CN112028120A - ZrO for plating optical thin filmxAnd method for preparing the same - Google Patents
ZrO for plating optical thin filmxAnd method for preparing the same Download PDFInfo
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
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- C03C2217/00—Coatings on glass
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- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
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Abstract
The invention provides a ZrO used for plating optical filmxAnd a method for preparing the same. The method mainly comprises the following steps: using ZrO2And ZrH2The powder is used as raw material, and is uniformly mixed according to a certain proportion, then is briquetted or granulated, then is solid-phase synthesized under high-temperature vacuum, and is cooled to room temperature under the vacuum state, so as to generate a new compound ZrOx. The melting point of the compound is lower than that of zirconium dioxide, and the material keeps stable chemical composition in the evaporation process, thereby being beneficial to the process control of the coating process. The optical film plated by the material has good stability and consistency, higher transmittance in the near ultraviolet to near infrared bands, compact and firm film, and stable chemical property, and can be used as a high-quality high-refractive-index material to be applied to optical film system design and batch film plating production.
Description
Technical Field
The invention belongs to the field of optical thin film materials, relates to an evaporation material for a high-quality high-refractive-index optical thin film and a preparation method thereof, and particularly relates to ZrO for plating an optical thin filmxAnd a method for preparing the same.
Background
The zirconium dioxide has higher refractive index, is easy to plate an optical film with low absorption, has firm, compact and stable film layer, and has extinction coefficient of 0.001 at the position of 0.25 mu m of short wave, thereby being also used for optical coating of ultraviolet wave band. The method for preparing the zirconium dioxide optical film comprises the following steps: direct evaporation of ZrO from zirconium dioxide evaporation materialxReactive vapor deposition, reactive sputtering of metallic zirconium, and the like. However, in the case of electron beam evaporation, since the melting point of zirconia is high, which is about 2700 ℃, the material is locally melted during evaporation, which makes it easy to dig a pit, the fluctuation of the coating rate is large, and the material utilization rate is low. Thus, ZrO having a lower melting point is selectedxWhen the coating material is used as an evaporation material, the local melting area during coating can be increased, the uniformity of film formation is facilitated, the stability of the coating process is increased, and the utilization rate of the material is improved.
Liaowen super grade adopts wet synthesis process to prepare ZrOxIt is prepared with ZrOCl2·8H2O is used as a raw material, and a surfactant CTAB auxiliary hydrothermal method is adopted to prepare nano ZrOxA photocatalyst. At nano ZrOxThe surface zirconium coexists in multiple valence states, and the corresponding zirconium oxide form is ZrO2、Zr2O3ZrO. In the patent "optical recording medium" of Torricelli Kagaku K.K. (CN1201225A), ZrO can be used as the high hardness layerx(x is more than or equal to 0.8 and less than or equal to 1.8) film or ZrOx(0.5. ltoreq. x. ltoreq.2) as a main component. The high-hardness layer is preferably formed by a reactive sputtering process from the viewpoints of film formation rate, material cost, and practicality. A low valence state zirconia optical coating material and a preparation method thereof, disclosed in the patent 201711124597.0 of Yongxing photoelectricity technology Limited of Beijing Fuxing Kai, the zirconium dioxide and the metal zirconium powder are ZrO in molar ratio2: metal zirconium powder is 50-90: 10-50, mixing, granulating or tabletting, and sintering in vacuum at 1350-200 deg.CLow-valence zirconium oxide with good conductivity is formed at 0 ℃. However, the metal zirconium powder used in the raw materials belongs to flammable and explosive dangerous chemicals, combustion and even explosion are very easy to occur, the zirconium powder needs to be stored in water in a sealed manner (not less than 25% of water is wetted and passivated) in transportation and storage, and the problems of the use safety of the raw materials and the proportioning metering stability need to be solved when the process is used for batch preparation. In the patent 201410841672.5 entitled "conductive zirconia rotary target and preparation method thereof" of Beijing Henglong technology Co., Ltd, 93-98% zirconia powder and 2-7% carbon powder are mixed and sintered for 6-10 hours in hydrogen atmosphere at 1500-xThe target material is rotated, but the requirements on reaction equipment and operation control technology are higher when the hydrogen atmosphere is adopted for roasting.
Disclosure of Invention
In order to solve the above problems, it is an object of the present invention to provide ZrO for plating optical thin filmsxThe preparation method is simple, safe and easy to operate.
The invention also provides ZrO prepared by adopting the preparation methodxA material.
In order to achieve the above object, the present invention provides ZrO for plating optical thin filmsxThe preparation method comprises the following steps:
(1) with ZrO2And ZrH2Weighing powder as a raw material according to a certain proportion, and then mechanically mixing until the powder is uniformly mixed;
(2) briquetting or granulating the uniformly mixed powder to obtain blocks or granules;
(3) carrying out solid-phase synthesis reaction on the obtained block or particle under high-temperature vacuum;
(4) after the reaction is finished, cooling to room temperature under vacuum to obtain ZrOxAnd (3) coating materials.
Ensuring the vacuum pump to continue to operate in the cooling process and preventing ZrO from being generated at high temperaturexReacts with air.
Further, ZrO in the step (1)2And ZrH2The raw material proportion is ZrO2 35wt％～75wt％，ZrH225 wt% -65 wt%; to ensure ZrOxStability of phase composition and melting point range, preferably ZrO2And ZrH2The raw material proportion is ZrO2 45wt％～65wt％，ZrH235 to 55 wt.%, e.g. ZrO2And ZrH2The mass ratio of 3:1, 5:2, 2:1, 3:2, 1:1 and 2: 3.
ZrH2ZrO of powder with stable property at normal temperature and usually used for synthesis reaction2And ZrH2The mesh number of the powder is required to be 250 meshes, the mesh number of the powder is increased, the surface energy of the powder is increased, and the solid-phase synthesis reaction is facilitated.
Further, the mixing manner in the step (1) is stirring mixing or ball milling mixing.
Further, ZrO in the step (1)2And ZrH2Mixing for 4-10 hours, preferably ZrO to ensure mixing uniformity and improve production efficiency2And ZrH2Mixing for 6-8 hours.
Furthermore, the briquetting is 300-800N/cm2Briquetting under the pressure of (1) to obtain a block body; the granulation is carried out at 300-800N/cm2Briquetting under the pressure of (1), crushing the obtained blocks, and sieving to obtain particles of 1-5 mm. The preferable pressure of the briquette is 400-600N/cm2。
Briquetting or granulation can be carried out by using an oil press, an isostatic press, a granulator and other equipment, and the briquetting increases the contact area of the powder and is beneficial to the solid-phase reaction.
According to the requirements of coating equipment and process, the common specification of the block material is as follows
And the like.
Furthermore, the high-temperature solid-phase synthesis temperature of the obtained block or particle is 1500-2100 ℃; the preferable synthesis temperature is 1700-2000 ℃. The high-temperature solid-phase synthesis adopts high-temperature vacuum equipment such as an intermediate frequency furnace, a carbon tube furnace, a hot pressing furnace and the like, and when the hot pressing furnace is adopted, the pressing and the solid-phase synthesis are carried out simultaneously without briquetting or pelleting; there may be some difference in the density of the material obtained at different temperatures.
Further, the vacuum degree of solid phase synthesis of the obtained block or particle is 10Pa to 1x10-3Pa; the preferred vacuum is 2X10-1Pa～5x10-2Pa. In the solid-phase synthesis process, the vacuum degree can be changed to a certain extent due to the dehydrogenation of zirconium hydride and the proceeding of the solid-phase synthesis reaction, and the vacuum degree gradually and stably rises along with the completion of the reaction.
Furthermore, the solid phase synthesis time of the obtained block or particle is 3-20 hours; in order to ensure complete reaction and improve production efficiency, the preferable synthesis time is 8-12 hours.
The invention also provides ZrO for plating optical films prepared according to the preparation methodx。
ZrOxIs mainly composed of Zr3O and ZrO2The melting point of the compound is about 2200 ℃, and the density of the compound is 5.0-5.4 g/cm by using a drainage method3. The melting point of the material is far lower than that of the zirconium dioxide, and the material keeps stable chemical composition in the evaporation process, thereby being beneficial to the process control of the coating process.
The invention has the beneficial effects that:
the invention provides a ZrO for plating optical thin filmxAnd a process for preparing the same, ZrO prepared therebyxThe (x is 0.8-1.2) optical coating material, the melting point is about 2200 ℃, the gas release amount is small during material evaporation, the evaporation is stable, the automatic control of the evaporation process is easy to realize, the stability and consistency of an optical coating layer coated by the material are good, the transmittance in the near ultraviolet to near infrared wave band is high, the coating layer is compact and firm, the chemical property is stable, and the material can be used as a high-quality high-refractive-index material to be applied to optical coating system design and batch coating production. The synthesis method adopted by the invention is a solid-phase reaction method, and the raw material ZrO used2And ZrH2The chemical property is stable, and the safety performance is good in mixing, granulating and vacuum synthesis reaction in the preparation process, and the method is suitable for industrial production.
Drawings
FIG. 1 shows ZrO for plating optical thin films according to the present inventionxThe preparation process is shown in the figure.
FIG. 2 shows ZrO produced in example 1 of the present inventionxA photograph of the particles.
FIG. 3 shows ZrO produced in example 2 of the present inventionxA photograph of the particles.
FIG. 4 shows ZrO obtained in example 2 of the present inventionxXRD pattern of the particles.
FIG. 5 shows the film-coated ZrO layer of example 2 of the present inventionxXRD pattern of the melt.
FIG. 6 shows ZrO produced in example 3 of the present inventionxA photograph of the particles.
Detailed Description
The following detailed and complete description of the embodiments of the present invention is provided to enable those skilled in the art to more easily understand the advantages and features of the present invention, and to clearly and clearly define the scope of the present invention.
ZrOxThe preparation process is shown in figure 1.
Example 1:
ZrO production by the procedure shown in FIG. 1x: reacting ZrH2Powder and ZrO2The powder is weighed according to the weight ratio of 2:5, a stirring mixer is adopted for mechanical mixing for 6 hours, and the mixed powder is processed by an oil press at 300N/cm2Pressing into blocks under the pressure of (1), crushing and sieving the block material to prepare particles with the particle size of 1-3mm, and performing vacuum degree of 2x10 at the temperature of 1650 DEG C-1The solid phase synthesis reaction was carried out under Pa for 6 hours, and cooled to room temperature under vacuum.
The material prepared in this way was a dark grey material (as shown in FIG. 2) and had a density of 5.0g/cm as measured by the drainage method3XRD analysis shows that the material consists of Zr as one new compound3O and partial ZrO2And (4) forming. When in use, the ZrOx material is fully pre-melted firstly, the material is filled in a water-cooling oxygen-free copper crucible for pre-melting, the pre-melting temperature is about 2300 ℃, splashing is not generated in the pre-melting process, and the surface of the material after pre-melting is basically in a molten state. The substrate for coating is a quartz substrate, and the coating is evaporated by electron beamsThe equipment carries out material evaporation with the vacuum degree of 1.6x10-2Pa, substrate temperature of 80 deg.C, evaporation temperature of 2400 deg.C, and evaporation rate of
The refractive index of the film coating film layer at 500nm is 2.02, the film layer is firm and compact, and the absorption in the near ultraviolet to near infrared wave band is small.
Example 2:
ZrO production by the procedure shown in FIG. 1x: reacting ZrH2Powder and ZrO2The powder is weighed according to the weight ratio of 2:3, a ball mill is adopted for mechanical mixing for 4 hours, and the mixed powder is prepared by an oil press at 600N/cm2Briquetting under pressure of (1), crushing and sieving to obtain granules with a particle size of 1-3mm, and making into granule at 1850 deg.C and vacuum degree of 5x10-2The solid phase synthesis reaction was carried out under Pa for 8 hours, and cooled to room temperature under vacuum.
The material prepared in this way was a dark grey material (as shown in FIG. 3) and had a density of 5.2g/cm as measured by the drainage method3XRD analysis shows that the material consists of Zr as one new compound3O and partial ZrO2Composition (as shown in fig. 4). When in use, the ZrOx material is fully pre-melted firstly, the material is filled in a water-cooling oxygen-free copper crucible for pre-melting, the pre-melting temperature is about 2300 ℃, splashing is not generated in the pre-melting process, and the surface of the material after pre-melting is basically in a molten state. The substrate for coating is quartz substrate, and evaporation coating is carried out by electron beam evaporation coating equipment with vacuum degree of 1.6x10-2Pa, substrate temperature of 80 deg.C, evaporation temperature of 2400 deg.C, and evaporation rate of
The refractive index of the film coating film layer at 500nm is 2.02, the film layer is firm and compact, and the absorption in the near ultraviolet to near infrared wave band is small. XRD analysis (as shown in FIG. 5) is carried out on the plating residue after plating, and the result shows that the structure of the plating residue is formed by a compound Zr3O and partial ZrO2The composition is consistent with the structural matrix of the material before use, which is beneficial to the stability of the evaporation process and the consistency of the film performance.
Example 3:
ZrO production by the procedure shown in FIG. 1x: reacting ZrH2Powder and ZrO2The powder is weighed according to the weight ratio of 3:2, a stirring mixer is adopted for mechanical mixing for 8 hours, and the mixed powder is prepared by an oil press at 500N/cm2Pressing into blocks under the pressure of (1), crushing and sieving the materials to prepare particles with the particle size of 1-5mm, and performing vacuum degree of 5x10 at the temperature of 2000 DEG C-3The solid phase synthesis reaction was carried out under Pa for 10 hours, and cooled to room temperature under vacuum.
The material prepared in this way was a dark grey material (as shown in FIG. 6) and had a density of 5.4g/cm as measured by the drainage method3XRD analysis shows that the material consists of Zr as one new compound3O and partial ZrO2And (4) forming. When in use, the ZrOx material is fully pre-melted firstly, the material is filled in a water-cooling oxygen-free copper crucible for pre-melting, the pre-melting temperature is about 2300 ℃, splashing is not generated in the pre-melting process, and the surface of the material after pre-melting is basically in a molten state. The substrate for coating is quartz substrate, and evaporation coating is carried out by electron beam evaporation coating equipment with vacuum degree of 1.6x10-2Pa, substrate temperature of 80 deg.C, evaporation temperature of 2400 deg.C, and evaporation rate of
The refractive index of the film coating film layer at 500nm is 2.02, the film layer is firm and compact, and the absorption in the near ultraviolet to near infrared wave band is small.
As can be seen from the above examples, the ZrO prepared according to the inventionxHas the advantages that:
(1) the raw materials of the equipment are simple and easy to obtain, the cost is low, the operation is simple, and the industrial production is easy.
(2) The process does not use hydrogen and metal zirconium powder, and the process is safe and reliable.
(3) The melting point of the obtained ZrOx is far lower than that of the zirconium dioxide, and the material keeps stable chemical composition in the evaporation process, thereby being beneficial to the process control of the coating process.
ZrO used in the inventionxThe preparation method does not need to use atmosphere protection such as hydrogen and the like, and has simple process; the used raw materials are safe, the raw material proportion is easy to control, and the product is obtainedThe composition of ZrOx is stable. The optical film plated by the material has good stability and consistency, higher transmittance in the near ultraviolet to near infrared bands, compact and firm film, and stable chemical property, and can be used as a high-quality high-refractive-index material to be applied to optical film system design and batch film plating production.
Through research, ZrO in the ZrOx preparation method provided by the invention is found2And ZrH2Purity of (ZrO)2And ZrH2Mass ratio of (3), solid phase synthesis temperature, holding time and degree of vacuum ofxThe quality of the product has a certain influence. Under the preferred process conditions, ZrO obtainedxThe quality is better.
The detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e., it is not meant that the present invention must rely on the above detailed process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. ZrO for plating optical thin filmxThe preparation method is characterized by comprising the following steps:
(1) with ZrO2And ZrH2The powder is taken as a raw material, and is mixed after being weighed according to a certain proportion;
(2) briquetting or granulating the uniformly mixed powder to obtain blocks or granules;
(3) carrying out solid-phase synthesis reaction on the obtained block or particle under high-temperature vacuum;
(4) after the reaction is finished, cooling to room temperature under vacuum to obtain ZrOxAnd (3) coating materials.
2. The ZrO layer for plating optical thin film according to claim 1xAnd a method for producing the same, ZrO in step (1)2And ZrH2The powder has a mesh number of-250 meshes and a raw material ratio of ZrO2 35wt％～75wt％，ZrH2 25wt％～65wt％。
3. The ZrO for plating optical thin film according to claim 2xThe preparation method is characterized in that the mixing mode in the step (1) is stirring mixing or ball milling mixing.
4. The ZrO layer for plating optical thin film according to claim 1xAnd a process for producing the same, characterized in that ZrO in the step (1)2And ZrH2The mixing time is 4-10 hours.
5. The ZrO layer for plating optical thin film according to claim 1xThe preparation method is characterized in that the briquetting is 300-800N/cm2Briquetting under the pressure of (1) to obtain a block body; the granulation is carried out at 300-800N/cm2Briquetting under the pressure of (1), crushing the obtained block, and screening to collect particles with the particle size of 1-5 mm.
6. The ZrO layer for plating optical thin film according to claim 1xThe preparation method is characterized in that the high-temperature solid-phase synthesis temperature of the obtained block or particle is 1500-2100 ℃.
7. A ZrO for plating optical films according to claim 1xAnd a process for producing the same, characterized in that the degree of vacuum of solid phase synthesis of the obtained block or particle is 10Pa to 1x10-3Pa。
8. The ZrO layer for plating optical thin film according to claim 1xThe preparation method is characterized in that the solid-phase synthesis time of the obtained block or particle is 3-20 hours.
9. ZrO for plating optical thin film according to any one of claims 1 to 8xPrepared by the preparation methodZrOxCharacterized in that the ZrOxWherein x is 0.8 to 1.2.
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| JPH02100249A (en) * | 1988-10-06 | 1990-04-12 | Denki Kagaku Kogyo Kk | Manufacture of thermal field emitter |
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| CN102206804A (en) * | 2010-03-31 | 2011-10-05 | W.C.贺利氏有限公司 | Sputtering target and preparation method thereof |
| CN102839354A (en) * | 2012-10-07 | 2012-12-26 | 复旦大学 | Preparation method for component-controlled ZrOx thin film |
| CN105331921A (en) * | 2015-11-30 | 2016-02-17 | 中国人民解放军装甲兵工程学院 | Spraying powder, hot-sprayed in-situ synthesized zirconium boride-zirconium carbide base ceramic coating and preparation method thereof |
| CN107840657A (en) * | 2017-11-14 | 2018-03-27 | 北京富兴凯永兴光电技术有限公司 | A kind of lower valency zirconium oxide optical filming material and preparation method |
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2019
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| JPH02100249A (en) * | 1988-10-06 | 1990-04-12 | Denki Kagaku Kogyo Kk | Manufacture of thermal field emitter |
| JPH03179670A (en) * | 1989-12-06 | 1991-08-05 | Yuasa Battery Co Ltd | Manufacture of solid electrolyte for fuel cell |
| CN102206804A (en) * | 2010-03-31 | 2011-10-05 | W.C.贺利氏有限公司 | Sputtering target and preparation method thereof |
| CN102839354A (en) * | 2012-10-07 | 2012-12-26 | 复旦大学 | Preparation method for component-controlled ZrOx thin film |
| CN105331921A (en) * | 2015-11-30 | 2016-02-17 | 中国人民解放军装甲兵工程学院 | Spraying powder, hot-sprayed in-situ synthesized zirconium boride-zirconium carbide base ceramic coating and preparation method thereof |
| CN107840657A (en) * | 2017-11-14 | 2018-03-27 | 北京富兴凯永兴光电技术有限公司 | A kind of lower valency zirconium oxide optical filming material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 陈全讯等: "《中国锆、铪》", 30 April 2014, 冶金工业出版社, pages: 150 - 151 * |
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