JP2784926B2 - Oxide garnet single crystal and method for producing the same - Google Patents
Oxide garnet single crystal and method for producing the sameInfo
- Publication number
- JP2784926B2 JP2784926B2 JP63246835A JP24683588A JP2784926B2 JP 2784926 B2 JP2784926 B2 JP 2784926B2 JP 63246835 A JP63246835 A JP 63246835A JP 24683588 A JP24683588 A JP 24683588A JP 2784926 B2 JP2784926 B2 JP 2784926B2
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- garnet single
- pbo
- oxide garnet
- producing
- 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
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は酸化物ガーネット単結晶およびその製造方
法、特に周波数100MHzから数10GHzのマイクロ波帯で使
用されるマイクロ波素子、例えばアイソレーター、サー
キュレーター用の新規な磁性膜や、磁気光学素子の光ア
イソレーター用の磁性膜として有用な酸化物ガーネット
単結晶およびその製造方法に関するものである。The present invention relates to an oxide garnet single crystal and a method for producing the same, particularly for a microwave element used in a microwave band having a frequency of 100 MHz to several tens of GHz, such as an isolator and a circulator. Garnet single crystal useful as a novel magnetic film, a magnetic film for an optical isolator of a magneto-optical element, and a method for producing the same.
（従来の技術とその問題点） 光アイソレーターやマイクロ波素子用の磁性材料とし
ては基板上に液相エピタキシャル法で育成したY3Fe5O12
（YIG）または（YBiFe）8O12で示される酸化物ガーネッ
ト単結晶が提案されている。(Conventional technology and its problems) As a magnetic material for an optical isolator or a microwave device, Y 3 Fe 5 O 12 grown on a substrate by a liquid phase epitaxial method is used.
An oxide garnet single crystal represented by (YIG) or (YBiFe) 8 O 12 has been proposed.
しかし、これらの酸化物ガーネット単結晶は基板と格
子定数が異なるために得られた酸化物ガーネット単結晶
はクラックが発生し易く、20μｍ以上の膜厚を得ること
は難しく、得られたとしても表面の凹凸が大きく、磁気
共鳴半値巾ΔＨが不均一で大きい値を示すため、これを
光アイソレーター素子用やマイクロ波素子用の基材に用
いることが難しいという欠点があった。However, since these oxide garnet single crystals have a different lattice constant from the substrate, the obtained oxide garnet single crystals are liable to crack, and it is difficult to obtain a film thickness of 20 μm or more. Is large and the magnetic resonance half width ΔH is non-uniform and shows a large value. Therefore, there is a disadvantage that it is difficult to use this as a substrate for an optical isolator element or a microwave element.
（発明の構成） 本発明はこのような不利を解決した高品質のマイクロ
波素子用材料や磁気光学素子用材料として有用な酸化物
ガーネット単結晶およびその製造方法に関するもので、
本発明は、液相エピタキシャル法によりフラックス融液
から基板上に厚さ20μｍ以上の（YBiFeN）8O12（ここに
ＮはAl、Ga、In、Scから選択される少なくとも１つの元
素）で示される膜状の酸化物ガーネット単結晶を育成す
るに当たり、フラックス成分としてのPbO、B2O3およびB
i2O3のモル比がPbO/2B2O3をＸ軸とし、2Bi2O3/PbOをＹ
軸としたXY平面において点Ａ（5.0,0）、Ｂ（6.0,0.
2）、Ｃ（30.0,0.2）、Ｄ（8.0,0）で囲まれた範囲（た
だしAD線上を除く）にあることを特徴とする酸化物ガー
ネット単結晶の製造方法、および液相エピタキシャル法
で基板上に育成された厚さ20μｍ以上の（YBiFeN）8O12
（ここにＮはAl、Ga、In、Scから選択される少なくとも
１つの元素）で示される膜状の酸化物ガーネット単結晶
において、磁気共鳴半値幅ΔＨが2.0Oe以下で、表面の
ストリエーション凹凸差が0.35μｍ以下であることを特
徴とする酸化物ガーネット単結晶を要旨とするものであ
る。(Constitution of the Invention) The present invention relates to a high-quality oxide garnet single crystal useful as a high-quality material for a microwave element or a material for a magneto-optical element which has solved such disadvantages, and a method for producing the same.
The present invention relates to a method in which a liquid phase epitaxial method is used to form (YBiFeN) 8 O 12 (where N is at least one element selected from Al, Ga, In, and Sc) on a substrate from a flux melt. In growing a film-like oxide garnet single crystal to be grown, PbO, B 2 O 3 and B as flux components
The molar ratio of i 2 O 3 is such that PbO / 2B 2 O 3 is the X axis and 2Bi 2 O 3 / PbO is the Y axis.
Points A (5.0,0) and B (6.0,0.
2) A method for producing an oxide garnet single crystal characterized by being in a range (excluding on the AD line) surrounded by C (30.0, 0.2) and D (8.0, 0), and a liquid phase epitaxial method. (YBiFeN) 8 O 12 with a thickness of 20 μm or more grown on a substrate
(Where N is at least one element selected from Al, Ga, In, and Sc), in a film-shaped oxide garnet single crystal, the magnetic resonance half width ΔH is 2.0 Oe or less, and the striation unevenness on the surface is obtained. A gist of the oxide garnet single crystal, wherein the difference is 0.35 μm or less.
すなわち、本発明者らは液相エピタキシャル法により
フラックス融液から基板上に厚さ20μｍ以上の（YBiFe
N）8O12（Ｎは前記に同じ）で示される酸化物ガーネッ
ト単結晶を育成する際に使用されるフラックス成分に着
目し、フラックス成分のPbO、B2O3およびBi2O3のモル比
がエピタキシャル膜の表面の凹凸および磁気共鳴半値巾
ΔＨ値に大きい影響を与えることを見出し、種々検討し
た結果、酸化物ガーネット単結晶が（YBiFeN）8O12（Ｎ
は前記に同じ）の育成において、PbO、B2O3、Bi2O3のモ
ル比がPbO/2B2O3をＸ軸とし、2Bi2O3/PbOをＹ軸としたX
Y平面において、点Ａ（5.0,0）、Ｂ（6.0,0.2）、Ｃ（3
0.0,0.2）およびＤ（8.0,0）で囲まれた第１図に示され
た範囲（ただしAD線上を除く）になるようにすると、ク
ラックが少なく、表面の凹凸が0.35μｍ以下で、ΔＨ値
が2.0Oe以下の、20μｍ以上の厚さの酸化物ガーネット
単結晶厚膜を得ることができることを確認して本発明を
完成させた。That is, the inventors of the present invention applied a liquid phase epitaxial method on a substrate having a thickness of 20 μm or more (YBiFe
Focusing on the flux components used for growing the oxide garnet single crystal represented by N) 8 O 12 (N is the same as above), the moles of the flux components PbO, B 2 O 3 and Bi 2 O 3 It has been found that the ratio has a great effect on the surface irregularities of the epitaxial film and the magnetic resonance half width ΔH, and as a result of various investigations, it has been found that the oxide garnet single crystal has (YBiFeN) 8 O 12 (N
In development of the same) to the, PbO, the molar ratio of B 2 O 3, Bi 2 O 3 is a PbO / 2B 2 O 3 and X-axis, the 2Bi 2 O 3 / PbO is Y-axis X
On the Y plane, points A (5.0, 0), B (6.0, 0.2), and C (3
0.0 (0.2) and D (8.0, 0), the cracks are reduced, the surface irregularities are 0.35 μm or less, and ΔH The present invention was completed by confirming that an oxide garnet single crystal thick film having a value of 2.0 Oe or less and a thickness of 20 μm or more can be obtained.
以下にこれを詳述する。 This will be described in detail below.
本発明で使用されるガーネット基板単結晶はガドリニ
ウム・ガリウム・ガーネット（以下GGGと略記する）、
サマリウム・ガリウム・ガーネット（以下SGGと略記す
る）、ネオジム・ガリウム・ガーネット（以下NGGと略
記する）、GGGにCa、Mg、Zr、Ｙの少なくとも１つで置
換したGGG系のSOG、NOG、YOG［いずれも信越化学工業
（株）商品名］とすればよく、これらはGd2O3、Sm2O3、
Nd2O3および必要に応じCaO、MgO、ZrO2、Y2O3などの置
換材をそれぞれGa2O3の所定量と共にルツボに仕込み、
高周波誘導で各々の融点以上に加熱して溶融したのち、
チョクラルスキー法で融液から単結晶を引上げることに
よって得ることができる。The garnet substrate single crystal used in the present invention is gadolinium gallium garnet (hereinafter abbreviated as GGG),
Samarium gallium garnet (hereinafter abbreviated as SGG), neodymium gallium garnet (hereinafter abbreviated as NGG), GGG-based SOG, NOG, and YOG in which GGG is substituted with at least one of Ca, Mg, Zr, and Y [Each brand name is Shin-Etsu Chemical Co., Ltd.], and these are Gd 2 O 3 , Sm 2 O 3 ,
A replacement material such as Nd 2 O 3 and, if necessary, CaO, MgO, ZrO 2 , Y 2 O 3 is charged into a crucible together with a predetermined amount of Ga 2 O 3 respectively,
After heating and melting above each melting point by high frequency induction,
It can be obtained by pulling a single crystal from the melt by the Czochralski method.
上記基板単結晶上に液相エピタキシャル法で成長させ
る酸化物ガーネット単結晶の組成式は（YBiFeN）8O
12（Ｎは前記に同じ）で示されるもので、この酸化物ガ
ーネット単結晶は、白金ルツボ中にY2O3、Fe2O3、Bi2O3
およびN2O3（Ｎは前記に同じ）をフラックスのPbO、B2O
3、Bi2O3と共に仕込み、1,100〜1,200℃に加熱して溶解
させたのち、過冷却状態の融液からエピタキシャル法
（LPE法）で単結晶を成長させることによって得ること
ができる。The composition formula of the oxide garnet single crystal grown on the substrate single crystal by the liquid phase epitaxial method is (YBiFeN) 8 O
12 (N is the same as described above), and this oxide garnet single crystal is composed of Y 2 O 3 , Fe 2 O 3 , and Bi 2 O 3 in a platinum crucible.
And N 2 O 3 (N is the same as above) with flux PbO, B 2 O
3 , can be obtained by charging together with Bi 2 O 3 , heating and melting at 1,100 to 1,200 ° C., and growing a single crystal from a supercooled melt by an epitaxial method (LPE method).
本発明では酸化物単結晶を液相エピタキシャル法で育
成する際に、融液のフラックス成分のPbO、B2O3、Bi2O3
のモル比を特定の範囲内とすることが必要とされるもの
で、PbO、B2O3、Bi2O3のモル比が第１図に示したように
PbO/2B2O3をＸ軸とし、2Bi2O3/PbOをＹ軸としたXY平面
において図中のＡ（5.0,0）、Ｂ（6.0,0.2）、Ｃ（30.
0,0.2）およびＤ（8.0,0）の４点で囲まれた範囲内にあ
るようにすることを特徴とするものである。In the present invention, when growing an oxide single crystal by a liquid phase epitaxial method, PbO, B 2 O 3 , Bi 2 O 3
It is necessary that the molar ratio of PbO, B 2 O 3 , and Bi 2 O 3 be within a specific range, as shown in FIG.
A (5.0, 0), B (6.0, 0.2), and C (30.30) in the figure on the XY plane with PbO / 2B 2 O 3 as the X axis and 2Bi 2 O 3 / PbO as the Y axis.
(0, 0.2) and D (8.0, 0).
フラックス成分のモル比をこの範囲内にすると、得ら
れる酸化物ガーネット単結晶はクラックがなく、また表
面の凹凸が0.35μｍ以下でしかもΔＨも2.0Oe以下の値
になるという効果が得られる。When the molar ratio of the flux component is within this range, the obtained oxide garnet single crystal has no cracks, and the surface irregularities are 0.35 μm or less, and ΔH is 2.0 Oe or less.
このように上記の方法で得られた酸化物ガーネット単
結晶厚膜は、クラックもなく、凹凸も小さく、またΔＨ
も小さいので、マイクロ波素子用材料としてすぐれた物
性をもつもので、例えば周波数100MHzから数10GHzのマ
イクロ波帯で使用されるマイクロ波素子用の磁性膜とし
て有用のほか、磁気光学素子の光アイソレーター、サー
キュレーター用の磁性膜としても有用である。As described above, the oxide garnet single crystal thick film obtained by the above method has no cracks, small irregularities, and a ΔH
Because of its small size, it has excellent physical properties as a material for microwave devices.For example, it is useful as a magnetic film for microwave devices used in the microwave band of frequencies from 100 MHz to several tens of GHz, and an optical isolator for magneto-optical devices. It is also useful as a magnetic film for a circulator.
つぎに本発明の実施例をあげるが例中における磁気共
鳴半値巾ΔＨはFMRを用いた破壊測定で求めたもの、ス
トリエーションはタリステップを用いて表面の凹凸の高
さの差を測定したもの、またクラックの有無は顕微鏡視
野内のひびの本数で評価したものである。Next, examples of the present invention will be described. In the examples, the magnetic resonance half width ΔH was obtained by destructive measurement using FMR, and the striation was obtained by measuring the difference in height of surface irregularities using tally steps. The presence or absence of cracks was evaluated based on the number of cracks in the visual field of the microscope.
（実施例１） 基板としてGGG単結晶ウェーハを用い、所定量のBi
2O3、Y2O3、Fe2O3、Ga2O3とフラックスのPbO、B2O3、Bi
2O3を、モル比で2Bi2O3/PbOを0.16、PbO/2B2O3を15.6と
して白金ルツボに仕込み、1,100℃に加熱して溶融させ
てこの融液から液相エピタキシャル法でGGG単結晶ウェ
−ハの（111）方向に式Ｙ2.9Bi0.1Fe4.1Ga0.9O12で示さ
れる酸化物ガーネット単結晶磁性膜を厚さ50μｍに育成
させた。(Example 1) A GGG single crystal wafer was used as a substrate, and a predetermined amount of Bi was used.
2 O 3 , Y 2 O 3 , Fe 2 O 3 , Ga 2 O 3 and flux PbO, B 2 O 3 , Bi
GGG the 2 O 3, 0.16 to 2Bi 2 O 3 / PbO in a molar ratio, with PbO / 2B 2 O 3 was charged in a platinum crucible as 15.6, a liquid phase epitaxial process from the melt is melted by heating to 1,100 ° C. An oxide garnet single crystal magnetic film represented by the formula Y 2.9 Bi 0.1 Fe 4.1 Ga 0.9 O 12 was grown to a thickness of 50 μm in the (111) direction of the single crystal wafer.
この磁性膜は、表面を顕微鏡で観察したところクラッ
ク、ヒビはみられず、磁気共鳴半値巾ΔＨ値は1.2Oeで
あり、ストリエーション凹凸差も0.16μｍであった。When the surface of the magnetic film was observed with a microscope, no cracks or cracks were observed. The magnetic resonance half width ΔH was 1.2 Oe, and the difference in striation was 0.16 μm.
【図面の簡単な説明】 第１図は本発明の方法による酸化物ガーネット単結晶育
成時におけるフラックス成分のPbO、B2O3、Bi2O3のモル
比を、PbO/2B2O3をＸ軸とし、2Bi2O3/PbOをＹ軸とした
ときのXY平面に示したものでる。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 of the flux components at the time of the oxide garnet single crystals according to the method of the present invention PbO, the molar ratio of B 2 O 3, Bi 2 O 3, a PbO / 2B 2 O 3 This is shown on the XY plane when the X axis is used and 2Bi 2 O 3 / PbO is used as the Y axis.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 丹野 雅行 群馬県安中市磯部２丁目13番１号 信越 化学工業株式会社精密機能材料研究所内 (56)参考文献 特開 昭49−93899（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01F 1/00 - 41/28 C30B 19/00 - 19/12──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masayuki Tanno 2-13-1 Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Precision Functional Materials Laboratory (56) References JP-A-49-93899 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) H01F 1/00-41/28 C30B 19/00-19/12
Claims (2)
液から基板上に厚さ20μｍ以上の（YBiFeN）8O12（ここ
にＮはAl、Ga、In、Scから選択される少なくとも１つの
元素）で示される膜状の酸化物ガーネット単結晶を育成
するに当たり、フラックス成分としてのPbO、B2O3およ
びBi2O3のモル比がPbO/2B2O3をＸ軸とし、2Bi2O3/PbOを
Ｙ軸としたXY平面において点Ａ（5.0,0）、Ｂ（6.0,0.
2）、Ｃ（30.0,0.2）、Ｄ（8.0,0）で囲まれた範囲（た
だしAD線上を除く）にあることを特徴とする酸化物ガー
ネット単結晶の製造方法。1. A liquid phase epitaxy method comprising the steps of: forming (YBiFeN) 8 O 12 (where N is at least one element selected from Al, Ga, In, and Sc) on a substrate from a flux melt; In growing the film-shaped oxide garnet single crystal shown, the molar ratio of PbO, B 2 O 3 and Bi 2 O 3 as flux components was PbO / 2B 2 O 3 on the X axis, and 2Bi 2 O 3 / On the XY plane with PbO as the Y axis, points A (5.0,0) and B (6.0,0.
2) A method for producing an oxide garnet single crystal, which is in a range (except on the AD line) surrounded by C (30.0, 0.2) and D (8.0, 0).
た厚さ20μｍ以上の（YBiFeN）8O12（ここにＮはAl、G
a、In、Scから選択される少なくとも１つの元素）で示
される膜状の酸化物ガーネット単結晶において、磁気共
鳴半値幅ΔＨが2.0Oe以下で、表面のストリエーション
凹凸差が0.35μｍ以下であることを特徴とする酸化物ガ
ーネット単結晶。2. A (YBiFeN) 8 O 12 (20 Nm or more) grown on a substrate by a liquid phase epitaxial method, wherein N is Al, G
a, at least one element selected from the group consisting of In, and Sc), has a magnetic resonance half-width ΔH of 2.0 Oe or less and a surface striation unevenness of 0.35 μm or less. An oxide garnet single crystal characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63246835A JP2784926B2 (en) | 1988-09-30 | 1988-09-30 | Oxide garnet single crystal and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63246835A JP2784926B2 (en) | 1988-09-30 | 1988-09-30 | Oxide garnet single crystal and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0294615A JPH0294615A (en) | 1990-04-05 |
| JP2784926B2 true JP2784926B2 (en) | 1998-08-13 |
Family
ID=17154402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63246835A Expired - Fee Related JP2784926B2 (en) | 1988-09-30 | 1988-09-30 | Oxide garnet single crystal and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2784926B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55143009A (en) * | 1979-04-26 | 1980-11-08 | Matsushita Electric Ind Co Ltd | Material for surface static magnetic wave |
| JPS5659695A (en) * | 1979-10-22 | 1981-05-23 | Nec Corp | Manufacture of oxide epitaxial film |
| JPS62268115A (en) * | 1986-05-16 | 1987-11-20 | Fujitsu Ltd | Method of controlling lattice constant matching in magnetic bubble garnet crystal and substrate |
-
1988
- 1988-09-30 JP JP63246835A patent/JP2784926B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0294615A (en) | 1990-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0354198A (en) | Oxide garnet single crystal | |
| US4624901A (en) | Intermediary layers for epitaxial hexagonal ferrite films | |
| Ballman et al. | The growth of single crystalline waveguiding thin films of piezoelectric sillenites | |
| Syvorotka et al. | Thick epitaxial YIG films with narrow FMR linewidth | |
| US6733587B2 (en) | Process for fabricating an article comprising a magneto-optic garnet material | |
| JPH11255600A (en) | Production of bismuth-substituted rare earth iron garnet single crystal thick film | |
| JP2784926B2 (en) | Oxide garnet single crystal and method for producing the same | |
| JP2869951B2 (en) | Magnetic garnet single crystal and microwave device material | |
| JPH02248398A (en) | Oxide garnet single crystal film and its production | |
| JP2794673B2 (en) | Oxide garnet single crystal magnetic film and method of manufacturing the same | |
| JPH07183114A (en) | Microwave element material and manufacture thereof | |
| JP2800973B2 (en) | Method for producing oxide garnet single crystal | |
| JP2756273B2 (en) | Oxide garnet single crystal and method for producing the same | |
| Syvorotka et al. | Growth peculiarities and magnetic properties of (LuBi) 3Fe5O12 films by LPE method | |
| JP3059332B2 (en) | Microwave device material | |
| US6368401B1 (en) | Method of producing magnetic garnet single crystal film and magnetic garnet single crystal film having a nonuniform thickness | |
| JP2779058B2 (en) | Magnetostatic wave filter | |
| JPH05117095A (en) | Production of bismuth-substituted rare earth iron garnet | |
| JP2800974B2 (en) | Garnet single crystal film and method for producing the same | |
| JP3089742B2 (en) | Materials for magnetostatic wave devices | |
| JP3547089B2 (en) | Microwave device material | |
| JPH02168606A (en) | Oxide garnet single crystal and microwave element | |
| JP3089741B2 (en) | Materials for magnetostatic wave devices | |
| JP2818343B2 (en) | Substrate holder for single crystal growth | |
| Huahui et al. | Epitaxial growth of highly Bi-substituted garnet films with narrow FMR linewidth and low optical absorption loss |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |