JPH03225972A - Manufacture of light-emitting element - Google Patents
Manufacture of light-emitting elementInfo
- Publication number
- JPH03225972A JPH03225972A JP2020699A JP2069990A JPH03225972A JP H03225972 A JPH03225972 A JP H03225972A JP 2020699 A JP2020699 A JP 2020699A JP 2069990 A JP2069990 A JP 2069990A JP H03225972 A JPH03225972 A JP H03225972A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- layer
- light
- intermediate layer
- light emitting
- 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 9
- 239000007789 gas Substances 0.000 claims abstract description 119
- 238000002347 injection Methods 0.000 claims abstract description 50
- 239000007924 injection Substances 0.000 claims abstract description 50
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 6
- 239000012495 reaction gas Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 22
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 18
- 238000010030 laminating Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002194 amorphous carbon material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 229910004613 CdTe Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- -1 and for example 02H Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000004065 semiconductor Substances 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.
Ｂ８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、
低圧の水素ガスとエヂレンガスと微量の水素化ケイ素ガ
スとを反応ガスとした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ると共に
、この発光層の両面側に、当核発光層の炭素量よりも少
ない炭素量のアモルファス炭素系膜よりなる２つの中間
層を形成し、更にプラズマ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良好であり、しかもこの特性を十分
引き出せるようにしたものである。B8 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, in which low pressure hydrogen gas, ethylene gas, and a trace amount of silicon hydride gas are reacted. An amorphous carbon-based film obtained by plasma chemical vapor deposition in the form of a gas is used as a light-emitting layer, and an amorphous carbon-based film with a carbon content smaller than that of the core light-emitting layer is formed on both sides of the light-emitting layer. By forming two intermediate layers and further using an amorphous silicon carbide film obtained by plasma CVD as a hole and electron injection layer, the light-emitting layer has good light-emitting properties, and these properties can be fully brought out. This is how it was done.
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 ＣａＰＣａＡ（２Ａｓ、Ｚｎ
５ｅｘＴｅ＋−ｘ Ｚｎｘ・ＣｄＴｅ、ＣｄＴｅなどが
ある。C1 Conventional technology Conventionally, light emitting materials include GaAs, GaAsP, CaPCaA (2As, Zn), which are materials for light emitting diodes.
5exTe+-x Znx・CdTe, CdTe, etc.
Ｄ 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
プカ月、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
。このため発光素側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。D Problems to be Solved by the 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 76 eV. The peak wavelength and the optical energy gap are unique to the luminescent material. For this reason, when you want to change the light emitting characteristics of the light emitting element, it is necessary to select a light emitting material that has the required characteristics, and in some cases it may not be possible to obtain the characteristics derived from the desired peak wavelength or optical energy gap. There was a problem that occurred.
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°Ｃ以下に保
ち、例えば１３３．３ｍＰａ〜６ｘ１３３．３Ｐ２Ｌ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（Ｐ−ＣＶＤ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 prepared by maintaining the substrate temperature at, for example, 300°C or less in a vacuum container and applying a high frequency voltage or DC voltage in the presence of hydrogen gas of, for example, 133.3 mPa to 6 x 133.3 P2L. It is generated by performing a plasma CVD method (P-CVD 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Ｅ ｇ ｏと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デユーナブ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). FIG. 3 shows the relationship between E g o and 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 also possible to create a light emitting element that repeatedly emits colors from red to blue.
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
」１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、ｐ（抵抗率）≦１０
６Ω・ｃＩｌｌを有するｐ型、ｎ型膜を作ることが非常
に難かしく、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 this injection layer is made of a p-type or n-type amorphous carbon-based material described in 1. It is best to use However, when using this material as an injection layer, the target characteristics are Ego>2eV, p(resistivity)≦10
It is very difficult to make p-type and n-type films having 6Ω·cIll, 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キャップ及び
発光特性を発光層にイ」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の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 impart arbitrary optical energy caps and light-emitting characteristics to a light-emitting layer, and can fully bring out the characteristics of the light-emitting layer. .
Ｅ 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」る工程と、低圧の水素ガスと炭化水素ガスと
微量の水素化ケイ素ガスとを反応ガスとしたプラズマ化
学的蒸着法によりアモルファス炭素系膜よりなる第１の
中間層、発光層及び第２の中間層をこの順に前記正孔注
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
み、第１の中間層及び第２の中間層の生成工程における
、炭化水素ガスに対する水素化ケイ素ガスの混合比は、
発光層の生成工程における前記水素化ケイ素ガスの混合
比よりも小さいことを特徴とする。E. 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 the decomposed gas. An amorphous layer is formed by a plasma chemical vapor deposition process using low-pressure hydrogen gas, hydrocarbon gas, and a trace amount of silicon hydride gas as reaction gases. A step of laminating a first intermediate layer made of a carbon-based film, a light emitting layer, and a second intermediate layer on the hole injection layer in this order, and a hydrocarbon gas, a silicon hydride gas, and an n-type impurity gas. 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 reaction gas is caused to glow discharge in a vacuum container to polymerize the decomposed gas; In the step of producing the first intermediate layer and the second intermediate layer, the mixing ratio of silicon hydride gas to hydrocarbon gas is:
It is characterized in that the mixing ratio of the silicon hydride gas is smaller than the mixing ratio of the silicon hydride gas in the step of producing the light emitting layer.
更に本発明では、発光層、正孔注入層、電子注入層、第
１の中間層及び第２の中間層の生成工程における基板温
度を夫々Ｔ＋、、ＴＰ、ＴＮ、ＴＭｌ及びＴ）Ｉｚとす
ると、これら基板温度の関係をＴＰ≧ＴＮ ＴＭＩ
ＴＮ２ ＞ ＴＮとすることが好ましい。Furthermore, in the present invention, when the substrate temperatures in the steps of forming the light emitting layer, the hole injection layer, the electron injection layer, the first intermediate layer, and the second intermediate layer are respectively T+, TP, TN, TMl, and T)Iz, , the relationship between these substrate temperatures is TP≧TN TMI
It is preferable that TN2 > TN.
Ｆ、実施例
第１図は本発明方法により得られた発光素子の実施例を
示す構成図である。第１図中１は例えば６３ｃｕ２程度
の面積をもつガラス基板、２は酸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「ａ−８ＩＣ膜」
という。）よりなる正孔注入層、４は２００ ｎｍの厚
さのアモルファス炭素系膜（以下ｒａ−Ｃ： Ｓ ｉ、
）−ＩＪという。）よりなる発光層、５はＰ”をドーパ
ントシた５０ｎｍ程度の厚さのｎ型のａ−９ｉＣ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 obtained by the method of the present invention. In Fig. 1, 1 is a glass substrate with an area of, for example, about 63 cu2, 2 is a transparent electrode made of tin oxide, and 3 is a PET doped with B3' with a thickness of about 30 nm.
type amorphous silicon carbide film (hereinafter referred to as “a-8IC film”)
That's what it means. ), 4 is an amorphous carbon-based film with a thickness of 200 nm (hereinafter ra-C: Si,
)-IJ. ), 5 is an electron injection layer made of an n-type a-9iC film doped with P'' and has a thickness of about 50 nm, and 6 is an aluminum electrode.
また７１．７２は夫々２０ｎｍの厚さのａ−Ｃ８ｉ、Ｈ
よりなる第１の中間層及び第２の中間層であり、ガス成
分が異なる他は発光層と同様の方法で作製される。71.72 is a-C8i, H with a thickness of 20 nm, respectively.
The first intermediate layer and the second intermediate layer are formed by the same method as the light emitting layer except that the gas components are different.
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Ｉ”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 I''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１８１１〜３）を以下に挙げる。Here are three examples of manufacturing conditions for manufacturing light emitting devices (
Trial 1811-3) is listed below.
（１）試料ｌについて
■ 正孔注入層
真空容器内混合ガス圧力 ２６．７Ｐａ（０，２Ｔｏ
ｒｒ）基板温度 ２５０°ＣＣｌ−Ｉ
４ガス Ｓ ｉ Ｉ−Ｌガス ＩＩ１１
Ｂ２Ｈ６ガス：（ＣＨ，ガス＋ＳｉＨ４ガス）３：１Ｏ
ＯＯ高周波電源電力 ＬＯＷ
（入力電極面積に対しＯ，Ｉ２５Ｗ／ｃが）■ 第１の
中間層
真空容器内混合ガス圧力 ２６．７Ｐａ（０，２Ｔｏ
ｒｒ）ＣＨ４ガスに対する５ＩＨ４ガスの混合比 ０５
％基板温度 ２５０°Ｃ高周波電源電
力 ＬＯＷ
■ 発光層
真空容器内混合ガス（ＣＨ□とＨ２とＳ ｉ ＨＪ圧力
２６．７Ｐａ（０，２Ｔｏｒｒ）
ＣＩ−１，ガスに対する５ｉｒ−１４ガスの混合比 ６
％基板温度 ２５０°Ｃ高周波電源電
力 １０Ｗ
■ 第２の中間層
２
第１の中間層と同じ条件で製造した。(1) About sample 1■ Mixed gas pressure in hole injection layer vacuum vessel 26.7Pa (0.2To
rr) Substrate temperature 250°CCl-I
4 gas S i I-L gas II11 B2H6 gas: (CH, gas + SiH4 gas) 3:1O
OO high-frequency power supply power LOW (O, I25W/c relative to the input electrode area) ■ Mixed gas pressure in the first intermediate layer vacuum vessel 26.7 Pa (0,2To
rr) Mixing ratio of 5IH4 gas to CH4 gas 05
%Substrate temperature 250°C High frequency power supply power LOW ■ Light-emitting layer mixed gas in vacuum container (CH□, H2 and Si HJ pressure 26.7 Pa (0.2 Torr) Mixing ratio of 5ir-14 gas to CI-1 gas 6
%Substrate temperature 250°C High frequency power supply power 10W ■Second intermediate layer 2 Manufactured under the same conditions as the first intermediate layer.
■
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ガス： Ｓ ｉ Ｈ４ガス
ＰＨ３ガス
（ＣＩ−Ｔ 、ガス＋ Ｓ ｉ Ｉ−Ｌガス）５０００
高周波電源電力
０Ｗ
（入力電極面積に対し０ 、 ＋ ２５ Ｗ／ｃｍ２）
（２）試料２について
■
正孔注入層、
電子注入層、
第１の中間層及
び第２の中間層
試料■と同じ条件で製造した。■ Electron injection layer vacuum chamber internal gas pressure 26.7 Pa (0.2 Torr) Substrate temperature 250°C CH4 gas: S i H4 gas PH3 gas (CI-T, gas + S i I-L gas) 5000 High frequency power supply power 0 W (0, +25 W/cm2 for input electrode area)
(2) Sample 2 ■ Hole injection layer, electron injection layer, first intermediate layer, and second intermediate layer manufactured under the same conditions as sample ■.
■ 発光層 ｉＨ４ ガスの混合比を４％とした他は試 料１と同じ条件で製造した。■ light emitting layer iH4 The gas mixture ratio was 4%. It was produced under the same conditions as Sample 1.
（３）試料３について
■ 正孔注入層、電子注入層、第１の中間層及び第２の
中間層
試料Ｉと同じ条件で製造した。(3) Regarding Sample 3 ■ The hole injection layer, the electron injection layer, the first intermediate layer, and the second intermediate layer were manufactured under the same conditions as Sample I.
■ 発光層
Ｓ ｉ Ｉ−１４ガスの混合比を２％とした他は試料１
と同じ条件で製造した。■ Light-emitting layer S i Sample 1 except that the mixture ratio of I-14 gas was 2%.
manufactured under the same conditions.
以」二の各試料１〜３について波長とＥＩ７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、発光層の製膜に
用いる水素化ケイ素ガスの濃度（メタンガスに対する濃
度（混合比））は０．５〜３０％、第１及び第２の中間
層の製膜に用いる水素化ケイ素ガスの混合比は０．３
〜１５容量％であることが好ましい。ただし第１の中間
層及び第２の中間層の生成工程における、炭化水素ガス
に対する水素化ケイ素ガスの混合比は、発光層の生成工
程における前記水素化ケイ素ガスの混合比よりも小さく
する必要がある。その理由は、ケイ素原子の含有量に対
する炭素原子の含有率について、発光層よりも中間層の
方を多くするためである。When the relationship between the wavelength and the EI7 intensity was investigated for each of the following 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 luminescent properties, the concentration of silicon hydride gas (concentration (mixing ratio) to methane gas) used for forming the luminescent layer must be between 0.5 and 30%, between the first and second The mixing ratio of silicon hydride gas used to form the layer is 0.3
It is preferably 15% by volume. However, the mixing ratio of the silicon hydride gas to the hydrocarbon gas in the step of producing the first intermediate layer and the second intermediate layer needs to be smaller than the mixing ratio of the silicon hydride gas in the producing step of the light-emitting layer. be. The reason for this is that the content ratio of carbon atoms to the content of silicon atoms is made larger in the intermediate layer than in the light emitting layer.
いずれの試料１〜３６目視て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２０
０ｍＡ／ｃｍ２てあった。また基板温度についてはａ−
Ｃ：Ｓｉ、Ｈ膜の耐熱性により制限されろが、ａ−Ｃ：
Ｓｉ、■（膜は３５０°Ｃ以」二に加熱されるとｆＥ、
ｇｏが低下し、かつ５
膜厚が小さくなるため、３５０℃程度が限界である。It was found that all of Samples 1 to 36 exhibited luminescence that was sufficiently observable with the naked eye, and had sufficient luminescent properties. The forward bias voltage used in the test was 5V, and the current density was 20
It was 0mA/cm2. Regarding the substrate temperature, a-
C: Although limited by the heat resistance of Si and H films, a-C:
Si, (when the film is heated above 350°C, fE,
The limit is about 350° C. because the go is lowered and the film thickness is smaller.
ここで上記の試料１〜３においては、中間層及び発光層
を生成する工程で用いる炭化水素ガスとしてＣＨ、ガス
を使用しているが、本発明ではＣＨ４ガスに限定される
ものではなく、例えば０２Ｈ，ガスを用いてもよい。こ
のように０２１１．ガスを用いて製造した試料（４〜６
）の製造条件を次に記述する。Here, in the above samples 1 to 3, CH gas is used as the hydrocarbon gas used in the process of generating the intermediate layer and the light emitting layer, but the present invention is not limited to CH4 gas, and for example 02H, gas may also be used. In this way, 0211. Samples produced using gas (4 to 6
) manufacturing conditions are described below.
（１）試料４について
■ 正孔注入層
真空容器内混合ガス圧力 ２６．７Ｐａ（０，２Ｔｏ
ｒｒ）基板温度 ２５０℃
ＣＨ４ガス：５ＩＨ４ガス ＩＩＩ
Ｅ２Ｈｏガス：（ＣＩ−（４ガス＋５ｉＨｔガス）３：
ｌ０００６
高周波電源電力 １０Ｗ
（入力電極面積に対しＯ，Ｉ２５Ｗ／ｃｚす■ 第１の
中間層
真空容器内混合ガス圧力 ２６．７Ｐａ（０，２Ｔｏ
ｒｒ）Ｃ２Ｉ−１、ガスに対するＳ ｉ Ｉ−Ｌガスの
混合比 １．０％基基板塵 ２５０°
Ｃ高周波電源電力 １０Ｗ
■ 発光層
真空容器内混合ガス（Ｃ７Ｈ，とトＩ２とＳ ｉ Ｈ４
）圧力２６．７Ｐａ（０，２Ｔｏｒｒ）
Ｃ２Ｔ−Ｉ 、ガスに対する５ｉＨｚガスの混合比 １
０％基板温度 ２５０°Ｃ高周波電源
電力 １０Ｗ
■ 第２の中間層
第１の中間層と同じ条件で製造した。(1) About sample 4■ Mixed gas pressure in hole injection layer vacuum container 26.7Pa (0.2To
rr) Substrate temperature 250°C CH4 gas: 5IH4 gas III E2Ho gas: (CI-(4 gas + 5iHt gas) 3:
l0006 High frequency power source power 10W (O, I25W/cz for input electrode area) Mixed gas pressure in first intermediate layer vacuum vessel 26.7Pa (0,2To
rr) C2I-1, mixture ratio of S i I-L gas to gas 1.0% substrate dust 250°
C high frequency power supply power 10W ■ Light emitting layer mixed gas in vacuum container (C7H, toto I2 and S i H4
) Pressure 26.7 Pa (0.2 Torr) C2T-I, Mixing ratio of 5iHz gas to gas 1
0% Substrate temperature: 250°C High frequency power source: 10W ■Second intermediate layer Manufactured under the same conditions as the first intermediate layer.
■ 電子注入層
真空容器内ガス圧力 ２６．７Ｐａ（０，２Ｔｏ
ｒｒ）基板温度 ２５０℃
ＣＨ４ガス；ＳｉＨ４ガス ｌ：■ＰＩ−１３ガス
：（ＣＩ−Ｌガス＋Ｓ ｉ Ｈ４ガス）５．８ ＋ １
０００高周波電源電力 １０Ｗ
（入力電極面積に対しＯ、Ｉ ２５Ｗ／ｃｚ’）（２）
試料５について
■ 正孔注入層、電子注入層、第１の中間層及び第２の
中間層試料１と同し条件で製造した。■ Electron injection layer vacuum chamber internal gas pressure 26.7Pa (0.2To
rr) Substrate temperature 250°C CH4 gas; SiH4 gas l: ■PI-13 gas: (CI-L gas + SiH4 gas) 5.8 + 1
000 High frequency power supply power 10W (O, I 25W/cz' for input electrode area) (2)
Regarding Sample 5 ■ Hole injection layer, electron injection layer, first intermediate layer, and second intermediate layer were manufactured under the same conditions as Sample 1.
■ 発光層
Ｓ ｉ Ｉ−１、ガスの混合比を５％とした他は試１！
４１と同じ条件で製造した。■ Trial 1 except that the light emitting layer S i I-1 and the gas mixture ratio were 5%!
It was manufactured under the same conditions as No. 41.
（３）試料６について
■ 正孔注入層、電子注入層、第１の中間層及び第２の
中間層試料１と同じ条件で製造した。(3) Regarding Sample 6 ■ The hole injection layer, the electron injection layer, the first intermediate layer, and the second intermediate layer were manufactured under the same conditions as Sample 1.
■ 発光層
（、Ｈ，ガスに対するＳｉＨ４ガスの混合比を３％とし
た他は試料１と同じ条件で製造した。(2) The light emitting layer was manufactured under the same conditions as Sample 1, except that the mixing ratio of SiH4 gas to H gas was 3%.
以上の各試料４〜６について波長とＥ Ｌ強度との関係
を調へたところ夫々試料１〜３の場合と同等の関係であ
った。このように良好な発光特性を得るためには、発光
層の製膜に用いる水素化ケイ素ガスの濃度（エヂレンガ
スに対する濃度（混合比））は０５〜３０％、第１及び
第２の中間層の製膜に用いる水素化ケイ素ガスの濃度は
０．３〜２０％であることが好ましい。When the relationship between the wavelength and the EL intensity was investigated for each of the above samples 4 to 6, the relationship was the same as that for samples 1 to 3, respectively. In order to obtain such good luminescent properties, the concentration of silicon hydride gas used for forming the luminescent layer (concentration (mixing ratio) relative to the air gas) must be 0.5 to 30%, and The concentration of silicon hydride gas used for film formation is preferably 0.3 to 20%.
いずれの試料４〜６も目視で十分観察できる発光を示し
、試料１〜３の場合と同様に十分な発光９
特性を有していることが判った。発光試験における条件
は試料１〜３と同じである。It was found that all Samples 4 to 6 exhibited luminescence that could be sufficiently observed visually, and had sufficient luminescence characteristics as in the case of Samples 1 to 3. The conditions in the luminescence test were the same as Samples 1-3.
更に本発明では、発光層、正孔注入層、電子注入層、第
１の中間層及び第２の中間層の生成工程における基板温
度を夫々ＴＬ、ＴＰ、ＴＮ、ＴＭＩ及びＴ、４２とする
と、これら基板温度の関係をＴＰ≧ＴＮ ＴＭＩ
ＴＮ２＞ＴＬとすることが好ましい。その理由について
は、正孔注入層、電子注入層及び中間層内のポロン等の
不純物が発光層内に拡散するのを防止するためである。Furthermore, in the present invention, when the substrate temperatures in the generation steps of the light emitting layer, hole injection layer, electron injection layer, first intermediate layer, and second intermediate layer are respectively TL, TP, TN, TMI, and T, 42, The relationship between these substrate temperatures is TP≧TN TMI
It is preferable that TN2>TL. The reason for this is to prevent impurities such as poron in the hole injection layer, electron injection layer, and intermediate layer from diffusing into the light emitting layer.
またＴＰ ＜ ＴＮ、 Ｔ）１１． ’Ｔ’＊＋、と
した場合には、電子注入層あるいは中間層を生成するこ
とにより正孔注入層内の不純物が発光層内に拡散するお
それがある。Also, TP < TN, T)11. In the case of 'T'*+, impurities in the hole injection layer may be diffused into the light emitting layer by forming an electron injection layer or an intermediate layer.
このような条件で製造した試料（７〜９）の具０ 体側を次に記述する。Samples (7 to 9) produced under these conditions had 0 The body side is described next.
（＋）試料７について
■ 正孔注入層
真空容器内混合ガス圧力 ２６．７Ｐａ（０，２Ｔｏ
ｒｒ）基板温度 ２８０℃
ＣＨ，ガス Ｓ ｉ ｌ−１４ガス １：ｌＢ２Ｈｅ
ガス：（ＣＨ４ガス＋ＳｉＨ，ガス）３：ｌ０００高周
波電源電力 １０Ｗ
（入力電極面積に対し０．１２５Ｗ／ｃｉす■ 第１の
中間層
真空容器内混合ガス圧力 ２６．７Ｐａ（０，２Ｔｏ
ｒｒ）ＣＨ，ガスに対するＳ ｉＨ４ガスの混合比 ０
５％基板温度 ２５０°Ｃ高周波電源
電力 １０Ｗ
■ 発光層
真空容器内混合ガス（Ｃｌ−１、とＨ２とＳ ｉ ＨＪ
圧力６
７Ｐａ（０
２ＴＯｒｒ）
ＣＩ−１，ガスに対するＳｉＨ，ガスの混合比６％
基板温度
２２５°Ｃ
高周波電源電力
０Ｗ
■
第２の中間層
第１の中間層と同じ条件で製造した。(+) About sample 7■ Mixed gas pressure in hole injection layer vacuum container 26.7Pa (0.2To
rr) Substrate temperature 280℃ CH, gas S i l-14 gas 1:lB2He
Gas: (CH4 gas + SiH, gas) 3:1000 High frequency power supply power 10W (0.125W/ci for input electrode area) Mixed gas pressure in first intermediate layer vacuum vessel 26.7Pa (0.2To
rr) Mixing ratio of SiH4 gas to CH, gas 0
5% Substrate temperature 250°C High frequency power supply power 10W ■ Light emitting layer mixed gas in vacuum container (Cl-1, H2 and S i HJ
Pressure 6 7 Pa (0 2 TOrr) CI-1, mixture ratio of SiH and gas to gas 6% Substrate temperature 225°C High frequency power source power 0 W ■Second intermediate layer Manufactured under the same conditions as the first intermediate layer.
■
電子注入層
真空容器内ガス圧力
６
７Ｐａ（０
２Ｔｏｒｒ）
基板温度
５０８Ｃ
ＣＨ４ガス
ＳｉＨ４ガス
■
ＰＨ３ガス
（ＣＨ４ガス＋ＳｉＨ４ガス）５
８：ｌ０００
高周波電源電力
０Ｗ
（入力電極面積に対し０
１２５Ｗ／ｃｘ”）
（２）試１！４．８について
■ 正孔注入層、電子注入層、第１の中間層及び第２の
中間層試料１と同じ条件で製造した。■ Gas pressure in electron injection layer vacuum chamber 67 Pa (02 Torr) Substrate temperature 508 C CH4 gas SiH4 gas ■ PH3 gas (CH4 gas + SiH4 gas) 58:1000 High frequency power supply power 0 W (0 125 W/cx for input electrode area) ) (2) Trial 1! Regarding 4.8 ■ The hole injection layer, the electron injection layer, the first intermediate layer, and the second intermediate layer were manufactured under the same conditions as Sample 1.
■ 発光層
ＳｉＨ４ガスの濃度を４％とした他は試料ｌと同し条件
で製造した。(2) Light emitting layer This was manufactured under the same conditions as Sample 1 except that the concentration of SiH4 gas was 4%.
（３）試料９について
■ 正孔注入層、電子注入層、第１の中間層及び第２の
中間層試料１と同じ条件で製造した。(3) Regarding Sample 9 ■ The hole injection layer, the electron injection layer, the first intermediate layer, and the second intermediate layer were manufactured under the same conditions as Sample 1.
■ 発光層
ＣＩ（４ガスに対するＳ ｉ Ｔ−１４ガスの濃度を２
％とした他は試料１と同じ条件で製造した。■ Light emitting layer CI (concentration of S i T-14 gas to 4 gases is 2)
It was manufactured under the same conditions as Sample 1 except that the values were set as %.
以」二の各試料７〜９について波長とＥＬ強度との関係
を調へたところ、試料１〜３の場合と同等の関係であっ
たが、各試料７〜９のいずれについても、先の試１′−
１１〜６に比べて、同じ電界をかけ３
たときの発光エネルギーのピーク値が高かった。When we investigated the relationship between wavelength and EL intensity for each of Samples 7 to 9 in 2 below, we found that the relationship was the same as that for Samples 1 to 3, but for each of Samples 7 to 9, Trial 1'-
Compared to Nos. 11 to 6, the peak value of the emission energy was higher when the same electric field was applied.
このように差の出た理由は、発光層の両側の層からの当
該発光層内への不純物の拡散り月防止されているためで
ある。The reason for this difference is that impurities from the layers on both sides of the light emitting layer are prevented from diffusing into the light emitting layer.
ところでｐ型のａ−８ｉＣ膜、ａ Ｃ： Ｓ ＋ −
。By the way, p-type a-8iC film, aC: S + -
.
Ｈ膜及びｎ型のａ−３ｉＣ膜を積層したｐ−ｉｎ型セル
を作った場合、ａ−Ｃ：Ｓｉ、Ｈ膜とａＳｉＣ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１〜９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。When a p-in type cell is made by laminating an H film and an n-type a-3iC film, the junction between the a-C:Si, H film and aSiC film (p-type or n-type) becomes a heterojunction. Therefore, the question was whether the junction could be made well, that is, whether holes (electrons) could be successfully injected from the injection layer to the light emitting layer.The diode characteristics of samples 1 to 9 were investigated. When you look,
It was found that it exhibited good characteristics and was well bonded.
Ｇ 発明の効果
４
本発明によれば、Ｐ−ＣＶＤ法により得られたａ−Ｃ５
ｉ１Ｈ膜を発光層として用いているため、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５ｉＩＩ
ａ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−８ｉＣ膜を正孔及び電
子の注入層として用い、更に発光層と正孔及び電子の注
入層との間に、発光層に含まれるＣ量よりも多く含まれ
る中間層が介在されるから、発光層と注入層とかへテロ
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す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λ−Ｃ：Ｓｉ、Ｈ膜
即ち発光層の膜部を十分に引き出すことができ、実用価
値の高い発光素子を得ることができる。また各層の基板
温度を先述したようにＴＰ≧ＴＮ、 ＴＭｌ、 Ｔ、４
ｔ＞ Ｔ ｔの関係にしているため、不純物の発光層へ
の拡散を防止できるから発光層のダメージが小さく、そ
の特性が失われない。G Effect of the invention 4 According to the present invention, a-C5 obtained by P-CVD method
Since the i1H film is used as the light-emitting layer, it has a large optical energy gap and has light emission characteristics of 5iII.
Since it can be controlled by changing the mixing amount of the a gas, a light-emitting layer that meets the needs can be easily obtained. Then, an a-8iC film obtained by the plasma CVD method is used as a hole and electron injection layer, and furthermore, between the light emitting layer and the hole and electron injection layer, a larger amount of carbon is contained than the amount of carbon contained in the light emitting layer. Since an intermediate layer is interposed between the light emitting layer and the 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 connected by a heterojunction, and the target characteristics in terms of optical energy gap and resistivity can be satisfied. Since the injection layer can be easily created, the λ-C:Si,H film, that is, the film portion of the light emitting layer, can be sufficiently brought out, and a light emitting device with high practical value can be obtained. Also, as mentioned above, the substrate temperature of each layer is TP≧TN, TMl, T, 4
Since the relationship t>Tt is established, impurities can be prevented from diffusing into the light emitting layer, so damage to the light emitting layer is small and its characteristics are not lost.
第１図は本発明の実施例に係る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Ｅｇｏ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、７
１．７２・・・中間層。FIG. 1 is a configuration diagram showing a light emitting element according to an embodiment of the present invention,
FIG. 2 is a characteristic diagram showing the light emitting characteristics of the diode, and FIG. 3 is a characteristic diagram showing the relationship between Ego and PL of the amorphous carbon film. 3. Hole injection layer, 4. Light emitting layer, 5. Electron injection layer, 7
1.72...middle class.
Claims (2)
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微量
の水素化ケイ素ガスとを反応ガス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第１の中間
層、発光層及び第２の中間層をこの順に前記正孔注入層
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み、 第１の中間層及び第２の中間層の生成工程における、炭
化水素ガスに対する水素化ケイ素ガスの混合比は、発光
層の生成工程における前記水素化ケイ素ガスの混合比よ
りも小さい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 first intermediate layer made of an amorphous carbon film is formed by a plasma chemical vapor deposition method using low-pressure hydrogen gas, hydrocarbon gas, and a trace amount of silicon hydride gas as reaction gases. , laminating a light-emitting layer and a second intermediate layer on the hole injection layer in this order; and glowing a low-pressure reaction gas containing a hydrocarbon gas, a silicon hydride gas, and an n-type impurity gas in a vacuum container. 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 of polymerizing decomposed gas by discharging the first intermediate layer and the second intermediate layer; A method for producing a light emitting device, wherein a mixing ratio of silicon hydride gas to hydrocarbon gas in the step of producing a light emitting layer is smaller than a mixing ratio of silicon hydride gas in the step of producing a light emitting layer.
及び第２の中間層の生成工程における基板温度を夫々Ｔ
＿Ｌ、Ｔ＿Ｐ、Ｔ＿Ｎ、Ｔ＿Ｍ＿１及びＴ＿Ｍ＿２とす
ると、これら基板温度の関係が Ｔ＿Ｐ≧Ｔ＿Ｎ、Ｔ＿Ｍ＿１、Ｔ＿Ｍ＿２＞Ｔ＿Ｌであ
る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) The substrate temperature in the generation process of the light-emitting layer, hole injection layer, electron injection layer, first intermediate layer, and second intermediate layer is T
2. The method of manufacturing a light emitting device according to claim 1, wherein the relationship between the substrate temperatures is T_P≧T_N and T_M_1, T_M_2>T_L, where _L, T_P, T_N, T_M_1, and T_M_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020699A JPH03225972A (en) | 1990-01-31 | 1990-01-31 | Manufacture of light-emitting element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020699A JPH03225972A (en) | 1990-01-31 | 1990-01-31 | Manufacture of light-emitting element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03225972A true JPH03225972A (en) | 1991-10-04 |
Family
ID=12034401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020699A Pending JPH03225972A (en) | 1990-01-31 | 1990-01-31 | Manufacture of light-emitting element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03225972A (en) |
-
1990
- 1990-01-31 JP JP2020699A patent/JPH03225972A/en active Pending
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