CN112028120B - ZrO for plating optical thin film x And method for preparing the same - Google Patents
ZrO for plating optical thin film x And 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
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- C03C2217/00—Coatings on glass
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- C03C2217/00—Coatings on glass
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- 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 film x And a method for preparing the same. The method mainly comprises the following steps: using ZrO 2 And ZrH 2 The 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 ZrO x . 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 wave bands, compact and firm film, 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 film x And a method for preparing the same.
Background
Zirconium dioxide has a high refractive index, is easy to plate a low-absorption optical thin film, has a firm, compact and stable film layer, and has an extinction coefficient of 0.001 at a short wave of 0.25 mu m, so that the zirconium dioxide is also used for optical coating of an ultraviolet band. The method for preparing the zirconium dioxide optical film comprises the following steps: direct evaporation of ZrO by using zirconium dioxide evaporation material x Reactive 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 pits, and the fluctuation of the coating rate is large, resulting in a low material utilization rate. Therefore, the temperature of the molten metal is controlled,ZrO with lower melting point x When 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 ZrO x It is prepared from ZrOCl 2 ·8H 2 O is used as a raw material, and a surfactant CTAB auxiliary hydrothermal method is adopted to prepare nano ZrO x A photocatalyst. At nano ZrO x The surface zirconium coexists in multiple valence states, and the corresponding zirconium oxide form is ZrO 2 、Zr 2 O 3 ZrO, or a mixture thereof. In the Japanese Toray corporation patent (CN 1201225A) "optical recording medium", zrO can be used as the high hardness layer x (x is more than or equal to 0.8 and less than or equal to 1.8) film or ZrO x (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 patent (201711124597.0) of Beijing Fuxing Kai Yongxing photoelectricity technology Limited company on a low-valence zirconium oxide optical coating material and a preparation method thereof 2 : metal zirconium powder = 50-90: 10-50, and then the mixture is granulated or pressed into tablets, and sintered in vacuum, and the sintering temperature is 1350-2000 ℃ to form the low-valence zirconia with good conductivity. 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 hermetically stored in water (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 of 201410841672.5, beijing Henglong scientific and technological Limited, zirconia powder with the concentration of 93-98% and carbon powder with the concentration of 2-7% are mixed and sintered for 6-10 hours in hydrogen atmosphere at the temperature of 1500-1700 ℃ to prepare conductive ZrO x The 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, the present invention provides a method for producing a semiconductor deviceZrO for plating optical film x The preparation method is simple, safe and easy to operate.
The invention also provides ZrO prepared by the preparation method x A material.
In order to achieve the above object, the present invention provides ZrO for plating optical thin films x The preparation method comprises the following steps:
(1) With ZrO 2 And ZrH 2 Weighing 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, the reaction solution is cooled to room temperature under vacuum to obtain ZrO x And (3) coating materials.
Ensuring the vacuum pump to continue to operate in the cooling process and preventing ZrO from being generated at high temperature x Reacts with air.
Further, zrO in the step (1) 2 And ZrH 2 The raw material proportion is ZrO 2 35wt％～75wt％， ZrH 2 25wt% -65 wt%; to ensure ZrO x Stability of phase composition and melting point range, preferably ZrO 2 And ZrH 2 The raw material proportion is ZrO 2 45wt％～65wt％，ZrH 2 35 to 55 wt.%, e.g. ZrO 2 And ZrH 2 Mass ratio 3.
ZrH 2 The powder has stable property at normal temperature and is usually used for ZrO of synthesis reaction 2 And ZrH 2 The 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) 2 And ZrH 2 Mixing for 4-10 hours, preferably ZrO to ensure mixing uniformity and improve production efficiency 2 And ZrH 2 Mixing for 6-8 hours.
Furthermore, the briquetting is 300-800N/cm 2 Briquetting under the pressure of (1) to obtain a block; the granulation is 300 to 800N/cm 2 Briquetting 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/cm 2 。
Briquetting or granulation can be carried out by using equipment such as an oil press, an isostatic press, a granulator and the like, 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, common specifications of block materials are as follows
And the like.
Furthermore, the high-temperature solid-phase synthesis temperature of the obtained block or particle is 1500-2100 ℃; the synthesis temperature is preferably 1700 to 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 density of the material obtained at different temperatures.
Further, the solid phase synthesis vacuum degree of the obtained block or particle is 10Pa to 1x10 -3 Pa; the preferred vacuum is 2X10 -1 Pa～5x10 -2 Pa. 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 synthesis time is preferably 8 to 12 hours.
The invention also provides ZrO prepared according to the preparation method for plating optical films x 。
ZrO x Is mainly composed of Zr 3 O and ZrO 2 The compound has a melting point of about 2200 deg.C, and a density of 5.0-5.4 g/cm 3 . The melting point of the zirconium dioxide 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 film coating process.
The invention has the beneficial effects that:
the invention provides a ZrO used for plating optical films x And a process for preparing the same, zrO prepared thereby x (x = 0.8-1.2) the optical coating material has a melting point of about 2200 ℃, the material has small gas release amount during evaporation, is stable in evaporation, is easy to realize automatic control of the evaporation process, and the optical coating layer plated by the material has good stability and consistency, has higher transmittance in near ultraviolet to near infrared bands, is compact and firm in coating layer and stable in chemical property, and 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 used raw material ZrO 2 And ZrH 2 The 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 invention x The preparation process is shown in the figure.
FIG. 2 is a view showing ZrO produced in example 1 of the present invention x A photograph of the particles.
FIG. 3 shows ZrO produced in example 2 of the present invention x A photograph of the particles.
FIG. 4 shows ZrO obtained in example 2 of the present invention x XRD pattern of the particles.
FIG. 5 shows the ZrO coated in example 2 of the present invention x XRD pattern of the melt.
FIG. 6 shows ZrO produced in example 3 of the present invention x A 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.
ZrO x The preparation process is shown in FIG. 1.
Example 1:
ZrO production by the Process shown in FIG. 1 x : reacting ZrH 2 Powder and ZrO 2 The powder is weighed according to the weight ratio of 2 to 5, and is mechanically mixed for 6 hours by adopting a stirring mixer, and the mixed powder is mixed by adopting an oil press at 300N/cm 2 Briquetting under the pressure of (1), crushing and screening the block material to obtain particles with the particle size of 1-3mm, and performing vacuum treatment at 1650 ℃ and 2x10 of vacuum degree -1 The 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 method 3 XRD analysis shows that the material consists of Zr as one new compound 3 O and partial ZrO 2 And (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 evaporation of material is carried out by electron beam evaporation coating equipment with vacuum degree of 1.6x10 -2 Pa, 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. 1 x : reacting ZrH 2 Powder and ZrO 2 Weighing the powder according to the weight ratio of 2 to 3, mechanically mixing for 4 hours by using a ball mill, and mixing the powder at 600N/cm by using an oil press 2 Briquetting under pressure of (1), crushing and sieving to obtain granules with particle size of 1-3mm, heating to 1850 deg.C and vacuum degree of 5x10 -2 Carrying out solid phase synthesis reaction under PaAfter 8 hours, the mixture was 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 method 3 XRD analysis shows that the material consists of Zr as one new compound 3 O and partial ZrO 2 Composition (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 ℃, the material does not splash in the pre-melting process, and the surface of the pre-melted material is basically in a molten state. The substrate for coating is quartz substrate, and evaporation coating equipment is used for evaporation coating of material with vacuum degree of 1.6x10 -2 Pa, 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 Zr 3 O and partial ZrO 2 The 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 Process shown in FIG. 1 x : reacting ZrH 2 Powder and ZrO 2 The powder is weighed according to the weight ratio of 3 to 2, a stirring mixer is adopted for mechanical mixing for 8 hours, and the mixed powder is prepared by an oil press at 500N/cm 2 Briquetting under pressure of (1), crushing and sieving to obtain granules with particle size of 1-5mm, temperature of 2000 deg.C and vacuum degree of 5x10 -3 The 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 method 3 XRD analysis shows that the material consists of Zr as one new compound 3 O and partial ZrO 2 And (4) forming. When in use, the ZrOx material is fully pre-melted firstly, and the material is filled in a water-cooling oxygen-free copper crucible for pre-melting, wherein the pre-melting temperature is about 2300 DEG CThe pre-melting process does not splash, and the surface of the pre-melted material is basically in a molten state. The substrate for coating is a quartz substrate, and evaporation of material is carried out by electron beam evaporation coating equipment with vacuum degree of 1.6x10 -2 Pa, substrate temperature of 80 deg.C, evaporation temperature of 2400 deg.C, and evaporation rate of
The refractive index of the film coating layer at 500nm is 2.02, the film coating 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 invention x Has 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 invention x The 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 obtained ZrOx has stable composition. 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 found 2 And ZrH 2 Purity of (ZrO) 2 And ZrH 2 Mass ratio of (b), solid phase synthesis temperature, holding time and degree of vacuum to the obtained ZrO x The quality of the product has a certain influence. Under the preferred process conditions, zrO is obtained x The 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 modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (7)
1. ZrO for plating optical film x The preparation method is characterized by comprising the following steps:
(1) With ZrO 2 And ZrH 2 The 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 ZrO x Coating materials;
wherein, zrO in the step (1) 2 And ZrH 2 The powder has a mesh number of-250 meshes and a raw material ratio of ZrO 2 35wt％～75wt％，ZrH 2 25wt％～65wt％；
The high-temperature solid-phase synthesis temperature of the block or the particle obtained in the step (3) is 1500-2100 ℃.
2. The ZrO layer for plating optical thin film according to claim 1 x The preparation method is characterized in that the mixing mode in the step (1) is stirring mixing or ball milling mixing.
3. The ZrO layer for plating optical thin film according to claim 1 x Characterized in that ZrO in step (1) 2 And ZrH 2 The mixing time is 4-10 hours.
4. The ZrO layer for plating optical thin film according to claim 1 x The preparation method is characterized in that the briquetting is 300-800N/cm 2 Pressing the mixture into blocks under the pressure ofTo a block; the granulation is 300 to 800N/cm 2 Briquetting under the pressure of (1), crushing the obtained block, and screening to collect particles with the particle size of 1-5 mm.
5. A ZrO for plating optical films according to claim 1 x The method is characterized in that the degree of vacuum of the obtained block or particle for solid phase synthesis is 10Pa to 1x10 -3 Pa。
6. The ZrO for plating optical thin film according to claim 1 x The method for producing (1) is characterized in that the solid phase synthesis time of the obtained block or granule is 3 to 20 hours.
7. ZrO for plating optical thin films according to any one of claims 1 to 6 x Preparation method of (1) x Characterized in that the ZrO x Wherein x =0.8 to 1.2.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2019
- 2019-12-30 CN CN201911396525.0A patent/CN112028120B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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