JPS6369796A - Method for growing li2b4o7 single crystal - Google Patents
Method for growing li2b4o7 single crystalInfo
- Publication number
- JPS6369796A JPS6369796A JP21511786A JP21511786A JPS6369796A JP S6369796 A JPS6369796 A JP S6369796A JP 21511786 A JP21511786 A JP 21511786A JP 21511786 A JP21511786 A JP 21511786A JP S6369796 A JPS6369796 A JP S6369796A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- raw material
- li2b4o7
- pipe
- growing
- 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 41
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000002109 crystal growth method Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 229910011131 Li2B4O7 Inorganic materials 0.000 abstract description 6
- 230000006698 induction Effects 0.000 abstract description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000155 melt Substances 0.000 description 10
- 229910052810 boron oxide Inorganic materials 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 238000010897 surface acoustic wave method Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
「技術分野」
本発明は、例えば弾性表面波素子などの基板に用いられ
るＬ ｊ２Ｂａ０７（四硼酸リチウム）単結晶の育成方
法に関する。DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to a method for growing L j2Ba07 (lithium tetraborate) single crystal used, for example, as a substrate for surface acoustic wave devices.
「従来技術およびその問題点」
Ｌｉ２Ｂ、＋０７単結晶は、結合係数が大きくて水晶と
同じくらい温度特性がよいので、弾性表面波素子などの
基板として用いられている。"Prior Art and its Problems" Li2B, +07 single crystal has a large coupling coefficient and has as good temperature characteristics as quartz, so it is used as a substrate for surface acoustic wave devices and the like.
Ｌｔ２Ｂ４Ｏ７単結晶は、いわゆるチョクラルスキー法
によって製造されている。すなわち、炭酸リチウム（Ｌ
ｉ２ＣＯ３）と、硼−酸（Ｈ３ＢＯ３）または酸化硼素
（Ｈ２０３）とを、リチウムと硼素とのモル比で１＝２
となるように秤量して混合し、これをルツボに入れて加
熱融解し、種結晶を融液に接触させ、回転させながら引
き上げることにより、種結晶（こＬｉＪａ０７％育成さ
せる方法である。The Lt2B4O7 single crystal is manufactured by the so-called Czochralski method. That is, lithium carbonate (L
i2CO3) and boric acid (H3BO3) or boron oxide (H203) at a molar ratio of lithium and boron of 1=2.
This is a method of growing seed crystals (LiJa07%) by weighing and mixing them, putting them in a crucible, heating and melting them, bringing the seed crystals into contact with the melt, and pulling them up while rotating.
これらの反応式は、次の通りである。These reaction formulas are as follows.
ＬｉｚｃＯ＋” ４８３ＢＯ３→ＬＩ２８４Ｏ７”
ＣＯ２↑ ＋ ６日２０Ｌｉ２ＣＯ３” ２８２０
３→Ｌｉ２Ｂ１＋０７” ＣＯ２↑しかしながら、上記
従来のＬｉＪＪ□単結晶の育成力法では、原料を加熱融
解した際に、反応によって発生するＣＯ２が融液中に多
量含有されるため、これをそのまま結晶育成しても、気
泡が結晶中に取込まれ、良質な単結晶を育成することが
できなかった。LizcO+” 483BO3→LI284O7”
CO2↑ + 6 days 20Li2CO3” 2820
3→Li2B1+07" CO2↑However, in the conventional LiJJ□ single crystal growth method described above, when the raw materials are heated and melted, a large amount of CO2 generated by the reaction is contained in the melt, so this cannot be directly used for crystal growth. However, air bubbles were incorporated into the crystal, making it impossible to grow a high-quality single crystal.
また、原料を融解した状態で１２時間以上保持すれば、
融液表面の気泡は消えるが、加熱中にＬｉ２Ｏ・５８２
０３が蒸発し、融液組成がリチウムリッチになってしま
い、良質な結晶は得られない。In addition, if the raw materials are kept in a molten state for more than 12 hours,
Bubbles on the surface of the melt disappear, but during heating Li2O.582
03 evaporates and the melt composition becomes lithium-rich, making it impossible to obtain high-quality crystals.
「発明の目的ｊ
本発明の目的は、気泡のない良質な単結晶を効率よく育
成することかできるようにしたＬｉ２Ｂ、＋０７単結晶
の育成方法を提供することにある。Object of the Invention An object of the present invention is to provide a method for growing a Li2B, +07 single crystal, which enables efficient growth of a high-quality single crystal without bubbles.
「発明の構成」
本発明１こよるＬｉＪ、、０７単結晶の育成方法は、チ
ヨクラルスキー法によりＬｉＪＪ７単結晶を育成する方
法において、炭酸リチウム（Ｌｉ２ＣＯ３）と、硼酸（
Ｈ２ＢＯ３）また（よ酸化硼素（Ｈ２０３）とを混合し
た原料を減圧下において融解した後、減圧を解除して酸
素含有ガスを導入し、その後種結晶を接液し引上げを開
始することを特徴とする。"Structure of the Invention" A method for growing a LiJJ7 single crystal according to the present invention 1 is a method for growing a LiJJ7 single crystal by the Czyochralski method, in which lithium carbonate (Li2CO3) and boric acid (
H2BO3) Also, after melting the raw material mixed with boron oxide (H203) under reduced pressure, the reduced pressure is released and oxygen-containing gas is introduced, after which a seed crystal is brought into contact with the liquid and pulling is started. do.
このよう（こ、減圧下で原料を融解することによ 。In this way, by melting the raw materials under reduced pressure.
す、反応によって発生するＣＯ２が融液中から抜き出さ
れ、気泡の殆どない融液が形成される。その後、酸素含
有ガスを導入して、種結晶の引上げを開始すれば、気泡
の混入のない良質の単結晶を育成することができる。こ
うして得られた単結晶は、弾性表面波素子などの基板材
料として好適なものである。First, the CO2 generated by the reaction is extracted from the melt, forming a melt with almost no bubbles. After that, by introducing an oxygen-containing gas and starting to pull up the seed crystal, it is possible to grow a high-quality single crystal without inclusion of bubbles. The single crystal thus obtained is suitable as a substrate material for surface acoustic wave devices and the like.
本発明の好ましい態様においては、前記酸素含有ガスと
して酸素を用いる。これ１こより、良好な組成の１！２
Ｂ４Ｏ７単結晶を得ることができる。ただし、酸素含有
ガスとしでは、空気なども使用可能である。In a preferred embodiment of the present invention, oxygen is used as the oxygen-containing gas. This one has a better composition than this one!
A B4O7 single crystal can be obtained. However, air can also be used as the oxygen-containing gas.
また、本発明のさらに好ましい態様においでは、原料を
減圧下１こおいて９１７℃以上に加熱して融解し、その
状態で０．５〜５ＦＲ闇保持した後、減圧を解除して酸
素含有ガスを導入する。上記のような条件によって融液
中から気泡を効果的に抜き出すことかできる。Further, in a more preferred embodiment of the present invention, the raw material is heated to 917°C or higher to melt it under reduced pressure, and after maintaining the raw material in the dark for 0.5 to 5 FR, the reduced pressure is released and the oxygen-containing gas is melted. will be introduced. Bubbles can be effectively extracted from the melt under the above conditions.
「発明の実施例」
第１図および第２図には、本発明を実施するための装置
の一例が示されている。"Embodiments of the Invention" FIGS. 1 and 2 show an example of an apparatus for carrying out the present invention.
すなわち、反応管１の外周には、高周波誘導コイル２が
配Ｈされ、内部を高温に加熱するよう１こなっている。That is, a high frequency induction coil 2 is arranged around the outer periphery of the reaction tube 1 to heat the inside to a high temperature.
また、反応管１には、ガス導入管３とガス排出管４とが
連結されている。ざらに、反応管１の下方には支持台５
が配置され、この支持台５上にはルツボ６が設置されて
いる。炭酸リチウム（Ｌｉ２ＣＯ３）と、硼酸（）Ｉ３
ＢＯｓ）または酸化硼素（Ｈ２０３）とからなる原料Ｙ
は、ルツボ６内に入れられるようになっている。そして
、ルツボ６の上方には、引上げ軸８が配置されており、
引上げ軸８は、第２図に示すように、回転しつつ上方に
引上げられるようになっている。さらに、引上げ軸８の
下端には、ＬＩ２８４Ｏ７単結晶からなる種結晶９が取
付けられるようになっている。Furthermore, a gas introduction pipe 3 and a gas discharge pipe 4 are connected to the reaction tube 1 . Roughly speaking, below the reaction tube 1 is a support stand 5.
is arranged, and a crucible 6 is installed on this support stand 5. Lithium carbonate (Li2CO3) and boric acid ()I3
Raw material Y consisting of boron oxide (BOs) or boron oxide (H203)
can be placed inside the crucible 6. A pulling shaft 8 is arranged above the crucible 6.
As shown in FIG. 2, the pulling shaft 8 is adapted to be pulled upward while rotating. Furthermore, a seed crystal 9 made of LI284O7 single crystal is attached to the lower end of the pulling shaft 8.
上記袋Ｍを用いた本発明のＬｉ２Ｂ４Ｏ７単結晶育成方
法を説明すれば、ます原料７をルツボ６に入れて支持台
５上に設置し・、ガス導入管３を閉してガス排出管４か
ら内部のガスを排出し、内部を減圧状態とする。この状
態で、高周波誘導コイル２によって反応管１の内部を高
温に加熱し、原料７を融解させる。原料７が融解した状
態でしばらく保持し、融液中から気泡を抜出す。その後
、ガス排出管４を閉し、ガス導入管３から酸素を導入す
る。この状態で、第２図に示すように、引上げ軸８の種
結晶９を融解した原料７に接触させ、引上げ軸８を回転
させながら徐々に上方に引上げる。To explain the Li2B4O7 single crystal growth method of the present invention using the bag M, the raw material 7 is placed in the crucible 6, placed on the support stand 5, the gas introduction pipe 3 is closed, and the gas is discharged from the gas discharge pipe 4. Exhaust the internal gas and reduce the pressure inside. In this state, the inside of the reaction tube 1 is heated to a high temperature by the high-frequency induction coil 2, and the raw material 7 is melted. The raw material 7 is held in a molten state for a while, and air bubbles are extracted from the melt. Thereafter, the gas exhaust pipe 4 is closed, and oxygen is introduced from the gas introduction pipe 3. In this state, as shown in FIG. 2, the seed crystal 9 of the pulling shaft 8 is brought into contact with the molten raw material 7, and the pulling shaft 8 is gradually pulled upward while rotating.
それによって、融解した原料７は、種結晶９を核として
結晶化し、種結晶９に付着した状態で上方に引上げられ
、Ｌｉ２Ｂ４Ｏ７単結晶が育成される。Thereby, the molten raw material 7 is crystallized using the seed crystal 9 as a core, and is pulled upward while adhering to the seed crystal 9, thereby growing a Li2B4O7 single crystal.
実施例１
炭酸リチウム７３．８９９および酸化硼素１３９．２４
９を秤量し、充分に混合して白金製ルツボに入れる。Example 1 Lithium carbonate 73.899 and boron oxide 139.24
Weigh 9, mix thoroughly and place in a platinum crucible.
これを上記装置の支持台上に設置し、真空ポンプを用い
て装置内を５×１０−２丁ｏｒｒ（こ減圧し、高周波誘
導コイル（こよっで徐々（こ加熱し、原料を融解させる
。このときの温度は９１７°Ｃである。この状態で１時
間保持した後、酸素ガスを内部に導入１］て常圧とする
。そして、種結晶を融液中に接触させ、引上げ軸を回転
させつつ徐々に引上げる。この結果、種結晶を核にして
結晶化し、Ｌｉ２Ｂ４Ｏ７単結晶か育成される。こうし
て得られたＬ１２Ｂａ０７単結晶は、気泡の入らない良
質なものであることが確認された。This is placed on the support stand of the above-mentioned apparatus, and the pressure inside the apparatus is reduced to 5 x 10-2 orr using a vacuum pump, and the raw material is gradually heated using a high-frequency induction coil to melt the raw material. The temperature at this time is 917°C. After maintaining this state for 1 hour, oxygen gas is introduced into the interior to bring it to normal pressure.Then, the seed crystal is brought into contact with the melt, and the pulling shaft is rotated. As a result, the L12Ba07 single crystal thus obtained was confirmed to be of high quality without bubbles. .
実施例２
炭酸リチウム？３．８９（ｌと硼酸２４７．３２９とを
秤量して充分（こ混合した後、実施例１と同様に白金製
ルツボに入れ、同様にしてＬｉ２Ｂｄ０７単結晶を育成
したところ、気泡の入らない良質な単結晶が再現性よく
得られることか確認された。Example 2 Lithium carbonate? Weighed out 3.89 liters of boric acid and 247.329 liters of boric acid. It was confirmed that single crystals can be obtained with good reproducibility.
「発明の効果」
以上説明したように、本発明によれば、減圧下で原料を
融解することにより、反応によって発生するＣ０２が融
液中から抜き出されるので、これを結晶化すること１こ
より、気泡の混入のない良質の単結晶を再現性よく育成
することができる。"Effects of the Invention" As explained above, according to the present invention, by melting the raw material under reduced pressure, the CO2 generated by the reaction is extracted from the melt, so that it is necessary to crystallize it. , high-quality single crystals without air bubbles can be grown with good reproducibility.
第１図および第２図は本発明を実施するための装置の一
例を示す模式図である。
図中、１は反応管、２は高周波誘導コイル、３はガス導
入管、４はガス排出管、５は支持台、６はルツボ、７は
原料、８は引上げ軸、９は種結晶である。FIGS. 1 and 2 are schematic diagrams showing an example of an apparatus for carrying out the present invention. In the figure, 1 is a reaction tube, 2 is a high-frequency induction coil, 3 is a gas introduction tube, 4 is a gas discharge tube, 5 is a support stand, 6 is a crucible, 7 is a raw material, 8 is a pulling shaft, and 9 is a seed crystal. .
Claims (3)
単結晶を育成する方法において、炭酸リチウム（Ｌｉ＿
２ＣＯ＿３）と、硼酸（Ｈ＿３ＢＯ＿３）または酸化硼
素（Ｂ＿２Ｏ＿３）とを混合した原料を減圧下において
融解した後、減圧を解除して酸素含有ガスを導入し、そ
の後種結晶の引上げを開始することを特徴とするＬｉ＿
２Ｂ＿４Ｏ＿７単結晶の育成方法。(1) Li_2B_4O_7 by Czochralski method
In the method of growing single crystals, lithium carbonate (Li_
2CO_3) and boric acid (H_3BO_3) or boron oxide (B_2O_3) is melted under reduced pressure, then the reduced pressure is released, oxygen-containing gas is introduced, and then pulling of the seed crystal is started. Li_
2B_4O_7 single crystal growth method.
スは酸素であるＬｉ＿２Ｂ＿４Ｏ＿７単結晶の育成方法
。(2) The method for growing a Li_2B_4O_7 single crystal according to claim 1, wherein the oxygen-containing gas is oxygen.
記原料を減圧下において９１７℃以上に加熱して融解し
、その状態で０．５〜５時間保持した後、減圧を解除し
て酸素含有ガスを導入するＬｉ＿２Ｂ＿４Ｏ＿７単結晶
の育成方法。(3) In claim 1 or 2, the raw material is heated to 917°C or higher under reduced pressure to melt it, held in that state for 0.5 to 5 hours, and then the reduced pressure is released. A method for growing Li_2B_4O_7 single crystal by introducing oxygen-containing gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21511786A JPS6369796A (en) | 1986-09-12 | 1986-09-12 | Method for growing li2b4o7 single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21511786A JPS6369796A (en) | 1986-09-12 | 1986-09-12 | Method for growing li2b4o7 single crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6369796A true JPS6369796A (en) | 1988-03-29 |
Family
ID=16667027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21511786A Pending JPS6369796A (en) | 1986-09-12 | 1986-09-12 | Method for growing li2b4o7 single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6369796A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013035702A (en) * | 2011-08-04 | 2013-02-21 | Ulvac Japan Ltd | Method of manufacturing lithium borate powder |
| JP2015013775A (en) * | 2013-07-05 | 2015-01-22 | 株式会社豊田中央研究所 | Ion conductive solid, method for producing the same, and solid-state battery |
| CN105624781A (en) * | 2016-01-14 | 2016-06-01 | 福建福晶科技股份有限公司 | Lithium tetraborate crystal preparation method and growth device |
| CN109579524A (en) * | 2018-11-22 | 2019-04-05 | 重庆大学 | A kind of high melt device based on intermediate frequency furnace |
-
1986
- 1986-09-12 JP JP21511786A patent/JPS6369796A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013035702A (en) * | 2011-08-04 | 2013-02-21 | Ulvac Japan Ltd | Method of manufacturing lithium borate powder |
| JP2015013775A (en) * | 2013-07-05 | 2015-01-22 | 株式会社豊田中央研究所 | Ion conductive solid, method for producing the same, and solid-state battery |
| CN105624781A (en) * | 2016-01-14 | 2016-06-01 | 福建福晶科技股份有限公司 | Lithium tetraborate crystal preparation method and growth device |
| CN109579524A (en) * | 2018-11-22 | 2019-04-05 | 重庆大学 | A kind of high melt device based on intermediate frequency furnace |
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