CN115403384B - Preparation method of multispectral zinc sulfide - Google Patents
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Abstract
The invention is disclosed inA preparation method of multispectral zinc sulfide is provided, which comprises the following steps: carrying out optical polishing processing on a standard zinc sulfide piece; plating Ag+ZnS mixed film, ag film and Al on the surface of zinc sulfide piece 2 O 3 A membrane; and carrying out hot isostatic pressing treatment on the coated zinc sulfide piece: the temperature is 750-950 ℃ and the pressure is 130-200MPa; and (3) finely grinding the two sides of the treated zinc sulfide piece, and removing the surface coating to obtain multispectral zinc sulfide. The invention can obviously reduce the hot isostatic pressing treatment time, has better optical uniformity, higher transmittance of visible light wave band, more uniform grain size of the treated material and good mechanical property.
Description
Technical Field
The invention relates to the technical field of chemical vapor deposition, in particular to a preparation method of multispectral zinc sulfide.
Background
The zinc sulfide (CVD) material prepared by adopting the chemical vapor deposition process has the advantages of high purity, uniform texture, low scattering, low absorption, low high-temperature radiation and the like, is an advanced infrared window material, and is used as an optical element such as a window, a head cover, a lens and the like of an infrared thermal imaging system. The CVD ZnS material has two specifications of standard ZnS and multispectral ZnS, the appearance of the standard ZnS is orange, the standard ZnS is mainly used for long-wave infrared (8-12 mu m) wave bands, the multispectral ZnS is colorless and transparent in appearance, and the transmission wave band covers the whole wave band from visible light to long-wave infrared (0.4-12 mu m), so that the material is the preferred material of the 'multiple light-in-one' composite light window.
The multispectral ZnS is obtained by carrying out hot isostatic pressing treatment on the standard ZnS, the grain size of the ZnS polycrystal material grows from 3-10 mu m of the standard ZnS to 50-100 mu m of the multispectral ZnS under the condition of high temperature and high pressure, and the crystal defects such as non-chemical proportion, scattering center and the like are obviously reduced, so that the optical performance is obviously improved, but the hot isostatic pressing treatment has great influence on the optical performance, such as the increase of the grain size, the decrease of the breaking strength of the material and the decrease of the 103MPa of the standard ZnS to 68MPa of the multispectral ZnS, and under the same condition, the larger the size of the material to be treated is, the thicker the thickness is, the longer the required treatment time is, the grain size is further increased, the grain size distribution is more dispersed, and the performance is further reduced.
U.S. patent publication No. US4944900, chinese patent publication No. CN102531040a, both propose methods for preparing multi-spectral ZnS, which are believed to accelerate the conversion of standard ZnS into multi-spectral ZnS by wrapping ZnS material with metal foils such as Pt, pd, etc. during the hot isostatic pressing process: under the hot isostatic pressing condition, pt, pd and the like can react with surface ZnS to form sulfide, S vacancies are formed in ZnS, and the excessive Zn plays a role in similar grain growth driving force in the diffusion process, so that the grain recombination and growth are promoted, and the defects are reduced. However, this method requires that the metal foil is adhered to the ZnS material surface, and the degree of tightness of the combination of the metal foil and ZnS material affects the effect of the hot isostatic pressing treatment, in particular, affects optical properties such as optical uniformity and transmittance in the visible light band.
With the development of infrared market, the requirements for high-quality multispectral ZnS large-size flat plates and spherical cover products are increasing, and the quality is difficult to be ensured by adopting the current hot isostatic pressing treatment method.
Disclosure of Invention
The invention aims to solve the technical problems and provide the preparation method of the multispectral zinc sulfide, which can obviously reduce the hot isostatic pressing treatment time, and compared with the traditional hot isostatic pressing treatment method, the treated ZnS has better optical uniformity, higher transmittance in the visible light wave band, more uniform grain size and better mechanical property.
In order to solve the technical problems, the invention provides a preparation method of multispectral zinc sulfide, which comprises the following steps:
(1) Surface treatment is carried out on the zinc sulfide part, and the surface finish is required to be better than 120-100;
(2) Cleaning the surface of the processed zinc sulfide part, and drying for later use;
(3) Zinc sulfide parts are put into a vacuum coating machine, and the background vacuum degree of a vacuum chamber of the vacuum coating machine is pumped to be better than 5 x 10 -3 Pa, heating the zinc sulfide part to 80-300 ℃;
(4) Heating and evaporating ZnS by using a double electron beam, and simultaneously heating and evaporating Ag by using another electron gun, wherein an Ag+ZnS mixed film is plated on the surface of the zinc sulfide part, and the thickness of the film is 10-30nm;
(5) Plating an Ag film on the Ag+ZnS mixed film by using a resistance heating evaporation method, wherein the deposition rate is 0.5-10nm/S, and the thickness of the film is 10-100nm;
(6) Plating a high-melting-point hard film on the Ag film by using an electron beam heating evaporation method, wherein the deposition rate is 0.5-5nm/S, the thickness of the film is 100-1000nm, and cooling to room temperature after film plating is finished to obtain a single-sided film plating part;
(7) Repeating the steps (3), (4), (5) and (6), and plating an Ag+ZnS mixed film, an Ag film and a high-melting-point hard film on the other surface of the ZnS piece to obtain a double-sided coated part;
(8) Placing the double-sided coated part into a crucible of a hot isostatic pressing machine, and vacuumizing to be lower than 50Pa;
(9) Hot isostatic pressing treatment is carried out on the double-sided coated part: firstly, the pressure is increased to 50-100MPa, then the temperature is increased to 750-950 ℃, and the temperature rising rate is increased: 5-15 ℃/min, and finally, raising the pressure to 130-200MPa, keeping constant temperature and pressure for a period of time: 10-100 hours;
(10) Cooling the hot isostatic pressing furnace to room temperature, wherein the cooling rate is as follows: 5-15 ℃/min, decompressing, and taking out to obtain the hot isostatic pressing part;
(11) And (3) performing double-sided fine grinding on the hot isostatic pressing part, removing the film layer plated on the surface, and obtaining the multispectral zinc sulfide material after the removal is completed.
Further, the zinc sulfide part is made of Zn and H 2 S is used as raw material and is prepared by adopting a chemical vapor deposition processIs prepared.
Further, in (1), the surface treatment is performed by sequentially adopting rough grinding, finish grinding and polishing.
Further, in (2), the surface cleaning is performed by sequentially using deionized water, isopropyl alcohol, and absolute ethyl alcohol.
Further, in the step (4), the purpose of plating the Ag+ZnS mixed film is to solve the problem of poor binding force between the Ag film and the ZnS part, and avoid the influence of the falling-off of the Ag film in the subsequent treatment process.
Further, in the step (4), the Ag+ZnS mixed film is plated by adopting a double-electron gun heating and mixed evaporation mode, one electron gun heats and evaporates ZnS, and the other electron gun heats and evaporates Ag, and the evaporation rates of ZnS and Ag can be simultaneously controlled by utilizing the electron gun mixed evaporation mode, so that the component proportion of the Ag+ZnS mixed film can be controlled.
Further, in the step (4), a Ag+ZnS mixed film is plated, a graphite crucible for evaporating ZnS by an electron gun is arranged in the graphite crucible, znS polycrystal film material is arranged in the graphite crucible, the Ag evaporated by the electron gun is a copper crucible, a layer of ZnS polycrystal film material is paved at the bottom of the copper crucible, and Ag particles are placed on the ZnS film material, so that other pollution caused in the Ag evaporation process by the electron gun is avoided, znS is evaporated firstly in the mixed evaporation process, ag is evaporated again after the evaporation of ZnS is stabilized, and the evaporation of Ag is stopped after the preset thickness is reached.
Furthermore, in the step (5), the purpose of plating the Ag film is that under the following hot isostatic pressing treatment technical condition, ag can react with ZnS to accelerate the hot isostatic pressing treatment process, and a resistance evaporation mode is adopted when the Ag film is plated, and the evaporation boat is a molybdenum boat.
Further, in (6), the high melting point hard film is a protective film layer made of Al 2 O 3 、SiO 2 、ZrO 2 、HfO 2 Or Y 2 O 3 The purpose of the protective film layer is to prevent Ag film plated on the ZnS part surface from forming Ag in the air exposing process 2 S layer, second, avoid ZnS part surface Ag membrane scratch or destroy in moving, thus influence the hot isostatic pressing treatment effect; preferably Al plating 2 O 3 Film, plating and collectingBy graphite crucible, al 2 O 3 Polycrystalline lump material.
Further, the crucible of the hot isostatic pressing machine is made of graphite.
Further, in (9), the pressure is first raised to 80MPa.
The invention has the beneficial effects that:
in the hot isostatic pressing treatment process of zinc sulfide, a metal film layer and a part are attached to form a whole in a surface Ag film plating mode, the metal film layer and the part are compact and inseparable, the treatment time can be remarkably reduced, meanwhile, the optical uniformity is better, the transmittance of a visible light wave band is higher, in addition, the grain size of the treated material is more uniform, and the mechanical property is better. Is especially suitable for preparing high-quality large-size flat plate, spherical cover and other anisotropic products.
Drawings
FIG. 1 is a schematic illustration of a preparation flow of the present invention;
FIG. 2 is a graph showing the transmittance of ZnS in the visible light bands of an unplated Ag film and an Ag film by the same hot isostatic pressing process according to this invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Referring to fig. 1, in one embodiment of the method for preparing multispectral zinc sulfide of the present invention, a large-size multispectral ZnS optical window is prepared by the method:
rough grinding, fine grinding and polishing zinc sulfide parts with the size of 400-300-30 mm, wherein the zinc sulfide parts are ZnS plane optical windows, and the surface finish is 100-80, one of which represents pits and the other represents scratches; znS planar optical window consists of Zn and H 2 S is used as a raw material and is prepared by adopting a chemical vapor deposition process;
cleaning the processed ZnS planar optical window with deionized water, isopropanol and absolute ethyl alcohol by using an ultrasonic cleaner, and then drying for later use;
loading ZnS planar optical window to be used in vacuum platingThe film machine, vacuum film plating machine model number ZZS1500, then vacuum pumping the background of the vacuum chamber to 4 x 10 -3 Pa, then heating ZnS planar window to 120 ℃;
plating Ag+ZnS mixed film, ag film and Al on the surface of ZnS planar optical window 2 O 3 Film: (1) A double electron beam heating and mixed steaming mode is utilized to plate an Ag+ZnS mixed film, one electron gun heats and evaporates ZnS, the power of the electron gun is 8KW, a graphite crucible is used as a film material, the evaporation rate is 0.2nm/S, meanwhile, the other electron gun heats and evaporates Ag, the power of the electron gun is 6KW, a layer of ZnS polycrystalline film material is paved at the bottom of the copper crucible, ag particle film materials are arranged on the ZnS film material, the evaporation rate is 0.3nm/S, znS is evaporated firstly in the mixed steaming process, ag is evaporated again after stabilization, and evaporation of ZnS and Ag is stopped in sequence after the film thickness reaches 10 nm. (2) An Ag film is plated by a resistance heating evaporation method, wherein an evaporation boat is a molybdenum boat, the deposition rate is 3nm/S, and the thickness of the film is 80nm. (3) Al plating by electron beam heating evaporation 2 O 3 Film, graphite crucible, al 2 O 3 The polycrystal block material has electron gun power of 8KW, deposition rate of 0.5nm/S and film thickness of 500nm, and the film is cooled to room temperature to obtain single-sided film coated part
Repeating the above coating steps, and coating Ag+ZnS mixed film, ag film and Al on the other surface of ZnS planar optical window 2 O 3 A membrane;
placing a ZnS planar optical window of the coating film into a crucible of a hot isostatic pressing machine, and vacuumizing to 30Pa;
hot isostatic pressing treatment is carried out on ZnS plane optical window: firstly, the pressure is increased to 80MPa, then the temperature is increased to 850 ℃, and the temperature rising rate is that: 10 ℃/min, and finally, the pressure is increased to 190MPa, and the constant temperature and the constant pressure time are carried out: 80 hours;
cooling the hot isostatic pressing furnace to room temperature, wherein the cooling rate is as follows: 10 ℃/min, decompressing, and taking out the ZnS planar optical window;
and finally, the processed ZnS planar optical window is subjected to double-sided fine grinding, surface coating is removed, and the multispectral ZnS planar optical window can be obtained after the processing process is completed.
And performing performance detection on the multispectral ZnS planar optical window obtained by processing: breaking strength 89.4MPa, optical propertyUniformity 15 x 10 -6 (@ 0.6328 μm), the technical indices all reach the international advanced level.
Example 2
The method of the invention is used for preparing the large-size multispectral ZnS spherical cap:
rough grinding, fine grinding and polishing are carried out on a hemispherical standard ZnS spherical cover with the caliber phi of 300mm, the convex curvature radius of 150mm and the center thickness of 9mm, and the surface finish is 100-80;
cleaning the processed ZnS ball cover with deionized water, isopropanol and absolute ethyl alcohol by using an ultrasonic cleaner, and drying for later use;
putting a ZnS ball cover to be used into a vacuum coating machine, vacuum coating the ZnS ball cover with a model number ZZS1500, and vacuumizing the background of a vacuum chamber to 2 x 10 -3 Pa, then heating ZnS planar window to 200 ℃;
plating Ag+ZnS mixed film, ag film and Al on the surface of ZnS planar optical window 2 O 3 Film: (1) A double electron beam heating and mixed steaming mode is utilized to plate an Ag+ZnS mixed film, one electron gun heats and evaporates ZnS, the power of the electron gun is 8KW, a graphite crucible is used as a film material, the evaporation rate is 0.3nm/S, meanwhile, the other electron gun heats and evaporates Ag, the power of the electron gun is 6KW, a layer of ZnS polycrystalline film material is paved at the bottom of the copper crucible, ag particle film materials are arranged on the ZnS film material, the evaporation rate is 0.2nm/S, znS is evaporated firstly in the mixed steaming process, ag is evaporated again after stabilization, and evaporation of ZnS and Ag is stopped in sequence after the film thickness reaches 15 nm. (2) An Ag film is plated by a resistance heating evaporation method, wherein an evaporation boat is a molybdenum boat, the deposition rate is 5nm/S, and the thickness of the film is 100nm. (3) Al plating by electron beam heating evaporation 2 O 3 Film, graphite crucible, al 2 O 3 The polycrystal block material has electron gun power of 8KW, deposition rate of 1nm/S and film thickness of 1000nm, and the film is cooled to room temperature to obtain single-sided film coated part
Repeating the above coating steps, and coating Ag+ZnS mixed film, ag film and Al on the other surface of ZnS planar optical window 2 O 3 A membrane;
placing the ZnS ball cover coated with the film into a crucible of a hot isostatic pressing machine, and vacuumizing to 50Pa;
hot isostatic pressing treatment is carried out on ZnS spherical cover: firstly, the pressure is increased to 80MPa, then the temperature is increased to 900 ℃, and the temperature rising rate is increased: 8 ℃/min, and finally, the pressure is increased to 150MPa, and the constant temperature and the constant pressure time are carried out: 50 hours;
cooling the hot isostatic pressing furnace to room temperature, wherein the cooling rate is as follows: 8 ℃/min, decompressing, and taking out the ZnS spherical cover;
the treated ZnS ball cover is subjected to double-sided fine grinding, surface coating is removed, and the multispectral ZnS ball cover is obtained after the treatment process is completed;
and performing performance detection on the multispectral ZnS spherical cover obtained by processing: the transmittance is 69% (@ 0.55 μm) and 72% (@ 1.064 μm), and the technical indexes reach the international advanced level. And the multispectral ZnS spherical cover is compared with the multispectral ZnS spherical cover prepared by non-coating film in the transmittance of visible light wave bands, as shown in figure 2, the multispectral ZnS spherical cover has a large difference.
The Ag film is plated on the surface of the ZnS part, so that the hot isostatic pressing treatment time can be remarkably reduced, the optical uniformity is better, the transmittance of a visible light wave band is higher, the grain size of the treated material is more uniform, and the mechanical property is good.
In summary, the method of plating Ag film on the surface of zinc sulfide replaces the existing method of coating zinc sulfide with Pt metal foil, the metal film layer and the part are attached to form a whole, the optical uniformity of the ZnS after treatment is better, the transmittance of the visible light wave band is higher, the grain size is more uniform, and the mechanical property is better.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting thereof; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for preparing multispectral zinc sulfide, which is characterized by comprising the following steps:
(1) Surface treatment is carried out on the zinc sulfide part;
(2) Cleaning the surface of the processed zinc sulfide part, and drying for later use;
(3) Zinc sulfide parts are put into a vacuum coating machine, and the background vacuum degree of a vacuum chamber of the vacuum coating machine is pumped to 5 x 10 -3 Pa, heating the zinc sulfide part to 80-300 ℃;
(4) Heating and evaporating ZnS by using a double electron beam, and simultaneously heating and evaporating Ag by using another electron gun, wherein an Ag+ZnS mixed film is plated on one surface of a zinc sulfide part, and the thickness of the film is 10-30nm;
(5) Plating an Ag film on the Ag+ZnS mixed film by using a resistance heating evaporation method, wherein the deposition rate is 0.5-10nm/s, and the thickness of the film is 10-100nm;
(6) Plating a high-melting-point hard film on the Ag film by using an electron beam heating evaporation method, wherein the deposition rate is 0.5-5nm/s, the thickness of the film is 100-1000nm, and cooling to room temperature after film plating is finished to obtain a single-sided film plating part;
(7) Repeating the steps (3), (4), (5) and (6), and plating an Ag+ZnS mixed film, an Ag film and a high-melting-point hard film on the other surface of the ZnS piece to obtain a double-sided coated part;
(8) Placing the double-sided coated part into a crucible of a hot isostatic pressing machine, and vacuumizing to be lower than 50Pa;
(9) Hot isostatic pressing treatment is carried out on the double-sided coated part: firstly, the pressure is increased to 50-100MPa, then the temperature is increased to 750-950 ℃, and the temperature rising rate is increased: 5-15 ℃/min, and finally, raising the pressure to 130-200MPa, keeping constant temperature and pressure for a period of time: 10-100 hours;
(10) Cooling the hot isostatic pressing furnace to room temperature, wherein the cooling rate is as follows: 5-15 ℃/min, decompressing, and taking out to obtain the hot isostatic pressing part;
(11) The double sides of the hot isostatic pressing part are finely ground, a film layer plated on the surface is removed, and the multispectral zinc sulfide material can be obtained after the removal is completed;
in (6), the high-melting-point hard film is a protective film layer made of Al 2 O 3 、SiO 2 、ZrO 2 、HfO 2 Or Y 2 O 3 The protective film layer is used for shielding and protecting the Ag film;
in (1), the surface treatment is performed by sequentially adopting a rough grinding, a fine grinding and a polishing.
2. The method of preparing multispectral zinc sulfide of claim 1, wherein the zinc sulfide component is prepared from Zn and H 2 S is used as a raw material and is prepared by adopting a chemical vapor deposition process.
3. The method for preparing multispectral zinc sulfide according to claim 1, wherein in (2), the surface cleaning is performed by sequentially using deionized water, isopropyl alcohol, and absolute ethyl alcohol.
4. The method for producing a multi-spectral zinc sulfide according to claim 1, wherein in (4), the ag+zns mixed film is plated by heating and co-evaporating ZnS with a double electron gun, while heating and evaporating Ag with another electron gun, and the evaporation rates of ZnS and Ag are controlled simultaneously by co-evaporating with an electron gun, thereby controlling the component ratio of the ag+zns mixed film.
5. The method for producing a multi-spectral zinc sulfide according to claim 1, wherein in (4), a mixed film of ag+zns is plated, a graphite crucible for ZnS is evaporated by an electron gun, a ZnS polycrystal film material is formed in the graphite crucible, ag is evaporated by the electron gun as a copper crucible, a layer of ZnS polycrystal film material is laid on the bottom of the copper crucible first, ag particles are placed on the ZnS film material, znS is evaporated first in the process of mixed evaporation, ag is evaporated again after stabilization, evaporation of ZnS is stopped first after a set thickness is reached, and evaporation of Ag is stopped.
6. The method for preparing multispectral zinc sulfide according to claim 1, wherein in (5), the plated Ag film is used for reacting Ag with ZnS under the following hot isostatic pressing treatment technical conditions to generate Zn vacancies, accelerating the hot isostatic pressing treatment process, and the evaporation boat is a molybdenum boat by adopting a resistance evaporation mode when the Ag film is plated.
7. The method of producing multispectral zinc sulfide according to claim 1, wherein in (8), the crucible material of the hot isostatic press is graphite.
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| US5126081A (en) * | 1980-12-29 | 1992-06-30 | Raytheon Company | Polycrystalline zinc sulfide and zinc selenide articles having improved optical quality |
| US4944900A (en) * | 1983-03-16 | 1990-07-31 | Raytheon Company | Polycrystalline zinc sulfide and zinc selenide articles having improved optical quality |
| TW546487B (en) * | 2001-09-27 | 2003-08-11 | Sumitomo Electric Industries | Ceramics optical part and manufacture method of the same |
| US20090000700A1 (en) * | 2007-06-29 | 2009-01-01 | Hogan Patrick K | Treatment method for optically transmissive body |
| US7790072B2 (en) * | 2007-12-18 | 2010-09-07 | Raytheon Company | Treatment method for optically transmissive bodies |
| US8071466B1 (en) * | 2007-12-28 | 2011-12-06 | Fairfield Crystal Technology, Llc | Zinc sulfide crystals for optical components |
| CN102531040A (en) * | 2010-12-24 | 2012-07-04 | 北京有色金属研究总院 | Process method for preparing multispectral zinc sulfide (ZnS) |
| EP2527309B1 (en) * | 2011-05-24 | 2016-08-03 | Rohm and Haas Company | Improved quality multi-spectral zinc sulfide |
| CN103466687B (en) * | 2013-09-10 | 2016-01-20 | 中国航天科工集团第三研究院第八三五八研究所 | A kind of preparation method of high-strength multispectral zinc sulfide |
| CN103774143B (en) * | 2014-02-28 | 2015-12-30 | 东莞星晖真空镀膜塑胶制品有限公司 | A kind of vacuum coating method of protective membrane |
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| CN111016322A (en) * | 2019-11-19 | 2020-04-17 | 有研国晶辉新材料有限公司 | Hot isostatic pressing treatment method for CVD ZnS infrared optical material coated with silver paper |
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