JPH01320296A - Production of bi12sio20 single crystal - Google Patents
Production of bi12sio20 single crystalInfo
- Publication number
- JPH01320296A JPH01320296A JP15399988A JP15399988A JPH01320296A JP H01320296 A JPH01320296 A JP H01320296A JP 15399988 A JP15399988 A JP 15399988A JP 15399988 A JP15399988 A JP 15399988A JP H01320296 A JPH01320296 A JP H01320296A
- Authority
- JP
- Japan
- Prior art keywords
- melt
- single crystal
- crystal
- bi12sio20
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000155 melt Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000004857 zone melting Methods 0.000 claims abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 7
- 238000002834 transmittance Methods 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 9
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はＢｊ＋ｚＳｉＯ１゜（以下ＢＳＯと記載する）
単結晶の製造法に関する。 ＢＳＯ単結晶は大きな電気
光学効果を有し、電圧センサー素子や画像記憶素子とし
て有用なものである。[Detailed description of the invention] Industrial application field The present invention is directed to Bj+zSiO1° (hereinafter referred to as BSO)
Concerning a method for producing single crystals. BSO single crystals have a large electro-optical effect and are useful as voltage sensor elements and image storage elements.
従来技術
従来、ＢＳＯ単結晶は結晶組成に近いＢｉｇＯｉ ：
５ｉＯｚ＝ ６ ： １組成融液から回転引上げ法で育
成することにより製造されてきた。Conventional technology Conventionally, BSO single crystal has a crystal composition similar to BigOi:
It has been produced by growing a 5iOz=6:1 composition melt using a rotary pulling method.
しかし、この方法で育成されたＢＳＯ単結晶は、ビスマ
ス成分が過剰に結晶中に取り込まれ、３８０〜５００ｎ
−の波長領域で純粋な化学量論比組成を持ったＢＳＯ単
結晶の理論特性よりもはるかに大きな光吸収を示す、し
かも、光吸収の度合は育成条件を敏感に反映するので、
育成条件が結晶育成時に変動すると、特性値（光透過率
）のバラツキが生ずる。また、結晶中のコア（あるいは
ファセット）と呼ばれる領域とそれ以外の領域では、光
吸収の度合が異なったり、両頭域の境界で歪が生したり
する。このような光学特性の不均一や結晶内歪の存在は
、素子の信頼性や素子製作の歩留まりを悪くする原因と
なっていた。However, in the BSO single crystal grown by this method, the bismuth component is excessively incorporated into the crystal, and
In the wavelength region of
If the growth conditions change during crystal growth, variations in characteristic values (light transmittance) will occur. Furthermore, the degree of light absorption differs between a region called the core (or facet) and other regions in the crystal, and distortion occurs at the boundary between the two head regions. Such non-uniform optical properties and the presence of intracrystalline strain have been a cause of deteriorating device reliability and device manufacturing yield.
発明の目的
本発明は従来法におけるＢＳＯ単結晶の欠点をなくそう
とするもので、その目的は光透過率が純粋なりＳＯ結晶
の理想特性に近く、しかも光学特性が均一で結晶内歪の
ないＢＳＯ単結晶を容易に製造することか可能な方法を
提供しようとするものである。Purpose of the Invention The present invention aims to eliminate the drawbacks of the BSO single crystal in the conventional method.The purpose of the present invention is to provide a material with pure light transmittance close to the ideal characteristics of an SO crystal, with uniform optical characteristics and no intracrystalline strain. The purpose of this invention is to provide a method that allows easy production of BSO single crystals.
発明の構成
本発明者らは前記目的を達成すべ（鋭意研究の結果、融
液から結晶を育成する方法において、その融ｅ組成を、
従来の結晶組成に近い一致溶融組成ではなく、それより
ビスマス成分の少ない（珪素成分の多い）特定範囲の組
成とすると、結晶中に取り込まれる過剰なビスマス成分
が少なくなり、また光学特性が均一で、結晶内量のない
優れたＢＳＯ単結晶を容易に製造し得られることを知見
し得た。この知見に基づいて本発明を完成した。Structure of the Invention The present inventors have achieved the above object (as a result of intensive research, in a method for growing crystals from a melt, the melt e composition is
Rather than a consistent melt composition close to the conventional crystal composition, if the composition is in a specific range with less bismuth (more silicon), the excess bismuth incorporated into the crystal will be reduced, and the optical properties will be more uniform. It has been found that an excellent BSO single crystal with no intracrystalline content can be easily produced and obtained. The present invention was completed based on this knowledge.
本発明の要旨は、融液からＢｌ＋ｇＳｉＯ□。単結晶を
育成する方法において、融液組成を珪素成分過剰なＳｉ
ＯＪ（Ｂｉｇｏｔ ＋Ｓｉりのモル分率＝０．１８〜０
．２８の範囲に保った融液から育成することを特徴とす
るＢ１１１ＳｉＯｔ＊単結晶の製造法にある。The gist of the present invention is to obtain Bl+gSiO□ from the melt. In the method of growing single crystals, the melt composition is changed to Si with excessive silicon content.
OJ (Bigot + Si mole fraction = 0.18~0
．． A method for producing a B111SiOt* single crystal is characterized in that it is grown from a melt maintained within a range of 28%.
前記モル分率が０．１８より小さいと、珪素成分を過剰
にした効果がなく、過剰ビスマス成分が結晶中に取り込
まれる。また、０．２８を趨えると珪素をより含んだ他
の固相が結晶中に析出しやすくなる。When the molar fraction is smaller than 0.18, there is no effect of excess silicon component, and the excess bismuth component is incorporated into the crystal. Further, when the value exceeds 0.28, other solid phases containing more silicon tend to precipitate in the crystal.
従って０．１８〜０．２８の範囲であることが必要であ
る。Therefore, it is necessary that it is in the range of 0.18 to 0.28.
本発明における融液から単結晶を育成する方法としては
、引上げ法２ブリンジマン法、帯溶融法。Methods for growing single crystals from melt in the present invention include pulling method 2Bringeman method and zone melting method.
フローティングゾーン法などいずれの方法でもよい、し
かし、育成結晶の高品質化が達成し易い点から引上げ法
、帯溶融法、フローティングゾーン法が好ましい。Any method such as the floating zone method may be used, but the pulling method, zone melting method, and floating zone method are preferable because it is easy to achieve high quality grown crystals.
本発明に用いる出発原料としては市販の９９．９９％純
度のＢｉＪｓ 、ＳｉＯ□でも良いができるだけ純度の
高い原料を使用するのが好ましい、フローティングゾー
ン法の場合には、それら出発原料粉末をＢｉｇＯｓ
：５ｉＯｔ＝６ ： １ （化学量論比組成）に混合し
、棒状に成形・焼結して原料棒とする。また、溶融帯の
融液組成を珪素成分過剰にするために、珪素成分過剰（
ＳｉＯｚ／ （Ｂｉｇ０３ ＋ ５ｉｆｔ ）モル分率
−〇、１８〜０．２８好ましくは０．２５程度）のペレ
ント状の焼結体（好ましくは溶融帯と同程度の容積を持
つ）を用意し、あらかじめ種結晶上に置き、加熱して融
解させ溶融帯を形成してから育成を始める。Commercially available 99.99% pure BiJs or SiO□ may be used as the starting raw material used in the present invention, but it is preferable to use a raw material with as high purity as possible.In the case of the floating zone method, these starting raw material powders are
:5iOt=6:1 (stoichiometric composition), formed into a rod shape and sintered to obtain a raw material rod. In addition, in order to make the melt composition in the molten zone excessive in silicon content,
A pellet-like sintered body (preferably having a volume comparable to that of the molten zone) of SiOz/ (Big03 + 5ift) molar fraction -〇, 18 to 0.28, preferably about 0.25) is prepared, and It is placed on a seed crystal, heated and melted to form a molten zone, and then growth begins.
本発明における結晶の成長速度は、０．１−１５Ｍ／時
、好ましくは０．５〜４．０ｍ／時である。育成雰囲気
は、酸素、窒素、空気のいずれでも可能である。The crystal growth rate in the present invention is 0.1-15 m/hr, preferably 0.5-4.0 m/hr. The growth atmosphere can be oxygen, nitrogen, or air.
フローティングゾーン法では、アフターヒーターなどを
利用して、成長した結晶の象、冷による割れなどを防ぐ
事が好ましい。さらに、育成した結晶は約７８０〜８２
０°Ｃで焼鈍する事が好ましい。In the floating zone method, it is preferable to use an after-heater or the like to prevent crystal growth and cracking due to cold. Furthermore, the grown crystals were approximately 780 to 82
It is preferable to anneal at 0°C.
実施例
市販の高純度（９９，９９９９％）ＢｉＪｓ とｓｔｏ
ｗ （純度９９．９９％）原料粉末を６：１のモル比で
混合し、１ ｔｏｎ／ｃｍ”の静水圧で棒状にラバープ
レス成形し、８１０°Ｃの酸素中で焼結し原料棒を作成
した。また、溶融帯の組成を珪素成分過剰にするために
、同様のプロセスで５ｉｆｔ／ （ＢｉｚＯｔ ＋Ｓｉ
ｎｇ）モル分率０，２６の組成をもった焼結ペレットを
用意した。次に、原料棒を回転楕円面鏡を用いた集光式
フローティングゾーン法単結晶製造装置に装填し、別に
準備した８５０種結晶を装填し、その種結晶上に焼結ペ
レットを置いた。雰囲気ガスとして窒素ガスを毎分２リ
ツトルの割合で流しながらランプ出力を上げて加熱し、
焼結ペレットを融解したところで原料棒と接合させ、安
定した溶融帯を形成した後、フローティングゾーン法の
常法に従って、結晶育成操作を行った。育成条件は、原
料棒及び種結晶の回転速度が逆方向にそれぞれ４０回／
分、結晶成長速度は３ｍｍ／時であった。得られたＢＳ
Ｏ単結晶を２０時間約８００ ’Ｃで焼鈍し、わずかに
黄色味を帯びた透明な結晶体を得た。Example Commercially available high purity (99,9999%) BiJs and sto
w (Purity 99.99%) Raw material powders were mixed at a molar ratio of 6:1, rubber press molded into a rod shape under a hydrostatic pressure of 1 ton/cm'', and sintered in oxygen at 810°C to form a raw material rod. In addition, in order to make the composition of the molten zone excessive in silicon content, 5ift/(BizOt +Si
ng) Sintered pellets having a composition with a mole fraction of 0.26 were prepared. Next, the raw material rod was loaded into a condensing floating zone method single crystal manufacturing apparatus using a spheroidal mirror, 850 seed crystals prepared separately were loaded, and sintered pellets were placed on the seed crystals. Heat the lamp by increasing the lamp output while flowing nitrogen gas as an atmospheric gas at a rate of 2 liters per minute.
After the sintered pellets were melted and joined to the raw material rod to form a stable molten zone, a crystal growth operation was performed according to the conventional floating zone method. The growth conditions are such that the rotation speed of the raw material rod and the seed crystal is reversed 40 times each.
The crystal growth rate was 3 mm/hour. Obtained BS
The O single crystal was annealed at about 800'C for 20 hours to obtain a transparent crystal with a slight yellow tinge.
得られたＢＳＯ単結晶を光学的に評価したところ、従来
の引上げ法で育成したものよりも、３９０〜〜５００
ｎｍの波長領域で著しく透過率が高くなっている事が判
明した。さらにコア領域とそれ以外の領域での光学特性
の差も、従来のＢＳＯ結晶よりもはるかに減少している
事が認められた。When the obtained BSO single crystal was optically evaluated, it was found that the BSO single crystal had a crystallinity of 390 to 500
It was found that the transmittance was significantly higher in the nm wavelength region. Furthermore, the difference in optical properties between the core region and other regions was also found to be much smaller than in conventional BSO crystals.
発明の効果
本発明の方法によると、高い光透過率を有し、しかも光
学特性の均質で結晶内量のないＢＳＯ単結晶を容易に製
造することができる。Effects of the Invention According to the method of the present invention, a BSO single crystal having high light transmittance, homogeneous optical properties, and no internal crystal content can be easily produced.
ＢＳＯ単結晶の電気光学効果を利用したセンサーや画像
記憶素子を製作する場合に、従来の方法で育成した単結
晶では光学特性不均一や結晶内歪の存在で、信鯨性に問
題があった。しかし、本発明により、より高品位なりＳ
Ｏ単結晶育成が可能となり、優れた特性を有する素子が
容易に得られる。When manufacturing sensors and image storage devices that utilize the electro-optic effect of BSO single crystals, single crystals grown using conventional methods have problems with reliability due to non-uniform optical properties and strain within the crystal. . However, with the present invention, higher quality and S
It becomes possible to grow an O single crystal, and a device with excellent characteristics can be easily obtained.
Claims (1)
する方法において、融液組成を珪素成分過剰なＳｉＯ＿
２／（Ｂｉ＿２Ｏ＿３＋ＳｉＯ＿２）のモル分率＝０．
１８〜０．２８の範囲に保った融液から育成することを
特徴とするＢｉ＿１＿２ＳｉＯ＿２＿０単結晶の製造方
法。 ２）融液から単結晶を育成する方法が、引上げ法、ブリ
ッジマン法、帯溶融法、フローティングゾーン法である
前記１）の製造方法。[Claims] 1) In a method of growing a Bi_1_2SiO_2_0 single crystal from a melt, the composition of the melt is changed to SiO_2_0 with an excessive silicon content.
Molar fraction of 2/(Bi_2O_3+SiO_2)=0.
1. A method for producing a Bi_1_2SiO_2_0 single crystal, characterized in that it is grown from a melt kept in the range of 18 to 0.28. 2) The manufacturing method of 1) above, wherein the method for growing a single crystal from the melt is a pulling method, a Bridgman method, a zone melting method, or a floating zone method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15399988A JPH01320296A (en) | 1988-06-22 | 1988-06-22 | Production of bi12sio20 single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15399988A JPH01320296A (en) | 1988-06-22 | 1988-06-22 | Production of bi12sio20 single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01320296A true JPH01320296A (en) | 1989-12-26 |
| JPH0521878B2 JPH0521878B2 (en) | 1993-03-25 |
Family
ID=15574702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15399988A Granted JPH01320296A (en) | 1988-06-22 | 1988-06-22 | Production of bi12sio20 single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01320296A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351202A (en) * | 2011-07-06 | 2012-02-15 | 陕西科技大学 | Preparation method of bismuth silicate powder |
| CN104562205A (en) * | 2015-01-28 | 2015-04-29 | 中国科学院上海硅酸盐研究所 | Anion-cation co-doped bismuth silicate scintillation crystal and preparation method thereof |
| CN112342622A (en) * | 2020-09-24 | 2021-02-09 | 彩虹集团（邵阳）特种玻璃有限公司 | High-purity single-phase Bi12SiO20Method for producing polycrystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51120693A (en) * | 1975-04-16 | 1976-10-22 | Sumitomo Electric Ind Ltd | Fablication method for photoconductive single-crystal |
| JPS5315299A (en) * | 1976-07-28 | 1978-02-10 | Sumitomo Electric Ind Ltd | Liquid-phase epitaxial growth method of electrooptical crystals |
-
1988
- 1988-06-22 JP JP15399988A patent/JPH01320296A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51120693A (en) * | 1975-04-16 | 1976-10-22 | Sumitomo Electric Ind Ltd | Fablication method for photoconductive single-crystal |
| JPS5315299A (en) * | 1976-07-28 | 1978-02-10 | Sumitomo Electric Ind Ltd | Liquid-phase epitaxial growth method of electrooptical crystals |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351202A (en) * | 2011-07-06 | 2012-02-15 | 陕西科技大学 | Preparation method of bismuth silicate powder |
| CN104562205A (en) * | 2015-01-28 | 2015-04-29 | 中国科学院上海硅酸盐研究所 | Anion-cation co-doped bismuth silicate scintillation crystal and preparation method thereof |
| CN112342622A (en) * | 2020-09-24 | 2021-02-09 | 彩虹集团（邵阳）特种玻璃有限公司 | High-purity single-phase Bi12SiO20Method for producing polycrystal |
| CN112342622B (en) * | 2020-09-24 | 2022-05-17 | 彩虹集团（邵阳）特种玻璃有限公司 | High-purity single-phase Bi12SiO20Method for producing polycrystal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0521878B2 (en) | 1993-03-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |