the effect of annealing or crystal reforming cannot be achieved after coating. , such as the formation of amorphous thin films, can not achieve specific optical effects.

In order to make the above-mentioned and other objects, features, and advantages of the present invention more obvious and easy to understand, several embodiments and comparative examples are given below, and are described in detail as follows:

Optical property test

UV-VIS-NIR spectrometer (Shimadzu UV-3600) was used to conduct ultraviolet, visible, near-infrared and other penetration and reflection experiments; Type JOEL-6400) analysis.

Preparation of Cesium Tungsten

Example 1

Take 500 grams of ammonium metatungstate (ammonium metatungstate) and 110 grams of cesium carbonate and add them to 4000 ml of deionized water to mix evenly, and then adjust the pH to 12 with an aqueous NH ₄ OH solution to form a precursor solution of composite tungsten oxide, which is then dried in an oven at 120°C. Then, the mixture was reacted at 400° C. for 60 minutes in a 10% H ₂ -Ar mixed atmosphere, and the powder was taken out and re-dispersed to obtain Cs _0.33 WO ₃ powder.

Target preparation

Embodiment 2

Take cesium tungsten Cs _0.33 WO ₃ powder and mixed oxide powder (weight ratio of 53:47) for material grinding and uniform mixing, sintering at 580 ° C for 1 hour, and then furnace cooling to obtain a composite metal Oxide block 1; after taking out and sintering, it was polished and ground with water sandpaper to obtain A _1.62 Cs _0.28 WO _2.93 target. The density of the target was tested by Archimedes method, and the density of the target was 94%.

Embodiment 3

Take cesium tungsten Cs _0.33 WO ₃ powder and mixed oxide powder (weight ratio of 73:23) for material grinding and uniform mixing, sintering at 580 ° C for 1 hour, and then furnace cooling to obtain a composite metal Oxide block 2; after taking out and sintering, it is polished and ground with water sandpaper to obtain A _0.63 Cs _0.28 WO _2.85 target, and the density of the target is tested by Archimedes method, and the density of the target is 93%.

Embodiment 4

Take cesium tungsten Cs _0.33 WO ₃ powder and mixed oxide powder (weight ratio of 42:58) for material grinding and uniform mixing, sintering at 580 ° C for 1 hour, and then furnace cooling to obtain a composite metal Oxide block 3; after taking out and sintering, it is polished and ground with water sandpaper to obtain A _1.88 Cs _0.23 WO _3.44 target. The density of the target is tested by Archimedes method, and the density of the target is 92%.

Coating

Embodiment 5

The target material of Example 2 was sputtered on a glass substrate with an area of 10*10cm ² and a thickness of 650um with a power of 55W and a pressure of 5.5 mtorr under the ambient atmosphere of Ar/O ₂ =5/4. (Corning Glass Eagle XG), the coating time was 12 minutes, and then heat treatment was carried out at 550 ° C for 15 minutes to obtain a film 1, and its thickness was measured by a film thickness profile measuring instrument (α-step, Sanpeng Instrument) to be 82 nm; The test results are shown in Table 1.

Embodiment 6

Take the target material of Example 2, under the ambient atmosphere of Ar/O ₂ =5/4, with 110W power and 5.5 mTorr pressure sputtering on a glass substrate (Corning glass ⁾ with an area of 10*10cm and a thickness of 650um. Eagle XG), the coating time was 20 minutes, and then heat treatment was carried out at 550 ° C for 15 minutes to obtain the second film, and the thickness was measured by a film thickness profile measuring instrument (α-step, Sanpeng Instrument) to be 150nm; Carry out optical testing, the results See Table 1 for details.

Embodiment 7

Take the target material of Example 3, under the ambient atmosphere of Ar/O ₂ =5/4, with 110W power and 5.5 mtorr pressure sputtering on a glass substrate (Corning glass with an area of 10*10cm ² and a thickness of 650um Eagle XG), the coating time was 12 minutes, and then heat treatment was carried out at 550 ° C for 15 minutes to obtain film 3, and its thickness was measured by a film thickness profile measuring instrument (α-step, Sanpeng Instrument) to be 85nm; Carry out optical testing, the results See Table 1 for details.

Embodiment 8

The target material of Example 4 was sputtered on a glass substrate with an area of 10*10cm ² and a thickness of 650um with a power of 110W and a pressure of 5.3 mtorr under the ambient atmosphere of Ar/O ₂ =5/4. (Corning Glass Eagle XG), the coating time was 20 minutes, and then heat treatment was carried out at 550 ° C for 15 minutes to obtain film 4, whose thickness was measured by a film thickness profiler (α-step, Sanpeng Instrument) to be 117 nm; The test results are shown in Table 1.

Comparative example

After grinding the cesium tungsten Cs _0.33 WO ₃ powder of Example 1 in an alcohol solvent, add 1 wt % polyvinyl butyral (PVB), dissolve and stir and disperse to form a colloid, and then drop the colloid On the glass (Corning Glass Eagle XG) with an area of 10*10cm ² , coating was carried out at 5000 rpm, and then it was taken out and baked in an oven at 95 ° C for 1 hour to obtain a comparative film. ) to measure its thickness as 200 nm, and conduct optical tests. The results are shown in Table 1.

Table I

As shown in Table 1, the thin film formed by the dry process using the composite metal oxide target of an embodiment of the present invention has good transmittance of infrared light, visible light and ultraviolet light, and good reflectance of visible light, which can shield the IR. , IR blocking effect, anti-UV and thermal blocking have excellent effects; in addition, it can be directly formed on the glass during the coating process, which has the effect of reducing cost and improving the life of the film.

To sum up, according to an embodiment of the present invention, the composite metal oxide target and the composite metal oxide film formed by the composite metal oxide target have functions such as UV resistance, visible light penetration, and infrared blocking. It saves the number of coating layers and the type of target material, and can directly coat the material on the glass, which can achieve multiple functions on building materials, vehicles, and electronic products.

Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Any person skilled in the art should be able to make some changes and modifications without departing from the spirit and scope of the present invention. The protection scope of the invention shall be determined by the scope defined by the appended claims.

Claims (15)

1. A composite metal oxide target material has a chemical formula A_xCs_yWO_zWherein x is more than or equal to 0.2 and less than or equal to 2, y is more than or equal to 0.2 and less than or equal to 0.4, z is more than or equal to 2.5 and less than or equal to 4, and A is selected from Bi, B, Al, Zn, Zr, Si, V and Co.

2. The composite metal oxide target according to claim 1, wherein x/y falls within a range of 2.2 to 8.3.

3. The composite metal oxide target of claim 1, wherein 0.63 ≦ x ≦ 1.88.

4. The composite metal oxide target according to claim 1, wherein 0.23. ltoreq. y.ltoreq.0.33.

5. The composite metal oxide target of any one of claims 1 to 4, wherein the composite metal oxide target has a density of greater than 90%.

6. A composite metal oxide film having the formula A_xCs_yWO_zWherein x is more than or equal to 0.2 and less than or equal to 2, y is more than or equal to 0.2 and less than or equal to 0.4, z is more than or equal to 2.5 and less than or equal to 4, and A is selected from Bi, B, Al, Zn, Zr, Si, V and Co.

7. The composite metal oxide thin film according to claim 6, wherein x/y falls within a range of 2.2 to 8.3.

8. The composite metal oxide film according to claim 6, wherein 0.63. ltoreq. x.ltoreq.1.88.

9. The composite metal oxide film according to claim 6, wherein 0.23. ltoreq. y.ltoreq.0.33.

10. The composite metal oxide thin film as claimed in any one of claims 6 to 9, wherein the thickness of the composite metal oxide thin film is greater than 0nm and less than or equal to 1000 nm.

11. The composite metal oxide thin film of claim 10, wherein the composite metal oxide thin film has a thickness greater than 0nm and less than or equal to 200 nm.

12. The complex metal oxide film of claim 6, wherein the infrared transmittance of the complex metal oxide film is less than or equal to 40%.

13. The composite metal oxide film of claim 6, wherein the composite metal oxide film has a visible light transmittance of greater than 50%.

14. The complex metal oxide film of claim 6, wherein the complex metal oxide film has a visible light reflectance of less than or equal to 25%.

15. The composite metal oxide film of claim 6, wherein the composite metal oxide film has an ultraviolet transmittance of less than or equal to 25%.