JPS63291898A - Production of bismuth germanate single crystal - Google Patents
Production of bismuth germanate single crystalInfo
- Publication number
- JPS63291898A JPS63291898A JP12889887A JP12889887A JPS63291898A JP S63291898 A JPS63291898 A JP S63291898A JP 12889887 A JP12889887 A JP 12889887A JP 12889887 A JP12889887 A JP 12889887A JP S63291898 A JPS63291898 A JP S63291898A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- melt
- crystal
- bismuth
- earth metal
- 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 62
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 10
- 229940119177 germanium dioxide Drugs 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract 2
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000000155 melt Substances 0.000 abstract description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011800 void material Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 101100336480 Drosophila melanogaster Gem2 gene Proteins 0.000 description 1
- 241000208152 Geranium Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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）
本発明はゲルマニウム酸ビスマス単結晶の製造方法、特
には光学用、γ線シンチレータ用として有用とされる式
Ｂｉ、Ｇｏ、Ｏ，，で示されるゲルマニウム酸ビスマス
単結晶の製造方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing bismuth germanate single crystals, particularly those having the formulas Bi, Go, O, etc., which are useful for optical applications and gamma-ray scintillator applications. The present invention relates to a method for producing bismuth germanate single crystals.
（従来の技術）
式Ｂｉ、Ｇｅ、Ｏ□２で示されるゲルマニウム酸ビスマ
ス単結晶は光学用、γ線シンチレータ用として使用され
ており、このものは酸化ビスマス（Ｂｉ２Ｏ２）、二酸
化ゲルマニウム（Ｇｅｍ２）粉の溶融体からのチョクラ
ルスキー法による単結晶引き上げ法によって製造されて
いる。しかし、このチョクラルスキー法による単結晶育
成法ではその結晶成長過程において成長中の結晶の固液
界面における温度のゆらぎおよび不純物の蓄積による結
晶成長速度のゆらぎが起り、これによって結晶中に取り
込まれる液体が凝固する際に固体と液体との密度差等の
原因によ゛るボイドが帯状に発生し、これが結晶中に取
り込まれるためにこの空隙が光の散乱体となり、得られ
る単結晶体の結晶品質を低下させると共に結晶化歩留り
を低下させるという不利がある。(Prior art) Bismuth germanate single crystals represented by the formulas Bi, Ge, O It is produced by pulling a single crystal from a melt using the Czochralski method. However, in the single crystal growth method using the Czochralski method, fluctuations in temperature at the solid-liquid interface of the growing crystal and fluctuations in the crystal growth rate occur due to the accumulation of impurities during the crystal growth process, which causes impurities to be incorporated into the crystal. When the liquid solidifies, band-shaped voids are generated due to density differences between the solid and the liquid, and as these are incorporated into the crystal, these voids become light scatterers, and the resulting single crystal is It has the disadvantage of reducing crystal quality and crystallization yield.
そのため、このようなボイドの発生を防止する方法も各
種提案されており、これについては例えば引上げ時の種
結晶の回転数を４０〜６０ｒｐｍとして成長結晶の直径
りと結晶の固液界面の凸出高Ｈとの比Ｈ／Ｄを−０，２
〜０．２の範囲となるようにし固液界面の平坦化を画っ
てボイドの発生量を少なくするという方法も知られてい
る（特公昭５８−４９５１７号公報参照）が、これには
直径の大きい長尺の単結晶を成長させることができない
という不利があり、このボイドの発生は完全には解決さ
れていない。Therefore, various methods have been proposed to prevent the occurrence of such voids, such as increasing the diameter of the growing crystal and protruding the solid-liquid interface of the crystal by setting the rotation speed of the seed crystal at 40 to 60 rpm during pulling. The ratio H/D with high H is -0,2
There is also a known method of flattening the solid-liquid interface to reduce the amount of voids within the range of ~0.2 (see Japanese Patent Publication No. 58-49517). It has the disadvantage that it is not possible to grow a long single crystal with a large size, and the occurrence of voids has not been completely solved.
（発明の構成）
本発明はこのような不利を解決したゲルマニウム酸ビス
マス単結晶の製造方法に関するもので、これは酸化ビス
マス（Ｂｉ、Ｏ，）、二酸化ゲルマニウム（Ｇｅｍ２）
の混合溶融液にアルカリ土類金属元素を添加溶融したの
ち、この融液にゲルマニウム酸ビスマス単結晶（Ｂｉ４
Ｇｅ３Ｏ１２）の種結晶を浸し、これを回転させながら
引き上げて単結晶体を得ることを特徴とするものである
。(Structure of the Invention) The present invention relates to a method for producing bismuth germanate single crystals that solves these disadvantages, and this invention relates to a method for producing bismuth germanate single crystals that solves the above disadvantages.
After adding and melting an alkaline earth metal element to the mixed melt, bismuth germanate single crystal (Bi4
This method is characterized by dipping a seed crystal of Ge3O12) and pulling it up while rotating to obtain a single crystal.
すなわち、本発明者らはＢｉ４Ｇｅ３Ｏ１２のチョクラ
ルスキー法による単結晶引上げ時におけるボイドの発生
を防止する方法について種々検討した結果、酸化ビスマ
ス（Ｂｉｚｏａ）、二酸化ゲルマニウム（Ｇ６０．）粉
末を溶融して得られるこれらの混合融体にＣａ、Ｍｇな
どのアルカリ土類金属元素を添加すると単結晶引上げ時
におけるボイドの発生がなくなるので光の透過率が高く
、散乱体も含まない品質のよいゲルマニウム酸ビスマス
（Ｂ ｉ。That is, the present inventors investigated various ways to prevent the generation of voids during pulling of a Bi4Ge3O12 single crystal using the Czochralski method. Adding alkaline earth metal elements such as Ca and Mg to these mixed melts eliminates the generation of voids when pulling a single crystal, resulting in high light transmittance and high quality bismuth germanate containing no scatterers. B i.
Ｇｓ、Ｏ，□）単結晶を得ることができることを見出す
と共に、この単結晶引上げ時に種結晶を１０ｒｐ＋ｗ以
上回転させるとより品質のよい単結晶が得られることを
確認して本発明を完成させた。The present invention was completed by discovering that a single crystal (Gs, O, □) can be obtained and also confirming that a single crystal of better quality can be obtained by rotating the seed crystal by 10 rp+w or more when pulling the single crystal. .
本発明の方法において出発原料とされる酸化ビスマス（
Ｂｉｚｏｉ）、二酸化ゲルマニウム（ＧｅＯ２）はでき
るだけ高純度のものとすることがよく、したがってこれ
らは純度が９９．９９％以上のものとすることが好まし
いが、これらはチョクラルスキー法による単結晶引上げ
のために平均粒径が５０μｍ以下に粉砕した酸化ビスマ
ス（Ｂｉｚｏ３）と二酸化ゲルマニウム（ＧｅＯ□）と
を当量宛混合してから１，０６５℃以上に加熱して混合
融液とすればよい。Bismuth oxide (
Geranium dioxide (GeO2) should be as pure as possible, and therefore preferably have a purity of 99.99% or higher; For this purpose, equal amounts of bismuth oxide (Bizo3) and germanium dioxide (GeO□) pulverized to an average particle size of 50 μm or less may be mixed and then heated to 1,065° C. or higher to form a mixed melt.
また、この混合融液からＢ１４Ｇｅ、ＯＬ□の単結晶を
引上げるために使用される種結晶は従来法で得られたＢ
ｉ、Ｇｅ３０□２の単結晶から切り出した５ ｍ Ｘ
５ ｍ程度のものとすればよい。In addition, the seed crystal used to pull the B14Ge, OL□ single crystal from this mixed melt was a B
i, 5 m x cut from a single crystal of Ge30□2
It should be about 5 m long.
本発明の方法は上記のようにして作られた酸化ビスマス
（Ｂｉ、Ｏ，）、二酸化ゲルマニウム（Ｇｅｍ２）の混
合融液にこの種結晶を浸漬し、チョクラルスキー法で単
結晶を引上げるのであるが、本発明の方法ではこの引上
げに先立ってこの混合融液にアルカリ土類金属元素が添
加溶融される。このアルカリ土類金属元素としてはＣａ
、Ｍｇ、Ｂａ、Ｓｒなどが例示されるが、このアルカリ
土類金属元素を酸化ビスマス（Ｂｉ、０３）、二酸化ゲ
ルマニウム（Ｇｅｍ、）の混合融液に添加するとこの融
液が凝固する際の固液界面におけるボイドの発生がなく
なるので、目的とするＢｉ４Ｇｅ３Ｏ１２の単結晶中に
空隙が入り込むことがなくなって単結晶の品質が低下し
たり、この結晶化歩留りが低下するということがなくな
るのであるが、このアルカリ土類金属元素の添加量は酸
化ビスマス（Ｂｘｚｏａ）、二酸化ゲルマニウム（Ｇｅ
Ｏ□）の混合融液に対して５ｐｐｍ以下では添加の効果
がなく、光の散乱体が発生し、１１００ｐｐ以上では、
得られた単結晶が着色し、その透過率が悪くなり、結晶
品質が劣化するので５ ｐｐｍ−１００ｐｐの範囲とす
ることが必要とされるが、この好ましい範囲は１０〜５
０ｐｐｍとされる。In the method of the present invention, the seed crystal is immersed in the mixed melt of bismuth oxide (Bi, O,) and germanium dioxide (Gem2) prepared as described above, and the single crystal is pulled using the Czochralski method. However, in the method of the present invention, an alkaline earth metal element is added and melted to this mixed melt prior to this pulling. This alkaline earth metal element is Ca
, Mg, Ba, Sr, etc., but when this alkaline earth metal element is added to a mixed melt of bismuth oxide (Bi, 03) and germanium dioxide (Gem), it will increase the solidity when this melt solidifies. Since the generation of voids at the liquid interface is eliminated, no voids will enter the target Bi4Ge3O12 single crystal, which will prevent the quality of the single crystal from deteriorating and the crystallization yield from decreasing. The amount of this alkaline earth metal element added is bismuth oxide (Bxzoa), germanium dioxide (Ge
If the amount is less than 5 ppm to the mixed melt of O
Since the obtained single crystal becomes colored, its transmittance becomes poor, and the crystal quality deteriorates, it is necessary to set it in the range of 5 ppm to 100 ppm, but this preferable range is 10 to 5 ppm.
It is assumed to be 0 ppm.
なお、この混合融液からの単結晶引上げに当っては二＼
に浸漬された種結晶の引上げ時にこの種結晶は少なくと
も１０ｒｐｍ以上で回転させることがよく、これによれ
ば上記したボイドの発生をより少なくすることができる
ので、得られる単結晶をより高品質のものとすることが
できる。In addition, when pulling a single crystal from this mixed melt, two
When pulling a seed crystal immersed in water, the seed crystal is preferably rotated at a speed of at least 10 rpm or higher. This can further reduce the occurrence of the above-mentioned voids, and the resulting single crystal can be of higher quality. can be taken as a thing.
つぎに本発明の実施例をあげるが１例中の部は重量部を
示したものであり、例中における単結晶の物性測定法は
つぎの方法による測定値を示したものである。Next, examples of the present invention will be given, and parts in each example indicate parts by weight, and the physical properties of the single crystal in the examples were measured by the following method.
（光透過率） ダブルビームニ光束分光光度計により測定する。(light transmittance) Measured using a double beam dual beam spectrophotometer.
（散乱体） 目視観測による。(Scatterer) Based on visual observation.
実施例、比較例
平均粒径が５０．ｍである純度９９．９９９％の酸化ビ
スマス（Ｂｉ２０３）１３．０ｋｇと二酸化ゲルマニウ
ム（ＧｅＯ，）４．３ｋｇとを直径１５０ｍ、深さ１５
０ｍの白金るつぼに装入し、高周波誘導加熱を用いて１
，０７０℃に加熱して溶融させたのち、この混合融液に
アルカリ士金属元素としてのＣａをＣａ ＣＯ，として
０．８７ｇ添加して溶融させた。Examples and Comparative Examples Average particle size is 50. 13.0 kg of bismuth oxide (Bi203) with a purity of 99.999% and 4.3 kg of germanium dioxide (GeO) were placed in a container with a diameter of 150 m and a depth of 15 m.
It was charged into a platinum crucible with a diameter of 0 m and heated to 1.
After heating to 070° C. and melting, 0.87 g of Ca as an alkali metal element (Ca 2 CO) was added to this mixed melt and melted.
ついでこの混合融液に５ ｍ Ｘ ５■のＢｉ、Ｇｅ。Next, add 5 m x 5 cm of Bi and Ge to this mixed melt.
ｏｉ２の種結晶を浸漬し、２０ｒｐｍで回転させながら
３ＩＩｌｌ／時の速度で引上げてＢ ｉ ４ Ｇ ８３
０１２の単結晶棒を引き上げたところ、この単結晶は第
１表に示したとおりの物性を示したが、比較のために上
記においてＣａＣ０，を添加せずに上記と同様に処理し
て得た単結晶の物性は第１表に併記したとおりのもので
あった。A seed crystal of oi2 was immersed and pulled up at a speed of 3 IIll/hour while rotating at 20 rpm to obtain B i 4 G 83.
When a single crystal rod of 012 was pulled up, this single crystal showed the physical properties as shown in Table 1, but for comparison, it was obtained by processing in the same manner as above without adding CaCO. The physical properties of the single crystal were as listed in Table 1.
また、ダブルビームニ光束分光光度計による光透過率の
結果を第１図に示す。Further, FIG. 1 shows the results of light transmittance measured by a double beam dual beam spectrophotometer.
第 １ 表Table 1
第１図は実施例において得られたゲルマニウム酸ビスマ
ス単結晶の光透過率を示したグラフである。FIG. 1 is a graph showing the light transmittance of bismuth germanate single crystals obtained in Examples.
Claims (1)
アルカリ土類金属元素を添加溶融したのち、この融液に
ゲルマニウム酸ビスマス単結晶（Ｂｉ＿４Ｇｅ＿３Ｏ＿
１＿２）の種結晶を浸し、これを回転させながら引き上
げて単結晶を得ることを特徴とするゲルマニウム酸ビス
マス単結晶の製造方法 ２、アルカリ土類金属元素がＭｇ、Ｃａ、Ｂａ、Ｓｒか
ら選択されたものである特許請求の範囲第１項記載のゲ
ルマニウム酸ビスマス単結晶の製造方法。 ３、アルカリ土類金属元素の添加量が酸化ビスマス・二
酸化ゲルマニウム量に対し５〜１００ｐｐｍとされる特
許請求の範囲第１項記載のゲルマニウム酸ビスマス単結
晶の製造方法。 ４、種結晶が引き上げ時１０ｒｐｍ以上に回転される特
許請求の範囲第１項記載のゲルマニウム酸ビスマス単結
晶の製造方法。[Claims] 1. After adding and melting an alkaline earth metal element to a mixed solution of bismuth oxide and germanium dioxide, bismuth germanate single crystal (Bi_4Ge_3O_
1_2) Manufacturing method of bismuth germanate single crystal characterized by dipping the seed crystal and pulling it while rotating to obtain a single crystal 2, the alkaline earth metal element is selected from Mg, Ca, Ba, and Sr; A method for producing a bismuth germanate single crystal according to claim 1. 3. The method for producing a bismuth germanate single crystal according to claim 1, wherein the amount of the alkaline earth metal element added is 5 to 100 ppm based on the amount of bismuth oxide and germanium dioxide. 4. The method for producing a bismuth germanate single crystal according to claim 1, wherein the seed crystal is rotated at 10 rpm or more during pulling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12889887A JPS63291898A (en) | 1987-05-26 | 1987-05-26 | Production of bismuth germanate single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12889887A JPS63291898A (en) | 1987-05-26 | 1987-05-26 | Production of bismuth germanate single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63291898A true JPS63291898A (en) | 1988-11-29 |
| JPH0367997B2 JPH0367997B2 (en) | 1991-10-24 |
Family
ID=14996080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12889887A Granted JPS63291898A (en) | 1987-05-26 | 1987-05-26 | Production of bismuth germanate single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63291898A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436958A (en) * | 2013-08-29 | 2013-12-11 | 陕西师范大学 | Preparation method of bismuth nanocrystalline |
-
1987
- 1987-05-26 JP JP12889887A patent/JPS63291898A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436958A (en) * | 2013-08-29 | 2013-12-11 | 陕西师范大学 | Preparation method of bismuth nanocrystalline |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0367997B2 (en) | 1991-10-24 |
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