JPH0728053B2 - Light emitting diode - Google Patents
Light emitting diodeInfo
- Publication number
- JPH0728053B2 JPH0728053B2 JP15532186A JP15532186A JPH0728053B2 JP H0728053 B2 JPH0728053 B2 JP H0728053B2 JP 15532186 A JP15532186 A JP 15532186A JP 15532186 A JP15532186 A JP 15532186A JP H0728053 B2 JPH0728053 B2 JP H0728053B2
- Authority
- JP
- Japan
- Prior art keywords
- znsxse
- type
- light emitting
- emitting diode
- layer
- 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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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、化合物基体、とりわけ、II−VI族化合物基体
を用いた発光ダイオードに関するものである。TECHNICAL FIELD The present invention relates to a light emitting diode using a compound substrate, particularly a II-VI compound substrate.
従来の技術 高輝度の発光ダイオード（以下、LEDと略称する）を作
成するためには、半導体材料がｐ−ｎ接合を形成するこ
とが可能であることが望ましい。しかし、たとえば、セ
レン化亜鉛（ZnSe）はｎ型伝導性を示すものは比較的容
易に得ることができるのに対し、ｐ型伝導性を示すもの
を得るのは困難である。この様に、一方の伝導型のみし
か得られないというのは広い禁制帯幅を持つ半導体一般
に見られる現象である。2. Description of the Related Art In order to produce a high-brightness light emitting diode (hereinafter abbreviated as LED), it is desirable that the semiconductor material be capable of forming a pn junction. However, for example, zinc selenide (ZnSe) that exhibits n-type conductivity can be obtained relatively easily, whereas it is difficult to obtain p-type conductivity. Thus, the fact that only one conductivity type can be obtained is a phenomenon generally found in semiconductors having a wide band gap.
発明が解決しようとする問題点 ところで、LED作成のためには、ｐ−ｎ接合が好ましい
がｐ型結合を得るのが困難な場合、金属−絶縁層−ｎ型
層（ｍ−ｉ−ｎ）構造を採用せざるを得ない。この場
合、電子がｎ型層（ｎ層）から絶縁層（ｉ層）に注入さ
れｉ層で発光する。Problems to be Solved by the Invention By the way, for LED fabrication, a pn junction is preferable, but when it is difficult to obtain a p-type coupling, a metal-insulating layer-n-type layer (m-i-n) There is no choice but to adopt the structure. In this case, electrons are injected from the n-type layer (n layer) into the insulating layer (i layer) to emit light in the i layer.
分子線エピタキシー（MBE）法や金属有機化合物を分解
して生成する気相成長（MOCVD）法でZnSe単結晶膜を成
長すると、不純物を添加しなくても比較的高品質のｎ型
結晶が得られる。このとき、絶縁層あるいはｐ型結晶を
得る目的で、ｐ型の不純物である窒素（Ｎ），リン
（Ｐ）砒素（As）等を添加すると、これらｐ型不純物が
SA中心と呼ばれる深い不純物準位を形成し、十分な発光
性能が得られない。Growing a ZnSe single crystal film by the molecular beam epitaxy (MBE) method or the vapor phase epitaxy (MOCVD) method generated by decomposing metal-organic compounds yields a relatively high-quality n-type crystal without adding impurities. To be At this time, if p-type impurities such as nitrogen (N) and phosphorus (P) arsenic (As) are added for the purpose of obtaining an insulating layer or p-type crystal, these p-type impurities are removed.
A deep impurity level called SA center is formed, and sufficient light emission performance cannot be obtained.
問題点を解決するための手段 本発明は、ZnSeとイオウ化亜鉛（ZnS）の混晶半導体で
あるセレン・イオウ化亜鉛ZnSxSe1-Xが、イオウ（Ｓ）
の組成ｘの選定により、高比抵抗の絶縁性結晶になると
いう事実に基づくもので、要約するに、良質のｎ型結晶
が得られるZnSeと、良質の絶縁性結晶が得られるZnSxSe
1-Xとの接合をそなえたLEDである。Means for Solving the Problems In the present invention, a mixed crystal semiconductor of ZnSe and zinc sulfur (ZnS), selenium-zinc sulfuride ZnSxSe 1-X, is sulfur (S).
It is based on the fact that a high specific resistance insulating crystal can be obtained by selecting the composition x of the above. In summary, ZnSe that can obtain a good n-type crystal and ZnSxSe that can obtain a good insulating crystal
It is an LED with a junction with 1-X .
作用 本発明によれば、MBEやMOCVD法を使用して、ｎ型ZnSeと
絶縁性の高いZnSxSe1-Xとを連続的に成長させ、容易に
高効率の青色LEDを作成することができる。Effect According to the present invention, n-type ZnSe and ZnSxSe 1-X having high insulation can be continuously grown by using MBE or MOCVD method to easily produce a highly efficient blue LED.
実施例 第１図は本発明実施例のLEDの断面図である。このLED
は、砒素ガリウム（GaAs）１の基板上に厚さ20μｍのｎ
型ZnSe層２を形成し、さらに、これに厚さ1.0μｍ以下
の高抵抗性ZnSxSe1-X層３を積層形成したもので、GaAs1
側の電極をゲルマニウム（Ge）含有の金（Au）蒸着層の
Ge・Au電極で、また、ZnSxSe1-X3側の電極をAu蒸着層の
Au電極５で形成する。この実施例では、ZnSxSe1-X層３
のイオウ（Ｓ）の組成比ｘを、ｘ＝0.1に選定し、青色
発光特性の青色LEDを形成した。Embodiment FIG. 1 is a sectional view of an LED according to an embodiment of the present invention. This LED
Is a 20 μm thick n film on a substrate of gallium arsenide (GaAs) 1.
Type ZnSe layer 2 is formed, and a high-resistivity ZnSxSe 1-X layer 3 having a thickness of 1.0 μm or less is further laminated thereon.
The electrode on the side of the gold (Au) deposition layer containing germanium (Ge)
Ge / Au electrode, and the ZnSxSe 1-X 3 side electrode is the Au deposition layer.
The Au electrode 5 is used. In this example, the ZnSxSe 1-X layer 3
The composition ratio x of sulfur (S) was selected as x = 0.1 to form a blue LED having blue emission characteristics.
第２図は、この実施例発光ダイオードの作成のために使
用したMOCVD成長装置の概略図を示したものである。亜
鉛原料にはジメチル亜鉛（DMZ）、セレン原料にはセレ
ン化水素（H2Se）イオウ原料には硫化水素（H2S）を用
いている。DMZは恒温槽内のバブラー11に入れられ、マ
スフローコントローラ12により流量制御された水素
（H2）をキャリアガスとして、反応管13内へ送られる。
一方H2SとH2Seは水素で10％に希釈されたものを用い、
マスフローコントローラ12により流量制御され反応管13
に送られる。FIG. 2 is a schematic view of the MOCVD growth apparatus used for manufacturing the light emitting diode of this example. Dimethyl zinc (DMZ) is used as the zinc raw material, hydrogen selenide (H 2 Se) is used as the selenium raw material, and hydrogen sulfide (H 2 S) is used as the sulfur raw material. The DMZ is put into a bubbler 11 in a constant temperature bath, and is sent into the reaction tube 13 using hydrogen (H 2 ) whose flow rate is controlled by the mass flow controller 12 as a carrier gas.
On the other hand, H 2 S and H 2 Se used were diluted with hydrogen to 10%,
Flow rate is controlled by mass flow controller 12 and reaction tube 13
Sent to.
基板14にはｎ型砒化ガリウム（GaAs）を用い、カーボン
サセプタ15上に設置され、同サセプタ15内のヒーターに
より、成長温度250℃に加熱される。反応管13内の圧力
はロータリーポンプ16により0.7トールの減圧状態に保
たれる。The substrate 14 is made of n-type gallium arsenide (GaAs), is placed on the carbon susceptor 15, and is heated to a growth temperature of 250 ° C. by a heater in the susceptor 15. The pressure inside the reaction tube 13 is maintained at a reduced pressure of 0.7 Torr by the rotary pump 16.
DMZの供給量を3.7×10-5mol/minとし、このDMZに対する
H2SとH2Seとの合計の比（VI/II）比を10倍として、当量
生成物が得られるように、一定に保ち、H2SとH2Seの供
給比を変化させて成長した結晶ZnSxSe1-XのＳ組成ｘを
Ｘ線回折で調べ、それをプロットしたものが第３図であ
る。H2SとH2Seの供給比を変化させることにより、任意
のＳ組成ｘを有するZnSxSe1-Xの結晶を成長することが
できる。The DMZ supply rate was 3.7 × 10 -5 mol / min, and
The ratio (VI / II) of the total of H 2 S and H 2 Se was set to 10 times and kept constant so that an equivalent product was obtained, and the supply ratio of H 2 S and H 2 Se was changed. The S composition x of the grown crystal ZnSxSe 1-X was examined by X-ray diffraction, and the plot is shown in FIG. By changing the supply ratio of H 2 S and H 2 Se, it is possible to grow a ZnSxSe 1-X crystal having an arbitrary S composition x.
Ｓ組成ｘ＝０の場合がZnSeで、上記の成長条件で、低抵
抗のｎ型となる。しかし、ZnSxSe1-Xは、第４図に、比
抵抗とＳ組成ｘとの関係で示すように、たとえば、Ｓ組
成ｘが0.02と非常に小さい場合でも比抵抗が104Ω−cm
以上であり、高抵抗層ないしは絶縁層になる。このよう
にGaAs基板上に、初めに、DMZとH2Seにより、厚さ約20
μｍの低抵抗ｎ型のZnSeを成長し、次にDMZとH2Seおよ
びH2Sにより、厚さ1.0μｍ以下の絶縁性のZnSxSe1-Xを
成長し、さらに、この上に金属の電極、たとえば金（A
u）を蒸着すれば（ｍ−ｉ−ｎ）構造のLEDを作成するこ
とができる。When the S composition x = 0, ZnSe is n-type with low resistance under the above growth conditions. However, as shown in the relationship between the specific resistance and the S composition x in FIG. 4, ZnSxSe 1-X has a specific resistance of 10 4 Ω-cm even when the S composition x is as very small as 0.02.
The above is the high resistance layer or the insulating layer. Thus on a GaAs substrate, first, the DMZ and H 2 Se, a thickness of about 20
μm low resistance n-type ZnSe is grown, then DMZ and H 2 Se and H 2 S are used to grow insulating ZnSxSe 1-X with a thickness of 1.0 μm or less. , For example, gold (A
By depositing u), an LED having a (m-i-n) structure can be prepared.
第５図は、ZnSxSe1-X結晶の77Kにおける青色のフォトル
ミネッセンス強度のＳ組成ｘに対する依存性である。FIG. 5 shows the dependence of the blue photoluminescence intensity of ZnSxSe 1-X crystal at 77K on the S composition x.
この経験によると、Ｓ組成ｘが大きくなるに従い、青色
発光強度が増大するが、SA発光と呼ばれる黄色の発光は
増加しない。According to this experience, the blue emission intensity increases as the S composition x increases, but the yellow emission called SA emission does not increase.
さらに、Ｓ組成ｘを大きくすると、結晶の禁制帯幅が大
きくなり、発光波長が視感度の低い紫外領域となる。こ
のような実情から、青色LEDとして適当なＳ組成ｘは０
＜ｘ0.2の範囲となる。Further, when the S composition x is increased, the band gap of the crystal is increased, and the emission wavelength is in the ultraviolet region where the visibility is low. From such circumstances, the S composition x suitable for a blue LED is 0.
It is in the range of <x0.2.
なお、ZnSxSe1-Xは絶縁性である必要はなく、ｐ型結晶
であればｐ−ｎ接合が形成され、さらに発光効率が向上
する。Note that ZnSxSe 1-X does not need to be insulating, and if it is a p-type crystal, a pn junction is formed and the luminous efficiency is further improved.
発明の効果 本発明によると、低抵抗のｎ型ZnSeと、絶縁性のZnSxSe
1-Xおよび金属の電極により、 （ｍ−ｉ−ｎ）構造の高発光効率の青色LEDが実現でき
る。According to the present invention, low-resistance n-type ZnSe and insulating ZnSxSe are used.
With the 1-X and metal electrodes, it is possible to realize a blue LED with a high luminous efficiency having a (m-n) structure.
第１図は本発明実施例のLED断面図、第２図は同LED製作
に使用したMOCVD成長装置の概略図、第３図〜第５図は
同LEDの結晶性ならびに特性例を示す図である。 １……GaAs基板、２……ZnSe層、３……ZnSxSe1-X層、
４……Ge・Au電極、５……Au電極。FIG. 1 is a sectional view of an LED of an embodiment of the present invention, FIG. 2 is a schematic view of a MOCVD growth apparatus used for manufacturing the LED, and FIGS. 3 to 5 are views showing crystallinity and characteristic examples of the LED. is there. 1 ... GaAs substrate, 2 ... ZnSe layer, 3 ... ZnSxSe 1-X layer,
4 ... Ge / Au electrode, 5 ... Au electrode.
Claims (2)
性あるいはｐ型の伝導性を有するセレン・イオウ化亜鉛
との接合をそなえた発光ダイオード。1. A light emitting diode having a junction between zinc selenide having n-type conductivity and insulating or zinc selenide having p-type conductivity.
の組成比Ｘが0.2以下でなる特許請求の範囲第（１）項
記載の発光ダイオード。2. The light emitting diode according to claim 1 , wherein the sulfur composition ratio X of selenium-zinc-sulfur ZnSxSe 1- x is 0.2 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15532186A JPH0728053B2 (en) | 1986-07-02 | 1986-07-02 | Light emitting diode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15532186A JPH0728053B2 (en) | 1986-07-02 | 1986-07-02 | Light emitting diode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6310577A JPS6310577A (en) | 1988-01-18 |
| JPH0728053B2 true JPH0728053B2 (en) | 1995-03-29 |
Family
ID=15603332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15532186A Expired - Fee Related JPH0728053B2 (en) | 1986-07-02 | 1986-07-02 | Light emitting diode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0728053B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5274248A (en) * | 1991-06-05 | 1993-12-28 | Matsushita Electric Industrial Co., Ltd. | Light-emitting device with II-VI compounds |
-
1986
- 1986-07-02 JP JP15532186A patent/JPH0728053B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6310577A (en) | 1988-01-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |