JPH03225971A - Manufacture of light-emitting element - Google Patents
Manufacture of light-emitting elementInfo
- Publication number
- JPH03225971A JPH03225971A JP2020697A JP2069790A JPH03225971A JP H03225971 A JPH03225971 A JP H03225971A JP 2020697 A JP2020697 A JP 2020697A JP 2069790 A JP2069790 A JP 2069790A JP H03225971 A JPH03225971 A JP H03225971A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- light
- injection layer
- hydrocarbon
- mixing ratio
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000007789 gas Substances 0.000 claims abstract description 138
- 238000002347 injection Methods 0.000 claims abstract description 46
- 239000007924 injection Substances 0.000 claims abstract description 46
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 15
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 10
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000012495 reaction gas Substances 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 abstract description 10
- 239000010408 film Substances 0.000 description 28
- 239000000758 substrate Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000004020 luminiscence type Methods 0.000 description 6
- 239000002194 amorphous carbon material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- -1 GaAsP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 101100407828 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) ptr-3 gene Proteins 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Landscapes
- Led Devices (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明はアモルファス半導体よりなる発光素子の製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method of manufacturing a light emitting device made of an amorphous semiconductor.
Ｂ９発明の概要
本発明は、発光層の両面に夫々正孔注入層及び電子注入
層を積層してなる発光素子の製造方法において、
低圧の水素ガスと炭化水素ガスとホスフィンまたはジボ
ランガスとを反応ガスとし、更にはまたこれに水素化ケ
イ素ガスを加えた混合ガスを反応ガスとして、プラズマ
化学的蒸着法により得られたアモルファス炭素系膜を発
光層として用い、プラズマＣＶＤ法により得られたアモ
ルファス炭化ケイ素膜を正孔及び電子の各注入層として
用いることによって、
発光層の発光特性が長孔であり、しかもこの特性を十分
引出せるようにしたものである。B9 Summary of the Invention The present invention provides a method for manufacturing a light emitting device in which a hole injection layer and an electron injection layer are laminated on both sides of a light emitting layer. Furthermore, an amorphous silicon carbide film obtained by a plasma CVD method is obtained by using a mixed gas obtained by adding silicon hydride gas as a reaction gas and using an amorphous carbon-based film obtained by a plasma chemical vapor deposition method as a light emitting layer. By using the film as a hole and electron injection layer, the light-emitting layer has elongated light-emitting properties, and this property can be fully exploited.
Ｃ１従来の技術
従来、発光材料としては、発光ダイオードの材料である
ＧａＡｓ、ＧａＡｓＰ、ＧａＰ、ＧａＡＱ Ａｓ、Ｚｎ
５ｅｘＴｅ＋−ｘ、Ｚｎｘ６Ｃｄ＋−ｘＴｅ。C1 Conventional technology Conventionally, light emitting materials include GaAs, GaAsP, GaP, GaAQ As, and Zn, which are materials for light emitting diodes.
5exTe+-x, Znx6Cd+-xTe.
ＣｄＴｅなどがある。Examples include CdTe.
Ｄ６発明が解決しようとする課題
しかしながら、このような従来の発光材料にあっては、
例えば、ＧａＰではビーク波長（発光エネルギーがピー
クとなる波長）が６９８ｎｍ、光学的エネルギーギャッ
プが１．７６ｅＶというように、ピーク波長、光学的エ
ネルギーギャップは、その発光材料に固有のものである
。このため発光素材としての発光特性を変えたいときは
、所要の特性を有する発光材料を選択することが必要と
なり、ともすると所要のピーク波長、光学的エネルギー
ギャップに由来する特性を得られない場合が生ずる問題
点があった。Problems to be solved by the D6 invention However, with such conventional luminescent materials,
For example, in GaP, the peak wavelength (the wavelength at which the emission energy peaks) is 698 nm and the optical energy gap is 1.76 eV, and the peak wavelength and optical energy gap are unique to the luminescent material. Therefore, when you want to change the luminescent properties of a luminescent material, it is necessary to select a luminescent material with the required properties, and in some cases, you may not be able to obtain the properties derived from the required peak wavelength and optical energy gap. There were some problems that arose.
こうしたことからＣＶＤ法を利用してアモルファス炭素
系物質を生成し、これを発光材料に適用することが検討
されている。具体的にはこのアモルファス炭素系物質は
、真空容器内で、基板温度を例えば３００℃以下に保ち
、例えば１３３．３ｍＰ ａ−６Ｘ １３３．３ Ｐ
２Ｌの水素ガス存在下で高周波電圧または直流電圧を印
加してプラズマＣＶＤ法（］） −ＣＶ Ｄ法）を行う
ことにより生成される。For this reason, it is being considered to generate an amorphous carbon-based material using the CVD method and apply it to a light-emitting material. Specifically, this amorphous carbon-based material is kept in a vacuum container at a substrate temperature of, for example, 300° C. or lower, and at a temperature of, for example, 133.3 mPa a-6X 133.3 P.
It is generated by applying a high frequency voltage or a direct current voltage in the presence of 2 L of hydrogen gas and performing a plasma CVD method (]) - CV D method).
このような物質よりなる発光材料は、大きな光学的エネ
ルギーギャップを有する（耐熱的には３００℃までその
ギャップは変化しない）と共に任意の光学的エネルギー
ギャップ及び発光特性を、ＣＶＤ法の条件のコントロー
ルにより得られるため、要望に応じた材料が容易に得ら
れるという利点がある。この発光材料よりなる膜は光学
的エネルギーギャップ（Ｅｇｏ）の大小により強力なフ
ォトルミネッセンス（Ｐ Ｌ ）が観察される。第３図
にＥｇｏＩ！：ＰＬのピーク値との関係を示す。特にＥ
ｇｏが３ｅＶ程度の膜は青白発光することからアモルフ
ァスの特性を生かした大面積の青色発光パネルを実現さ
せる可能性がある。更に種々のＥｇｏを選択することに
より赤から青までの色をチューナプルに出す発光素子を
作ることもできる。Luminescent materials made of such substances have a large optical energy gap (in terms of heat resistance, the gap does not change up to 300°C), and can have arbitrary optical energy gaps and luminescent properties by controlling the conditions of the CVD method. Therefore, it has the advantage that it is easy to obtain a material that meets your needs. In a film made of this luminescent material, strong photoluminescence (P L ) is observed depending on the size of the optical energy gap (Ego). Figure 3 shows EgoI! : Indicates the relationship with the peak value of PL. Especially E
Since a film with a go of about 3 eV emits blue-white light, it is possible to realize a large-area blue light-emitting panel that takes advantage of its amorphous properties. Furthermore, by selecting various Ego's, it is possible to create a light emitting element that emits colors from red to blue to the tuner pull.
またＥｇｏの大小によるＰＬ強度についても室温観察で
非常に強い発光を示し、大画面を有するフラットパネル
デイスプレィへと応用を広げることのできる発光素子材
料（Ｒ，Ｇ、Ｂ３元色を作るもの）として有望なもので
ある。Furthermore, regarding the PL intensity depending on the size of Ego, it shows very strong light emission when observed at room temperature, and is a light-emitting element material (one that creates three primary colors of R, G, and B) that can be used to expand its application to flat panel displays with large screens. It is promising as a.
ところでこのような物質よりなる膜を発光層としたＬＥ
Ｄ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇｄｉｏｄｅ）を作
る場合、電子と正孔を発光層に注入する注入層が必要で
あり、この注入層としては、半導体化したｐ型、ｎ型の
上記のアモルファス炭素系物質を用いることが最良であ
る。しかしながらこの物質を注入層として用いる場合、
目標特性であるＥｇｏ＞２ｅＶ、ρ（抵抗率）＜１０１
１Ω・ｃｍを有するｐ型、ｎ型膜を作ることが非常に難
しく、この問題点が上記のアモルファス炭素系物質の発
光素子への適用を妨げている。By the way, LE with a film made of such a substance as a light-emitting layer
When creating a D (Light Emitting Diode), an injection layer is required to inject electrons and holes into the light emitting layer, and as this injection layer, the above-mentioned amorphous carbon-based material of semiconducting p-type or n-type can be used. is the best. However, when using this material as an injection layer,
Target characteristics Ego>2eV, ρ (resistivity)<101
It is very difficult to make p-type and n-type films having a resistance of 1 Ω·cm, and this problem prevents the application of the above-mentioned amorphous carbon-based material to light-emitting devices.
本発明の目的は、任意の光学的エネルギーギャップ及び
発光特性を発光層に付与することができ、しかも発光層
の特性を十分に引き出すことができる発光素子の製造方
法を提供することにある。An object of the present invention is to provide a method for manufacturing a light-emitting element that can provide a light-emitting layer with an arbitrary optical energy gap and light-emitting characteristics, and can fully bring out the characteristics of the light-emitting layer.
８０課題を解決するための手段
本発明は、炭化水素ガスと水素化ケイ素ガスとｐ型不純
物ガスとを含む低圧の反応ガスを真空容器内でグロー放
電させて分解ガスを重合させるプラズマ化学的蒸着法に
よりｐ型のアモルファス炭化ケイ素膜よりなる正孔注入
層を生成する工程と、低圧の水素ガスと炭化水素ガスと
ボスフィンまたはジボランガスとを反応ガスとし、炭化
水素ガスに対するボスフィンまたはジボランガスの混合
比を０．００１〜ｌＯ％としたプラズマ化学的蒸着法に
よりアモルファス炭素系膜よりなる発光層を前記正孔注
入層上に積層する工程と、炭化水素ガスと水素化ケイ素
ガスとｎ型不純物ガスとを含む低圧の反応ガスを真空容
器内でグロー放電させて分解ガスを重合させるプラズマ
化学的蒸着法によりｎ型のアモルファス炭化ケイ素膜よ
りなる電子注入層を前記発光層上に積層する工程とを含
むことを特徴とする。80 Means for Solving the Problems The present invention is a plasma chemical vapor deposition method in which a low-pressure reaction gas containing a hydrocarbon gas, a silicon hydride gas, and a p-type impurity gas is glow-discharged in a vacuum container to polymerize a decomposed gas. A step of generating a hole injection layer made of a p-type amorphous silicon carbide film by a method, and using low-pressure hydrogen gas, hydrocarbon gas, and bosfin or diborane gas as reaction gases, and adjusting the mixing ratio of bosfin or diborane gas to the hydrocarbon gas. a step of laminating a light-emitting layer made of an amorphous carbon film on the hole injection layer by plasma chemical vapor deposition at a concentration of 0.001 to 10%; laminating an electron injection layer made of an n-type amorphous silicon carbide film on the light-emitting layer by a plasma chemical vapor deposition method in which a low-pressure reactive gas containing a glow discharge is caused to polymerize the decomposed gas in a vacuum container; It is characterized by
また発光層を生成工程において、更に水素化ガスを混合
するようにしてもよく、水素ガス、炭化水素ガス、水素
化ケイ素ガス及びホスフィンガスを反応ガスとする場合
には、炭化水素ガスに対する水素化ケイ素ガスの混合比
を０．１〜１５％、ホスフィンガスの混合比を０．００
１〜ＩＯ％とし、ホスフィンガスに代えてジボランガス
を用いる場合には、炭化水素ガスに対するジボランガス
の混合比を０．００１〜５％とする。Further, in the process of producing the light emitting layer, a hydrogenation gas may be further mixed. When hydrogen gas, hydrocarbon gas, silicon hydride gas, and phosphine gas are used as reaction gases, hydrogenation of the hydrocarbon gas may be performed. The mixing ratio of silicon gas is 0.1 to 15%, and the mixing ratio of phosphine gas is 0.00.
When diborane gas is used instead of phosphine gas, the mixing ratio of diborane gas to hydrocarbon gas is 0.001 to 5%.
Ｆ、実施例
第１図は本発明方法により製造した発光素子の実施例を
示す構成図である。第１図中Ｉは例えば６３ｃｍ’程度
の面積をもつガラス基板、２は酸０化錫よりなる透明電
極、３はＢ３−をドーパントした３０ｎｍ程度の厚さの
ｐ型のアモルファス炭化ケイ素膜（以下ｒａ−８ｉＣ膜
」という。）よりなる正孔注入層、４は３００ｎｍの厚
さのアモルファス炭素系膜（以下ｒａ−Ｃ：ＰＳＨ膜」
という。）よりなる発光層、５はＰ”をドーパントした
５０ｎｍ程度の厚さのｎ型のａ−６ｉＣ膜よりなる電子
注入層、６はアルミニウム電極である。F. Example FIG. 1 is a block diagram showing an example of a light emitting device manufactured by the method of the present invention. In FIG. 1, I is a glass substrate with an area of, for example, about 63 cm, 2 is a transparent electrode made of tin oxide, and 3 is a p-type amorphous silicon carbide film doped with B3- and about 30 nm thick (hereinafter referred to as 4 is an amorphous carbon-based film with a thickness of 300 nm (hereinafter referred to as "RA-C:PSH film").
That's what it means. ), 5 is an electron injection layer made of an n-type a-6iC film doped with P'' and having a thickness of about 50 nm, and 6 is an aluminum electrode.
各アモルファス薄膜は、真空槽、ガス導入系、ガス排気
系あるいは高周波電源（または直流電源）等を具備した
一般的なＰ−ＣＶＤ装置により作製することができる。Each amorphous thin film can be produced using a general P-CVD apparatus equipped with a vacuum chamber, a gas introduction system, a gas exhaust system, a high frequency power supply (or a DC power supply), and the like.
ここで発光素子を製造する場合の製造条件の３つの例（
試料１〜３）を以下に挙げる。Here are three examples of manufacturing conditions for manufacturing light emitting devices (
Samples 1 to 3) are listed below.
（１）試料ｌについて
■ 正孔注入層
真空容器内ガス圧力 ２６．７Ｐａ（０，２Ｔｏｒｒ
）基板温度 ２５００Ｃ
Ｃ１，１人・Ｓ ｉ ）Ｉ 、ガス
１：１Ｂ２Ｈｏｉス： （ＣＨＪＸ＋５ｉ）ＩＪλ）
３・１０００高周波電源電力 １０Ｗ
１
（入力電極面積に対し０．１２５Ｙ／ｃｍ’）■
発光層
真空容器内混合ガス（ＣＬとＨ７とＰＨ３）圧力２６．
７Ｐａ（０，２Ｔｏｒｒ）
ＣＨ４ガスに対するＰＨ３ガスの混合比０．００２％
基板温度
２００℃
高周波電源電力
０Ｗ
■
電子注入層
真空容器内ガス圧力
２６．７Ｐａ（０，２Ｔｏｒｒ）
基板温度
２５０℃
ＣＩ＋４１ス：５ｉＨ−’Ｉｆス
１：１
ＰＨＪス： （ＣＨ４１ス＋５ｉＨＪ人）５．８：１０
００
高周波電源電力
０Ｗ
（人力電極面積に対し０．１２５Ｗ／ｃｍ’ ）２
（２）試料２について
■ 正孔注入層及び電子注入層
試料１と同じ条件で製造した
■ 発光層
Ｐ Ｈｓガスの同混合比を０．００５％とした他は試料
１と同じ条件で製造した。(1) About sample 1■ Gas pressure inside the hole injection layer vacuum container 26.7 Pa (0.2 Torr
) Substrate temperature 2500C C1, 1 person・S i ) I, gas
1:1B2Hois: (CHJX+5i)IJλ)
3.1000 high frequency power supply power 10W 1 (0.125Y/cm' for the input electrode area) ■ Mixed gas (CL, H7, and PH3) pressure in the luminescent layer vacuum container 26.
7 Pa (0.2 Torr) Mixing ratio of PH3 gas to CH4 gas 0.002% Substrate temperature 200°C High frequency power source power 0W ■ Gas pressure in electron injection layer vacuum vessel 26.7 Pa (0.2 Torr) Substrate temperature 250°C CI+41S: 5iH-'If S1:1 PHJ S: (CH41 S+5iHJ person) 5.8:10
00 High-frequency power supply power 0 W (0.125 W/cm' for the area of the manual electrode) 2 (2) Regarding sample 2 ■ Hole injection layer and electron injection layer ■ Light-emitting layer PH manufactured under the same conditions as sample 1 Same as Hs gas It was manufactured under the same conditions as Sample 1 except that the mixing ratio was 0.005%.
（３）試料３について ■ 正孔注入層及び電子注入層 試料ｌと同じ条件で製造した。(3) About sample 3 ■ Hole injection layer and electron injection layer It was manufactured under the same conditions as Sample 1.
■ 発光層
Ｐ Ｈ３ガスの同混合比を０．０１％とした他は試料１
と同じ条件で製造した。■ Light-emitting layer P Sample 1 except that the same mixing ratio of H3 gas was 0.01%.
manufactured under the same conditions.
以上の各試料１〜３について波長とＥＬ強度との関係を
調べたところ第２図に示す関係が得られた。同図中実線
■〜■のグラフは夫々試料１〜３に対応する。このよう
に良好な発光特性を得るためには、発光層の製膜を用い
るホスフィン（ＰＨ３）ガスの炭化水素ガスに対する混
合比はｏ、ｏｏｔ〜１０％であることが好ましい。いず
れの試料１〜３も目視で十分観察できる発光を示し、十
分な発光特性を有していることが判った。試験に用いた
順方向バイアス電圧は５Ｖであり、電流密度は２００
ｍＡ／ ｃ ｍ”であった。以上の実施例では、ａ−８
ｉＣ膜としてＥｇｏが２．ＯｅＶ、ｐがｌＯ°Ω”ｃｍ
のものを用いたが、Ｅｇｏが２．ＯｅＶよりも大きく、
ρが１０８Ω・ｃｍよりも小さいものを用いれば発光特
性は更に良くなる。When the relationship between wavelength and EL intensity was investigated for each of the above samples 1 to 3, the relationship shown in FIG. 2 was obtained. In the same figure, solid lines ■ to ■ correspond to samples 1 to 3, respectively. In order to obtain such good light-emitting characteristics, the mixing ratio of phosphine (PH3) gas to hydrocarbon gas in forming the light-emitting layer is preferably o,oot to 10%. It was found that all Samples 1 to 3 exhibited sufficient luminescence that could be observed visually, and had sufficient luminescent properties. The forward bias voltage used in the test was 5V, and the current density was 200V.
mA/cm". In the above example, a-8
Ego is used as an iC film. OeV, p is lO°Ω”cm
I used one with an Ego of 2. greater than OeV,
If a material with ρ smaller than 10 8 Ω·cm is used, the light emission characteristics will be even better.
次に発光層の生成工程において、ホスフィンガスの代わ
りにシボランガスを用いた場合の３つの例（試料４〜６
）を以下に挙げる。Next, in the generation process of the light emitting layer, three examples (Samples 4 to 6
) are listed below.
（１）試料４について
■
正孔注入層
真空容器内ガス圧力
２６．７Ｐａ（０
２Ｔｏｒｒ）
基板温度
２５０℃
ＣＨ４ガス： Ｓ ｉ ｔ（ｔガス
８２ Ｈｏガス：（ＣＨ，ｉス＋Ｓ ｉ Ｈ、’Ａス）
０００
高周波電源電力
０Ｗ
（人力電極面積に対し０．１２５Ｗ／ｃｍ２）■
発光層
真空容器内混合ガス（ＣＨ，とＨ７とＢ、Ｈ，）圧力６
７Ｐａ（０
２Ｔｏｒｒ）
Ｃ１１４ガスに対するＢ 、Ｈ６ガスの混合比００２％
基板温度
２００℃
高周波電源電力
０Ｗ
５
■ 電子注入層
真空容器内ガス圧力 ２６．７Ｐａ（０，２Ｔｏｒ
ｒ）基板温度 ２５０°Ｃ
Ｃｌ４１ス：５ｉＨＪス ｌ：Ｉ
Ｐ）１３１ス：（ＣＨＪス＋５ＩＨ４ガス） ５
．８：１０００高周波電源電力 １０Ｗ
（人力電極面積に対し０．１２５１／ｃｍ’ ）（２）
試料５について
■ 正孔注入層及び電子注入層
試料４と同じ条件で製造した。(1) About sample 4■ Hole injection layer vacuum vessel internal gas pressure 26.7 Pa (0 2 Torr) Substrate temperature 250°C CH4 gas: S i t (t gas 82 Ho gas: (CH, i S + S i H,' A)
000 High-frequency power supply power 0W (0.125W/cm2 for the area of the manual electrode) ■ Light-emitting layer mixed gas in the vacuum container (CH, H7 and B, H,) Pressure 67Pa (02Torr) B for C114 gas, H6 gas Mixing ratio: 0.2% Substrate temperature: 200°C High-frequency power supply: 0W 5 ■ Electron injection layer vacuum chamber internal gas pressure: 26.7Pa (0.2 Torr)
r) Substrate temperature 250°C Cl41S:5iHJS l:I
P) 131s: (CHJs+5IH4 gas) 5
．． 8:1000 high frequency power source power 10W (0.1251/cm' for the area of the human electrode) (2)
Regarding Sample 5 ■ Hole injection layer and electron injection layer Manufactured under the same conditions as Sample 4.
■ 発光層
Ｂ、Ｈｅガスの同混合比を０．００５％とした他は試料
４と同じ条件で製造した。(2) Light-emitting layer B was manufactured under the same conditions as Sample 4, except that the same mixing ratio of He gas was 0.005%.
（３）試料６について ■ 正孔注入層及び電子注入層 ６ 試料４と同じ条件で製造した。(3) About sample 6 ■ Hole injection layer and electron injection layer 6 It was manufactured under the same conditions as Sample 4.
■ 発光層
Ｂ ｙ Ｈｅガスの同混合比を０．０１％とした他は試
料４と同じ条件で製造した。(2) Light Emitting Layer A light emitting layer was produced under the same conditions as Sample 4 except that the mixing ratio of B y He gas was 0.01%.
以上の各試料４〜６について波長とＥＬ強度との関係を
調べたところ、夫々試料１〜３と同様な結果が得られた
。いずれの試料４〜６も目視で十分観察できる発光を示
し、十分な発光特性を有していることがわかった。この
ように良好な発光特性を得るためには、発光層の製膜に
用いるシボランガスの炭化水素ガスに対する混合比は０
．００１〜ＩＯ％であることが好ましい。試料１〜６に
ついて良好な発光特性が得られる理由は、シボラン、ホ
スフィンはいずれも非常に反応性の高いガスであるため
、このガスを含む反応ガスを用いて発光層を生成するこ
とにより、Ｂと０１あるいはＰとＣの結合が良好になさ
れ、発光層内の格子欠陥が少なくなるからであると推察
される。When the relationship between wavelength and EL intensity was investigated for each of the above samples 4 to 6, results similar to those of samples 1 to 3 were obtained. It was found that all Samples 4 to 6 exhibited luminescence that could be sufficiently observed visually, and had sufficient luminescence characteristics. In order to obtain such good luminescent properties, the mixing ratio of ciborane gas to hydrocarbon gas used for forming the luminescent layer must be 0.
．． It is preferable that it is 001 to IO%. The reason why good luminescent properties are obtained for Samples 1 to 6 is that both siborane and phosphine are highly reactive gases, and by producing a luminescent layer using a reactive gas containing these gases, B It is presumed that this is because good bonding between and 01 or P and C is achieved, reducing the number of lattice defects in the light emitting layer.
次に発光層を生成する工程において、ホスフィンガスと
水素化ケイ素ガスを用いた場合の３つの例（試料７〜９
）を以下に挙げる。Next, in the step of generating a light-emitting layer, three examples (samples 7 to 9) using phosphine gas and silicon hydride gas are shown.
) are listed below.
（１）試料７について
■ 正孔注入層
真空容器内ガス圧力 ２６．７Ｐａ（０，２Ｔｏｒｒ
）基板温度 ２５０℃
ＣＨ４ガス：５ｉＨＪス ｌ：ＩＢ
２ｎＪス： （ＣＨ，ガス＋ＳｉＨ４万ス） ３：１
０００高周波電源電力 １０Ｗ
（入力電極面積に対し０．１２５Ｗ／ｃｍ’）■ 発光
層
真空容器内混合ガス（ＣＨ４とＨ７とＰＨ３）圧力２６
．７Ｐａ（０，２Ｔｏｒｒ）
Ｃ１１，ガスに対するＳ ｉ Ｉｌ ４ガスの混合比２
％
ＣＨ４ガスに対するＰＨ３ガスの混合比０．００２％
基板温度
２５０℃
高周波電源電力
０Ｗ
■
電子注入層
真空容器内ガス圧力
２６．７Ｐａ（０，２Ｔｏｒｒ）
基板温度
２５０°Ｃ
ＣＨ４′ＩＪス：５ｉＨＪス
■＝１
ＰＨ３ガス
（Ｃ１１，方ス＋Ｓ＋ＨＪス）
５．８：１０００
高周波電源電力
０Ｗ
（入力電極面積に対し０．１２５Ｙ／Ｃｍ”）９
（２）試料８について
■ 正孔注入層及び電子注入層
試料７と同じ条件で製造した。(1) Regarding sample 7 ■ Hole injection layer vacuum chamber internal gas pressure 26.7 Pa (0.2 Torr
) Substrate temperature 250℃ CH4 gas: 5iHJsu l:IB
2nJ s: (CH, gas + SiH 40,000 s) 3:1
000 High frequency power supply power 10W (0.125W/cm' for input electrode area) ■ Mixed gas (CH4, H7, and PH3) pressure in luminescent layer vacuum container 26
．． 7 Pa (0,2 Torr) C11, mixture ratio of S i Il 4 gas to gas 2
% Mixing ratio of PH3 gas to CH4 gas 0.002% Substrate temperature 250°C High frequency power supply power 0W ■ Electron injection layer vacuum chamber internal gas pressure 26.7 Pa (0.2 Torr) Substrate temperature 250°C CH4'IJ: 5iHJ ■=1 PH3 gas (C11, direction + S + HJ) 5.8:1000 High frequency power supply power 0W (0.125Y/Cm" for input electrode area) 9 (2) Regarding sample 8■ Hole injection layer and electron injection Manufactured under the same conditions as layer sample 7.
■ 発光層
Ｓ ｉ Ｈ４ガスの同混合比を１％、Ｐ Ｔ−ｒ３ガス
の同混合比を０．００５％とした他は試料７と同じ条件
で製造した。(2) Light emitting layer The light emitting layer was manufactured under the same conditions as Sample 7, except that the mixing ratio of SiH4 gas was 1% and the mixing ratio of PTr3 gas was 0.005%.
（３）試料９について
■ 正孔注入層及び電子注入層
試料７と同じ条件で製造した
■ 発光層
Ｓ ｉ Ｈ４ガスの同混合比を０５％。Ｐ Ｈ３ガスの
同混合比を０．０１％とした他は試料４と同じ条件で製
造した。(3) Regarding sample 9 ■ Hole injection layer and electron injection layer ■ Light-emitting layer manufactured under the same conditions as sample 7 The same mixing ratio of S i H4 gas was 0.5%. It was manufactured under the same conditions as Sample 4 except that the mixing ratio of P H3 gas was 0.01%.
以上の各試料７〜９について波長とＥＬ強度と０
の関係を調べたところ、夫々試料１〜３と同様な結果が
得られた。いずれの・試料７〜９も目視で十分観察でき
る発光を示し、十分な発光特性を有していることがわか
った。ただしフォトルミネセンス強度は試料１〜６より
も大きかった。このように良好な発光特性を得るために
は、発光層の製膜に用いるホスフィンガスの炭化水素ガ
スに対する混合比は０．００１〜１０％、水素化ケイ素
ガスの同混合比は０．１〜１５％であることが好ましい
。When the relationship between wavelength, EL intensity, and 0 was investigated for each of the above samples 7 to 9, results similar to those of samples 1 to 3 were obtained. It was found that all Samples 7 to 9 exhibited luminescence that could be sufficiently observed visually, and had sufficient luminescence characteristics. However, the photoluminescence intensity was higher than Samples 1-6. In order to obtain such good luminescent properties, the mixing ratio of phosphine gas to hydrocarbon gas used in forming the light emitting layer should be 0.001 to 10%, and the mixing ratio of silicon hydride gas should be 0.1 to 10%. Preferably it is 15%.
次に発光層を生成する工程において、シボランガスと水
素化ケイ素ガスを用いた場合の３つの例（試料１０〜１
２）を以下に挙げる。Next, in the step of generating a light-emitting layer, three examples (Samples 10 to 1) using ciborane gas and silicon hydride gas are shown.
2) is listed below.
（１）試料１０について
■ 正孔注入層
真空容器内ガス圧力
６
７Ｐａ（０，２Ｔｏｒｒ）
基板温度
２５０°Ｃ
ＣＨ，ガス・５ｉ１１．、ＩＩス
Ｂ ２Ｈｏガス
（ＣＨ，ガス＋５ＩＨ４ガス）
０００
高周波電源電力
０Ｗ
（入力電極面積に対し０．１２５Ｗ／ａｍ２）■
発光層
真空容器内混合ガス（ＣＩＬとＨ７とＢ 、ＩＩ ｏ）
圧力６
７Ｐａ（０
２Ｔｏｒｒ）
Ｃ１＋４ガスに対する５ＩＨ４ガスの混合比２％
Ｃ１ｌ、ガスに対するＢ、Ｉｌ、）ガスの混合比００２
％
基板温度
２５０ ’Ｃ
高周波電源電力
ＯＷ
■ 電子注入層
真空容器内ガス圧力 ２６．７Ｐａ（０，２Ｔｏｒ
ｒ）基板温度
２５０℃
ＣＩＬＩス：５ｉＨＪ１ １ ：
１ｐＨ３ｉス：（ＣＨ４ガス＋５ｉＨＪス） ５
．８：１０００高周波電源電力 １０Ｗ
（入力電極面積に対し０．１２５Ｗ／ａｍ２）（２）試
料１１について
■ 正孔注入層及び電子注入層
試料ｌＯと同じ条件で製造した。(1) About sample 10■ Hole injection layer vacuum container gas pressure 67 Pa (0.2 Torr) Substrate temperature 250°C CH, gas 5i11. , II S B 2Ho gas (CH, gas + 5 IH4 gas) 000 High frequency power supply power 0 W (0.125 W/am2 for input electrode area) ■ Mixed gas in luminescent layer vacuum container (CIL, H7 and B, II o)
Pressure 6 7 Pa (0 2 Torr) Mixing ratio of 5IH4 gas to C1+4 gas 2% Mixing ratio of B, Il, ) gas to C1l gas 002
% Substrate temperature 250'C High frequency power supply power OW ■ Electron injection layer vacuum chamber internal gas pressure 26.7 Pa (0.2 Tor
r) Substrate temperature 250℃ CILIS: 5iHJ1 1:
1pH3i gas: (CH4 gas + 5iHJ gas) 5
．． 8:1000 High frequency power supply power 10W (0.125W/am2 for input electrode area) (2) Regarding sample 11 ■ Hole injection layer and electron injection layer Manufactured under the same conditions as sample IO.
■ 発光層
５ｉＨａガスの同混合比を１％、Ｂ ｔ Ｈａガスの同
混合比を０．００５％とした他は試料１０と同じ条件で
製造した。(2) Light emitting layer 5 It was manufactured under the same conditions as Sample 10, except that the mixing ratio of iHa gas was 1% and the mixing ratio of B t Ha gas was 0.005%.
（３）試料１２について ３ ■ 正孔注入層及び電子注入層 試料１０と同じ条件で製造した ■ 発光層 ５ｉＨａガスの同混合比を０．５％、Ｂ２Ｈ。(3) About sample 12 3 ■ Hole injection layer and electron injection layer Manufactured under the same conditions as sample 10 ■ Luminous layer The same mixing ratio of 5iHa gas is 0.5% and B2H.
ガスの同混合比を０．０１％とした他は試料ｌＯと同じ
条件で製造した。It was manufactured under the same conditions as sample IO except that the gas mixture ratio was 0.01%.
以上の各試料１０〜１２について波長とＥＬ強度との関
係を調べたところ、夫々試料１〜３と同様な結果が得ら
れた。いずれの試料１０〜１２も目視で十分観察できる
発光を示し、十分な発光特性を有していることがわかっ
た。ただしフォトルミネセンス強度は試料１〜６よりも
大きかった。When the relationship between wavelength and EL intensity was investigated for each of the above samples 10 to 12, results similar to those of samples 1 to 3 were obtained. It was found that all Samples 10 to 12 exhibited sufficient luminescence that could be observed visually, and had sufficient luminescent properties. However, the photoluminescence intensity was higher than Samples 1-6.
このように良好な発光特性を得るためには、発光層の製
膜に用いるシボランガスの炭化水素ガスに対する混合比
は０．００１〜５％、水素化ケイ素４
ガスの同混合比は０．１〜１５％であることが好ましい
。In order to obtain such good luminescent properties, the mixing ratio of ciborane gas to hydrocarbon gas used in forming the light emitting layer should be 0.001 to 5%, and the mixing ratio of silicon hydride gas should be 0.1 to 5%. Preferably it is 15%.
試料７〜１２のフォトルミネセンス強度が試料１〜６よ
りも大きかった理由については、ケイ素と炭素は容易に
ＳｉＣとして結合して格子結陥の少ない膜となるため、
ホスフィンやシボランといった活性体が介在することに
よって、より一層格子結陥の少ない良質な膜が得られる
からであると推察される。The reason why the photoluminescence intensity of Samples 7 to 12 was higher than that of Samples 1 to 6 is that silicon and carbon easily combine as SiC to form a film with few lattice defects.
This is presumed to be because a high-quality film with even fewer lattice defects can be obtained by the presence of active substances such as phosphine and ciborane.
」１記の試料１〜１２を作製する場合の基板温度は、発
光層のアモルファス炭素系膜の耐熱性により制限される
が、この膜は３５０°Ｃ以上に加熱されるとＥｇｏが低
下し、かっ膜厚が小さくなるため、３５０℃程度が限界
である。The substrate temperature when producing Samples 1 to 12 in Section 1 is limited by the heat resistance of the amorphous carbon film of the light emitting layer, but when this film is heated to 350°C or higher, Ego decreases, The limit is about 350° C. since the thickness of the coating becomes small.
ところでｐ型のａ−８ｉＣ膜、アモルファス炭素系膜（
発光層）及びｎ型のａ−３ｉＣ膜を積層したｐ−１〜ｎ
型セルを作った場合、アモルファス炭素系膜とａ−Ｓｉ
Ｃ膜（ｐ型またはｎ型）との接合はへテロ接合となるか
ら、その接合が良好になされるか否か、即ち注入層から
発光層に正孔（電子）がうまく注入されるか否かが問題
であったが、試料１〜１２についてダイオード特性を調
べてみると、良好な特性を示し、接合が良好になされて
いることが判った。By the way, p-type a-8iC film, amorphous carbon-based film (
p-1 to n layered with n-type a-3iC film (emitting layer) and n-type a-3iC film
When making a type cell, an amorphous carbon-based film and a-Si
Since the junction with the C film (p-type or n-type) is a heterojunction, it is important to check whether the junction is good or not, that is, whether holes (electrons) are successfully injected from the injection layer to the light emitting layer. However, when the diode characteristics of Samples 1 to 12 were examined, it was found that they exhibited good characteristics and that the junctions were well formed.
Ｇ１発明の効果
本発明によれば、Ｐ−ＣＶＤ法を利用し、反応ガスとし
て炭化水素ガスとホスフィンあるいはシボランガスとを
用い、更には水素化ケイ素ガスを加えているから、実施
例に詳述したように大きな光学的エネルギーギャップを
有すると共に発光特性をホスフィンガス、シボランガス
あ、るいは水素化ケイ素ガスの混合量を変えることによ
りコントロールできるから要望に応じた発光層が容易に
得られる。そしてプラズマＣＶＤ法により得られたａ−
３ｉＣ膜を正孔及び電子の注入層として用いているため
、発光層と注入層とがヘテロ接合により結合されていて
も電子及び正孔がうまく発光層に注入されると共に、光
学的エネルギーギャップ及び抵抗率について目標特性を
満足させる注入層を容易に作り出すことができるから、
これによりアモルファス炭素系膜即ち発光層の特性を十
分に引出すことができ、実用価値の高い発光素子を得る
ことができる。G1 Effects of the Invention According to the present invention, the P-CVD method is used, and hydrocarbon gas and phosphine or ciborane gas are used as reaction gases, and silicon hydride gas is further added, so that It has such a large optical energy gap and its luminescent properties can be controlled by changing the mixing amount of phosphine gas, ciborane gas, or silicon hydride gas, making it easy to obtain a luminescent layer that meets your needs. And a- obtained by plasma CVD method
Since the 3iC film is used as a hole and electron injection layer, electrons and holes can be successfully injected into the light emitting layer even if the light emitting layer and the injection layer are coupled by a heterojunction, and the optical energy gap and Because it is possible to easily create an injection layer that satisfies the target characteristics regarding resistivity,
Thereby, the characteristics of the amorphous carbon film, that is, the light emitting layer can be fully brought out, and a light emitting device with high practical value can be obtained.
第１図は本発明方法により製造した発光素子を示す構成
図、第２図はダイオードの発光特性を示す特性図、第３
図はアモルファス炭素系膜のＥｇ。
とＰＬとの関係を示す特性図である。
３・・・正孔注入層、４・・・発光層、５・・・電子注
入層。FIG. 1 is a configuration diagram showing a light emitting device manufactured by the method of the present invention, FIG. 2 is a characteristic diagram showing the light emitting characteristics of a diode, and FIG.
The figure shows the Eg of an amorphous carbon film. It is a characteristic diagram showing the relationship between and PL. 3... Hole injection layer, 4... Light emitting layer, 5... Electron injection layer.
Claims (3)
スとを含む低圧の反応ガスを真空容器内でグロー放電さ
せて分解ガスを重合させるプラズマ化学的蒸着法により
ｐ型のアモルファス炭化ケイ素膜よりなる正孔注入層を
生成する工程と、低圧の水素ガスと炭化水素ガスとホス
フィンまたはジボランガスとを反応ガスとし、炭化水素
ガスに対するホスフィンまたはジボランガスの混合比を
０．００１〜１０％としたプラズマ化学的蒸着法により
アモルファス炭素系膜よりなる発光層を前記正孔注入層
上に積層する工程と、 炭化水素ガスと水素化ケイ素ガスとｎ型不純物ガスとを
含む低圧の反応ガスを真空容器内でグロー放電させて分
解ガスを重合させるプラズマ化学的蒸着法によりｎ型の
アモルファス炭化ケイ素膜よりなる電子注入層を前記発
光層上に積層する工程とを含むことを特徴とする発光素
子の製造方法。(1) A p-type amorphous silicon carbide film is produced using a plasma chemical vapor deposition method in which a low-pressure reaction gas containing hydrocarbon gas, silicon hydride gas, and p-type impurity gas is glow-discharged in a vacuum container and the decomposed gas is polymerized. A step of generating a hole injection layer consisting of a plasma containing low-pressure hydrogen gas, a hydrocarbon gas, and phosphine or diborane gas as reaction gases, and a mixing ratio of phosphine or diborane gas to the hydrocarbon gas of 0.001 to 10%. A step of laminating a light-emitting layer made of an amorphous carbon-based film on the hole injection layer by a chemical vapor deposition method, and supplying a low-pressure reaction gas containing a hydrocarbon gas, a silicon hydride gas, and an n-type impurity gas in a vacuum container. A method for manufacturing a light-emitting device, comprising the step of laminating an electron injection layer made of an n-type amorphous silicon carbide film on the light-emitting layer by a plasma chemical vapor deposition method in which a glow discharge is caused to polymerize decomposed gas. .
水素ガスと水素化ケイ素ガスとホスフィンガスとを反応
ガスとし、炭化水素ガスに対する水素化ケイ素ガスの混
合比を０．１〜１５％、炭化水素ガスに対するホスフィ
ンガスの混合比を０．００１〜１０％としたプラズマ化
学的蒸着法を用いたことを特徴とする請求項（１）記載
の発光素子の製造方法。(2) In the step of generating the light-emitting layer, low-pressure hydrogen gas, hydrocarbon gas, silicon hydride gas, and phosphine gas are used as reaction gases, and the mixing ratio of silicon hydride gas to hydrocarbon gas is 0.1 to 15. %, and a plasma chemical vapor deposition method using a mixing ratio of phosphine gas to hydrocarbon gas of 0.001 to 10%.
、ホスフィンガスに代えてジボランガスを用い、炭化水
素ガスに対するジボランガスの混合比を０．００１〜５
％としたことを特徴とする発光素子の製造方法。(3) In the method for manufacturing a light emitting device according to claim (2), diborane gas is used instead of phosphine gas, and the mixing ratio of diborane gas to hydrocarbon gas is 0.001 to 5.
%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020697A JPH03225971A (en) | 1990-01-31 | 1990-01-31 | Manufacture of light-emitting element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020697A JPH03225971A (en) | 1990-01-31 | 1990-01-31 | Manufacture of light-emitting element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03225971A true JPH03225971A (en) | 1991-10-04 |
Family
ID=12034348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020697A Pending JPH03225971A (en) | 1990-01-31 | 1990-01-31 | Manufacture of light-emitting element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03225971A (en) |
-
1990
- 1990-01-31 JP JP2020697A patent/JPH03225971A/en active Pending
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