CN116377593B - Method for reducing magnesium fluoride crystal vacancy defects - Google Patents
Method for reducing magnesium fluoride crystal vacancy defects Download PDFInfo
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- CN116377593B CN116377593B CN202310329642.5A CN202310329642A CN116377593B CN 116377593 B CN116377593 B CN 116377593B CN 202310329642 A CN202310329642 A CN 202310329642A CN 116377593 B CN116377593 B CN 116377593B
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- 239000013078 crystal Substances 0.000 title claims abstract description 88
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 title claims abstract description 87
- 229910001635 magnesium fluoride Inorganic materials 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000007547 defect Effects 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 22
- 239000010439 graphite Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 17
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000005429 filling process Methods 0.000 claims description 3
- -1 fluoride ions Chemical class 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 11
- 238000002834 transmittance Methods 0.000 abstract description 10
- 230000003471 anti-radiation Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
- C30B31/08—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state the diffusion materials being a compound of the elements to be diffused
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a method for reducing magnesium fluoride crystal vacancy defects, which comprises the steps of adopting a vacuum furnace, arranging a support rod and a heater in the vacuum furnace, arranging a graphite tray at the top of the support rod, wherein the support rod is used for adjusting the height of the graphite tray in the vacuum furnace, firstly cutting and cleaning to remove impurities on the surface of a magnesium fluoride crystal blank, then wrapping the magnesium fluoride crystal blank on the graphite tray in the vacuum furnace by using high-purity lead fluoride powder, then removing impurities in the furnace by matching vacuum with 99.9999% high-purity argon, and then filling CF 4 gas into the vacuum furnace to compensate F-ion vacancies in the magnesium fluoride crystal blank; and after the diffusion process is finished, extracting residual gas in the furnace, and taking out magnesium fluoride crystals. The invention has low treatment cost, and can effectively improve the transmittance and the anti-radiation performance on the premise of not influencing the optical quality of the crystal.
Description
Technical Field
The invention relates to the field of new materials, in particular to a method for reducing magnesium fluoride crystal vacancy defects.
Background
Magnesium fluoride (MgF 2) crystal is an excellent optical crystal material, has higher transmittance from vacuum ultraviolet to infrared wave band, has high hardness, good mechanical property and stable chemical property, is not deliquescent or corroded, is not easy to crack and crack in the processing process, and is widely applied to various optical elements in civil and military fields such as optical fiber communication, infrared detection, imaging and the like. With the increasing application of deep ultraviolet and vacuum ultraviolet lasers, the further popularization of excimer laser applications, and the rapid development of high-precision imaging technology and semiconductor lithography technology, magnesium fluoride becomes one of the best optical materials for use as a deep ultraviolet excimer laser window. However, magnesium fluoride crystals usually have a certain number of fluorine vacancy defects due to lattice structures, preparation technology and the like, and the defects can be absorbed at 200-300 nm, so that when the magnesium fluoride crystals are used for 193nm, 248nm and other deep ultraviolet excimer lasers, the fluorine vacancy absorption can reduce the transmittance of incident laser, especially the absorption at 220-260 nm is up to more than 4%, even macroscopic crystal device coloring phenomenon occurs, the magnesium fluoride crystals are reduced in transmittance and laser irradiation resistance, the magnesium fluoride crystals are limited to be used as optical devices such as deep ultraviolet windows, rochones and the like, and the service life of materials is shortened.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for reducing the vacancy defect of magnesium fluoride crystals, which has low treatment cost and can effectively improve the transmittance and the anti-radiation performance on the premise of not influencing the optical quality of the crystals.
In order to solve the technical problems, the invention provides a method for reducing the defect of magnesium fluoride crystal vacancy, which adopts a vacuum furnace, wherein a support rod and a heater are arranged in the vacuum furnace, a graphite tray is arranged at the top of the support rod, and the support rod is used for adjusting the height of the graphite tray in the vacuum furnace, and comprises the following steps:
step 1) directionally cutting magnesium fluoride crystals into required device sizes to obtain magnesium fluoride crystal blanks, and then cleaning to remove impurities remained in the surface processing process of the magnesium fluoride crystal blanks;
Step 2) placing a layer of lead fluoride powder with purity of over 99.99% on a graphite tray in a vacuum furnace, then placing a magnesium fluoride crystal blank on the lead fluoride powder, covering the upper part and the periphery of the magnesium fluoride crystal blank with the lead fluoride powder with the same purity, and adjusting the height of a heater to ensure that the temperature gradient difference of the heights of the magnesium fluoride crystal blank and the lead fluoride powder is less than 0.5 ℃/cm so as to prevent crystal cracking, wherein the crystal is likely to crack when the temperature gradient difference is large, in addition, the temperature can influence the ion diffusion rate, and the smaller temperature gradient can ensure that the quantity of ions diffused into each position of a magnesium fluoride element is the same;
Step 3) under the condition of room temperature, vacuumizing the furnace to 10 -3 Pa, starting a heating program, heating to 300 ℃ at the speed of 20 ℃/h, then filling 99.9999% high-purity argon into the vacuum furnace until the pressure inside and outside the furnace is balanced, and repeating the vacuumizing and argon filling processes for more than three times after maintaining for more than 1 hour;
Step 4) vacuum pumping the furnace to more than 10 -5 Pa, heating to 500 ℃ at the speed of 20 ℃/h, maintaining for more than 10 hours, then charging CF 4 gas into the vacuum furnace, heating to 950 ℃ at the speed of 20 ℃/h after maintaining for 2 hours, and maintaining at a constant temperature for more than 100 hours, wherein the CF 4 gas is decomposed to generate fluoride ions, so as to compensate F-ion vacancies in magnesium fluoride crystal blanks;
And 5) after the diffusion process is finished, cooling to room temperature at a speed of 10 ℃/h, and taking out magnesium fluoride crystals after residual gas in the furnace is pumped out.
Further, a temperature measuring device and a heat preservation cylinder are arranged in the vacuum furnace, the vacuum furnace is also connected with a vacuumizing device and an air charging device, and the vacuumizing device is a mechanical pump and a molecular pump.
Further, in the step 1), the magnesium fluoride crystal after directional cutting is soaked in alcohol or acetone for more than 1 hour, then is washed clean by deionized water, and is dried by blowing, thus finishing the cleaning.
Further, in step 2), the thickness of the layer of lead fluoride powder placed on the graphite tray is not less than 5mm, and the spacing between adjacent magnesium fluoride crystal blanks is not less than 10mm.
Further, the amount of CF 4 gas charged is not less than the total volume of the magnesium fluoride crystal blank.
Further, the graphite trays are multiple and stacked.
The invention has the beneficial effects that:
The absorption of the magnesium fluoride crystal after the ion exchange compensation treatment of the invention can be reduced from more than 2% to less than 0.1% within the range of 220 nm-260 nm. The method does not need to change the crystal growth process, has simple equipment and low treatment cost, does not influence the optical quality of the crystal because all ion diffusion and exchange processes have no participation of metal ions and oxygen impurities, and can effectively improve the utilization efficiency of magnesium fluoride crystal blanks and the transmittance and anti-irradiation performance of components.
Drawings
FIG. 1 is a schematic view of the internal structure of a vacuum furnace according to the present invention;
FIG. 2 is a graph of product transmittance versus time before and after treatment in accordance with the present invention;
FIG. 3 is a schematic view of a magnesium fluoride crystal blank of the present invention when placed using a jig;
FIG. 4 is a schematic view of a magnesium fluoride crystal blank of the present invention held by a jig.
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 reducing the defect of magnesium fluoride crystal vacancy, a graphite tray 2 is arranged in a vacuum furnace 1, the diameter phi of the graphite tray is 150mm, the graphite tray is supported by a support rod 3 made of graphite, a heating body 4 is arranged on the outer side of the graphite tray, the heating body is made of graphite, the inner diameter is 180mm, the height is 250mm, a temperature measuring device is a tungsten-rhenium type 325 thermocouple, the temperature measuring position is consistent with the height of the graphite tray, a heat preservation cylinder 5 is wrapped outside the heating body, the thickness is 80mm, the height is 300mm, a vacuumizing device and an inflating device are positioned on a vacuum furnace chassis, and the vacuumizing device is formed by matching a mechanical pump and a molecular pump.
The method comprises the steps of directionally cutting magnesium fluoride crystals into rectangular strips with the size of 30mm x 20mm x 10mm, wherein the surface of 30 x 20 is the (001) surface of magnesium fluoride, the surface of 20 x 10 is the (100) surface of magnesium fluoride, soaking the cut magnesium fluoride crystal blank 7 in alcohol for 10 hours, then cleaning the magnesium fluoride crystal blank in an ultrasonic cleaning machine by deionized water, drying the magnesium fluoride crystal blank, completely removing impurities remained in the surface processing process of the magnesium fluoride crystal blank, ensuring that no residual water stain exists on the surface of the magnesium fluoride crystal blank, placing a layer of lead fluoride powder 6 with the purity of more than 99.99%, the thickness of the powder layer is 20mm on a graphite tray, then placing 10 pieces of the magnesium fluoride crystal blank on the lead fluoride powder, covering the magnesium fluoride crystal blank with the lead fluoride powder, and the thickness of the powder layer is 20mm; the combination capability of lead fluoride and oxygen is higher than that of magnesium, and trace impurities in graphite can be ion-diffused with magnesium fluoride element at high temperature, and the device is completely wrapped by lead fluoride, so that only gaseous F ions can diffuse through the gaps of powder, and the exposed part of magnesium fluoride crystal is prevented from being oxidized or entering other impurity ions, and the transmittance of the device is influenced.
Under the room temperature condition, vacuumizing the furnace to 10 -3 Pa by a combination of a mechanical pump and a molecular pump, starting a heating program, heating to 300 ℃ at a speed of 20 ℃/h, and then filling 99.9999% high-purity argon into the vacuum furnace until the pressure inside and outside the furnace is balanced, and repeating the vacuumizing and argon filling processes again after keeping for 2 hours to completely remove impurities in the vacuum furnace; when the vacuum degree in the furnace reaches more than 10 -5 Pa, the temperature is raised to 500 ℃ at the speed of 20 ℃/h, CF 4 gas is filled into the vacuum furnace after the vacuum furnace is kept for 20 hours, the volume of the filled CF 4 gas is 0.1L, the temperature is raised to 950 ℃ at the speed of 20 ℃/h after the vacuum furnace is kept for 10 hours, and the constant temperature is kept for 200 hours, so that the intrinsic defects of the magnesium fluoride crystal are compensated by an ion diffusion mode. And after the diffusion process is finished, cooling is started, the temperature is reduced to room temperature at the speed of 10 ℃/h, and the internal reference gas of the furnace is pumped out and then the crystal is taken out.
Referring to fig. 2, compared with the transmittance of the magnesium fluoride devices which are not treated in the same batch, the invention solves the technical problem of vacancy defect absorption of magnesium fluoride crystals within the range of 200 nm-300 nm, after magnesium fluoride crystal blanks are directionally sliced into required device sizes, the devices are subjected to ion exchange treatment in fluorine atmosphere before optical processing (polishing/coating), so that fluorine ions in the atmosphere enter crystal lattices of the crystals to occupy missing fluorine vacancies, the number of vacancy defects of the processed magnesium fluoride blank sheets is greatly reduced or eliminated, and the transmittance, the laser irradiation resistance and other performances of polished magnesium fluoride optical elements are improved. The magnesium fluoride device treated by the method has low cost, can carry out ion exchange treatment according to the size of the required finished magnesium fluoride optical device to carry out vacancy defect compensation, does not need to change the crystal growth condition and process, and avoids the reduction of the crystal performance caused by uncontrollability of the growth process. The technology needs simple equipment, is suitable for being popularized to large-scale production, expands the application field of the magnesium fluoride element from the ultraviolet-visible range above 300nm wave band to the deep ultraviolet and vacuum ultraviolet region, and can improve the optical performance of the magnesium fluoride element.
Referring to fig. 3 and 4, in order to facilitate the accuracy of the position of the magnesium fluoride crystal blank when being placed, the invention also provides a fixture convenient to position, which comprises a placing bottom plate 1, two side edges of the placing bottom plate corresponding to the length direction are respectively provided with a vertical plate 2, one side edge of the placing bottom plate between the two vertical plates is provided with a limit convex part 3, the surface of the placing bottom plate between the two vertical plates is used for placing the magnesium fluoride crystal blank 4, two sides of the magnesium fluoride crystal blank are respectively provided with a spacing block 5 for providing a standard spacing distance, the fixture also comprises two fixed beams 6 and movable beams 7 which are arranged in parallel, two ends of the fixed beams and the movable beams are respectively fixed through connecting plates 8 and form a frame structure, the fixed beams and the movable beams are respectively provided with a clamping plate 9, and the two clamping plates are matched to clamp the magnesium fluoride crystal blank. The connecting plate is provided with a guide sliding slot hole, one end of the movable beam is locked by a screw, and the fixed beam and the connecting plate can be locked and connected or welded and fixed.
When the magnesium fluoride crystal blank is used, firstly, the magnesium fluoride crystal blank is placed on the surface of the placing base plate, one end of the magnesium fluoride crystal blank is abutted against the limiting convex part, then, spacing blocks are placed between the magnesium fluoride crystal blanks and between the magnesium fluoride crystal blank and the vertical plates, the magnesium fluoride crystal blank can be pushed to one side, then, the frame structure for clamping and transferring is placed on the two vertical plates, the clamping plates of the fixed beam are located above the limiting convex part, the clamping plates of the movable beam are located on the other side, and then, the movable beam is moved, so that the two clamping plates clamp the magnesium fluoride crystal blank, then the movable beam is locked, the fixing is realized, all the magnesium fluoride crystal blanks can be fixed and transferred through one-time clamping, the frame structure is transferred into the crucible, and then, the fixing of the movable beam is released, so that the effect of placing a plurality of magnesium fluoride crystal blanks at intervals can be realized.
After the clamping, the spacer blocks are not fixed and remain on the placement base plate during transfer. In order to improve the stability during transfer, the locking bolts 10 are arranged on the two clamping plates, so that a better clamping and fixing effect is provided. After the locking bolt is arranged, the movable beam is of a cylindrical structure, the movable beam and the corresponding clamping plate can be connected through the rotary sleeve, the convenience in clamping operation is improved, clamping can be realized only by operating the locking bolt, and the movable beam is not required to be adjusted. A placement positioning plate 11 is also arranged on one of the connecting plates and is used for limiting the placement position of the whole frame structure.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (5)
1. The method for reducing the defect of the magnesium fluoride crystal vacancy is characterized in that a vacuum furnace is adopted, a supporting rod and a heater are arranged in the vacuum furnace, a graphite tray is arranged at the top of the supporting rod, and the supporting rod is used for adjusting the height of the graphite tray in the vacuum furnace, and the method comprises the following steps:
step 1) directionally cutting magnesium fluoride crystals into required device sizes to obtain magnesium fluoride crystal blanks, and then cleaning to remove impurities remained in the surface processing process of the magnesium fluoride crystal blanks;
Step 2) placing a layer of lead fluoride powder with purity of more than 99.99% on a graphite tray in a vacuum furnace, then placing a magnesium fluoride crystal blank on the lead fluoride powder, covering the upper part and the periphery of the magnesium fluoride crystal blank with the lead fluoride powder with the same purity, and adjusting the height of a heater to ensure that the temperature gradient difference of the heights of the magnesium fluoride crystal blank and the lead fluoride powder is less than 0.5 ℃/cm;
Step 3) under the condition of room temperature, vacuumizing the furnace to 10 -3 Pa, starting a heating program, heating to 300 ℃ at the speed of 20 ℃/h, then filling 99.9999% high-purity argon into the vacuum furnace until the pressure inside and outside the furnace is balanced, and repeating the vacuumizing and argon filling processes for more than three times after maintaining for more than 1 hour;
Step 4) vacuum pumping the furnace to more than 10 -5 Pa, heating to 500 ℃ at the speed of 20 ℃/h, maintaining for more than 10 hours, then charging CF 4 gas into the vacuum furnace, heating to 950 ℃ at the speed of 20 ℃/h after maintaining for 2 hours, and maintaining at a constant temperature for more than 100 hours, wherein the CF 4 gas is decomposed to generate fluoride ions, so as to compensate F-ion vacancies in magnesium fluoride crystal blanks;
step 5), cooling after the diffusion process is finished, cooling to room temperature at a speed of 10 ℃/h, and taking out magnesium fluoride crystals after residual gas in the furnace is pumped out;
In the step 2), the thickness of a layer of lead fluoride powder placed on the graphite tray is not less than 5mm, and the interval between adjacent magnesium fluoride crystal blanks is not less than 10mm;
The fixture comprises a placing bottom plate, vertical plates are arranged on two corresponding side edges of the placing bottom plate along the length direction, limit protruding portions are arranged on one side edge of the placing bottom plate between the two vertical plates, the surface of the placing bottom plate between the two vertical plates is used for placing magnesium fluoride crystal blanks, spacing blocks are arranged on two sides of the magnesium fluoride crystal blanks and used for providing standard spacing distances, the fixture further comprises two fixing beams and movable beams which are arranged in parallel, two ends of each fixing beam and each movable beam are fixed through connecting plates and form a frame structure, clamping plates are arranged on the fixing beams and the movable beams, and the two clamping plates are matched with the magnesium fluoride crystal blanks.
2. The method for reducing vacancy defects of magnesium fluoride crystals according to claim 1, wherein a temperature measuring device and a heat preservation cylinder are arranged in the vacuum furnace, the vacuum furnace is further connected with a vacuumizing device and an inflating device, and the vacuumizing device is a mechanical pump and a molecular pump.
3. The method for reducing vacancy defects of magnesium fluoride crystals as set forth in claim 1, wherein in the step 1), the directionally cut magnesium fluoride crystals are soaked in alcohol or acetone for more than 1 hour, then rinsed with deionized water, and then dried by blowing, thereby completing the cleaning.
4. The method of reducing magnesium fluoride crystal vacancy defects of claim 1 wherein the amount of CF 4 gas charged is not less than the total volume of the magnesium fluoride crystal blank.
5. The method of reducing magnesium fluoride crystal vacancy defects of claim 1 wherein said graphite trays are a plurality and stacked.
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| RU2421552C1 (en) * | 2009-10-28 | 2011-06-20 | Закрытое акционерное общество "ИНКРОМ" | Method of annealing crystals of group iia metal fluorides |
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| US6773501B2 (en) * | 2001-08-27 | 2004-08-10 | Corning Incorporated | Method of making a <250 nm wavelength optical fluoride crystal and device |
| JP4425185B2 (en) * | 2005-06-21 | 2010-03-03 | 株式会社トクヤマ | Annealing method of metal fluoride single crystal |
| CN109056075B (en) * | 2018-09-20 | 2020-11-24 | 秦皇岛本征晶体科技有限公司 | Annealing device and annealing method for optical crystal |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2421552C1 (en) * | 2009-10-28 | 2011-06-20 | Закрытое акционерное общество "ИНКРОМ" | Method of annealing crystals of group iia metal fluorides |
| CN204174312U (en) * | 2014-09-17 | 2015-02-25 | 蓝思科技股份有限公司 | A kind of sapphire eyeglass annealing furnace fixture and discharge and feed apparatus thereof |
| CN211497727U (en) * | 2019-12-30 | 2020-09-15 | 江苏孚尔姆焊业股份有限公司 | High-frequency online annealing device |
| CN213680979U (en) * | 2020-10-29 | 2021-07-13 | 南京理工宇龙新材料科技股份有限公司 | Ultra-high temperature sapphire crystal bar annealing furnace |
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