JP3216297B2 - Liquid phase epitaxial growth equipment - Google Patents
Liquid phase epitaxial growth equipmentInfo
- Publication number
- JP3216297B2 JP3216297B2 JP01968693A JP1968693A JP3216297B2 JP 3216297 B2 JP3216297 B2 JP 3216297B2 JP 01968693 A JP01968693 A JP 01968693A JP 1968693 A JP1968693 A JP 1968693A JP 3216297 B2 JP3216297 B2 JP 3216297B2
- Authority
- JP
- Japan
- Prior art keywords
- epitaxial growth
- liquid phase
- crucible
- phase epitaxial
- melt
- 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.)
- Expired - Fee Related
Links
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- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は下地基板の表面に単結晶
膜を液相エピタキシャル成長法によって育成する装置、
特に磁性ガーネット単結晶膜を育成するための液相エピ
タキシャル成長装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for growing a single crystal film on a surface of a base substrate by a liquid phase epitaxial growth method.
In particular, the present invention relates to a liquid phase epitaxial growth apparatus for growing a magnetic garnet single crystal film.
【０００２】[0002]
【従来の技術】従来、遅延線フィルター，発振器，非線
形デバイスなどの静磁波（ＭＳＷ）デバイス、およびフ
ァラデー回転効果を利用した光アイソレータ，サーキュ
レータまたはスイッチなどの磁気光学素子等に磁性ガー
ネット単結晶が広く用いられている。この磁性ガーネッ
ト単結晶の主な製造方法として、液相エピタキシャル成
長法（ＬＰＥ法）が知られている。2. Description of the Related Art Conventionally, magnetic garnet single crystals have been widely used in magnetostatic wave (MSW) devices such as delay line filters, oscillators, and nonlinear devices, and in magneto-optical devices such as optical isolators, circulators, and switches utilizing the Faraday rotation effect. Used. As a main production method of the magnetic garnet single crystal, a liquid phase epitaxial growth method (LPE method) is known.
【０００３】従来の液相エピタキシャル成長法による磁
性ガーネット単結晶の育成方法は、縦型加熱炉内に所定
条件に保持された白金製坩堝に、ガーネットを構成する
元素の酸化物および溶剤としてＰｂＯとＢ2 Ｏ3 とを充
填し、約１２００℃で均質化を行い溶融化する。次に、
この融液を過冷却状態、即ち液相線（Liquidus) の下方
近傍温度（約９００℃前後）に保持した後、この融液中
に基板保持具で保持された下地基板であるＧｄ3 Ｇａ5
Ｏ12（ＧＧＧ）基板を浸漬し、一定位置で回転させなが
ら所定時間エピタキシャル成長を行うことによって、下
地基板の表面に磁性ガーネット単結晶膜を育成するもの
である。[0003] A conventional method of growing a magnetic garnet single crystal by liquid phase epitaxy is a method in which PbO and B as oxides of a garnet element and a solvent are placed in a platinum crucible kept in a vertical heating furnace under predetermined conditions. It is charged with 2 O 3 , homogenized at about 1200 ° C. and melted. next,
After maintaining the melt in a supercooled state, that is, at a temperature near the liquidus (approximately 900 ° C.) below the liquidus (Liquidus), the base substrate Gd 3 Ga 5 held in the melt by a substrate holder is held.
The magnetic garnet single crystal film is grown on the surface of the base substrate by immersing the O 12 (GGG) substrate and performing epitaxial growth for a predetermined time while rotating the substrate at a predetermined position.
【０００４】[0004]
【発明が解決しようとする課題】ところが、溶剤として
使われているＰｂＯはＰｔとの反応性が高く、上記方法
で磁性ガーネット単結晶膜を育成すると、ＰｂＯとＰｔ
との反応により坩堝および基板保持具が腐食されたり、
Ｐｔ粒子が粒成長を起こしてしまう。このため、溶液中
にＰｔ粒子が溶出したり、基板保持具の強度低下による
融液振り切り中の下地基板の落下、更には坩堝から融液
がしみ出るといった問題があった。この問題を解決する
手段として、ＰｔにＺｒＯ2 粉末を混ぜる方法や、ガラ
ス作製によく用いられる手段であるが、ＰｔにＡｕを混
ぜる方法がある。ＺｒＯ2粉末を混ぜたＰｔは粒界が層
状になっているため、ＰｂＯ系融液中でＰｔ粒子が粒成
長しにくく、強度的に優れている。しかし、ＰｂＯ系融
液との濡れ性が良く、Ｐｔ粒子の溶出量は純Ｐｔと殆ど
変わらない。溶出されたＰｔ粒子が磁性ガーネット単結
晶膜中に取り込まれると、Ｆｅ3+と電荷補償を起こした
り、ピットの生成原因となるため、静磁波素子として用
いると、特性にバラツキが生じることになる。一方、Ａ
ｕを混ぜたＰｔはＰｂＯ融液との濡れ性が悪くなり、Ｐ
ｔ粒子の溶出は抑制できるが、粒成長による強度低下ま
では抑制できない。そこで、本発明の主たる目的は、Ｐ
ｂＯ系溶剤による腐食に強く、良質の単結晶膜を得るこ
とができる液相エピタキシャル成長装置を提供すること
にある。However, PbO used as a solvent has high reactivity with Pt, and when a magnetic garnet single crystal film is grown by the above method, PbO and Pt
Reaction with the crucible and the substrate holder,
Pt particles cause grain growth. For this reason, there were problems that Pt particles eluted into the solution, the base substrate dropped during shaking off of the melt due to a decrease in the strength of the substrate holder, and the melt exuded from the crucible. As a means for solving this problem, there is a method of mixing ZrO 2 powder with Pt, and a method of mixing Au with Pt, which is a method often used for glass production. Since Pt mixed with ZrO 2 powder has a layered grain boundary, Pt particles are unlikely to grow in a PbO-based melt and are excellent in strength. However, the wettability with the PbO-based melt is good, and the elution amount of Pt particles is almost the same as pure Pt. When the eluted Pt particles are taken into the magnetic garnet single crystal film, they cause charge compensation with Fe 3+ or cause formation of pits. Therefore, when used as a magnetostatic wave device, the characteristics are varied. . On the other hand, A
Pt mixed with u has poor wettability with the PbO melt,
Although elution of t particles can be suppressed, it cannot be suppressed until the strength decreases due to grain growth. Therefore, the main object of the present invention is to
An object of the present invention is to provide a liquid phase epitaxial growth apparatus that is resistant to corrosion by a bO-based solvent and can obtain a high-quality single crystal film.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するた
め、本発明の液相エピタキシャル成長装置は、坩堝およ
び基板保持具を、白金を主体とし、ＺｒＯ2 粉末が０．
０５〜１．００重量％、Ａｕが１〜３０原子％の範囲で
含有されている材料で形成したものである。In order to achieve the above object, in the liquid phase epitaxial growth apparatus of the present invention, the crucible and the substrate holder are mainly made of platinum, and the crucible and the ZrO 2 powder are used in an amount of 0.1%.
It is formed of a material containing 0.05 to 1.00% by weight of Au and 1 to 30 atom% of Au.
【０００６】[0006]
【作用】純ＰｔはＰｂＯとの濡れ性が高いため、融液中
へのＰｔの溶出、Ｐｔ粒子の粒成長による強度低下が避
けられない。ＺｒＯ2 粉末を０．１５〜１．００重量％
点火したＰｔは、粒界が層状になるため粒成長が抑えら
れ、強度的には純Ｐｔより優れている。しかし、濡れ性
は純Ｐｔと殆ど変わらないため、Ｐｔ溶出量に関しては
差異はない。Ａｕを１〜３０原子％添加したＰｔは、Ｐ
ｂＯとの濡れ性は悪くなり、Ｐｔ溶出量は抑制できた
が、Ｐｔ粒子の粒成長による強度面での欠点がある。そ
こで、ＺｒＯ2 粉末を０．０５〜１．００重量％とＡｕ
を１〜３０原子％添加したＰｔは強度面および濡れ性の
双方で優れており、これを坩堝および基板保持具に使用
することで、良質の単結晶膜を再現性よく製作すること
ができる。Since pure Pt has high wettability with PbO, elution of Pt into the melt and a decrease in strength due to the growth of Pt particles are inevitable. 0.15 to 1.00% by weight of ZrO 2 powder
The ignited Pt has a layered grain boundary, thereby suppressing grain growth, and is superior in strength to pure Pt. However, since the wettability is almost the same as that of pure Pt, there is no difference in the Pt elution amount. Pt to which 1 to 30 atomic% of Au is added is Pt
Although the wettability with bO became worse and the Pt elution amount could be suppressed, there was a drawback in strength due to the grain growth of Pt particles. Therefore, ZrO 2 powder is added in an amount of 0.05 to 1.00% by weight and Au
Is excellent in both the strength surface and the wettability, and by using it for a crucible and a substrate holder, a high-quality single crystal film can be manufactured with good reproducibility.
【０００７】この発明において、ＺｒＯ2 粉末の重量％
を０．０５〜１．００％と限定するのは、ＺｒＯ2 粉末
の含有量が０．０５重量％より少ないと強度を大きくす
ることが出来ず、１．００重量％より多いと、含有した
ＺｒＯ2 が不純物として融液中に混入してしまうためで
ある。一方、、Ａｕを１〜３０原子％に限定するのは、
Ａｕが１原子％より少ないと、ＰｂＯとの濡れ性が十分
に悪くならず、３０原子％より多くなると、融点低下に
より使用中に貴金属が変形してしまうからである。In the present invention, the weight percentage of ZrO 2 powder
Is limited to 0.05 to 1.00% because if the content of the ZrO 2 powder is less than 0.05% by weight, the strength cannot be increased, and if the content is more than 1.00% by weight, the ZrO 2 powder is contained. This is because ZrO 2 is mixed into the melt as an impurity. On the other hand, limiting Au to 1 to 30 atomic% is as follows.
If Au is less than 1 atomic%, the wettability with PbO will not be sufficiently deteriorated, and if it is more than 30 atomic%, the noble metal will be deformed during use due to a decrease in melting point.
【０００８】[0008]
【実施例】図１は本発明の一例である磁性ガーネット単
結晶膜を育成するための液相エピタキシャル成長装置を
示す。アルミナ製の縦型円筒形炉心管１の内側には、支
持台２によって底面が支持された坩堝３が配置され、こ
の坩堝３内には磁性ガーネット単結晶膜の原料と溶剤と
が充填されている。この坩堝３は、０．０５〜１．００
重量％のＺｒＯ2 粉末と１〜３０原子％のＡｕを含有し
た白金で形成されている。炉心管１の外側には上，中，
下の３段の抵抗加熱ヒータ４，５，６が設けられてお
り、坩堝３は中ヒータ５の内側に配置されている。炉心
管１内の坩堝３は上記ヒータ４〜６の輻射熱により加熱
され、ガーネット原料および溶剤が溶解されて融液７化
されるとともに、炉心管１内の雰囲気が所定温度に保持
されている。なお、加熱方法は、抵抗加熱法に限らず、
誘導加熱法を用いてもよい。1 shows a liquid phase epitaxial growth apparatus for growing a magnetic garnet single crystal film according to an embodiment of the present invention. Inside the vertical cylindrical furnace tube 1 made of alumina, a crucible 3 whose bottom is supported by a support base 2 is arranged, and the crucible 3 is filled with a raw material of a magnetic garnet single crystal film and a solvent. I have. This crucible 3 is 0.05 to 1.00
It is formed of platinum containing 1 wt% of ZrO 2 powder and 1 to 30 atomic% of Au. The upper, middle, and
Lower three-stage resistance heaters 4, 5, and 6 are provided, and the crucible 3 is disposed inside the middle heater 5. The crucible 3 in the furnace tube 1 is heated by the radiant heat of the heaters 4 to 6, the garnet raw material and the solvent are dissolved to form a melt 7, and the atmosphere in the furnace tube 1 is maintained at a predetermined temperature. In addition, the heating method is not limited to the resistance heating method,
An induction heating method may be used.
【０００９】ＧＧＧ基板よりなる円板状の下地基板８
は、基板保持具９によって取り外し自在にかつ水平に保
持されている。この基板保持具９も０．０５〜１．００
重量％のＺｒＯ2 粉末と１〜３０原子％のＡｕを含有し
た白金で形成されている。基板保持具９の上端部はアル
ミナ製支持棒１０に固定されており、支持棒１０の上端
部は駆動手段（図示せず）に連結され、回転および上下
方向の昇降が可能である。炉心管１の上端には、炉内へ
の冷気の侵入を抑制する石英ガラス製のシャッタ１１が
載置されており、このシャッタ１１の中心部に上記支持
棒１０が挿通されている。Disc-shaped base substrate 8 made of a GGG substrate
Are detachably and horizontally held by the substrate holder 9. This substrate holder 9 is also 0.05 to 1.00.
It is formed of platinum containing 1 wt% of ZrO 2 powder and 1 to 30 atomic% of Au. The upper end of the substrate holder 9 is fixed to a support rod 10 made of alumina. The upper end of the support rod 10 is connected to a driving means (not shown), and can rotate and move up and down. At the upper end of the furnace tube 1, a quartz glass shutter 11 for suppressing intrusion of cool air into the furnace is mounted. The support rod 10 is inserted through the center of the shutter 11.
【００１０】本発明における磁性ガーネット単結晶膜の
育成方法は、従来の液相エピタキシャル成長法による育
成方法と同様である。即ち、坩堝３の中でガーネット単
結晶膜の原料と溶剤とを混合し、１２００℃で加熱溶解
した後、融液７を約９００℃に降温して過冷却状態とす
る。一方、支持棒１０を降下させ、下地基板８を保持し
た基板保持具９を融液７中に浸漬する。そして、支持棒
１０を一方向あるいは正逆に回転させて下地基板８の表
面に磁性ガーネット単結晶膜を数時間等温育成する。育
成終了後、下地基板８を融液７から高速度で回転させな
がら引き上げ、磁性ガーネット単結晶膜上の付着融液を
遠心力により振り切る。The method of growing a magnetic garnet single crystal film in the present invention is the same as the conventional method of growing by liquid phase epitaxial growth. That is, the raw material of the garnet single crystal film and the solvent are mixed in the crucible 3 and heated and melted at 1200 ° C., and then the melt 7 is cooled to about 900 ° C. to be in a supercooled state. On the other hand, the support rod 10 is lowered, and the substrate holder 9 holding the base substrate 8 is immersed in the melt 7. Then, the support bar 10 is rotated in one direction or forward and reverse to grow the magnetic garnet single crystal film on the surface of the base substrate 8 isothermally for several hours. After the growth, the base substrate 8 is pulled up from the melt 7 while rotating it at a high speed, and the melt attached to the magnetic garnet single crystal film is shaken off by centrifugal force.
【００１１】表１は、坩堝および基板保持具として純Ｐ
ｔを用いた場合と、ＺｒＯ2 粉末とＡｕとを含有したＰ
ｔを用いた場合とにおいて、融液中に溶出したＰｔの
量、ＺｒＯ2 の溶出量、および坩堝や基板保持具の変形
の有無を示したものである。Table 1 shows that pure crucible and substrate holder are pure P
t, and P containing ZrO 2 powder and Au
When t is used, the amount of Pt eluted in the melt, the amount of ZrO 2 eluted, and the presence or absence of deformation of the crucible and the substrate holder are shown.
【００１２】[0012]
【表１】 表１において、Ｎｏ．１〜３および８，９は本発明の範
囲外である。[Table 1] In Table 1, No. 1-3 and 8, 9 are outside the scope of the present invention.
【００１３】表１から明らかなように、本発明（Ｎｏ．
４〜７）ではＰｔ溶出量およびＺｒＯ2 溶出量が少な
く、ＰｂＯ系溶剤に対する耐腐食性が高くなったことが
判る。さらに、Ｐｔ粒子が粒成長を起こさなくなったこ
とで、強度が向上し、基板保持具９から下地基板８が落
下したり、坩堝３から融液がしみ出すこともなくなり、
安定して効率よく磁性ガーネット単結晶膜を育成するこ
とが可能となった。As apparent from Table 1, the present invention (No.
4 to 7), it can be seen that the amount of Pt eluted and the amount of ZrO 2 eluted were small, and the corrosion resistance to PbO-based solvents was increased. Further, since the Pt particles do not cause grain growth, the strength is improved, and the base substrate 8 does not drop from the substrate holder 9 and the melt does not exude from the crucible 3.
It has become possible to stably and efficiently grow a magnetic garnet single crystal film.
【００１４】[0014]
【発明の効果】以上の説明で明らかなように、本発明に
よれば、坩堝および基板保持具を、白金を主体とし、Ｚ
ｒＯ2 粉末が０．０５〜１．００重量％、Ａｕが１〜３
０原子％の範囲で含有されている材料で形成したので、
ＰｂＯ系溶剤による腐食に強く、良質の単結晶膜を得る
ことができる。As is apparent from the above description, according to the present invention, the crucible and the substrate holder are made mainly of platinum,
0.05 to 1.00% by weight of rO 2 powder, 1 to 3 of Au
Since it was formed from a material containing 0 atomic%,
A high-quality single crystal film that is resistant to corrosion by a PbO-based solvent can be obtained.
【図１】本発明にかかる液相エピタキシャル成長装置の
浸漬前の縦断面図である。FIG. 1 is a longitudinal sectional view of a liquid phase epitaxial growth apparatus according to the present invention before immersion.
１ 炉心管 ３ 坩堝 ７ 融液 ８ 下地基板 ９ 基板保持具 DESCRIPTION OF SYMBOLS 1 Furnace tube 3 Crucible 7 Melt 8 Base substrate 9 Substrate holder
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−206791（ＪＰ，Ａ) 特開 平３−45589（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-206791 (JP, A) JP-A-3-45589 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C30B 1/00-35/00
Claims (1)
物とＰｂＯ系溶剤とを充填して溶融化し、この融液中に
基板保持具に保持された下地基板を浸漬し、所定時間エ
ピタキシャル成長を行うことにより、下地基板の表面に
磁性ガーネット単結晶膜を育成する液相エピタキシャル
成長装置において、 上記坩堝および基板保持具は、白金を主体とし、ＺｒＯ
2 粉末が０．０５〜１．００重量％、Ａｕが１〜３０原
子％の範囲で含有されている材料で形成されていること
を特徴とする液相エピタキシャル成長装置。A crucible is filled with an oxide of an element constituting garnet and a PbO-based solvent and melted. A base substrate held by a substrate holder is immersed in the melt, and epitaxial growth is performed for a predetermined time. In the liquid phase epitaxial growth apparatus for growing a magnetic garnet single crystal film on the surface of the base substrate, the crucible and the substrate holder are mainly made of platinum,
(2) A liquid phase epitaxial growth apparatus, wherein the powder is formed of a material containing 0.05 to 1.00% by weight and Au in a range of 1 to 30 atomic%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01968693A JP3216297B2 (en) | 1993-01-11 | 1993-01-11 | Liquid phase epitaxial growth equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01968693A JP3216297B2 (en) | 1993-01-11 | 1993-01-11 | Liquid phase epitaxial growth equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06206793A JPH06206793A (en) | 1994-07-26 |
| JP3216297B2 true JP3216297B2 (en) | 2001-10-09 |
Family
ID=12006128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01968693A Expired - Fee Related JP3216297B2 (en) | 1993-01-11 | 1993-01-11 | Liquid phase epitaxial growth equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3216297B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4591219B2 (en) * | 2005-06-08 | 2010-12-01 | Ｔｄｋ株式会社 | Single crystal growth crucible |
-
1993
- 1993-01-11 JP JP01968693A patent/JP3216297B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06206793A (en) | 1994-07-26 |
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