JP3144247B2 - Liquid phase epitaxial growth method - Google Patents
Liquid phase epitaxial growth methodInfo
- Publication number
- JP3144247B2 JP3144247B2 JP30086294A JP30086294A JP3144247B2 JP 3144247 B2 JP3144247 B2 JP 3144247B2 JP 30086294 A JP30086294 A JP 30086294A JP 30086294 A JP30086294 A JP 30086294A JP 3144247 B2 JP3144247 B2 JP 3144247B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid phase
- gap
- epitaxial growth
- phase epitaxial
- type
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/02—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux
- C30B19/04—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux the solvent being a component of the crystal composition
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/12—Liquid-phase epitaxial-layer growth characterised by the substrate
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Led Devices (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＧａＰ基板上に、液相
エピタキシャル成長法によってＧａＰ赤色発光ダイオー
ド用のＧａＰ層を成長する方法に関し、更に詳しくは酸
素をドープしたｐ型ＧａＰ層を成長する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for growing a GaP layer for a GaP red light emitting diode on a GaP substrate by liquid phase epitaxial growth, and more particularly, to a method for growing a p-type GaP layer doped with oxygen. About.
【０００２】[0002]
【発明の背景技術】ＧａＰ赤色発光ダイオードは、通
常、液相エピタキシャル成長法によって、ｎ型ＧａＰ基
板上にｎ型及びｐ型ＧａＰ層を順次積層形成してなるＧ
ａＰ赤色発光ダイオード用エピタキシャルウェーハを製
造し、これを素子化することにより得られる。2. Description of the Related Art A GaP red light emitting diode is generally formed by sequentially forming an n-type and a p-type GaP layer on an n-type GaP substrate by liquid phase epitaxial growth.
It is obtained by manufacturing an epitaxial wafer for an aP red light emitting diode and converting it into an element.
【０００３】ＧａＰはｐｎ接合を形成したままでは赤色
発光しないので、亜鉛（Ｚｎ）及び酸素（Ｏ）をｐ型Ｇ
ａＰ層にドープし、然る後約５００℃で熱処理すること
により、発光中心となるＺｎ−Ｏ対をｐ型ＧａＰ層内に
形成させる。このＧａＰ赤色発光ダイオードはピーク波
長７００ｎｍ前後の赤色発光をする。Since GaP does not emit red light when a pn junction is formed, zinc (Zn) and oxygen (O) are converted to p-type G
By doping the aP layer and then performing heat treatment at about 500 ° C., a Zn—O pair serving as a light emission center is formed in the p-type GaP layer. This GaP red light emitting diode emits red light having a peak wavelength of about 700 nm.
【０００４】[0004]
【発明が解決しようとする課題】上記のように、ＧａＰ
赤色発光ダイオードのｐ型ＧａＰ層にはＺｎとＯがドー
プされており、高輝度の発光ダイオードを得るにはＺｎ
−Ｏ対の濃度を高くすればよいが、そのためには多量の
Ｏをドープする必要がある。通常、入手し易い或いは計
量し易いという理由で、粉末状のＧａ2 Ｏ3 を用い、こ
の粉末状のＧａ2Ｏ3 をＯドープ源として添加した液相
エピタキシャル成長用Ｇａ溶液を用いてＯドープｐ型Ｇ
ａＰ層を成長していた。As described above, GaP
The p-type GaP layer of the red light emitting diode is doped with Zn and O. To obtain a high-brightness light emitting diode, Zn is used.
Although the concentration of the -O pair may be increased, a large amount of O needs to be doped. Usually, because it is easily available or easy to measure, powdered Ga 2 O 3 is used, and O-doped p is added using a Ga solution for liquid phase epitaxial growth to which this powdered Ga 2 O 3 is added as an O-doping source. Type G
The aP layer was growing.
【０００５】しかし、粉末状のＧａ2 Ｏ3 はＧａ溶液と
の濡れ性が悪く、Ｇａ溶液への溶解が極めて不安定であ
るため、斯かるＧａ2 Ｏ3 を添加した液相エピタキシャ
ル成長用Ｇａ溶液を用いて成長したＯドープｐ型ＧａＰ
層においては、該ｐ型ＧａＰ層中のＯ濃度が不安定とな
り、ひいては発光輝度が不安定或いは不均一となってし
まう。その上、高輝度化をはかるために、より多量の粉
末状のＧａ2 Ｏ3 をＧａ溶液に添加すると、粉末状のＧ
ａ2 Ｏ3 はＧａ溶液に完全に溶解できずに粉末状のまま
残ってしまう。この粉末状の残溜Ｇａ2 Ｏ3 は、成長さ
れたｐ型ＧａＰ層表面にＧａ2 Ｏ3 析出物として付着
し、面不良率が増加するという問題があった。However, powdered Ga 2 O 3 has poor wettability with a Ga solution and is extremely unstable in dissolving in a Ga solution. Therefore, a Ga solution for liquid phase epitaxial growth to which such Ga 2 O 3 is added is used. -Doped p-type GaP grown by using
In the layer, the O concentration in the p-type GaP layer becomes unstable, and the emission luminance becomes unstable or non-uniform. In addition, when a larger amount of powdered Ga 2 O 3 is added to the Ga solution in order to increase the brightness, the powdered G
a 2 O 3 cannot be completely dissolved in the Ga solution and remains as a powder. This powdery residual Ga 2 O 3 adheres to the surface of the grown p-type GaP layer as a Ga 2 O 3 precipitate, which causes a problem that the surface defect rate increases.
【０００６】そこで本発明は、多量の酸素がドープさ
れ、且つ酸化ガリウム（Ｇａ2 Ｏ3 ）の析出物の極めて
少ないｐ型ＧａＰ層を成長させることができ、従って高
輝度のＧａＰ赤色発光ダイオードを高収率で製造するこ
とを可能とした液相エピタキシャル成長法を提供するこ
とを目的とする。Accordingly, the present invention is capable of growing a p-type GaP layer doped with a large amount of oxygen and having very few gallium oxide (Ga 2 O 3 ) precipitates. It is an object of the present invention to provide a liquid phase epitaxial growth method capable of producing a high yield.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決するため
に、本発明は、ＧａＰ赤色発光ダイオード用エピタキシ
ャルウェーハを製造するにあたり、酸化ガリウム（Ｇａ
2 Ｏ3 ）を添加したＧａ溶液を用い液相エピタキシャル
成長法によって酸素をドープしたｐ型ＧａＰ層を積層す
る方法において、前記Ｇａ2 Ｏ3 として見かけ密度３．
０〜５．９ｇ／ｃｍ3 （２５℃）のＧａ2 Ｏ3固結体を
用いることを特徴とする。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention relates to a method of manufacturing an epitaxial wafer for a GaP red light-emitting diode, which uses gallium oxide (Ga).
In a method of stacking a p-type GaP layer doped with oxygen by a liquid phase epitaxial growth method using a Ga solution to which 2 O 3 ) has been added, an apparent density of Ga 2 O 3 is 3.
It is characterized by using a Ga 2 O 3 compact of 0 to 5.9 g / cm 3 (25 ° C.).
【０００８】該Ｇａ2 Ｏ3 固結体の大きさは、０．０３
ｃｍ3 （２５℃）以上のものが好適に用いられる。ま
た、該Ｇａ2 Ｏ3 固結体は焼結体であるのが好ましい。
さらに、該Ｇａ2 Ｏ3 固結体が、結合剤を用いた焼結体
であってもよい。該結合剤としては酸化珪素（Ｓｉ
Ｏ2 ）又は酸化亜鉛（ＺｎＯ）を用いるのが好適であ
る。The size of the Ga 2 O 3 compact is 0.03.
Those having cm 3 (25 ° C.) or more are preferably used. Further, the Ga 2 O 3 compact is preferably a sintered body.
Further, the Ga 2 O 3 compact may be a sintered body using a binder. Silicon oxide (Si
O 2 ) or zinc oxide (ZnO) is preferably used.
【０００９】[0009]
【実施例】以下、本発明方法の対象となるＧａＰ赤色発
光ダイオード用エピタキシャルウェーハについて図面を
参照して説明する。図１は、ＧａＰ赤色発光ダイオード
用エピタキシャルウェーハの一例を示す概略断面説明図
である。このＧａＰ赤色発光ダイオード用エピタキシャ
ルウェーハ１０は、ｎ型ＧａＰ基板上１上に、ｎ型Ｇａ
Ｐ層２及びｐ型ＧａＰ層３が順次形成されている。ｎ型
及びｐ型となるドーパントは、各々例えば硫黄（Ｓ）及
び亜鉛（Ｚｎ）である。また、ｐ型ＧａＰ層３にはＺｎ
とともに酸素がドープされている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An epitaxial wafer for a GaP red light-emitting diode which is a subject of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic sectional explanatory view showing an example of an epitaxial wafer for a GaP red light emitting diode. The epitaxial wafer 10 for a GaP red light emitting diode has an n-type GaP substrate 1 on an n-type GaP substrate.
A P layer 2 and a p-type GaP layer 3 are sequentially formed. The n-type and p-type dopants are, for example, sulfur (S) and zinc (Zn), respectively. The p-type GaP layer 3 has Zn
At the same time, oxygen is doped.
【００１０】次に上記ＧａＰ赤色発光ダイオード用エピ
タキシャルウェーハ１０の製造方法の一例を以下に示
す。まず、例えば液体封止チョクラルスキー法（ＬＥＣ
法）により育成されたｎ型ＧａＰ単結晶をウェーハ加工
してｎ型ＧａＰ基板１を製造する。このｎ型ＧａＰ基板
１の上に、各ＧａＰ層２、３を液相エピタキシャル成長
法により形成させる。即ち、液相エピタキシャル成長法
でｎ型ＧａＰ層２を形成した後、該ｎ型ＧａＰ層２上
に、図２に示す成長プログラムで、ｐ型ＧａＰ層３を成
長させる。Next, an example of a method of manufacturing the epitaxial wafer 10 for the GaP red light emitting diode will be described below. First, for example, the liquid-sealed Czochralski method (LEC
The n-type GaP substrate 1 is manufactured by processing the n-type GaP single crystal grown by the method (1) into a wafer. Each of the GaP layers 2 and 3 is formed on the n-type GaP substrate 1 by a liquid phase epitaxial growth method. That is, after the n-type GaP layer 2 is formed by the liquid phase epitaxial growth method, the p-type GaP layer 3 is grown on the n-type GaP layer 2 by a growth program shown in FIG.
【００１１】図２において、まず、ｐ型ＧａＰ層３の成
長開始となる温度（例えば１０５０℃）で、Ｚｎ、Ｇａ
2 Ｏ3 及びＧａＰ多結晶を溶解したＧａ溶液（１０５０
℃におけるＧａＰの飽和Ｇａ溶液）を、前記ｎ型ＧａＰ
基板１上にｎ型ＧａＰ層２を形成してなる基板（以下、
「ｎ型多層ＧａＰ基板」という。）上に配置する。In FIG. 2, first, at a temperature (for example, 1050 ° C.) at which growth of the p-type GaP layer 3 starts, Zn, Ga
Ga solution (1050) dissolving 2 O 3 and GaP polycrystal
C.) with the n-type GaP.
A substrate having an n-type GaP layer 2 formed on a substrate 1 (hereinafter referred to as a
It is called "n-type multilayer GaP substrate". ) On top.
【００１２】次に、温度を１０５０℃（成長開始温度、
図２におけるＡ）から９８０℃（成長終了温度、図２に
おけるＢ）まで降温し、前記Ｇａ溶液中のＧａＰを前記
ｎ型多層ＧａＰ基板のｎ型ＧａＰ層２上に析出させてｐ
型ＧａＰ層３を成長させた後、この温度において前記Ｇ
ａ溶液を基板から切り離す。この様にして、Ｚｎ及びＯ
がドープされたｐ型ＧａＰ層３が形成される。次いで、
５０℃まで冷却して基板を取り出し、然る後、約５００
℃で熱処理を施して発光中心となるＺｎ−Ｏ対をｐ型Ｇ
ａＰ層３内に形成させる。Next, the temperature is raised to 1050 ° C. (growth starting temperature,
The temperature was lowered from A) in FIG. 2 to 980 ° C. (growth end temperature, B in FIG. 2), and GaP in the Ga solution was deposited on the n-type GaP layer 2 of the n-type multi-layer GaP substrate to form p.
After growing the GaP-type GaP layer 3, the G
a Separate the solution from the substrate. In this way, Zn and O
Is formed to form a p-type GaP layer 3 doped with. Then
After cooling to 50 ° C., the substrate is taken out, and then about 500
The Zn—O pair serving as the emission center is subjected to a heat treatment at
It is formed in the aP layer 3.
【００１３】上記の様にして、ｎ型ＧａＰ基板１上にｎ
型ＧａＰ層２及びｐ型ＧａＰ層３が順次積層形成された
ＧａＰ赤色発光ダイオード用エピタキシャルウェーハ１
０が製造される。このエピタキシャルウェーハ１０のｎ
型ＧａＰ基板１の下面にｎ電極、ｐ型ＧａＰ層３上にｐ
電極を形成し、ダイシング後、その半導体チップを支持
体に固着し、ワイヤボンディング後、樹脂封止すること
によりＧａＰ赤色発光ダイオードが得られる。As described above, n-type GaP substrate 1 has n
Wafer 1 for a GaP red light-emitting diode in which a p-type GaP layer 2 and a p-type GaP layer 3 are sequentially laminated.
0 is produced. N of the epitaxial wafer 10
Electrode on the lower surface of the p-type GaP substrate 1 and p-type electrode on the p-type GaP layer 3
After forming an electrode, dicing, fixing the semiconductor chip to a support, wire bonding, and sealing with a resin, a GaP red light emitting diode is obtained.
【００１４】次に、実験例及び実施例により本発明を更
に具体的に説明する。 （実験例１）液相エピタキシャル成長用Ｇａ溶液に添加
するＧａ2 Ｏ3 を、粉末状のＧａ2Ｏ3 、その添加濃度
を０．１〜０．４５重量％として、前記した成長法によ
りｐ型ＧａＰ層３を成長し、ＧａＰ赤色発光ダイオード
用エピタキシャルウェーハ１０を製造した。Next, the present invention will be described more specifically with reference to experimental examples and examples. (Experimental Example 1) Ga 2 O 3 to be added to a Ga solution for liquid phase epitaxial growth was powdered Ga 2 O 3 , and the addition concentration was 0.1 to 0.45% by weight. The GaP layer 3 was grown to produce a GaP red light emitting diode epitaxial wafer 10.
【００１５】図３は、ｐ型ＧａＰ層３の成長に用いたＧ
ａ溶液中のＧａ2 Ｏ3 の濃度（重量％）と前記エピタキ
シャルウェーハ１０から得たＧａＰ赤色発光ダイオード
の輝度（相対輝度）の平均値との関係を示す。図から、
相対輝度が４５以上の高輝度発光ダイオードを得るに
は、ｐ型ＧａＰ層３の成長に用いるＧａ溶液中のＧａ2
Ｏ3 濃度を０．３５％以上とする必要があることが分
る。FIG. 3 shows a graph of G used for growing the p-type GaP layer 3.
The relationship between the concentration (% by weight) of Ga 2 O 3 in the solution a and the average value of the luminance (relative luminance) of the GaP red light emitting diode obtained from the epitaxial wafer 10 is shown. From the figure,
In order to obtain a high-brightness light emitting diode having a relative luminance of 45 or more, Ga 2 in a Ga solution used for growing the p-type
It is understood that the O 3 concentration needs to be 0.35% or more.
【００１６】しかし、高輝度のＧａＰ赤色発光ダイオー
ドを得るために、Ｇａ2 Ｏ3 濃度を０．３５重量％以上
にすると、ｐ型ＧａＰ層３にＧａ2 Ｏ3 析出物が多数発
生し、図４に示す様にＧａ2 Ｏ3 析出物起因の面不良率
が４５％以上になってしまう。また面不良率を１０％以
下にするために、Ｇａ2 Ｏ3 濃度を０．２重量％以下に
すると、図３から明らかの様に高輝度化が達成できな
い。ここで、Ｇａ2 Ｏ3析出物起因の面不良率（％）
は、下記式（１）により算出した。However, if the concentration of Ga 2 O 3 is set to 0.35% by weight or more in order to obtain a high-luminance GaP red light emitting diode, a large number of Ga 2 O 3 precipitates are generated in the p-type GaP layer 3. As shown in FIG. 4, the surface defect rate caused by the Ga 2 O 3 precipitate becomes 45% or more. Further, if the concentration of Ga 2 O 3 is set to 0.2% by weight or less in order to reduce the surface defect rate to 10% or less, high brightness cannot be achieved as is apparent from FIG. Here, the percentage of surface defects caused by Ga 2 O 3 precipitates (%)
Was calculated by the following equation (1).
【００１７】[0017]
【数１】 (ａ／ｂ）×１００・・・・・・・・・・・・・・・・・・（１）(1) (a / b) × 100 (1)
【００１８】上記式（１）中、ａはＧａ2 Ｏ3 析出物起
因の不良エピタキシャルウェーハの枚数、ｂはｐ型Ｇａ
Ｐ層成長工程に投入のｎ型多層ＧａＰ基板の枚数であ
る。In the above formula (1), a is the number of defective epitaxial wafers caused by Ga 2 O 3 precipitates, and b is p-type Ga
This is the number of n-type multilayer GaP substrates input to the P layer growth step.
【００１９】また、Ｇａ2 Ｏ3 析出物起因の不良エピタ
キシャルウェーハとは、Ｇａ2 Ｏ3析出物の個数＞１０
個／ｃｍ2 であるエピタキシャルウェーハを云う。[0019] In addition, the failure epitaxial wafer of Ga 2 O 3 precipitates due, the number of Ga 2 O 3 precipitates> 10
Pieces / cm 2 .
【００２０】（実施例１）Ｇａ2 Ｏ3 として、見かけ密
度３．０、３．９、４．６、５．２及び５．９ｇ／ｃｍ
3 （２５℃）、大きさが、各々０．０３、０．０５、
０．０８及び０．１５ｃｍ3 （２５℃）のＧａ2 Ｏ3 成
形焼結体を用いた。該Ｇａ2 Ｏ3 焼結体を、０．４０重
量％で、液相エピタキシャル成長用Ｇａ溶液に添加し、
実験例１と同一の方法でｐ型ＧａＰ層３を成長してＧａ
Ｐ赤色発光ダイオード用エピタキシャルウェーハ１０を
製造した。Example 1 As Ga 2 O 3 , apparent densities of 3.0, 3.9, 4.6, 5.2 and 5.9 g / cm.
3 (25 ° C), the sizes are 0.03, 0.05,
The Ga 2 O 3 sintered compact of 0.08 and 0.15cm 3 (25 ℃) was used. The Ga 2 O 3 sintered body was added at 0.40% by weight to a Ga solution for liquid phase epitaxial growth,
The p-type GaP layer 3 was grown in the same manner as
An epitaxial wafer 10 for a P-red light emitting diode was manufactured.
【００２１】図５に、上記した方法で得られたＧａＰ赤
色発光ダイオード用エピタキシャルウェーハ１０のうち
Ｇａ2 Ｏ3 焼結体の大きさが０．０５ｃｍ3 における、
添加したＧａ2 Ｏ3 焼結体の密度とＧａ2 Ｏ3 析出物起
因の面不良率（実験例１と同一方法で算出）との関係、
及び添加したＧａ2 Ｏ3 焼結体の密度と前記エピタキシ
ャルウェーハ１０から得たＧａＰ赤色発光ダイオードの
輝度（相対輝度）の平均値との関係を示す（●：面不良
率、○：相対輝度）。FIG. 5 shows that the Ga 2 O 3 sintered body in the GaP red light emitting diode epitaxial wafer 10 obtained by the above-described method has a size of 0.05 cm 3 .
Relationship between the density of the added Ga 2 O 3 sintered body and the percentage of surface defects caused by Ga 2 O 3 precipitates (calculated by the same method as in Experimental Example 1),
And the relationship between the density of the added Ga 2 O 3 sintered body and the average value of the luminance (relative luminance) of the GaP red light emitting diode obtained from the epitaxial wafer 10 (●: surface defect rate, ○: relative luminance) .
【００２２】Ｇａ2 Ｏ3 焼結体の見かけ密度が３．０ｇ
／ｃｍ3 以上であれば、Ｇａ2 Ｏ3析出物起因の面不良
率は７％以下（見かけ密度４．５ｇ／ｃｍ3 では不良率
ほぼゼロ％）と、粉末状Ｇａ2 Ｏ3 の場合の不良率約５
５％（図４参照）に対し大幅の改善が達成できるととも
に、発光輝度（相対輝度）の平均値も約４５と高輝度で
あった。また、Ｇａ2 Ｏ3 成形焼結体の大きさが、０．
０３、０．０８、０．１５ｃｍ3 の場合についても、前
記した０．０５ｃｍ3 の場合と同一の効果が達成され
た。The apparent density of the Ga 2 O 3 sintered body is 3.0 g.
If / cm 3 or more, Ga 2 O 3 precipitates due surfaces 7% or less failure rate (apparent density 4.5 g / cm 3 in the failure rate substantially zero%), in the case of powdered Ga 2 O 3 Defective rate about 5
A significant improvement over 5% (see FIG. 4) was achieved, and the average value of the emission luminance (relative luminance) was as high as about 45. Further, the size of the Ga 2 O 3 molded sintered body is set to 0.
If for also 03,0.08,0.15cm 3, the same effect as the 0.05 cm 3 described above have been achieved.
【００２３】従って、ｐ型ＧａＰ層３の成長に用いるＧ
ａ溶液に添加するＧａ2Ｏ3 として、見かけ密度３．０
〜５．９ｇ／ｃｍ3 （２５℃）のＧａ2Ｏ3焼結体であ
り、その大きさが０．０３ｃｍ3 （２５℃）以上のＧａ
2Ｏ3焼結体を用いることにより、Ｇａ溶液中にＧａ2Ｏ
3 を０．３５重量％以上と多量に含有（高輝度化の必須
条件）させても、ｐ型ＧａＰ層３に析出するＧａ2Ｏ3
析出物の極めて少ない、面状態の良好なＧａＰ赤色発光
ダイオード用エピタキシャルウェーハを高収率で製造す
ることができることが確認できた。Accordingly, the G used for growing the p-type GaP layer 3
a) As Ga 2 O 3 added to the solution a, an apparent density of 3.0
~5.9g / cm 3 is Ga 2 O 3 sintered body (25 ° C.), its magnitude 0.03cm 3 (25 ℃) more Ga
By using a 2 O 3 sintered body, Ga 2 O
3 is contained in a large amount of 0.35% by weight or more (indispensable condition for higher brightness), Ga 2 O 3
It was confirmed that an epitaxial wafer for a GaP red light-emitting diode with very few precipitates and a good surface condition could be produced in high yield.
【００２４】上記実施例１においては、結合剤なしのＧ
ａ2Ｏ3焼結体を用いた例を示したが、結合剤としてＳｉ
Ｏ2又はＺｎＯを用いたＧａ2 Ｏ3焼結体についても同様
の結果が得られることについても確認した。また、Ｇａ
2 Ｏ3焼結体の適用例を示したが、Ｇａ2 Ｏ3焼結体以外
のＧａ2 Ｏ3固結体、例えば晶析体を用いても本発明の
作用効果が達成されることも確認してある。In Example 1 above, G without binder was used.
Although the example using the a 2 O 3 sintered body was shown,
It was also confirmed that similar results were obtained for Ga 2 O 3 sintered bodies using O 2 or ZnO. Also, Ga
Although example of application 2 O 3 sintered body, Ga 2 O 3 sintered body other than the Ga 2 O 3 Katayuitai, for example crystal also is also achieved operation and effect of the present invention with reference to析体I have confirmed.
【００２５】[0025]
【発明の効果】以上のべたごとく、本発明によれば、多
量の酸素がドープされ、且つ酸化ガリウム（Ｇａ
2 Ｏ3 ）の析出物の極めて少ないｐ型ＧａＰ層を成長さ
せることができ、従って高輝度のＧａＰ赤色発光ダイオ
ードを高収率で製造することができるという効果を奏す
る。As described above, according to the present invention, a large amount of oxygen is doped and gallium oxide (Ga
It is possible to grow a p-type GaP layer having extremely few precipitates of 2 O 3 ), and thus to produce a high-luminance GaP red light-emitting diode in a high yield.
【図１】ＧａＰ赤色発光ダイオード用エピタキシャルウ
ェーハの一例を示す概略断面図である。FIG. 1 is a schematic sectional view showing an example of an epitaxial wafer for a GaP red light emitting diode.
【図２】ＧａＰ赤色発光ダイオード用エピタキシャルウ
ェーハ製造のための液相エピタキシャル成長プログラム
を示す図面である。FIG. 2 is a view illustrating a liquid phase epitaxial growth program for manufacturing an epitaxial wafer for a GaP red light emitting diode.
【図３】ｐ型ＧａＰ層の成長に用いたＧａ溶液中のＧａ
2 Ｏ3 の濃度とＧａＰ赤色発光ダイオード用エピタキシ
ャルウェーハから得たＧａＰ赤色発光ダイオードの輝度
（相対輝度）の平均値との関係を示すグラフである。FIG. 3 shows Ga in a Ga solution used for growing a p-type GaP layer.
4 is a graph showing the relationship between the concentration of 2 O 3 and the average value of the luminance (relative luminance) of a GaP red light emitting diode obtained from an epitaxial wafer for a GaP red light emitting diode.
【図４】ｐ型ＧａＰ層の成長に用いたＧａ溶液中の粉末
状Ｇａ2 Ｏ3の濃度とＧａ2 Ｏ3析出物起因の面不良率と
の関係を示すグラフである。FIG. 4 is a graph showing the relationship between the concentration of powdered Ga 2 O 3 in a Ga solution used for growing a p-type GaP layer and the percentage of surface defects caused by Ga 2 O 3 precipitates.
【図５】実施例１において、焼結体の大きさが０．０５
ｃｍ3における、添加したＧａ2 Ｏ3 焼結体の密度とＧａ
2 Ｏ3 析出物起因の面不良率との関係、及び添加したＧ
ａ2 Ｏ3 焼結体の密度とＧａＰ赤色発光ダイオード用エ
ピタキシャルウェーハから得たＧａＰ赤色発光ダイオー
ドの輝度（相対輝度）の平均値との関係を示すグラフで
ある。FIG. 5 is a cross-sectional view of Example 1 in which the size of the sintered body is 0.05
cmThreeGa added inTwo OThreeDensity of sintered body and Ga
TwoOThreeRelationship with the percentage of surface defects due to precipitates and the added G
aTwoOThreeDensity of sintered body and energy for GaP red LED
GaP red light emitting diode obtained from a epitaxial wafer
Is a graph showing the relationship between the average luminance (relative luminance) and the average
is there.
１ ｎ型ＧａＰ基板 ２ ｎ型ＧａＰ層 ３ ｐ型ＧａＰ層 １０ エピタキシャルウェーハ Reference Signs List 1 n-type GaP substrate 2 n-type GaP layer 3 p-type GaP layer 10 epitaxial wafer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 遠藤 正久 群馬県安中市磯部２丁目13番１号 信越 半導体株式会社 磯部工場内 (56)参考文献 特開 昭50−156873（ＪＰ，Ａ) 特開 昭50−146268（ＪＰ，Ａ) 特開 昭49−60680（ＪＰ，Ａ) 特開 昭60−239397（ＪＰ，Ａ) 特開 昭47−26311（ＪＰ，Ａ) 特開 昭49−29098（ＪＰ，Ａ) 特開 昭50−51080（ＪＰ，Ａ) 特開 昭50−51081（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 H01L 21/208 H01L 33/00 ＣＡ（ＳＴＮ) ＪＩＣＳＴファイル（ＪＯＩＳ)──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masahisa Endo 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Semiconductor Co., Ltd. Isobe Plant (56) References Japanese Patent Laid-Open No. 50-156873 (JP, A) JP-A-50-146268 (JP, A) JP-A-49-60680 (JP, A) JP-A-60-239397 (JP, A) JP-A-47-26311 (JP, A) JP-A-49-29098 (JP, A) JP, A) JP-A-50-51080 (JP, A) JP-A-50-51081 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C30B 1/00-35/00 H01L 21/208 H01L 33/00 CA (STN) JICST file (JOIS)
Claims (5)
ャルウェーハを製造するにあたり、酸化ガリウム（Ｇａ
2 Ｏ3 ）を添加したＧａ溶液を用い液相エピタキシャル
成長法によって酸素をドープしたｐ型ＧａＰ層を積層す
る方法において、前記Ｇａ2 Ｏ3 として見かけ密度３．
０〜５．９ｇ／ｃｍ3 （２５℃）のＧａ2 Ｏ3固結体を
用いることを特徴とする液相エピタキシャル成長法。In manufacturing an epitaxial wafer for a GaP red light emitting diode, gallium oxide (Ga) is used.
In a method of stacking a p-type GaP layer doped with oxygen by a liquid phase epitaxial growth method using a Ga solution to which 2 O 3 ) has been added, an apparent density of Ga 2 O 3 is 3.
A liquid phase epitaxial growth method characterized by using a Ga 2 O 3 compact of 0 to 5.9 g / cm 3 (25 ° C.).
０３ｃｍ3 （２５℃）以上であることを特徴とする請求
項１に記載の液相エピタキシャル成長法。2. The size of the Ga 2 O 3 compact is 0.
2. The liquid phase epitaxial growth method according to claim 1, wherein the temperature is not less than 03 cm 3 (25 ° C.).
ことを特徴とする請求項１または請求項２に記載の液相
エピタキシャル成長法。3. The liquid phase epitaxial growth method according to claim 1, wherein the Ga 2 O 3 compact is a sintered body.
た焼結体であることを特徴とする請求項１または請求項
２に記載の液相エピタキシャル成長法。4. The liquid phase epitaxial growth method according to claim 1, wherein the Ga 2 O 3 compact is a sintered body using a binder.
は酸化亜鉛（ＺｎＯ）であることを特徴とする請求項４
に記載の液相エピタキシャル成長法。5. The binder according to claim 4, wherein the binder is silicon oxide (SiO 2 ) or zinc oxide (ZnO).
3. The liquid phase epitaxial growth method according to 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30086294A JP3144247B2 (en) | 1994-12-05 | 1994-12-05 | Liquid phase epitaxial growth method |
| TW084101065A TW270215B (en) | 1994-12-05 | 1995-02-08 | Liquid phase extension growing process |
| KR1019950029402A KR0177007B1 (en) | 1994-12-05 | 1995-09-07 | Method for liquid phase epitaxial growth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30086294A JP3144247B2 (en) | 1994-12-05 | 1994-12-05 | Liquid phase epitaxial growth method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08157300A JPH08157300A (en) | 1996-06-18 |
| JP3144247B2 true JP3144247B2 (en) | 2001-03-12 |
Family
ID=17890016
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30086294A Expired - Fee Related JP3144247B2 (en) | 1994-12-05 | 1994-12-05 | Liquid phase epitaxial growth method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3144247B2 (en) |
| KR (1) | KR0177007B1 (en) |
| TW (1) | TW270215B (en) |
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1994
- 1994-12-05 JP JP30086294A patent/JP3144247B2/en not_active Expired - Fee Related
-
1995
- 1995-02-08 TW TW084101065A patent/TW270215B/en active
- 1995-09-07 KR KR1019950029402A patent/KR0177007B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR0177007B1 (en) | 1999-03-20 |
| KR960023268A (en) | 1996-07-18 |
| TW270215B (en) | 1996-02-11 |
| JPH08157300A (en) | 1996-06-18 |
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