JPH01115897A - Production of magnesium fluoride single crystal - Google Patents
Production of magnesium fluoride single crystalInfo
- Publication number
- JPH01115897A JPH01115897A JP27331187A JP27331187A JPH01115897A JP H01115897 A JPH01115897 A JP H01115897A JP 27331187 A JP27331187 A JP 27331187A JP 27331187 A JP27331187 A JP 27331187A JP H01115897 A JPH01115897 A JP H01115897A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- raw material
- crucible
- purity
- magnesium fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 25
- 229910001635 magnesium fluoride Inorganic materials 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 title claims description 9
- 239000010453 quartz Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003708 ampul Substances 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005162 X-ray Laue diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
見匪二致亙分互
本発明は、フッ化マグネシウム（以下ＭｇＦ２と記す、
）単結晶の製造方法に関するものである。[Detailed Description of the Invention] The present invention relates to magnesium fluoride (hereinafter referred to as MgF2),
) This relates to a method for producing a single crystal.
来 とその−占
ＭｇＦ、は波長０．１μｍの真空紫外領域から波長７．
５μ慣の赤外領域にかけての光線の透過性能が良好なた
め、レーザー用の窓材、及びレンズのコーティング材、
赤外線機器用窓材等に使用される。特に、レーザー用の
光学部品として、最近のレーザーの出力増大に伴い、そ
の高品質化、高純度化が要求されてきつつある。This and its MgF range from the vacuum ultraviolet region with a wavelength of 0.1 μm to 7.5 μm.
Due to its good transmission performance for light in the 5μ infrared region, it is used as a window material for lasers, a coating material for lenses,
Used for window materials for infrared equipment, etc. In particular, as optical parts for lasers, higher quality and higher purity are being required as the output of lasers increases recently.
光学部品用ＭｇＦ、の製造方法としては、原料粉末をホ
ットプレス等により高密度化して多結晶体を得る方法と
、ブリッジマン法等により融液がら結晶を成長させ単結
晶を得る方法がある。Methods for producing MgF for optical components include a method in which a raw material powder is densified by hot pressing or the like to obtain a polycrystalline body, and a method in which a crystal is grown from a melt by the Bridgman method or the like to obtain a single crystal.
多結晶のものは、大型寸法が要求される分野でよく使用
されるが、単結晶に比べて紫外領域での光透過性が著し
く劣り、また可視から赤外にかけての領域でも約ｌＯχ
光透過率が低い。Polycrystalline materials are often used in fields where large dimensions are required, but compared to single crystals, their optical transparency in the ultraviolet region is significantly inferior, and even in the visible to infrared region, their optical transparency is approximately 1Oχ
Light transmittance is low.
単結晶のものは、光学的に高度な品質が要求される分野
で使用されるが、原料として光学用純度（３Ｎ）のもの
を用いる場合でも真空昇華法や乾燥ＨＦ気流中での加熱
処理等により精製してから単結晶化させないと光散乱の
少ない良質の単結晶が得られない。以上の問題点を解決
すべく鋭意検討した結果、本発明者等は以下の発明をな
した。Single crystals are used in fields that require high optical quality, but even when using optically pure (3N) materials as raw materials, they cannot be processed using vacuum sublimation, heat treatment in a dry HF stream, etc. A high-quality single crystal with low light scattering cannot be obtained unless it is purified and then single crystallized. As a result of intensive studies to solve the above problems, the present inventors have made the following invention.
見１度１弐
本発明は、融点付近の温度勾配が大きいたて型ゾーンリ
ファイニングで処理を繰り返すことを特徴とする高純度
フッ化マグネシウム単結晶の製造方法に関する。又、上
記発明の実施態様として、以下の発明を提供する。The present invention relates to a method for producing a high-purity magnesium fluoride single crystal, which is characterized by repeating the process in a vertical zone refining process with a large temperature gradient near the melting point. Furthermore, the following invention is provided as an embodiment of the above invention.
融帯移動速度が１０ｍｍ／ｈ以下であることを特徴とす
る前記高純度フッ化マグネシウム単結晶の製造方法、融
点付近の温度勾配が１８℃／ｃｆｆｉ以上であることを
特徴とする前記高純度フッ化マグネシウム単結晶の製造
方法及び原料をグラッシーカーボン製るつぼに充填し、
これを石英管に高純度アルゴン雰囲気にて封入すること
を特徴とする前記高純度フッ化マグネシウム単結晶の製
造方法である。The method for producing the high-purity magnesium fluoride single crystal, characterized in that the melting zone movement speed is 10 mm/h or less; Method for manufacturing magnesium chloride single crystal and filling raw materials into a glassy carbon crucible,
The method for producing the high-purity magnesium fluoride single crystal is characterized in that it is sealed in a quartz tube in a high-purity argon atmosphere.
発１！υＵ幻寛履朋− 以下１本発明の内容を詳細に述べる。Release 1! υU Genkanariho- The contents of the present invention will be described in detail below.
原料ＭｇＦ、は純度４Ｎ級以上であり粉末でも塊でも良
い。これを表面がガラス状で緻密なグラッシーカーボン
製るつぼに充填することが好ましい。るつぼは、一般の
黒鉛製るつぼを使用すると、炭素が混入してくるため良
質の結晶が得られない。また、石英管に直接入れると、
石英とＭｇＦ、が反応してしまう、原料を充填したるつ
ぼは、外部からの不純物の混入を避けるために高純度ア
ルゴン雰囲気で第１図のごとく石英管に封入する。グラ
ッシーカーボン製るつぼが直接石英管に接触して反応す
るのを防ぐために黒鉛性キャップを使用する。The raw material MgF has a purity of 4N class or higher and may be in the form of powder or lump. It is preferable to fill this into a crucible made of glassy carbon whose surface is glassy and dense. If a normal graphite crucible is used, it will not be possible to obtain high-quality crystals because carbon will be mixed in. Also, if you put it directly into a quartz tube,
The crucible filled with raw materials, in which quartz and MgF react, is sealed in a quartz tube in a high-purity argon atmosphere as shown in Figure 1 to avoid contamination with external impurities. A graphite cap is used to prevent the glassy carbon crucible from directly contacting and reacting with the quartz tube.
石英管は、ＭｇＦ、の融点（１２５５℃）付近では軟化
するため、内部の気圧が高温時に大気圧と平衡になるよ
うに設定し、石英管が変形するのを防いである。Since the quartz tube softens near the melting point of MgF (1255° C.), the internal pressure is set to be in equilibrium with the atmospheric pressure at high temperatures to prevent the quartz tube from deforming.
例えば第１図に示した石英管を加熱炉に投入する。加熱
炉は縦型が用いられる。通常のゾーンリファイニングと
異なりたて型でありブリッジマン法とごとく全体を溶融
しないがブリッジマン法に似た結晶成長が起こり、単結
晶化が促進されるからである。このような加熱炉を使っ
てゾーンリファイニング処理を繰り返した。炉内温度分
布の一例を第３図に示す。ゾーンリファイニングを開始
する前に一定のスピード例えば１００〜３００ｍｍ／ｈ
でるつぼを降下させ原料ＭｇＦｔを融解させ円柱状に固
める。ゾーンリファイニング開始時には、るつぼの先端
は第２図のごとくヒーターの中央に位置している。炉内
温度が１２５０〜１３５０”Ｃの所定の値に達した後、
１０ｍｍ八以下へ速度で石英管を原料充填量に応じて適
切な時間下降させる。下降が終了した後、炉内を常温ま
で冷却してからるつぼを引き上げ再びゾーンリファイニ
ングを行う、ゾーンリファイニングを４回以上繰り返し
た後、インゴットを取り出す。回数が多いほど純度も高
くなり単結晶化の率が高まるからである。このように原
料をるつぼ内に仕込んでから取り出すまで、外部からの
不純物の混入をまったく受けること無く精製することが
できる。得られたＭｇＦ、インゴットの精製部は無色透
明であり、Ｈｅ−Ｎｅレーザービーム（波長６３２゜８
ｒｖ＋、出力１ｍｍＷ、ビーム径０．８ｍｍ）をあてて
も散乱がまったく無いため、結晶内では、光線の光路が
見えなくなった。ＭｇＦ、インゴットの精製部をカット
、研磨し、板材に加工され、高出力レーザー用等の光学
部品に用いられる。For example, the quartz tube shown in FIG. 1 is placed in a heating furnace. A vertical heating furnace is used. This is because, unlike normal zone refining, it is vertical and does not melt the entire body like the Bridgman method, but crystal growth similar to the Bridgman method occurs and single crystallization is promoted. The zone refining process was repeated using such a heating furnace. An example of the temperature distribution in the furnace is shown in Fig. 3. A certain speed e.g. 100-300 mm/h before starting zone refining
The crucible is lowered and the raw material MgFt is melted and solidified into a cylindrical shape. At the start of zone refining, the tip of the crucible is located at the center of the heater as shown in FIG. After the furnace temperature reaches a predetermined value of 1250-1350"C,
The quartz tube is lowered at a speed of 10 mm or less for an appropriate time depending on the amount of raw material filled. After the descent is completed, the inside of the furnace is cooled to room temperature, the crucible is pulled up, and zone refining is performed again. After zone refining is repeated four or more times, the ingot is taken out. This is because the greater the number of times, the higher the purity and the higher the rate of single crystallization. In this way, from the time the raw material is charged into the crucible to the time it is taken out, it can be purified without being contaminated by any impurities from the outside. The purified part of the obtained MgF ingot was colorless and transparent, and was heated with a He-Ne laser beam (wavelength 632°8).
rv+, output 1 mmW, beam diameter 0.8 mm), there was no scattering at all, so the optical path of the light ray could not be seen inside the crystal. The refined part of the MgF ingot is cut and polished, processed into a plate material, and used for optical parts for high-power lasers and the like.
失凰五
４Ｎ ＭｇＦ、、粒子（粒径８−６ ｍｅｓｈ） ３６
４ｇを第１図のごとく石英管に封入し、第３図の温度分
布を持つ抵抗加熱炉（第２図）中を２００ｍｎ＋／ｈで
２時間半降下させ、原料を融解、固化させた。炉内を常
温まで冷却した後、石英管を引き上げ、再び炉内温度が
第３図の温度分布を持つまで昇温してから、１０ｍｍ／
ｈで３０時間降下させゾーンリファイニングを行った。Loss 4N MgF, particles (particle size 8-6 mesh) 36
4 g was sealed in a quartz tube as shown in Fig. 1, and lowered at 200 m+/h for 2 and a half hours in a resistance heating furnace (Fig. 2) having the temperature distribution shown in Fig. 3 to melt and solidify the raw material. After cooling the inside of the furnace to room temperature, pull up the quartz tube, raise the temperature in the furnace again until it has the temperature distribution shown in Figure 3, and then
Zone refining was performed by lowering the sample at h for 30 hours.
ゾーンリファイニングは５回繰り返した。得られたイン
ゴットは、直径２４．５ｍｎ＋、長さ２４０＋ｕ＋で、
Ｈｅ−Ｎｅ ル−ザーピームをまったく散乱させ
ないほどに精製された部分の長さは１００ａ＋ｍであっ
た。精製部をカット、研磨し、直径２４．５＋ａｍ、厚
さ５ｆｆＩＩ１１の板材に加工した。この板材の結晶性
を背面反射ラウェ法により観察したところ、第４図のと
とくラウェ斑点が規則性を持って検出されており、単結
晶であることが確認された。また、紫外領域から赤外領
域にかけての光吸収係数を測定したところ、第５図に示
すごとく、市販品に比べ小さい値が得られ、光透過性が
優れていることが判明した。Zone refining was repeated five times. The obtained ingot had a diameter of 24.5 mm+ and a length of 240+ u+.
The length of the portion purified to the extent that He-Ne loser beam was not scattered at all was 100 a+m. The refined portion was cut, polished, and processed into a plate material with a diameter of 24.5+am and a thickness of 5ffII11. When the crystallinity of this plate material was observed by the back-reflection Lawe method, Lawe spots shown in FIG. 4 were detected with regularity, and it was confirmed that it was a single crystal. Furthermore, when the light absorption coefficient from the ultraviolet region to the infrared region was measured, as shown in FIG. 5, a value smaller than that of the commercially available product was obtained, and it was found that the light transmittance was excellent.
見匪五羞困
（１）市販品に比べ本発明品は、紫外領域から赤外領域
にかけての光吸収係数が小さい値を示し、光透過性が優
れている。(1) Compared to commercially available products, the product of the present invention exhibits a smaller light absorption coefficient from the ultraviolet region to the infrared region, and has excellent light transmittance.
（２）紫外領域から赤外領域にかけての光透過性が極め
て良好で、高出力レーザー用光学部品として使用できる
ＭｇＦ２単結晶が得られた。(2) An MgF2 single crystal with extremely good light transmittance from the ultraviolet region to the infrared region and usable as an optical component for high-power lasers was obtained.
（３）原料ＭｇＦ、の精製と同時に単結晶化を行うこと
ができ、製造工程を短縮できる。(3) Single crystallization can be performed simultaneously with the purification of raw material MgF, and the manufacturing process can be shortened.
（４）任意の直径を持・った定径の単結晶ＭｇＦ２イン
ゴットを容易に製造することができる。(4) A fixed-diameter single-crystal MgF2 ingot having an arbitrary diameter can be easily produced.
第１図は石英管層のアンプルであり、第２図は引下炉の
内部構造である。第３図は炉内の温度分布であり、第４
図は本発明製品の結晶構造を示す背面反射ラウェ図形の
図面代用写真であり、第５図は吸収係数を示す。FIG. 1 shows an ampoule with a quartz tube layer, and FIG. 2 shows the internal structure of a drawing furnace. Figure 3 shows the temperature distribution inside the furnace, and Figure 4 shows the temperature distribution inside the furnace.
The figure is a photograph substituted for a drawing of a back reflection Laue pattern showing the crystal structure of the product of the present invention, and FIG. 5 shows the absorption coefficient.
Claims (4)
イニングで処理を繰り返すことを特徴とする高純度フッ
化マグネシウム単結晶の製造方法。(1) A method for producing a high-purity magnesium fluoride single crystal, which is characterized by repeating the process by vertical zone refining with a large temperature gradient near the melting point.
徴とする特許請求の範囲第（１）項記載の高純度フッ化
マグネシウム単結晶の製造方法。(2) The method for producing a high-purity magnesium fluoride single crystal according to claim (1), characterized in that the fusion zone movement speed is 10 mm/h or less.
とを特徴とする特許請求の範囲第（１）項記載の高純度
フッ化マグネシウム単結晶の製造方法。(3) The method for producing a high-purity magnesium fluoride single crystal according to claim (1), wherein the temperature gradient near the melting point is 18° C./cm or more.
れを石英管に高純度アルゴン雰囲気にて封入することを
特徴とする特許請求の範囲第（１）項記載の高純度フッ
化マグネシウム単結晶の製造方法。(4) A high-purity magnesium fluoride single crystal according to claim (1), characterized in that the raw material is filled in a glassy carbon crucible and sealed in a quartz tube in a high-purity argon atmosphere. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27331187A JPH01115897A (en) | 1987-10-30 | 1987-10-30 | Production of magnesium fluoride single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27331187A JPH01115897A (en) | 1987-10-30 | 1987-10-30 | Production of magnesium fluoride single crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01115897A true JPH01115897A (en) | 1989-05-09 |
Family
ID=17526106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27331187A Pending JPH01115897A (en) | 1987-10-30 | 1987-10-30 | Production of magnesium fluoride single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01115897A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003078345A1 (en) * | 2002-03-18 | 2003-09-25 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Metal fluoride in powder or granular form, method for the production thereof and determination of purity |
| WO2003079062A1 (en) * | 2002-03-18 | 2003-09-25 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Optical element, method for the production thereof and for determining its optical properties |
| EP1449013A4 (en) * | 2001-03-02 | 2006-09-20 | Corning Inc | Method of making high repetition rate excimer laser crystal optics and uv-200nm transmitting optical floride crystal |
-
1987
- 1987-10-30 JP JP27331187A patent/JPH01115897A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1449013A4 (en) * | 2001-03-02 | 2006-09-20 | Corning Inc | Method of making high repetition rate excimer laser crystal optics and uv-200nm transmitting optical floride crystal |
| WO2003078345A1 (en) * | 2002-03-18 | 2003-09-25 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Metal fluoride in powder or granular form, method for the production thereof and determination of purity |
| WO2003079062A1 (en) * | 2002-03-18 | 2003-09-25 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Optical element, method for the production thereof and for determining its optical properties |
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