CN102400212B - Method for obtaining polycrystal optical zinc selenide - Google Patents
Method for obtaining polycrystal optical zinc selenide Download PDFInfo
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- CN102400212B CN102400212B CN201110214950.0A CN201110214950A CN102400212B CN 102400212 B CN102400212 B CN 102400212B CN 201110214950 A CN201110214950 A CN 201110214950A CN 102400212 B CN102400212 B CN 102400212B
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Abstract
The invention, belonging to the optical medium technology field, provides a method for obtaining polycrystal optical material, particularly a method for obtaining polycrystal optical zinc selenide. The method comprises heating and evaporating of the raw material. The steam is condensed upon the heated substrate. The raw material carries out evaporation at a temperature ranging from 1050 DEG C to 1150 DEG C, with the steam being condensed upon the substrate while the substrate being heated to a temperature within the range of 950 to 1050 DEG C. To improve the quality of the obtained product, the speed of the steam depositing upon the substrate shall be controlled. The cultivated blank shall be cooled down via the specific technology, thereby decreasing the internal stress of the blank. The method improves the technology for obtaining large-sized optical material blanks, raises the optical quality of the material used within the visible light and infrared spectrum range, and improves the yield of the qualified products.
Description
Technical field
Invention belongs to optical material technology field, obtains the method for polycrystal optical material, and this material is transparent to visible and ir radiation in wide spectral range.
Background technology
Sulfur family zinc and cadmium (ZnSe, ZnS, CdTe, ZnTe) and their sosoloid have comprehensive physicals, these performances can make its be applied to optics and electronics different field (see H. Γ. this tal fibre Ren Siji, Ъ .B. Ge Liniefu, Л .M. markon Qin Siciji, B. Д. Lei Kefu are " with compd A
iIb
vIfor the scintillator of base, obtain, performance and service condition ", Kharkov city, single crystal institute, 2007,296 pages).When light-electric instrument camera lens to wide spectral range and protection cabin are designed, polycrystal zinc selenide is the optical material being widely used the most.Zinc selenide can adopt diverse ways to obtain: both can suppress acquisition by vacuum hotpressing, also can obtain by vapour deposition (seeing E.M. Jia Fulishuke " the polycrystal zinc selenide of infrared optics ", inorganic materials, 2003, the 19 volumes 1031～1049).
For obtaining optics polycrystalline zinc selenide, vapour deposition process is at present most popular.
From state of the art, the certain methods and the equipment quilt that obtain polycrystal zinc selenide are extensively cognitive, they are all Applied Physics deposition principles, be that zinc selenide vapor deposition is to substrate, the index M ∏ KC4B 35/00 of institute and CO9K11/10 in the russian patent № 844609 publishing on July 7th, 1981, apply for obtaining the method for the sulfur family zinc of optical ceramics and the polycrystalline bulk of cadmium, its content is: make steam pass through porous graphite, carbon graphite or silicon oxide cloth, deposit in heated substrate by physical deposition method, the sedimentation rate of this steam is 0.005～0.15mol/cm
2h, in order to deposit zinc selenide, substrate should be heated to 600～900 DEG C.
Obtain polycrystalline bulk with aforesaid method, its crystal grain is of a size of 50～100 μ m and (λ=10 μ is m) time at exemplar thickness 5mm, its optical transparency is 65～70%, but after cooling its density reach theoretical density 99.7 ± 0.2% time, it is opaque that the optical material of applying for is actually in visible spectrum range, and near, middle infrared internal transmission factor is lower, overall optical property according to zinc selenide transparency in whole spectral ranges, above-mentioned technique is difficult to obtain desirable sample.
Index M ∏ KC30B25/00 in № 2031985 Russian Federation's patents of publishing March 27 nineteen ninety-five, 29/48, described a kind of method and apparatus that obtains polycrystal zinc selenide, the method is used: carry out vapour deposition supplying with respectively under the mixed airflow of Selenium hydride and argon and the mixed airflow condition of zinc and argon.Be deposited on the wall of square reactor; this reactor has input unit flange with holes; the effect in this hole is gas mixture in order to supply with Selenium hydride and argon and zinc and argon-mixed vapour stream; distributing for supplying with the hole of shielding gas by concentric(al) circles round each hole; use the method and apparatus of this application can improve useful output and the corresponding productivity of from Selenium hydride, extracting zinc selenide; but the weak point of the method is, the complicacy of structure of reactor and the lasting technology stability depositing on reactor wall.
The polycrystal zinc selenide method of obtaining of applying in № 2031986 Russian Federation's patents of publishing March 27 nineteen ninety-five is: in the reactor of heating, supply with the Selenium hydride of gas mixture form and the vapour stream of zinc with argon to substrate, its mole ratio is 0.8～1.3, and in reactor, the Selenium hydride flow of pressure 6～10torr and the transversal unit surface of reactor is 35-42 μ mol/ (cm
2min) coefficient is no more than 110 to 10.6 mum wavelengths
-3in visible ray and near infrared spectral range, the transparency of material is little, should think that this is the shortcoming of this inoculation method, and this method has limited the possibility of this material application.
Also have a kind of method of obtaining zinc selenide optics polycrystal piece to be, the index M ∏ KC30B23/00 in № 2019586 Russian Federation's patents of publication on September 15th, 1994,29/48 is is also checked and approved as sample of the present invention.Present method is: the zinc selenide of 5 kilograms is packed in crystal vessel so that distillation, in this zinc selenide, silicone content is 0.004%, packs into put into airtight body of heater after substrate and be evacuated to 10
-4mmHg, is heated to 1030 DEG C, stops heating when sublimation process finishes, and makes container be cooled to room temperature, and after cultivating, selenizing spelter grinds and polishing again, and this block has the transmitance of 70-71% in the time of 10.6 mum wavelength.
The optical performance parameter of the polycrystal zinc selenide that this method is cultivated in visible region and near, middle infrared is lower, and this is the shortcoming of this method.This has just limited it and be employed to obtain possibility in light-electric instrument, and the technique that this application manufactures a product is difficult to carry out.
Summary of the invention
The task of invention is: can be mass polycrystal zinc selenide, and zinc selenide should have high optical property in multiple spectral regions, also can improve the output of qualified product.
Invention task is resolved by a kind of method of obtaining optics polycrystal zinc selenide, the operation that the method comprises is: the heating of raw material and evaporation, make on its substrate that condenses to heating, the difference of it and above-mentioned sample method is: evaporation raw material carries out at 1050-1150 DEG C of temperature, and vapor condensation is to substrate, this substrate is heated to 950-1050 DEG C.
The temperature case of raw materials evaporate and substrate temperature are that approach is selected and confirmation by experiment.
From improving the purity of condensable product and improving resulting materials transmissivity this purpose the infrared range of spectrum of visible ray, the intermediate condensation of carrying out steam in labyrinth and porous filtering layer is suitable, in container, settle for this purpose the dividing plate of porous, contained impurity on this plate, the steam of evaporated material being carried out intermediate condensation and deposits raw material.
It is best carrying out condensation with the 0.2-0.8mm/h speed of growth, and in order to improve the output of qualified product and quality, this is ideal operating mode.
In order to reduce the internal stress in gained optical material, the container of cultivating zinc selenide blank is preferably undertaken cooling by selected cooling operating mode: certainly cultivate temperature and be cooled to 900 DEG C, its speed is 50-100 DEG C/h, speed of cooling within the scope of 900-600 DEG C is 30-50 DEG C/h, carries out furnace cooling from 600 DEG C of containers with blank together with equipment.
The processing of raw material is preferably carried out in rare gas element (as argon) medium, its temperature to 1200 DEG C, the cycle is 10-15h, this raw material is made up of pulverulent mixture and closely knit zinc metal sheet.Processing can be removed the impurity that is difficult to volatilization like this, and makes the component of steam close to stoichiometry.
Technological achievement is: improve and obtain the technique of big scale optical material blank, and by this process improving the optical quality of material, to obtain and use in visible ray and infrared range of spectrum.
Qualified samples and this material that the above-mentioned method of preparing polycrystal zinc selenide can obtain high yield have following optical characteristics: cultivating blank diameter to 500mm and thickness during to 50mm: transmissivity is respectively: wavelength 0.6 μ m place 30%, 1.06 μ m places 60%, 3-5 μ m place 69%, 8-12.5 μ m71%, the double refraction in optical material is no more than 100nm/cm.
Specific embodiment
Example 1
Raw material is zinc selenide powder, for example: its trade mark is ETO.035.011.TY (Russian Federation commercially available prod) (impurity composition: Cu, Mg < 10
-5%, Al < 10
-5%, Mn < 10
-5%, Ni < 10
-5%, Ti < 10
-5%, Ag < 10
-5%, Bi < 10
-5%; Fe < 10
-4%, Sn < 10
-4%, Cr < 10
-4%, Pb < 10
-4% quality), 38 kilograms of quantity pack the bottom of crystal vessel into, settle the porous graphite dividing plate with double-layer graphite cloth Γ Γ H-2M, condensing chamber and graphite substrate-lid, the container installing is put into vacuum oven, is evacuated to surplus pressure 110
-3mmHg also makes container be heated to the temperature of 1130 DEG C, in 75h, carries out the evaporation of raw material and vapor condensation is to substrate subsequently, and now substrate temperature is 1040 DEG C.
In the time finishing cultivation (being condensation process), there is the cooling of control: the speed with 70 DEG C/h during to 900 DEG C is carried out cooling, speed when then to 600 DEG C is 40 DEG C/h, whole equipment naturally cools to room temperature after this, the blank of cultivating is undertaken cooling by specific technique, thereby reduces the internal stress of blank.Technological achievement is: improve and obtain the technique of large size optical material blank, and improved this material optical quality to obtain application in visible ray and infrared range of spectrum, and improve the output of qualified product.
Then open equipment, take out and dismantle with the container of cultivating circular blanks, cultivate the weighing of blank, measure its thickness, then carry out mechanical workout (grinding and polishing), deposit with 0.5mm/h speed at steam, the zinc selenide blank of cultivating is of a size of: diameter 470mm, and when thickness 32mm, its transmissivity is as follows: wavelength 0.6 μ m place 33%, 1.06 μ m places 65%, 3-5 μ m place 69%, 8-12.5 μ m71%, in optical material, double refraction is no more than 150mm/cm.
Vapor deposition is controlled to the quality that can improve products obtained therefrom to the speed on substrate.
In addition, in implementation process repeatedly, learn: vaporization temperature is 1050-1150 DEG C, when underlayer temperature is 950-1050 DEG C, can obtain effect described in the present embodiment 1; For example, under the mode of deposition of the vaporization temperatures of 1050 DEG C, 950 DEG C of underlayer temperatures, 0.2mm/h sedimentation velocity and 1150 DEG C of vaporization temperatures, 1050 DEG C of underlayer temperatures, 0.8mm/h sedimentation velocity, carry out zinc selenide crystal deposition, obtained the zinc selenide polycrystalline bulk of identical optical performance; And: when cooling, technological process can be also: the speed with 50-100 DEG C/h while being cooled to 900 DEG C is carried out, and the speed of cooling within the scope of 900 DEG C-600 DEG C is 30-50 DEG C/h, from 600 DEG C, naturally cools to room temperature.
Example 2
Raw material is closely knit zinc selenide fragment, quantity is 32 kilograms, for example, in rare gas element (argon gas etc.) medium pre-annealing, its temperature is 1200 DEG C of time 10h, then raw material is packed in container to cultivate blank, all operations are subsequently same as Example 1, in other application processes, learn: annealing time is lengthened to 15h always and is also fine.The diameter of zinc selenide blank is 350mm, and thickness is 40mm, and it obtains under vapor deposition speed 0.35mm/h, and in 2.5-14 μ m spectral range, its transmissivity is 68%, and the double refraction in optical material is no more than 100mm/cm.
Claims (2)
1. a method that obtains polycrystal optics zinc selenide, comprises step: in the situation that vacuumizing, carry out heating and the evaporation of zinc selenide raw material, simultaneously by vapor condensation to heating substrate on; It is characterized in that: raw-material evaporation is carried out at 1050-1150 DEG C of temperature, and vapor condensation is on the substrate of 950-1050 DEG C to Heating temperature;
Wherein: described vapor condensation is to carry out with the speed of 0.2-0.8mm/h to the process on substrate;
Wherein: after the step at described vapor condensation to the substrate of heating, undertaken cooling by controlling operating mode, this operating mode is such: the speed with 50-100 DEG C/h while being cooled to 900 DEG C is carried out, speed of cooling within the scope of 900 DEG C-600 DEG C is 30-50 DEG C/h, from 600 DEG C, naturally cools to room temperature.
2. the method for acquisition polycrystal optics zinc selenide as claimed in claim 1, it is characterized in that: described raw material is the zinc selenide raw material of powdery or closely knit shred, before the heating and evaporation of carrying out raw material, in rare gas element, anneal in advance, annealing temperature is 1200 DEG C, and annealing time is 10～15h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2010132967 | 2010-08-02 | ||
| RU2010132967/05A RU2490376C2 (en) | 2010-08-02 | 2010-08-02 | Method of producing polycrystalline optical zinc selenide |
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| Publication Number | Publication Date |
|---|---|
| CN102400212A CN102400212A (en) | 2012-04-04 |
| CN102400212B true CN102400212B (en) | 2014-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201110214950.0A Active CN102400212B (en) | 2010-08-02 | 2011-07-29 | Method for obtaining polycrystal optical zinc selenide |
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|---|---|
| CN (1) | CN102400212B (en) |
| RU (1) | RU2490376C2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2516557C2 (en) * | 2012-08-22 | 2014-05-20 | Елена Ивановна Смирнова | Method of obtaining optic polycrystalline materials based on zinc selenide |
| CN104651927A (en) * | 2014-12-30 | 2015-05-27 | 盱眙新远光学科技有限公司 | Zinc selenide crystal |
| CN107634107B (en) * | 2017-08-30 | 2019-03-26 | 中建材（合肥）新能源有限公司 | A kind of preparation method enhancing efficiency of light absorption type nano photovoltaic material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2019586C1 (en) * | 1992-05-12 | 1994-09-15 | Научно-производственное объединение "Государственный институт прикладной химии" | Method of preparing of optic polycrystallic blocks of zinc selenide |
| RU2031986C1 (en) * | 1991-10-04 | 1995-03-27 | Даданов Александр Юрьевич | Method for production of polycrystalline zinc selenide |
| RU2046843C1 (en) * | 1992-07-31 | 1995-10-27 | Институт химии высокочистых веществ РАН | Method of producing polycrystalline zinc selenide |
| RU2253705C1 (en) * | 2004-01-14 | 2005-06-10 | Институт химии высокочистых веществ Российской академии наук (ИХВВ РАН) | Method of production of polycrystal zinc selenide |
| CN1915803A (en) * | 2006-09-08 | 2007-02-21 | 华中科技大学 | Method for preparing polycrystalline Nano film of zinc selenide |
| US7279040B1 (en) * | 2005-06-16 | 2007-10-09 | Fairfield Crystal Technology, Llc | Method and apparatus for zinc oxide single crystal boule growth |
| CN101665983A (en) * | 2008-09-01 | 2010-03-10 | 西北工业大学 | Zinc selenide single crystal growing method and zinc selenide single crystal growing container |
| CN101665245A (en) * | 2008-09-01 | 2010-03-10 | 西北工业大学 | Preparation method of zinc selenide polycrystalline material for single crystal growth |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1670001A1 (en) * | 1988-06-23 | 1991-08-15 | Институт металлургии Уральского отделения АН СССР | Method of producing polycrystalline clusters of zinc or cadmium chalkohalides for optical components |
-
2010
- 2010-08-02 RU RU2010132967/05A patent/RU2490376C2/en not_active IP Right Cessation
-
2011
- 2011-07-29 CN CN201110214950.0A patent/CN102400212B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2031986C1 (en) * | 1991-10-04 | 1995-03-27 | Даданов Александр Юрьевич | Method for production of polycrystalline zinc selenide |
| RU2019586C1 (en) * | 1992-05-12 | 1994-09-15 | Научно-производственное объединение "Государственный институт прикладной химии" | Method of preparing of optic polycrystallic blocks of zinc selenide |
| RU2046843C1 (en) * | 1992-07-31 | 1995-10-27 | Институт химии высокочистых веществ РАН | Method of producing polycrystalline zinc selenide |
| RU2253705C1 (en) * | 2004-01-14 | 2005-06-10 | Институт химии высокочистых веществ Российской академии наук (ИХВВ РАН) | Method of production of polycrystal zinc selenide |
| US7279040B1 (en) * | 2005-06-16 | 2007-10-09 | Fairfield Crystal Technology, Llc | Method and apparatus for zinc oxide single crystal boule growth |
| CN1915803A (en) * | 2006-09-08 | 2007-02-21 | 华中科技大学 | Method for preparing polycrystalline Nano film of zinc selenide |
| CN101665983A (en) * | 2008-09-01 | 2010-03-10 | 西北工业大学 | Zinc selenide single crystal growing method and zinc selenide single crystal growing container |
| CN101665245A (en) * | 2008-09-01 | 2010-03-10 | 西北工业大学 | Preparation method of zinc selenide polycrystalline material for single crystal growth |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102400212A (en) | 2012-04-04 |
| RU2490376C2 (en) | 2013-08-20 |
| RU2010132967A (en) | 2012-02-10 |
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