JPS63274694A - Production of titanium sapphire single crystal having high quality - Google Patents
Production of titanium sapphire single crystal having high qualityInfo
- Publication number
- JPS63274694A JPS63274694A JP10952287A JP10952287A JPS63274694A JP S63274694 A JPS63274694 A JP S63274694A JP 10952287 A JP10952287 A JP 10952287A JP 10952287 A JP10952287 A JP 10952287A JP S63274694 A JPS63274694 A JP S63274694A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- partial pressure
- crystal
- oxygen partial
- titanium sapphire
- 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 45
- 239000010936 titanium Substances 0.000 title claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 21
- 239000010980 sapphire Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims abstract description 14
- -1 titanium ions Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 230000003071 parasitic effect Effects 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-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
本発明はレーザ発振波長域での光吸収が格段に低い波長
可変レーザ用として有効な高品質チタンサファイヤ単結
晶の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a high quality titanium sapphire single crystal that is effective for use in a wavelength tunable laser and has extremely low light absorption in the laser oscillation wavelength range.
本発明におけるチタンサファイヤ単結晶とは、少量の三
二酸化チタン（ＴｉｚＯｓ）を含む酸化アルミニウム（
八１ｔＯｘ）の単結晶である。チタンサファイヤ単結晶
は広い波長可変域を持つ波長可変レーザ用結晶として注
目を集めている素材である。The titanium sapphire single crystal in the present invention refers to aluminum oxide (aluminum oxide) containing a small amount of titanium sesquioxide (TizOs).
It is a single crystal of 81tOx). Titanium sapphire single crystal is a material that is attracting attention as a crystal for wavelength tunable lasers with a wide wavelength tuning range.
従来技術
従来、チタンサファイヤ単結晶は熱交換法、温度勾配徐
冷法、引上げ法、フローティングゾーン法により製造さ
れている。雰囲気はチタンイオンの価数が通常の酸化雰
囲気中では４価であることから、これを３価にする目的
で、還元性のものを用いている。しかし、得られた結晶
には、最も効率良くレーザ発振が起こる７００〜９００
ｎ−の波長域を覆う幅広い吸収帯がある。特に高効率発
振を期待して高濃度のチタン導入を行った結晶ではこの
吸収帯が顕著に現れる。この吸収帯は寄生吸収帯と呼ば
れ、その発生原因は明らかになっていなく、これを防止
する方法は知られていない。Prior Art Conventionally, titanium sapphire single crystals have been produced by a heat exchange method, a temperature gradient slow cooling method, a pulling method, and a floating zone method. Since the valence of titanium ions is 4 in a normal oxidizing atmosphere, a reducing atmosphere is used for the purpose of making titanium ions trivalent. However, the obtained crystal has a 700 to 900
There is a broad absorption band covering the n- wavelength range. In particular, this absorption band appears prominently in crystals into which a high concentration of titanium has been introduced in hopes of achieving high efficiency oscillation. This absorption band is called a parasitic absorption band, and the cause of its occurrence is not clear, and there is no known method to prevent it.
発明の目的
本発明の目的は寄生吸収帯の発生のないチタンサファイ
ヤ単結晶の製造方法を提供するにある。OBJECTS OF THE INVENTION An object of the present invention is to provide a method for producing a titanium sapphire single crystal without the generation of parasitic absorption bands.
発明の構成
本発明者はこの寄生吸収帯の発生原因について、数多く
の実験的検討を加えた結果、寄生吸収帯は３価のチタン
イオン、２価のチタンイオン及び空の酸素イオン格子の
３者が結晶中で集合体を作るため、あるいはこの集合体
に類似したものより結晶欠陥が生ずることにより起こる
ことを知見し得た。Structure of the Invention As a result of numerous experimental investigations into the causes of the occurrence of this parasitic absorption band, the present inventor found that the parasitic absorption band consists of three types: trivalent titanium ions, divalent titanium ions, and empty oxygen ion lattices. We found that this occurs due to the formation of aggregates in the crystal, or due to the generation of crystal defects that are similar to these aggregates.
このような集合体を除去するには、７ ｔ Ｚ＋を除去
することが効果的である。そのためには雰囲気の酸素分
圧を高くすればよいが、酸素分圧を高くし過ぎると二酸
化チタンの析出を誘発し、散乱による光損失を増加させ
るので好ましくない、また二酸化チタンの析出が起こる
程酸素分圧が高くなくとも、Ｔｉ”が生じて寄生吸収帯
に似た光吸収が現れ光損失を増加する。従って雰囲気条
件には適切な範囲がある。酸素分圧と光吸収係数との関
係を示すと第１図の通りである。このように、酸素分圧
を調整して単結晶中に３価以外のチタンイオンが残存し
ないようにすればよいことが分かった。To remove such aggregates, it is effective to remove 7 t Z+. To achieve this, it is possible to increase the oxygen partial pressure in the atmosphere, but if the oxygen partial pressure is too high, it induces the precipitation of titanium dioxide and increases light loss due to scattering, which is undesirable. Even if the oxygen partial pressure is not high, Ti'' is generated and optical absorption similar to a parasitic absorption band appears, increasing optical loss.Therefore, there is an appropriate range of atmospheric conditions.Relationship between oxygen partial pressure and optical absorption coefficient is shown in Fig. 1. In this way, it has been found that the oxygen partial pressure can be adjusted to prevent titanium ions other than trivalent from remaining in the single crystal.
この知見に基づいて本発明を完成した。The present invention was completed based on this knowledge.
本発明の要旨は、
チタンサファイヤ単結晶の成長およびまたは成長後の焼
鈍に際して、雰囲気中の酸素分圧を調整して単結晶中に
３価以外のチタンイオンが無視できる程度まで少なくな
るように、単結晶中のチタンイオンの価数制御を行うこ
とを特徴とする高品質チタンサファイヤ単結晶の製造方
法にある。The gist of the present invention is to adjust the oxygen partial pressure in the atmosphere during the growth and/or post-growth annealing of a titanium sapphire single crystal so that the amount of titanium ions other than trivalent in the single crystal is reduced to a negligible level. The present invention provides a method for producing a high-quality titanium sapphire single crystal, which is characterized by controlling the valence of titanium ions in the single crystal.
本発明における酸素分圧とは雰囲気中の酸素の量を圧力
の単位で表わしたものである。The oxygen partial pressure in the present invention is the amount of oxygen in the atmosphere expressed in units of pressure.
具体的な焼鈍における雰囲気条件としては、前記したよ
うにチタンの含有量にもよるが、ｌｏｇ Ｐｏｔ＝Ｔ／
２００−２２＋ ３で示される条件である。ただし、Ｔ
は摂氏で示した温度、Ｐｏｔは気圧単位で示した酸素分
圧である。As mentioned above, the specific atmospheric conditions for annealing depend on the titanium content, but log Pot=T/
The condition is expressed as 200-22+3. However, T
is the temperature in degrees Celsius, and Pot is the oxygen partial pressure in atmospheric pressure units.
焼鈍温度は７００〜２０００℃、好ましくは１３００〜
１９５０℃である。所定の酸素分圧を得るためには、気
体種を用いても、あるいは制御された真空を用いてもよ
いが、Ｃ０ｔｌｌ！、 ＣＯ□＋ＣＯ，ＨｔＯ＋ Ｈｚ
、 ＨｔＯ＋ Ｃｏ。Annealing temperature is 700~2000℃, preferably 1300~
The temperature is 1950°C. To obtain a predetermined oxygen partial pressure, gaseous species or a controlled vacuum may be used, but C0tll! , CO□+CO,HtO+ Hz
, HtO+Co.
あるいはこれらに不活性気体（Ａｒやｈなど）を混合し
たものを用いることが好ましい、特に好ましくはｃｏｔ
＋ｔｔｔ、 ｃｏｔ＋ｃｏ、 ｕｚｏ＋ｔｔｔあるいは
これらに不活性気体を混合したものである。Alternatively, it is preferable to use a mixture of these and an inert gas (Ar, h, etc.), particularly preferably cot.
+ttt, cot+co, uzo+ttt, or a mixture of these with an inert gas.
焼鈍時間は特に制限はないが、寄生吸収帯を十分に低下
させることができる範囲で、生産性を高めるためにでき
るだけ短時間であることが望ましい。Although there are no particular restrictions on the annealing time, it is desirable that the annealing time be as short as possible in order to increase productivity and within a range that can sufficiently reduce the parasitic absorption band.
適切な焼鈍条件における酸素分圧及び温度の範囲は第２
図の通りである。The oxygen partial pressure and temperature range under appropriate annealing conditions are
As shown in the figure.
このような焼鈍雰囲気°は、結晶成長雰囲気として用い
ると焼鈍を行わなくても寄生吸収帯が極めて小さいチタ
ンサファイヤ単結晶を合成することができる。When such an annealing atmosphere is used as a crystal growth atmosphere, a titanium sapphire single crystal with an extremely small parasitic absorption band can be synthesized without annealing.
融液からの単結晶成長に際しては、融点が約２０００℃
であるので、前記酸素分圧式で示す酸素分圧範囲での１
０−”〜ｌＱ−＋ｓ気圧、更に好ましくは１０−１６〜
１０− ”気圧であることがよい。When growing a single crystal from a melt, the melting point is approximately 2000°C.
Therefore, 1 in the oxygen partial pressure range shown in the oxygen partial pressure formula above.
0-” to lQ-+s atmospheric pressure, more preferably 10-16 to
Preferably, the pressure is 10-”atm.
融点降下剤を添加して、サファイヤよりも低い融点を持
つ溶液から単結晶を成長させる場合は第２図に示される
酸素分圧範囲を利用する。When a single crystal is grown from a solution having a melting point lower than that of sapphire by adding a melting point depressant, the oxygen partial pressure range shown in FIG. 2 is used.
チタンサファイヤ単結晶を高品質性に確保するためには
、結晶成長時及び焼鈍時の酸素分圧を前記のように調整
した雰囲気下で行うことが好ましい。In order to ensure a high quality titanium sapphire single crystal, it is preferable to perform crystal growth and annealing in an atmosphere in which the oxygen partial pressure is adjusted as described above.
実施例１゜
Ａ１□Ｏ３に混入させたチタン濃度がＴｉｚＯ３のモル
％で表わして０．３％のチタンサファイヤ単結晶（７φ
Ｘ６１ｍ）を、０．０２％ＣＯｚ＋９９．９８％Ｈ！（
ＰＧ。Example 1 Titanium sapphire single crystal (7φ
x61m), 0.02%COz+99.98%H! (
P.G.
−１０−”・５気圧）の酸素分圧に調整した雰囲気下、
屏
１７６０℃で金時間焼鈍した。得られたチタンサファイ
ヤ単結晶のＣ軸方向に透過する波長８００ ｎｍの光の
吸収係数は０．０１ａｍ−’であった。In an atmosphere adjusted to an oxygen partial pressure of -10-"・5 atm),
The plate was annealed at 1,760°C for an hour. The absorption coefficient of light with a wavelength of 800 nm transmitted in the C-axis direction of the obtained titanium sapphire single crystal was 0.01 am-'.
気圧）（不純物ガスに起因）として実施例１と同条件の
温度１時間焼鈍した。得られた波長８００ｎ−の光の吸
収係数は０．８０ｃｍ−’であった。Atmospheric pressure) (due to impurity gas), and was annealed at the same temperature as in Example 1 for 1 hour. The absorption coefficient of the obtained light with a wavelength of 800 n- was 0.80 cm-'.
実施例２゜
ＡＩ、Ｏ，に混入させたチタン濃度がＴｉｚＯ，のモル
％で表わして０．２％のチタンサファイヤ単結晶を、集
光式ＦＺ法（フローティングゾーン法）によって、その
雰囲気を９５．５１１ｉ＾ｆ＋５％■２に１．５ Ｘｌ
０−’気圧の１１８０を加え、酸素分圧を１０−”気圧
とし、単結晶を育成した。得られた単結晶のＣ軸方向に
透過する波長８００ ｎｍの光の吸収係数は０゜Ｏｌｃ
ｍ−’以下であった。Example 2 A titanium sapphire single crystal with a titanium concentration of 0.2% expressed as mol% of TizO mixed in AI, O, was heated to an atmosphere of 95% by concentrating FZ method (floating zone method). .511i^f+5%■2 to 1.5 Xl
A single crystal was grown by applying 0-'atm of 1180 to make the oxygen partial pressure 10-'atm.The absorption coefficient of light with a wavelength of 800 nm transmitted in the C-axis direction of the obtained single crystal was 0°Olc.
m-' or less.
比較例２、
実施例２における雰囲気を９５％Ａｒ＋５％Ｈ３のみで
単結晶を育成した。得られた単結晶のＣ軸方向に透過す
る波長８００ｎ−の光の喋収係数は０．３０ｃｍ−’で
あった。Single crystals were grown in Comparative Example 2 and Example 2 using only 95% Ar + 5% H3 atmosphere. The absorption coefficient of light with a wavelength of 800 n-' transmitted in the C-axis direction of the obtained single crystal was 0.30 cm-'.
第１図はチタンサファイヤ単結晶の焼鈍雰囲気中の酸素
分圧による波長８００ ｎ−の光の吸収係数の変化図、
第２図は高品質チタンサファイヤ単結晶の焼鈍又は成長
における適切な雰囲気条件の範囲図を示す。
：：１．ブ、−２ “−
第１図
ｏｇＰｏ２
第 ２ 図
温度（０Ｃ）Figure 1 is a diagram of changes in the absorption coefficient of light with a wavelength of 800 n- due to oxygen partial pressure in the annealing atmosphere of titanium sapphire single crystal.
FIG. 2 shows a range diagram of suitable atmospheric conditions for annealing or growing high quality titanium sapphire single crystals. ::1. -2 "- Figure 1 ogPo2 Figure 2 Temperature (0C)
Claims (1)
の焼鈍に際して、雰囲気中の酸素分圧を調整して単結晶
中に３価以外のチタンイオンが無視できる程度まで少な
くなるように単結晶中のチタンイオンの価数制御を行う
ことを特徴とする高品質チタンサファイヤ単結晶の製造
方法。 ２）雰囲気中の酸素分圧をｌｏｇＰｏ＿２＝Ｔ／２００
−２２±３（Ｐｏ＿２は気圧単位で示した酸素分圧、Ｔ
は摂氏で示した温度を表わす）とする特許請求の範囲第
１項記載の製造方法。 ３）雰囲気中の酸素分圧を調整する方法が雰囲気中にＣ
Ｏ＿２＋Ｈ＿２、ＣＯ＿２＋ＣＯ、Ｈ＿２Ｏ＋Ｈ＿２、
Ｈ＿２Ｏ＋ＣＯあるいはこれらに不活性気体を混合した
ものを導入することによって行う特許請求の範囲第１項
記載の製造方法。[Claims] 1) During the growth of a titanium sapphire single crystal and/or annealing after growth, the oxygen partial pressure in the atmosphere is adjusted so that titanium ions other than trivalent titanium ions in the single crystal are reduced to a negligible level. A method for producing a high-quality titanium sapphire single crystal, which is characterized by controlling the valence of titanium ions in the single crystal. 2) The oxygen partial pressure in the atmosphere is logPo_2=T/200
-22±3 (Po_2 is oxygen partial pressure in atmospheric pressure units, T
2. The manufacturing method according to claim 1, wherein: represents the temperature in degrees Celsius. 3) The method of adjusting the oxygen partial pressure in the atmosphere is
O_2+H_2, CO_2+CO, H_2O+H_2,
The manufacturing method according to claim 1, which is carried out by introducing H_2O+CO or a mixture thereof with an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10952287A JPS63274694A (en) | 1987-05-01 | 1987-05-01 | Production of titanium sapphire single crystal having high quality |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10952287A JPS63274694A (en) | 1987-05-01 | 1987-05-01 | Production of titanium sapphire single crystal having high quality |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63274694A true JPS63274694A (en) | 1988-11-11 |
| JPH042558B2 JPH042558B2 (en) | 1992-01-20 |
Family
ID=14512389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10952287A Granted JPS63274694A (en) | 1987-05-01 | 1987-05-01 | Production of titanium sapphire single crystal having high quality |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63274694A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6641939B1 (en) | 1998-07-01 | 2003-11-04 | The Morgan Crucible Company Plc | Transition metal oxide doped alumina and methods of making and using |
| JP2004250283A (en) * | 2003-02-20 | 2004-09-09 | National Institute Of Advanced Industrial & Technology | Method and device for preparing sample by controlling oxygen partial pressure |
| WO2011125897A1 (en) * | 2010-03-31 | 2011-10-13 | 独立行政法人産業技術総合研究所 | Manufacturing method of metal compound crystal, ornament manufacturing method, and metal compound crystal |
| JP2017197411A (en) * | 2016-04-28 | 2017-11-02 | 日本電信電話株式会社 | Method for manufacturing single crystal fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61266394A (en) * | 1985-05-20 | 1986-11-26 | ユニオン・カ−バイド・コ−ポレ−シヨン | Method of heightening fluorescence degree of ti:al203 tunable laser crystal by annealing |
-
1987
- 1987-05-01 JP JP10952287A patent/JPS63274694A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61266394A (en) * | 1985-05-20 | 1986-11-26 | ユニオン・カ−バイド・コ−ポレ−シヨン | Method of heightening fluorescence degree of ti:al203 tunable laser crystal by annealing |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6641939B1 (en) | 1998-07-01 | 2003-11-04 | The Morgan Crucible Company Plc | Transition metal oxide doped alumina and methods of making and using |
| JP2004250283A (en) * | 2003-02-20 | 2004-09-09 | National Institute Of Advanced Industrial & Technology | Method and device for preparing sample by controlling oxygen partial pressure |
| WO2011125897A1 (en) * | 2010-03-31 | 2011-10-13 | 独立行政法人産業技術総合研究所 | Manufacturing method of metal compound crystal, ornament manufacturing method, and metal compound crystal |
| JP2017197411A (en) * | 2016-04-28 | 2017-11-02 | 日本電信電話株式会社 | Method for manufacturing single crystal fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH042558B2 (en) | 1992-01-20 |
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