JPS6132798B2 - - Google Patents
Info
- Publication number
- JPS6132798B2 JPS6132798B2 JP54127114A JP12711479A JPS6132798B2 JP S6132798 B2 JPS6132798 B2 JP S6132798B2 JP 54127114 A JP54127114 A JP 54127114A JP 12711479 A JP12711479 A JP 12711479A JP S6132798 B2 JPS6132798 B2 JP S6132798B2
- Authority
- JP
- Japan
- Prior art keywords
- light
- thin film
- zns
- luminescent
- 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
Links
- 239000010409 thin film Substances 0.000 claims description 23
- BOTHRHRVFIZTGG-UHFFFAOYSA-K praseodymium(3+);trifluoride Chemical compound F[Pr](F)F BOTHRHRVFIZTGG-UHFFFAOYSA-K 0.000 claims 1
- 230000005684 electric field Effects 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- -1 Si 3 N 4 Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】
本発明は交流電界の印加に依つてEL（Electro
Luminescene）発光を呈する薄膜EL素子に関す
るものである。[Detailed Description of the Invention] The present invention utilizes EL (Electro
This relates to thin film EL devices that emit light (luminescene).
従来、交流動作の薄膜EL素子に関して、発光
層に規則的に高い電界（106V/cm程度）を印加
し、絶縁耐圧、発光効率及び動作の安定性等を高
めるために、0.1〜2.0wt％のMn（あるいはCu、
Al、Br等）をドープしたZnS、ZnSe等の半導体
発光層をY2O3、TiO2等の誘電体薄膜でサンドイ
ツチした三層構造ZnS：Mn（又はZnSe：Mn）
EL素子が開発され、発光諸特性の向上が確かめ
られている。この薄膜EL素子は数KHzの交流電
界印加によつて高輝度発光し、しかも長寿命であ
るという特徴を有している。またこの薄膜EL素
子の発光に関しては印加電圧を昇圧していく過程
と高電圧側より降圧していく過程で、同じ印加電
圧に対して発光輝度が異なるといつたヒステリシ
ス特性を有していることが発見され、そしてこの
ヒステリシス特性を有する薄膜EL素子の印加電
圧を昇圧する過程に於いて、光、電界、熱等が付
与されると薄膜EL素子はその強度に対応した発
光輝度の状態に励起され、光、電界、熱等を除去
して元の状態に戻しても発光輝度は高くなつた状
態で維持される、いわゆるメモリー現象が表示技
術の新たな利用分野を開拓するに到つた。 Conventionally, for AC-operated thin-film EL devices, a high electric field (about 10 6 V/cm) is regularly applied to the light-emitting layer to improve dielectric strength, luminous efficiency, operation stability, etc. %Mn (or Cu,
A three-layer structure ZnS:Mn (or ZnSe:Mn) in which a semiconductor light-emitting layer such as ZnS, ZnSe, etc. doped with Al, Br , etc. is sandwiched with a dielectric thin film such as Y 2 O 3 , TiO 2, etc.
EL devices have been developed, and improvements in various light-emitting characteristics have been confirmed. This thin-film EL element emits high-intensity light when an alternating current electric field of several KHz is applied, and has a long lifespan. Furthermore, regarding the light emission of this thin film EL element, it has a hysteresis characteristic in which the light emission brightness differs for the same applied voltage in the process of increasing the applied voltage and in the process of decreasing the voltage from the high voltage side. was discovered, and in the process of increasing the voltage applied to a thin film EL element with this hysteresis characteristic, when light, electric field, heat, etc. are applied, the thin film EL element is excited to a state of luminance corresponding to the intensity. The so-called memory phenomenon, in which the luminance remains high even after light, electric field, heat, etc. are removed and the display returns to its original state, has opened up a new field of application for display technology.
薄膜EL素子の１例としてZnS：Mn薄膜EL素子
の基本的構造を第１図に示す。 As an example of a thin film EL device, the basic structure of a ZnS:Mn thin film EL device is shown in FIG.
第１図に基いて薄膜EL素子の構造を具体的に
説明すると、ガラス基板１上にln2O3、SnO2等の
透明電極２、さらにその上に積層してY2O3、
TiO2、Al2O3、Si3N4、SiO2等からなる第１の誘
電体層３がスパツタあるいは電子ビーム蒸着法等
により重畳形成されている。第１の誘電体層３上
にはZnS：Mn焼結ペレツトを電子ビーム蒸着す
ることにより得られるZnS発光層４が形成されて
いる。この時蒸着用のZnS：Mn焼結ペレツトに
は活性物質となるMnが目的に応じた濃度に設定
されたペレツトが使用される。ZnS発光層４上に
は第１の誘電体層３と同様の材質から成る第２の
誘電体層５が積層され、更にその上にAl等から
成る背面電極６が蒸着形成されている。透明電極
２と背面電極６は交流電源７に接続され、薄膜
EL素子が駆動される。 The structure of a thin film EL element will be explained in detail based on FIG. 1. A transparent electrode 2 made of ln 2 O 3 , SnO 2 , etc. is placed on a glass substrate 1, and Y 2 O 3 , etc.
A first dielectric layer 3 made of TiO 2 , Al 2 O 3 , Si 3 N 4 , SiO 2 or the like is formed in an overlapping manner by sputtering or electron beam evaporation. A ZnS light emitting layer 4 is formed on the first dielectric layer 3 by electron beam evaporation of ZnS:Mn sintered pellets. At this time, the ZnS:Mn sintered pellets used for deposition are pellets in which the concentration of Mn, which is an active substance, is set to suit the purpose. A second dielectric layer 5 made of the same material as the first dielectric layer 3 is laminated on the ZnS light emitting layer 4, and a back electrode 6 made of Al or the like is further deposited thereon. The transparent electrode 2 and the back electrode 6 are connected to an AC power source 7, and the thin film
The EL element is driven.
電極２，６間にAC電圧を印加すると、ZnS発
光層４の両側の誘電体層３，５間に上記AC電圧
が誘起されることになり、従つてZnS発光層４内
に発生した電界によつて伝導帯に励起されかつ加
速されて充分なエネルギーを得た電子が、直接
Mn発光センターを励起し、励起されたMn発光セ
ンターが基底状態に戻る際に黄色の発光を行な
う。即ち高電界で加速された電子がZnS発光層４
中の発光センターであるZnサイトに入つたMn原
子の電子を励起し、基底状態に落ちる時、略々
5850Åをピークに幅広い波長領域で、強い発光を
呈する。 When an AC voltage is applied between the electrodes 2 and 6, the above AC voltage is induced between the dielectric layers 3 and 5 on both sides of the ZnS luminescent layer 4, and therefore the electric field generated within the ZnS luminescent layer 4 Therefore, electrons that are excited and accelerated into the conduction band and have obtained sufficient energy can directly
The Mn luminescent center is excited, and when the excited Mn luminescent center returns to the ground state, it emits yellow light. In other words, electrons accelerated by a high electric field reach the ZnS light emitting layer 4.
When the electron of the Mn atom that enters the Zn site, which is the luminescent center of the inside, is excited and falls to the ground state, approximately
It emits strong light in a wide wavelength range with a peak of 5850 Å.
上記の如き構造を有する薄膜EL素子はスペー
ス・フアクタの利点を生かした平面薄型デイスプ
レイ・デバイスとして、文字及び図形を含むコン
ピユーターの出力表示端末機器その他種々の表示
装置に文字、記号、静止画像、動画像等の表示手
段として利用することができる。平面薄型表示装
置としての薄膜ELパネルは従来のブラウス管
（CRT）と比較して動作電圧が低く、同じ平面型
デイスプレイ・デバイスであるプラズマデイスプ
レイパネル（PDP）と比較すれば重量や強度面で
優れており、液晶（LCD）に比べて動作可能温
度範囲が広く、応答速度が速い等多くの利点を有
している。また純固定マトリツクス型パネルとし
て使用できるため動作寿命が長く、そのアドレス
の正確さとともにコンピユーター等の入出力表示
手段として非常に有効なものである。 The thin film EL element having the structure described above can be used as a flat thin display device that takes advantage of the space factor to display characters, symbols, still images, moving images, etc. It can be used as a means of displaying images, etc. Thin-film EL panels as flat flat display devices have a lower operating voltage than conventional blouse tubes (CRTs), and are superior in terms of weight and strength compared to plasma display panels (PDPs), which are also flat display devices. It has many advantages over liquid crystals (LCDs), such as a wider operating temperature range and faster response speed. Furthermore, since it can be used as a pure fixed matrix type panel, it has a long operating life, and its address accuracy makes it very effective as an input/output display means for computers and the like.
上記従来の薄膜EL素子は黄色発光を行なうも
のであるが、黄色発光以外の発光色を得るための
技術開発も試みられている。しかしながら同一発
光層中に複数種の発光センターを導入し、それぞ
れの発光センター固有の発光を得るとともにこれ
らの発光を混合させ、混色発光を得ることは非常
に困難であつた。従つて任意の発光色特に白色に
発光する薄膜EL素子を単純な構造で実現するこ
とのできる技術の開発が従来より切望されてい
た。 Although the conventional thin film EL device described above emits yellow light, attempts have also been made to develop technologies to obtain light emitting colors other than yellow light. However, it has been extremely difficult to introduce a plurality of types of luminescent centers into the same luminescent layer, to obtain luminescence specific to each luminescent center, and to mix these luminescent lights to obtain mixed-color luminescence. Therefore, there has been a long-awaited desire for the development of a technology that can realize a thin film EL element that emits light of any color, especially white, with a simple structure.
本発明は上記現状に鑑み、発光層４に導入する
発光センターとして希土類のプラセオジウムのフ
ツ化物を使用することにより、容易に発光色の白
色化を可能とした新規有用な薄膜EL素子を提供
することを目的とするものである。 In view of the above-mentioned current situation, the present invention provides a new and useful thin-film EL element that can easily whiten the luminescent color by using a rare earth praseodymium fluoride as a luminescent center introduced into the luminescent layer 4. The purpose is to
以下、本発明の１実施例を製造工程順に詳細に
説明する。 Hereinafter, one embodiment of the present invention will be described in detail in the order of manufacturing steps.
第１図に於いて、ガラス基板１上にIn2O3等の
透明電極２を形成し、透明電極２上にSiO2、
Si3N4系の誘電体層３を約2000Å程度形成する。
更に誘電体層３上に発光層４としてZnS：PrF3を
4000〜9000Å程度蒸着する。この時ZnSの発光層
４に含有されるPrF3の濃度は0.1〜1.5mol％の範
囲に選定する。プラセオジウムはPrF3以外にPr
単体あるいはPrCl3等の化合物としてZnS中にド
ープすることも考られるが、PrF3以外の形でド
ープした場合には発光効率が低下して実用性が確
保されない。即ち、プラセオジウムを発光層４中
にドープする場合には、上述の如くフツ化物の形
でドープすると最も輝度の高いEL発光が得られ
また発光の減衰時間も長くなる。この理由はZnS
中で金属Prの周囲をＦがとり囲むことによつて
ZnS母材との相互作用をＦが遮蔽し、Prの励起さ
れた電子のエネルギーを効率良く光エネルギーへ
変換することができるためであると推測されるが
詳細については未解明な点が残されている。次に
発光層４上にSi3N4、Al2O3系の誘電体層５を約
2000Å程度形成し、更に背面電極６としてAlを
蒸着形成する。 In FIG. 1, a transparent electrode 2 made of In 2 O 3 or the like is formed on a glass substrate 1, and SiO 2 , etc. is formed on the transparent electrode 2.
A Si 3 N 4 based dielectric layer 3 is formed to a thickness of about 2000 Å.
Furthermore, ZnS:PrF 3 is formed as a light emitting layer 4 on the dielectric layer 3.
Deposit about 4000 to 9000 Å. At this time, the concentration of PrF 3 contained in the ZnS light emitting layer 4 is selected to be in the range of 0.1 to 1.5 mol %. Praseodymium is Pr in addition to PrF 3
It is possible to dope ZnS as a single substance or as a compound such as PrCl 3 , but if it is doped in a form other than PrF 3 , the luminous efficiency decreases and practicality is not ensured. That is, when doping praseodymium into the light emitting layer 4, doping in the form of fluoride as described above provides the highest brightness of EL light and also lengthens the decay time of the light emission. The reason for this is ZnS
By surrounding the metal Pr inside, F surrounds it.
It is presumed that this is because F blocks the interaction with the ZnS base material and can efficiently convert the energy of the excited electrons of Pr into light energy, but the details remain unclear. ing. Next, a Si 3 N 4 , Al 2 O 3 based dielectric layer 5 is deposited on the light emitting layer 4.
A thickness of about 2000 Å is formed, and then Al is further formed as a back electrode 6 by vapor deposition.
以上の工程を介して製作された薄膜発光素子は
交流電圧を印加すると第２図に示す発光スペクト
ルで約5000Å及び約6500Å付近に強い発光をもつ
プラセオジウム特有の発光色を放射する。このプ
ラセオジウムによる発光色を色座標上にプロツト
すると第３図に示す如く白色に近い発光色である
ことがわかる。尚、第３図は国際標準色度図上で
の上記実施例の薄膜発光素子の発光色位置を示
す。 When an alternating current voltage is applied to the thin film light emitting device manufactured through the above steps, it emits a luminescent color peculiar to praseodymium, which has strong luminescence in the vicinity of about 5000 Å and about 6500 Å in the emission spectrum shown in FIG. 2. When the luminescent color due to praseodymium is plotted on the color coordinates, it can be seen that the luminescent color is close to white, as shown in FIG. Incidentally, FIG. 3 shows the emission color position of the thin film light emitting device of the above example on the international standard chromaticity diagram.
以上詳説した如く、発光層に添加する発光セン
ター形成用不純物として希土類プラセオジウムを
使用することにより２種以上の発光センターを使
用しなくても白色の発光色を呈する薄膜EL素子
を容易に得ることができる。 As explained in detail above, by using the rare earth praseodymium as an impurity for forming luminescent centers added to the luminescent layer, it is possible to easily obtain a thin film EL device that emits white light without using two or more types of luminescent centers. can.
第１図は薄膜EL素子の構造を説明する構成図
である。第２図は本発明の１実施例に係る薄膜
EL素子の発光スペクトルを示す説明図である。
第３図は本発明の１実施例に係る薄膜EL素子の
発光色を説明する国際標準色度図である。
３，５……誘電体層、４……発光層。
FIG. 1 is a block diagram illustrating the structure of a thin film EL element. FIG. 2 shows a thin film according to one embodiment of the present invention.
FIG. 2 is an explanatory diagram showing the emission spectrum of an EL element.
FIG. 3 is an international standard chromaticity diagram illustrating the emission color of a thin film EL device according to an embodiment of the present invention. 3, 5...dielectric layer, 4...light emitting layer.
Claims (1)
層の母材中に発光センターを形成するための不純
物としてプラセオジウムのフツ化物を0.1〜
1.5mol％の濃度範囲でドープするとともに該発光
層を蒸着層で構成しかつその両主面を誘電体層で
被覆することにより白色のEL発光を生起するよ
うにしたことを特徴とする薄膜EL素子。1 Praseodymium fluoride is added in an amount of 0.1 to 0.1 to
A thin film EL characterized in that it is doped in a concentration range of 1.5 mol %, the light emitting layer is composed of a vapor deposited layer, and both main surfaces thereof are covered with a dielectric layer to generate white EL light. element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12711479A JPS5650084A (en) | 1979-09-29 | 1979-09-29 | Thin film el element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12711479A JPS5650084A (en) | 1979-09-29 | 1979-09-29 | Thin film el element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5650084A JPS5650084A (en) | 1981-05-07 |
| JPS6132798B2 true JPS6132798B2 (en) | 1986-07-29 |
Family
ID=14951945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12711479A Granted JPS5650084A (en) | 1979-09-29 | 1979-09-29 | Thin film el element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5650084A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4740582B2 (en) * | 2004-03-19 | 2011-08-03 | 富士フイルム株式会社 | Electroluminescent device |
-
1979
- 1979-09-29 JP JP12711479A patent/JPS5650084A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5650084A (en) | 1981-05-07 |
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