JP2003303539A - Electron emission source and its manufacturing method - Google Patents
Electron emission source and its manufacturing methodInfo
- Publication number
- JP2003303539A JP2003303539A JP2002107991A JP2002107991A JP2003303539A JP 2003303539 A JP2003303539 A JP 2003303539A JP 2002107991 A JP2002107991 A JP 2002107991A JP 2002107991 A JP2002107991 A JP 2002107991A JP 2003303539 A JP2003303539 A JP 2003303539A
- Authority
- JP
- Japan
- Prior art keywords
- film
- particles
- electron emission
- emission source
- cnt
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、平板型表示装置
などに用いられる電子放出源に関するものであり、特
に、電子放出材料としてカーボン系の材料を使用する冷
陰極電子源、及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron emission source used for a flat panel display device and the like, and more particularly to a cold cathode electron source using a carbon-based material as an electron emission material and a method for manufacturing the same. It is a thing.
【０００２】[0002]
【従来の技術】カーボンナノチューブ（以下、ＣＮＴと
記す）は直径１０〜５００Å、長さ数μｍ〜１００μｍ
の炭素分子からなる。その形状から、電界放出の電子放
出源(以下、電子源と記す)として用いたとき、先端部に
強い電界を発生することができるため、低い電圧で電界
放出により電子を発生させることが可能となる。また、
安定な構造であるため、表面状態の変化による電界放出
特性の変化が少ない利点がある。2. Description of the Related Art A carbon nanotube (hereinafter referred to as CNT) has a diameter of 10 to 500 Å and a length of several μm to 100 μm.
It consists of carbon molecules. Due to its shape, when used as a field emission electron emission source (hereinafter referred to as an electron source), a strong electric field can be generated at the tip portion, so that it is possible to generate electrons by field emission at a low voltage. Become. Also,
Since the structure is stable, there is an advantage that the change in the field emission characteristics due to the change in the surface state is small.
【０００３】特開平１１−２６０２４９号公報には、Ｃ
ＮＴを含むペーストを作製し、これを印刷して厚膜と
し、膜の基材から突き出したＣＮＴから電子を放出させ
る電子源について示されている。以下にこの電子源の製
造方法について説明する。ＣＮＴはグラファイト電極に
よるアーク放電や熱ＣＶＤなどの方法により製造され
る。不純物としてのグラファイト粒子とともにＣＮＴは
粉砕され、ビヒクルとＡｇやＰｂＯを主成分とするフリ
ットガラス等と混合してペースト化される。このペース
トを塗布、乾燥、焼成して電子源となる厚膜を作製す
る。このようにして作製された厚膜は、光源や蛍光表示
管、ＣＲＴの電子源等、ディスプレイデバイスへの適用
が期待されている。ＣＮＴを含むペーストを印刷塗布し
て厚膜とし、電界放出電子源とする方法は他にも、特開
２０００−２６８７０７号公報、特開２０００−３６２
４３号公報、特開２００１−４３７９２号公報等に述べ
られている。In Japanese Patent Laid-Open No. 11-260249, C
An electron source is shown in which a paste containing NT is prepared, printed into a thick film, and electrons are emitted from CNTs protruding from the base material of the film. The method of manufacturing this electron source will be described below. CNTs are manufactured by a method such as arc discharge using a graphite electrode or thermal CVD. CNTs are crushed together with graphite particles as impurities, mixed with a vehicle and frit glass containing Ag or PbO as a main component, and made into a paste. This paste is applied, dried, and fired to form a thick film serving as an electron source. The thick film thus produced is expected to be applied to a display device such as a light source, a fluorescent display tube, an electron source of a CRT, or the like. In addition to the method of applying a paste containing CNT by printing to form a thick film and using it as a field emission electron source, JP-A-2000-268707 and 2000-362 are known.
No. 43, Japanese Patent Application Laid-Open No. 2001-43792, and the like.
【０００４】[0004]
【発明が解決しようとする課題】従来の電子源は以上の
ように製造されており、上記ＣＮＴを含むペーストは、
ＣＮＴ粒子及びグラファイト粒子よりなる炭素粒子とビ
ヒクルだけで構成すると、ビヒクルは焼成により消失す
るため、ペーストを印刷・乾燥・焼成した後の膜はグラ
ファイト粒子及びＣＮＴ粒子よりなる炭素粒子の凝集体
であり、膜強度が弱く、振動や電界の印加によりグラフ
ァイト粒子、ＣＮＴ粒子等の各炭素粒子が離脱し易い。
低電圧で電界放出させるためには、引き出し電極をでき
るだけ電子源に近接させる必要があるが、上記のように
離脱した各炭素粒子が引き出し電極との間に挟まり、引
き出し電極とカソード電極との間の短絡が容易に発生す
るという問題があった。The conventional electron source is manufactured as described above, and the paste containing the above CNT is
If only the carbon particles consisting of CNT particles and graphite particles and the vehicle are composed, the vehicle disappears by firing, so the film after printing, drying and firing the paste is an aggregate of carbon particles consisting of graphite particles and CNT particles. However, the film strength is weak, and carbon particles such as graphite particles and CNT particles are easily separated by the application of vibration or an electric field.
In order to perform field emission at a low voltage, it is necessary to bring the extraction electrode as close as possible to the electron source, but the carbon particles that have separated as described above are sandwiched between the extraction electrode and the extraction electrode and the cathode electrode. However, there is a problem that the short circuit is easily generated.
【０００５】また、上記ペーストを印刷・乾燥・焼成し
ただけでは、ＣＮＴは膜表面から露出しにくく、良好な
電子放出特性が得られないため、刃で筋をいれたり、レ
ーザアブレ−ジョンによってＣＮＴを露出させている。
しかし、膜に傷をつける方法では筋をいれた部分しか、
ＣＮＴが露出しない。膜全体に傷をつけるために研磨し
ようとすると、膜を構成する粒子間の結合力が弱いた
め、膜そのものが容易に無くなってしまうという問題が
あった。また、レーザアブレ−ジョンによる方法では、
膜表面のみを制御性よく除去することが難しいという問
題があった。Further, CNTs are difficult to be exposed from the film surface and good electron emission characteristics cannot be obtained only by printing, drying and firing the above-mentioned paste, and therefore, the CNTs can be streaked or the CNTs can be cut by laser abrasion. Exposed.
However, in the method of scratching the membrane, only the streaked part,
CNT is not exposed. When polishing is performed to scratch the entire film, there is a problem that the film itself is easily lost because the bonding force between particles forming the film is weak. Moreover, in the method by laser abrasion,
There is a problem that it is difficult to remove only the film surface with good controllability.
【０００６】膜の強度を上げ、膜と基板との密着力を上
げるために、ペースト中に導電体であるＡｇ粒子やＰｂ
Ｏを主成分とするガラス粒子を混合させることが試みら
れている。しかしながら、Ａｇ粒子やＰｂＯを含む低融
点ガラスからなるガラス粒子を混合した場合、後から大
気中での４００〜５００℃の焼成工程があると、混合し
たＡｇ粒子やＰｂＯを主成分とするガラス粒子の影響
で、炭素粒子が酸化され易く、グラファイト粒子、ＣＮ
Ｔ粒子ともに消失してしまうという問題があった。電子
源を光源やディスプレイに適用する場合、ＣＮＴを含む
ペーストを印刷し、ペーストパターンを形成した後、さ
らに複数の熱工程が不可欠である。先ず、ペーストパタ
ーンに含まれるビヒクルを除去するために、溶剤の乾燥
と３５０〜４００℃での焼成が必要である。ビヒクルは
ペーストの印刷に好適な粘度を与えるために、有機溶剤
にエチルセルロース等の樹脂成分を加えて作製される。
ビヒクルが残存すると、真空環境に置いたときにこれが
分解して、真空環境を汚染する可能性があるため、焼成
が必要となる。また、光源として用いるためには、通常
フリットガラスを用いたガラス封体の真空封止が必要で
あり、その際、４００〜５００℃程度に温度を上げる。
また、真空排気の際も加熱しながら排気する。このとき
の排気温度も脱ガスを加速し、排気時間を短縮するため
には３００℃以上が望ましい。そこで、ＣＮＴを含むペ
ーストに混合する材料として、焼成してもＣＮＴ粒子及
びグラファイト粒子の減少が少なく、かつ焼成後、各炭
素粒子間の密着力、及び膜と基板との間の密着力を向上
できる材料が求められていた。In order to increase the strength of the film and the adhesion between the film and the substrate, Ag particles or Pb, which are conductors, are contained in the paste.
Attempts have been made to mix glass particles containing O as a main component. However, when glass particles made of a low-melting glass containing Ag particles or PbO are mixed, if there is a firing step at 400 to 500 ° C. in the air later, the mixed Ag particles or glass particles containing PbO as a main component. The carbon particles are easily oxidized under the influence of
There is a problem that both T particles disappear. When the electron source is applied to a light source or a display, after printing a paste containing CNTs to form a paste pattern, a plurality of heating steps are indispensable. First, in order to remove the vehicle contained in the paste pattern, it is necessary to dry the solvent and bake at 350 to 400 ° C. The vehicle is prepared by adding a resin component such as ethyl cellulose to an organic solvent in order to give a viscosity suitable for printing the paste.
If the vehicle remains, it may decompose when placed in a vacuum environment and contaminate the vacuum environment, thus requiring firing. Further, in order to use as a light source, it is usually necessary to vacuum seal a glass envelope using frit glass, and at that time, the temperature is raised to about 400 to 500 ° C.
Also, during vacuum exhaust, the exhaust is performed while heating. The exhaust temperature at this time is also preferably 300 ° C. or higher in order to accelerate degassing and shorten the exhaust time. Therefore, as a material to be mixed with a paste containing CNTs, there is little reduction in CNT particles and graphite particles even after firing, and after firing, the adhesion between each carbon particle and the adhesion between the film and the substrate are improved. There was a demand for materials that could be made.
【０００７】この発明は、上記のような問題点を解決す
るためになされたものであり、電子源において、基板と
の密着力が強く、粒子が離脱し難く、３００〜５００℃
の焼成工程でＣＮＴが消失しにくい膜を得ることを目的
としており、さらにこのような膜を有する電子源の製造
方法を提供することを目的とするものである。The present invention has been made in order to solve the above problems, and in an electron source, particles have a strong adhesion to a substrate, particles are difficult to separate, and the temperature is 300 to 500 ° C.
The present invention aims to obtain a film in which CNTs are less likely to disappear in the firing step, and further to provide a method for producing an electron source having such a film.
【０００８】[0008]
【課題を解決するための手段】本発明の第１の構成によ
る電子源は、基板上に設けられた膜より電子を放出させ
る電子放出源において、上記膜はＣＮＴを含む炭素粒子
とＳｉＯ2を主成分とする無機材料とで構成されたもの
である。The electron source according to the first aspect of the present invention is an electron emission source for emitting electrons from a film provided on a substrate, wherein the film contains carbon particles containing CNT and SiO 2 . It is composed of an inorganic material as a main component.
【０００９】また、本発明の第２の構成による電子源
は、ＳｉＯ2を主成分とする無機材料が、ＳｉＯ2微粒子
の凝集体であるものである。In the electron source according to the second aspect of the present invention, the inorganic material containing SiO 2 as a main component is an aggregate of SiO 2 fine particles.
【００１０】また、本発明の電子源の製造方法は、ＣＮ
Ｔを含む炭素粒子とコロイダルシリカを分散させた溶剤
とを混合したペーストを、基板上に印刷して膜を形成す
る工程、形成された膜を乾燥する工程、及び膜を焼成す
る工程を施すものである。The method of manufacturing an electron source according to the present invention is
A step of printing a paste obtained by mixing a carbon particle containing T and a solvent in which colloidal silica is dispersed on a substrate to form a film, a step of drying the formed film, and a step of baking the film Is.
【００１１】また、本発明の電子源の製造方法は、上記
製造方法に対し、さらに膜を研磨する工程を施すもので
ある。Further, the electron source manufacturing method of the present invention is the same as the above manufacturing method, except that a film polishing step is further performed.
【００１２】[0012]
【発明の実施の形態】実施の形態１．以下、本発明の実
施の形態１を図を用いて説明する。図１に本実施の形態
１による電子源の主要部の断面を示す。図１において、
１０１はガラス基板、１０２はカソード電極となる透明
電極膜、１０３は電子源となる厚膜、１０４はＣＮＴ粒
子、１０５はグラファイト粒子、１０６はＳｉＯ2を主
成分とする無機材料であり、ＳｉＯ2の微粒子の凝集体
である。ガラス基板１０１上に透明電極膜１０２を介し
てＣＮＴを含む厚膜１０３が形成されており、厚膜１０
３は、ＣＮＴ粒子１０４と、グラファイト粒子１０５
と、これらの間に介在するＳｉＯ2の微粒子の凝集体１
０６とからなる。ＣＮＴ粒子１０４とグラファイト粒子
１０５とは凝集し、ＣＮＴ１０４の一部は膜の表面から
露出している。ＣＮＴ１０４は凝集したグラファイト粒
子１０５等を介して厚膜１０３の下地にある透明電極膜
１０２と電気的に接触している。一方ＳｉＯ 2微粒子の
凝集体１０６は焼成により互いに強く凝集している。こ
のため、グラファイト粒子１０５及びＣＮＴ粒子１０４
を含みながら、機械的強度が強く、かつ基板との密着性
の良い膜が形成できる。BEST MODE FOR CARRYING OUT THE INVENTION Embodiment 1. Hereinafter, the fruit of the present invention
The first embodiment will be described with reference to the drawings. This embodiment is shown in FIG.
1 shows a cross section of the main part of the electron source according to 1. In FIG.
101 is a glass substrate, 102 is a transparent cathode electrode
Electrode film, 103 is a thick film serving as an electron source, 104 is CNT particles
105, graphite particles, 106 SiO2The Lord
Inorganic material as a component, SiO2Aggregate of fine particles of
Is. Through the transparent electrode film 102 on the glass substrate 101
The thick film 103 containing CNTs is formed.
3 is CNT particles 104 and graphite particles 105
And SiO interposed between these2Aggregate 1 of fine particles
It consists of 06. CNT particles 104 and graphite particles
105 aggregates, and part of CNT 104 is from the surface of the film.
Exposed. CNT104 is an aggregated graphite particle
Transparent electrode film underlying the thick film 103 via the child 105 and the like
It is in electrical contact with 102. On the other hand, SiO 2Particulate
The aggregates 106 are strongly aggregated with each other by firing. This
Therefore, graphite particles 105 and CNT particles 104
With high mechanical strength and adhesion to the substrate
A good film can be formed.
【００１３】なお、本実施の形態では、ＳｉＯ2を主成
分とする無機材料１０６をＳｉＯ2微粒子の凝集体とし
たが、真空中で焼成することにより互いに結合したガラ
ス状態のＳｉＯ2としてもよく、その後の大気中での焼
成において、炭素粒子の酸化を促進する効果は無く、グ
ラファイト粒子及びＣＮＴ粒子を固定する効果が得られ
る。In the present embodiment, the inorganic material 106 containing SiO 2 as a main component is an aggregate of SiO 2 fine particles, but it may be glassy SiO 2 bonded to each other by firing in a vacuum. In the subsequent firing in the atmosphere, there is no effect of promoting the oxidation of carbon particles, and an effect of fixing graphite particles and CNT particles can be obtained.
【００１４】本実施の形態の電子源における厚膜の製造
方法を説明する。グラファイト電極のアーク放電により
作製したＣＮＴを含む炭素粒子を粉砕して作製した粉体
に、ブチルカルビトールアセテート（以下、ＢＣＡと記
す）とブチルカルビトール（以下、ＢＣと記す）とエチ
ルセルロースを加えて混合した。この混合物に、さら
に、ＢＣＡに径１００〜２００Åのコロイダルシリカを
分散した溶剤を混合して、印刷ペーストを作製した。こ
のときの、ＣＮＴを含む炭素粒子と分散したコロイダル
シリカとの重量比は１：１である。コロイダルシリカ
は、径１００〜２００Åの、ほぼ球形のＳｉＯ2の微粒
子の表面にＳｉＯＨ基、ＯＨ基がついており、これがイ
オン化して負に帯電し、粒子間の静電的な反発により液
中に分散したものであり、グラファイト粒子及びＣＮＴ
粒子との混合が良好である。この印刷ペースト用いて、
スクリーン印刷により透明電極膜（ＩＴＯ膜）が形成さ
れたガラス基板上に３ｍｍ角のパターンを形成した。ペ
ーストの溶剤を１２０℃で乾燥し、膜厚６〜９μｍの厚
膜が得られた。A method of manufacturing a thick film in the electron source of this embodiment will be described. To a powder prepared by crushing carbon particles containing CNT prepared by arc discharge of a graphite electrode, butyl carbitol acetate (hereinafter referred to as BCA), butyl carbitol (hereinafter referred to as BC) and ethyl cellulose were added. Mixed. A solvent in which BCA was dispersed with colloidal silica having a diameter of 100 to 200Å was mixed with this mixture to prepare a printing paste. At this time, the weight ratio of CNT-containing carbon particles and dispersed colloidal silica is 1: 1. Colloidal silica has SiOH groups and OH groups attached to the surface of SiO 2 fine particles with a diameter of 100 to 200 Å, which are ionized and negatively charged. Dispersed, graphite particles and CNTs
Good mixing with particles. With this printing paste,
A 3 mm square pattern was formed on a glass substrate on which a transparent electrode film (ITO film) was formed by screen printing. The paste solvent was dried at 120 ° C. to obtain a thick film having a film thickness of 6 to 9 μm.
【００１５】次に、得られた厚膜を１０００番の研磨テ
ープで０．２ｇ／ｍｍ2の面圧で研磨した。研磨により
最大突起２４μｍが１１μｍに減少した。また、研磨に
より表面にはＣＮＴの露出がみられた。研磨後は切削さ
れた粒子や研磨粒子が発生するため、エアーブローや超
音波洗浄などにより、これらを除去する必要がある。Next, the obtained thick film was polished with a No. 1000 polishing tape at a surface pressure of 0.2 g / mm 2 . By polishing, the maximum protrusion 24 μm was reduced to 11 μm. In addition, CNT was exposed on the surface due to polishing. After polishing, cut particles and abrasive particles are generated, so it is necessary to remove them by air blow, ultrasonic cleaning, or the like.
【００１６】次に、研磨後に、ペーストに含まれるエチ
ルセルロースの除去とコロイダルシリカの凝集を目的に
大気中で５００℃で焼成し、電子源の厚膜を作製した。Next, after polishing, baking was performed at 500 ° C. in the atmosphere for the purpose of removing ethyl cellulose contained in the paste and agglomeration of colloidal silica to prepare a thick film of the electron source.
【００１７】従来の厚膜で用いられるＡｇ粒子やＰｂＯ
を含むフリットガラスを混合したペーストにおいては、
ペーストパターンを形成後、同様の条件で焼成した後は
酸化により著しいグラファイト粒子及びＣＮＴ粒子の減
少が見られるが、本実施の形態によるペーストではグラ
ファイト粒子及びＣＮＴ粒子の減少は見られなかった。Ag particles and PbO used in conventional thick films
In the paste mixed with frit glass containing
After forming the paste pattern and firing under the same conditions, a marked decrease in graphite particles and CNT particles was observed due to oxidation, but no decrease in graphite particles and CNT particles was observed in the paste according to the present embodiment.
【００１８】なお、本実施の形態では印刷ペーストの作
製の際、径１００〜２００Åのコロイダルシリカを分散
した溶剤を用いたが、径１００〜２００ÅのＳｉＯ2の
微粒子からなる粉体を直接混合してもよく同様の効果が
得られる。但し、コロイダルシリカを用いた方が、グラ
ファイト粒子及びＣＮＴ粒子との混合に際し、粉体の場
合よりも、ＳｉＯ2微粒子の凝集が無く、グラファイト
粒子及びＣＮＴ粒子との混合が良好である。また、焼成
に際し、ＳｉＯ2微粒子の表面のシラノール基が脱水し
結合するため、互いに強く凝集する。In the present embodiment, a solvent in which colloidal silica having a diameter of 100 to 200Å is dispersed is used in the production of the printing paste, but a powder made of fine particles of SiO 2 having a diameter of 100 to 200Å is directly mixed. However, the same effect can be obtained. However, when colloidal silica is used, when the particles are mixed with the graphite particles and the CNT particles, the SiO 2 particles do not aggregate, and the mixing with the graphite particles and the CNT particles is better than when using the powder. Further, upon firing, the silanol groups on the surface of the SiO 2 fine particles are dehydrated and bonded, so that they strongly aggregate with each other.
【００１９】また、本実施の形態では、研磨を焼成前に
実施したが、焼成後でも研磨工程に絶え得る膜強度があ
るので研磨後に実施しても良い。Further, in the present embodiment, the polishing is carried out before the baking, but it may be carried out after the polishing since the film strength that can withstand the polishing process is maintained even after the baking.
【００２０】このようにして作製した電子源の厚膜に、
基板表面から３０μｍの距離に、電圧を印加したアノー
ド電極を対向させ、１０-6Ｐａの真空環境で電子放出特
性を測定した。結果を図２のグラフに示す。図２は複数
の作製試料に対して測定されたものであり、特性のばら
つきは少ない。In the thick film of the electron source thus manufactured,
Electron emission characteristics were measured in a vacuum environment of 10 −6 Pa with a voltage-applied anode electrode facing the substrate at a distance of 30 μm. The results are shown in the graph of FIG. FIG. 2 is measured for a plurality of fabricated samples, and there is little variation in characteristics.
【００２１】また、図３にアノード電極を蛍光体／透明
電極／ガラス基板で構成したときの、５つの電子源に対
する発光分布を示す。図３において、白の領域は発光部
分であり、カソードの電子放出ポイントを示す。図３よ
り電子放出ポイントが各電子源において膜面全体に在る
ことがわかる。電子放出ポイントが膜面全体に分布して
いるため、カソードによる放出電流のばらつきも少な
く、電子放出特性も良好である。Further, FIG. 3 shows the light emission distributions for five electron sources when the anode electrode is composed of phosphor / transparent electrode / glass substrate. In FIG. 3, a white area is a light emitting portion, and indicates an electron emission point of the cathode. It can be seen from FIG. 3 that the electron emission points are on the entire film surface in each electron source. Since the electron emission points are distributed over the entire film surface, variations in emission current due to the cathode are small and electron emission characteristics are good.
【００２２】さらに、上記厚膜を用いた電子源により表
示素子を作製した。図４に本実施の形態の電子源を用い
た表示素子の一例を示す。図４において、４０１は表示
素子の引き出し電極となる金属板、４０２は表示素子の
カソードとなるＡｇ電極、４０３は放出された電子、４
０４は表示素子の前面ガラス基板、４０５は表示素子の
蛍光体、４０６は蛍光体の表面を覆うＡｌ膜、４０７は
引き出し電極となる金属板に形成された穴、４０８は電
子の拡散を押さえる金属電極である。電子源の下層にあ
る透明電極膜（ＩＴＯ膜）１０２上にはＡｇ電極４０２
が形成されており、Ａｇ電極４０２はガラスの真空外囲
器（図示を省略）の外へ引き出されている。また、電子
源の厚膜１０３の上部にはハーフエッチングにより作製
されたへこみを形成した金属板４０１が貼り付けられて
いる。金属板４０１にはカソード部に網状の穴４０７が
形成されている。金属板４０１にカソード電極４０２に
対し２００〜４００Ｖの電圧を印加すると、金属板４０
１と厚膜１０３との間に電界がかかる。金属板４０１と
厚膜１０３との間の隙間は３０μｍ程度と小さいので、
厚膜１０３の表面は上記電圧においても、１０5Ｖ／ｃ
ｍの強い電界となり、ＣＮＴから電子４０３が放出され
る。放出された電子４０３は真空空間中を前面ガラス基
板４０４に向かう。なぜなら前面ガラス基板４０４上に
電子線励起用蛍光体４０５及びＡｌ膜４０６が形成され
ており、Ａｌ膜４０６には１０ｋＶ程度の高電圧が印加
されているからである。Ａｌ膜４０６に衝突した電子は
Ａｌ膜４０６を透過し、蛍光体４０５に衝突して蛍光体
を発光させる。金属電極４０８にはＡｌ膜４０６と同じ
電位が与えられ、電子線の画素以上の広がりを防止す
る。本表示素子では３ｍｍ角の電子源を２５６個形成
し、それを別々に駆動することによって、ＲＧＧＢを一
画素とする６４個の画素を表示する。Further, a display element was manufactured by an electron source using the above thick film. FIG. 4 shows an example of a display element using the electron source of this embodiment. In FIG. 4, 401 is a metal plate that serves as an extraction electrode of the display element, 402 is an Ag electrode that serves as the cathode of the display element, 403 is emitted electrons, and 4
Reference numeral 04 is a front glass substrate of the display element, 405 is a phosphor of the display element, 406 is an Al film covering the surface of the phosphor, 407 is a hole formed in a metal plate to be an extraction electrode, and 408 is a metal that suppresses diffusion of electrons. It is an electrode. An Ag electrode 402 is formed on the transparent electrode film (ITO film) 102 below the electron source.
Is formed, and the Ag electrode 402 is drawn out of a glass vacuum envelope (not shown). Further, a metal plate 401 having a dent formed by half etching is attached on the thick film 103 of the electron source. A mesh-shaped hole 407 is formed in the cathode portion of the metal plate 401. When a voltage of 200 to 400 V is applied to the metal plate 401 with respect to the cathode electrode 402, the metal plate 40
An electric field is applied between 1 and the thick film 103. Since the gap between the metal plate 401 and the thick film 103 is as small as about 30 μm,
Also in the surface above the voltage of the thick film 103, 10 5 V / c
A strong electric field of m is generated, and the electrons 403 are emitted from the CNT. The emitted electrons 403 head toward the front glass substrate 404 in the vacuum space. This is because the electron beam excitation phosphor 405 and the Al film 406 are formed on the front glass substrate 404, and a high voltage of about 10 kV is applied to the Al film 406. The electrons that collide with the Al film 406 pass through the Al film 406 and collide with the phosphor 405 to cause the phosphor to emit light. The same potential as that of the Al film 406 is applied to the metal electrode 408 to prevent the electron beam from spreading beyond the pixels. In this display element, 256 3 mm square electron sources are formed and driven separately to display 64 pixels with RGGB as one pixel.
【００２３】ＳｉＯ2を混入しない、グラファイト粒子
及びＣＮＴ粒子とビヒクルとのみから作製された従来の
ペーストを用いて同様の上記表示素子を試作したとこ
ろ、厚膜１０３と金属板４０１との間の短絡が発生し易
かった。しかし、本実施の形態のペーストを用いて作製
された表示素子においては、上記短絡の発生が無く、安
定な電子放出特性が得られた。A similar display device was manufactured by using a conventional paste made of only graphite particles and CNT particles and a vehicle without mixing SiO 2 , and a short circuit between the thick film 103 and the metal plate 401 was observed. Was easy to occur. However, in the display element manufactured using the paste of this embodiment, the above-mentioned short circuit did not occur, and stable electron emission characteristics were obtained.
【００２４】[0024]
【発明の効果】以上のように、この発明によれば、基板
上に設けられた膜より電子を放出させる電子放出源にお
いて、上記膜はＣＮＴを含む炭素粒子とＳｉＯ2を主成
分とする無機材料とで構成されているので、膜の強度及
び下地層との密着性が向上し、焼成工程でもＣＮＴが消
失しにくい膜が得られる。As described above, according to the present invention, in the electron emission source that emits electrons from the film provided on the substrate, the film is an inorganic particle containing CNT-containing carbon particles and SiO 2. Since it is composed of a material, the strength of the film and the adhesion to the underlayer are improved, and a film in which CNTs are hard to disappear even in the firing step can be obtained.
【００２５】また、この発明によれば、ＳｉＯ2を主成
分とする無機材料が、ＳｉＯ2微粒子の凝集体であるの
で、ＣＮＴを含む炭素粒子と良く混合し、それらを互い
に結合させ、膜の強度を上げる効果がある。Further, according to the present invention, since the inorganic material containing SiO 2 as a main component is an aggregate of SiO 2 fine particles, it is mixed well with the carbon particles containing CNT, and they are bonded to each other to form a film. Has the effect of increasing strength.
【００２６】さらに、この発明によれば、ＣＮＴを含む
炭素粒子とコロイダルシリカを分散させた溶剤とを混合
したペーストを、基板上に印刷して膜を形成する工程、
形成された膜を乾燥する工程、及び膜を焼成する工程を
施すことにより電子源を製造したので、膜の強度及び下
地層との密着性が向上し、焼成工程でもＣＮＴが消失し
にくい膜が得られる。また、ペースト作製の際、ＣＮＴ
を含む炭素粒子とコロイダルシリカとが良く混合するた
め、ＣＮＴを含む炭素粒子間が互いに結合され、膜の強
度を上げる効果がある。Further, according to the present invention, a step of forming a film by printing a paste in which carbon particles containing CNTs and a solvent in which colloidal silica is dispersed is printed on a substrate,
Since the electron source was manufactured by performing the step of drying the formed film and the step of baking the film, the strength of the film and the adhesion to the underlying layer are improved, and the film in which the CNT does not easily disappear even in the baking step is formed. can get. Also, when making the paste, CNT
Since the carbon particles containing C and the colloidal silica are well mixed with each other, the carbon particles containing CNTs are bonded to each other, which has the effect of increasing the strength of the film.
【００２７】さらに、この発明によれば、電子源を製造
する際に、さらに膜を研磨する工程を施すので、ＣＮＴ
からなる電子放出ポイントが増加し、全面一様に電子放
出が可能な電子源を形成できる効果がある。Further, according to the present invention, when the electron source is manufactured, the step of further polishing the film is performed, so that the CNT is used.
The number of electron emission points is increased, and an electron source capable of uniformly emitting electrons is formed.
【図１】 本発明の実施の形態１による電子源の主要部
の構成を模式的に示す断面図である。FIG. 1 is a sectional view schematically showing a configuration of a main part of an electron source according to a first embodiment of the present invention.
【図２】 本発明の実施の形態１による電子源の電子放
出特性を示す図である。FIG. 2 is a diagram showing electron emission characteristics of the electron source according to the first embodiment of the present invention.
【図３】 本発明の実施の形態１による電子源の電子放
出ポイントを示す図である。FIG. 3 is a diagram showing electron emission points of the electron source according to the first embodiment of the present invention.
【図４】 本発明の実施の形態１による電子源を用いた
表示素子の構成を示す断面構成図である。FIG. 4 is a sectional configuration diagram showing a configuration of a display element using the electron source according to the first embodiment of the present invention.
１０１ 基板、１０２ 透明電極膜、１０３ 厚膜、１
０４ ＣＮＴ粒子、１０５ グラファイト粒子、１０６
ＳｉＯ2を主成分とする無機材料、４０１金属板、４
０２ Ａｇ電極、４０３ 放出された電子、４０４ 前
面ガラス基板、４０５ 蛍光体、４０６ Ａｌ膜、４０
７ 穴、４０８ 金属電極。101 substrate, 102 transparent electrode film, 103 thick film, 1
04 CNT particles, 105 graphite particles, 106
Inorganic material composed mainly of SiO 2 , 401 metal plate, 4
02 Ag electrode, 403 Emitted electron, 404 Front glass substrate, 405 Phosphor, 406 Al film, 40
7 holes, 408 metal electrodes.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 開 正明 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 (72)発明者 柴山 耕三郎 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 Ｆターム(参考） 5C036 EE01 EE08 EE14 EE19 EF01 EF06 EF09 EG12 EH11 5C127 AA01 BA09 BA13 BB07 BB18 CC03 DD18 DD19 DD63 DD64 DD69 EE16 5C135 AA09 AA13 AB07 HH16 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masaaki Kai 2-3 2-3 Marunouchi, Chiyoda-ku, Tokyo Inside Ryo Electric Co., Ltd. (72) Inventor Kozaburo Shibayama 2-3 2-3 Marunouchi, Chiyoda-ku, Tokyo Inside Ryo Electric Co., Ltd. F-term (reference) 5C036 EE01 EE08 EE14 EE19 EF01 EF06 EF09 EG12 EH11 5C127 AA01 BA09 BA13 BB07 BB18 CC03 DD18 DD19 DD63 DD64 DD69 EE16 5C135 AA09 AA13 AB07 HH16
Claims (4)
せる電子放出源において、上記膜はカーボンナノチュー
ブを含む炭素粒子とＳｉＯ2を主成分とする無機材料と
で構成されていることを特徴とする電子放出源。1. An electron emission source for emitting electrons from a film provided on a substrate, wherein the film is composed of carbon particles containing carbon nanotubes and an inorganic material containing SiO 2 as a main component. And an electron emission source.
ｉＯ2微粒子の凝集体であることを特徴とする請求項１
記載の電子放出源。2. The inorganic material mainly composed of SiO 2 is S
An aggregate of iO 2 fine particles, which is characterized in that
The described electron emission source.
コロイダルシリカを分散させた溶剤とを混合したペース
トを、基板上に印刷して膜を形成する工程、形成された
膜を乾燥する工程、及び膜を焼成する工程を施したこと
を特徴とする電子放出源の製造方法。3. A step of forming a film by printing a paste, which is a mixture of carbon particles containing carbon nanotubes and a solvent in which colloidal silica is dispersed, on a substrate, a step of drying the formed film, and a step of forming the film. A method for manufacturing an electron emission source, which is characterized in that a firing step is performed.
する請求項３記載の電子放出源の製造方法。4. The method for manufacturing an electron emission source according to claim 3, wherein a step of polishing the film is performed.
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| JP2002107991A JP2003303539A (en) | 2002-04-10 | 2002-04-10 | Electron emission source and its manufacturing method |
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