JPH02220481A - Manufacture of semiconductor light-emitting element - Google Patents
Manufacture of semiconductor light-emitting elementInfo
- Publication number
- JPH02220481A JPH02220481A JP1040862A JP4086289A JPH02220481A JP H02220481 A JPH02220481 A JP H02220481A JP 1040862 A JP1040862 A JP 1040862A JP 4086289 A JP4086289 A JP 4086289A JP H02220481 A JPH02220481 A JP H02220481A
- Authority
- JP
- Japan
- Prior art keywords
- type
- crystal
- light
- light emitting
- iodine
- 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.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052740 iodine Inorganic materials 0.000 abstract description 10
- 239000011630 iodine Substances 0.000 abstract description 10
- 229910052951 chalcopyrite Inorganic materials 0.000 abstract description 5
- -1 chalcopyrite compound Chemical class 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical class [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、カルコパイライト型化合物半導体であるＣ
ｕ （Ａ ｌｘＧ ａｌ−ｘ） （ＳＹＳ ｅ＋−ｖ
） ＊を用いた発光素子の製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a chalcopyrite compound semiconductor
u (A lxG al-x) (SYS e+-v
) *This relates to a method of manufacturing a light emitting device using.
従来の技術
カルコパイライト型化合物半導体であるＣｕ（ＡＩＸＧ
ａ＋−ｘ）Ｃ８ｖＳ ｅｔ−Ｙ）２は、禁制帯幅Ｅｇが
ＣｕＧａ５５歳でＥ ｇ＝ １． ７ ｅ ７％ Ｃ
ｕ Ｇ ａ Ｓ２でＥｇ＝２．５ｅＶ１ ＣｕＡｌ５窒
＊でＥｇ＝２゜７ｅＶｓ ＣｕＡｌ５窒でＥｇ＝３．
５ｅＶとワイドギャップであり、伝導特性がいずれもｐ
型になりやすいことから、伝導特性がｎ型でＥｇが２．
７ｅＶ以上であるＺｎ （ＳｚＳ ｅ＋−ｚ）との組合
せによるｐｎ接合型青色発光素子の形成が一般に期待さ
れている。今までに、ＧａＰ基板上にＣｕＧａ５５のエ
ピタキシャル成長が試みられている。 ［Ｋ、Ｈａｒａ
ｅｔ ａｌ、、 ”Ｅｐｉｔａｘｉａｌ Ｇｒｏｗｔ
ｈ ｏｆ ＣｕＧａＳ２ ｂｙｌｌｅｔａｌｏｒｇａｎ
ｌｃ Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏ
ｓｉｔｉｏｎ”、 シ゛エイ、ジエイ、工仁ピー
（Ｊ、Ｊ、ム、Ｐ） 、、２Ｂ（１９８７）、Ｌｉ２
Ｏ２−Ｌ■０９．参照］
発明が解決しようとする課題
しかしながら、現在までのところ、カルコパイライト型
化合物に関して、良質な結晶のエビタキシャル膜は得ら
れていない。このような現状から、本発明ハ、良質なカ
ルコパイライト型化合物結晶を得、これを用いた発光特
性の良いｐｎ接合型青色発光素子を製造する方法を提供
することを目的とする。Conventional technology Cu (AIXG), which is a chalcopyrite-type compound semiconductor
a+-x)C8vS et-Y)2, the forbidden band width Eg is CuGa 55 years old and Eg=1. 7 e 7% C
u Ga S2 Eg=2.5eV1 CuAl5Nitrogen* Eg=2°7eVs CuAl5Nitrogen Eg=3.
It has a wide gap of 5eV, and its conduction characteristics are p.
Because the conduction characteristics are n-type and Eg is 2.
It is generally expected that a pn junction type blue light emitting device will be formed by combining Zn (SzS e+-z) with a voltage of 7 eV or higher. Until now, attempts have been made to epitaxially grow CuGa55 on a GaP substrate. [K, Hara
et al,, “Epitaxial Growt
h of CuGaS2 bylletaorgan
lc Chemical Vapor Depo
location”, siei, jiei, engineering
(J, J., Mu, P.), 2B (1987), Li2
O2-L■09. Reference] Problems to be Solved by the Invention However, to date, no high-quality crystalline epitaxial film has been obtained for chalcopyrite-type compounds. Under these circumstances, an object of the present invention is to obtain a high-quality chalcopyrite compound crystal and to provide a method for manufacturing a pn junction blue light-emitting device with good light-emitting characteristics using the same.
課題を解決するための手段
本発明は、良質なカルコパイライト型化合物結晶として
ヨウ素輸送法により得られたバルク結晶を用いてｐ型化
し、そのｐ型カルコパイライト型化合物結晶上へｎ型Ｚ
ｎ （ＳｚＳ ｅ ＋−ｚ）成長層をエピタキシャル
成長し、このｐｎ接合を発光層とする半導体発光素子の
製造方法である。Means for Solving the Problems The present invention uses a bulk crystal obtained by an iodine transport method as a high-quality chalcopyrite compound crystal, converts it into a p-type, and injects an n-type Z onto the p-type chalcopyrite compound crystal.
This is a method for manufacturing a semiconductor light emitting device in which an n (SzS e + -z) growth layer is epitaxially grown and this pn junction is used as a light emitting layer.
作用
本発明は、前記した構成により、ヨウ素輸送法で作製し
たＣｕ （ＡｌＸ、Ｇａ１−Ｘ）（ＳＹＳｅ１−ｖ）２
結晶を用い、この結晶は双晶境界のない均一性に富んだ
Ｘ線的にも良質な単結晶で、この結晶上にｎ型のＺｎ
（ＳｚＳ ｅ＋−ｚ）結晶層を積層させ、このｐｎ接合
を発光層として発光接合を形成することにより、電流−
電圧特性が良好で素子特性的にも、また、プロセス的に
も優れた青色発光素子を作製することができる。Effect of the present invention With the above-described configuration, the present invention provides Cu (AlX, Ga1-X) (SYSe1-v)2 produced by the iodine transport method.
This crystal is a highly uniform single crystal with no twin boundaries and has good X-ray quality, and on this crystal is n-type Zn.
(SzS e+-z) By stacking crystal layers and forming a light-emitting junction using this pn junction as a light-emitting layer, current -
A blue light-emitting element with good voltage characteristics and excellent device characteristics and process can be manufactured.
実施例
第１図は本発明の第１の実施例における半導体発光素子
の製造方法を示すものである。第１図に示すように、ヨ
ウ素輸送法で得られたｐ型Ｃｕ（Ａ Ｉ＠、ｓＧ ａｓ
、ｓ） （Ｓｓ、ｓＳ ｅ＠、ｓ） ＊結晶１に格子
整合したｎ型Ｚ ｎ （Ｓ＠、？？Ｓ ｅｓ、２ｓ）
エピタキシャル膜２を積層形成させ、ｐｎ接合型発光素
子を構成した。ｐ型Ｃｕ （Ａ ｌａ、ｓＧ ａｓ、ｓ
） （Ｓ＠、５Ｓｅａ、ｓ）＊結晶１の裏面にはｐ型
電極としてＡｕ電極３が、また、ｎ型Ｚ ｎ （Ｓａ、
７ｖＳ ｅ＠、２＊） −ｒ−ビタキシャル膜２の裏面
にはｎ型電極としてＡｕ電極３がそれぞれ形成されてい
る。まず、ｐ型Ｃｕ（Ａ ｌｓ、ｓＧ ａｓ、ｓ）
（Ｓｓ、ｓＳ ｅｓ、ｓ） を結晶をヨウ素輸送法によ
って作製した。ヨウ素輸送法における成長条件は原料量
４ｘ１０−’ｍｏ ｌ／ｃｍ’、ヨウ素量５ｍｇ／ｃｍ
’、原料部温度８００℃、結晶成長部温度７００℃、成
長時間は１０日間である。Embodiment FIG. 1 shows a method of manufacturing a semiconductor light emitting device according to a first embodiment of the present invention. As shown in Figure 1, p-type Cu (A I@, sG as
, s) (Ss, sS e@, s) *n-type Z n lattice matched to crystal 1 (S@, ??S es, 2s)
The epitaxial film 2 was laminated to form a pn junction type light emitting device. p-type Cu (A la, sG as, s
) (S@, 5Sea, s) *On the back surface of the crystal 1, there is an Au electrode 3 as a p-type electrode, and an n-type Z n (Sa,
7vS e@, 2*) -r- On the back surface of the bitaxial film 2, an Au electrode 3 is formed as an n-type electrode. First, p-type Cu (Als, sGa as, s)
A crystal of (Ss, sS es, s) was prepared by the iodine transport method. The growth conditions for the iodine transport method are a raw material amount of 4 x 10-'mol/cm' and an iodine amount of 5 mg/cm.
', the temperature of the raw material part was 800°C, the temperature of the crystal growth part was 700°C, and the growth time was 10 days.
得られた結晶を飽和Ｓ ｓ、ｓ Ｓ ｅ ＠、ｓ中で８
００℃Ｘ２４時間のアニールを行うことによりｐ型化さ
せた。得られたｐ型Ｃｕ （Ａ ｌｓ、ｓＧ ａｓ、ｓ
） （Ｓｓ。The obtained crystals were heated in saturated S s, s S e @, 8
By performing annealing at 00° C. for 24 hours, it was made into a p-type. The obtained p-type Cu (A ls, sG as, s
) (Ss.
ｉｓ ｅ＠、ｓ） ２結晶の上に、原料としてジメチル
亜鉛、硫化水素、および、セレン化水素を用いたＭＯＣ
ＶＤ法により、Ｚ ｎ （Ｓ＠、ｔｖＳ ｅ＠、＊ａ）
−’ビタキシャル膜を成長させた。ＭＯＣＶＤ法にお
ける成長条件は、ジメチル亜鉛、硫化水素、およびセレ
ン化水素の流速がそれぞれ５μｍｏｌ／ｍ１ｎ１２８０
μｍｏ １／ｍｉ ｎｔ ２００μｍｏ ｌ／ｍｉｎ
で、成長温度３００″Ｃ１成長時の圧力が０．４Ｔｏｒ
ｒである。この際、ｎ型ドーパントとしてヨウ化エチル
（ＣａＨｓＩ）を用いてＩ（ヨウ素）を添加することに
より、ｎ型低抵抗化させる。ＡＵ各オーミック電極を真
空蒸着により形成する。is e@, s) MOC using dimethyl zinc, hydrogen sulfide, and hydrogen selenide as raw materials on 2 crystals
By the VD method, Z n (S@, tvS e@, *a)
−' Bitaxial film was grown. The growth conditions in the MOCVD method are such that the flow rate of dimethyl zinc, hydrogen sulfide, and hydrogen selenide is 5 μmol/ml each.
μmo 1/min 200μmol/min
The growth temperature was 300″ and the pressure during C1 growth was 0.4 Tor.
It is r. At this time, by adding I (iodine) using ethyl iodide (CaHsI) as an n-type dopant, the n-type resistance is lowered. Each AU ohmic electrode is formed by vacuum deposition.
このようにして得られた発光素子は、ｐｎ接合の正常な
電流−電圧特性を示し、また、良好な青色発光を示し、
優れた発光特性を示す素子が得られた。なお、第１の実
施例において、Ｚｎ（Ｓｓ。The light emitting device thus obtained exhibits normal current-voltage characteristics of a pn junction, and also exhibits good blue light emission.
A device exhibiting excellent luminescent properties was obtained. Note that in the first example, Zn(Ss.
ｙｔｓ ｅ＠、ｔｓ）エピタキシャル膜の成長法として
、ＭＯＣＶＤ法としたが、他の気相成長法やＭＢＥ法と
してもよい。また、第１の実施例ではカルコパイライト
型化合物結晶をヨウ素輸送法によって作製したが、カル
コパイライト型化合物結晶を直接溶融法によって作製し
ても同様のｐｎ接合型半導体発光素子を得ることができ
、同様の効果が得られる。直接溶融法とは各構成元素を
化合物の融点以上で保持し、化合物化させる方法である
。yts e@, ts) Although the MOCVD method was used as the epitaxial film growth method, other vapor phase growth methods or MBE methods may be used. Further, in the first example, the chalcopyrite type compound crystal was produced by the iodine transport method, but a similar pn junction type semiconductor light emitting device can also be obtained by producing the chalcopyrite type compound crystal by the direct melting method. A similar effect can be obtained. The direct melting method is a method in which each constituent element is held at a temperature higher than the melting point of the compound to form a compound.
発明の詳細
な説明したように、本発明によれば、ヨウ素輸送法で得
られたＣ ｕ （Ａ ｌｓ、ｓＧ ａ＠、ｓ） （Ｓ
ＩＩ。DETAILED DESCRIPTION OF THE INVENTION According to the present invention, C u (Als, sG a@, s) (S
II.
ｓｓ ｅｓ、ｓ） を単結晶を用い、Ｚｎ （Ｓ＠、ｔ
ｖＳｅｉ、ｓりをエピタキシャル成長させることによっ
て、良好な青色発光特性を示すｐｎ接合型半導体発光素
子が得られ、その実用的効果は大きい。ss es, s) using a single crystal, Zn (S@, t
By epitaxially growing vSei, s, a pn junction semiconductor light emitting device exhibiting good blue light emission characteristics can be obtained, and its practical effects are significant.
図は本発明における一実施例のｐｎ接合型発光素子を示
す図である。
ｌｅ＊＊ｐ型Ｃｕ （Ａｌｓ、５Ｇａｓ、ｓ） （Ｓｓ
、５Ｓｅｓ、ｓ）２結晶、２・・・ｎ型Ｚｎ （Ｓｓ、
ｖｔＳ ｅｓ。The figure is a diagram showing a pn junction type light emitting device according to an embodiment of the present invention. le**p-type Cu (Als, 5Gas, s) (Ss
, 5Ses, s) 2 crystal, 2... n-type Zn (Ss,
vtS es.
Claims (2)
Ｓｅ＿１＿−＿Ｙ）＿２（０≦Ｘ≦１、０≦Ｙ≦１）と
ｎ型Ｚｎ（Ｓ＿ＺＳｅ＿１＿−＿Ｚ）（０≦Ｚ≦１）と
から構成されるｐｎ接合型半導体発光素子の製造方法に
おいて、ヨウ素輸送法により得られたＣｕ（Ａｌ＿Ｘ、
Ｇａ＿１＿−＿Ｘ）（Ｓ＿ＹＳｅ＿１＿−＿Ｙ）＿２単
結晶をｐ型処理し、この上にｎ型Ｚｎ（Ｓ＿ＺＳｅ＿１
＿−＿Ｚ）をエピタキシャル成長させたことを特徴とす
る半導体発光素子の製造方法。(1) p-type Cu (Al_XGa_1_-_X) (S_Y
In a method for manufacturing a p-n junction semiconductor light emitting device composed of Se_1_-_Y)_2 (0≦X≦1, 0≦Y≦1) and n-type Zn (S_ZSe_1_-_Z) (0≦Z≦1), Cu(Al_X,
Ga_1_-_X)(S_YSe_1_-_Y)_2 single crystal is p-type treated, and n-type Zn(S_ZSe_1
A method for manufacturing a semiconductor light emitting device, characterized in that _-_Z) is epitaxially grown.
＿１＿−＿Ｙ）＿２単結晶を直接溶融法により作製した
ことを特徴とする特許請求の範囲第１項に記載の半導体
発光素子の製造方法。(2) Cu(Al_XGa_1_-_X)(S_YSe
_1_-_Y)_2 The method for manufacturing a semiconductor light emitting device according to claim 1, wherein the single crystal is produced by a direct melting method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1040862A JPH02220481A (en) | 1989-02-21 | 1989-02-21 | Manufacture of semiconductor light-emitting element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1040862A JPH02220481A (en) | 1989-02-21 | 1989-02-21 | Manufacture of semiconductor light-emitting element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02220481A true JPH02220481A (en) | 1990-09-03 |
Family
ID=12592346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1040862A Pending JPH02220481A (en) | 1989-02-21 | 1989-02-21 | Manufacture of semiconductor light-emitting element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02220481A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007281438A (en) * | 2006-03-17 | 2007-10-25 | Canon Inc | Light-emitting element, and manufacturing method of light-emitting element |
-
1989
- 1989-02-21 JP JP1040862A patent/JPH02220481A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007281438A (en) * | 2006-03-17 | 2007-10-25 | Canon Inc | Light-emitting element, and manufacturing method of light-emitting element |
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