JP3008852B2 - Electron emitting device and method of manufacturing the same - Google Patents
Electron emitting device and method of manufacturing the sameInfo
- Publication number
- JP3008852B2 JP3008852B2 JP16150696A JP16150696A JP3008852B2 JP 3008852 B2 JP3008852 B2 JP 3008852B2 JP 16150696 A JP16150696 A JP 16150696A JP 16150696 A JP16150696 A JP 16150696A JP 3008852 B2 JP3008852 B2 JP 3008852B2
- Authority
- JP
- Japan
- Prior art keywords
- electron
- pores
- emitting device
- carbon nanotubes
- oxide film
- 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 - Fee Related
Links
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ディスプレイ、陰
極線管、エミッター、ランプ、電子銃等に用いられ、優
れた電流強度安定性を示す電子放出素子およびその製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron-emitting device which is used in displays, cathode ray tubes, emitters, lamps, electron guns and the like and has excellent current intensity stability, and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、ディスプレイ装置の薄型化、およ
びその画像の高輝度化、高コントラスト化、広視野角化
に対する要請がますます強まってきている。これにとも
ない、ディスプレイ装置用の電子源についても、従来の
熱電子放出電子源から冷陰極電子源への移行がさかんに
検討されている。例えば、特開平７−２２０６１９号公
報や特開平７−９４０８２号公報等に開示されているよ
うに、金属酸化膜に細孔を設け、該細孔内に微小な金属
電極を配置した構造の冷陰極電子源が種々開発されてい
る。2. Description of the Related Art In recent years, there has been an increasing demand for thinner display devices and higher brightness, higher contrast and wider viewing angles of images. In connection with this, with respect to the electron source for the display device, the transition from the conventional thermionic emission electron source to the cold cathode electron source has been actively studied. For example, as disclosed in Japanese Unexamined Patent Application Publication No. 7-220609 and Japanese Unexamined Patent Application Publication No. 7-94082, a metal oxide film is provided with pores, and a cooling structure having a fine metal electrode disposed in the pores. Various cathode electron sources have been developed.
【０００３】[0003]
【発明が解決しようとする課題】ところで、ディスプレ
イの薄膜化、高画像化を実現するためには一画素あたり
の電流強度が時間的に安定していることが必須となる。
ところが、従来の電子源においては個々の電子源の電流
値の時間変動率が大きいため、この点を克服することが
必要であった。このため、単位面積あたりの電子源の数
を増やすことにより個々の電子源の特性のばらつきを抑
えるとともに、それぞれの電子源についても先端の曲率
半径を小さくする等により電子放出効率を高めること
が、重要な技術課題となっている。本発明の目的は上記
課題を解決し、電流強度が時間的に安定した電子放出素
子を提供するものである。By the way, in order to realize a thin display and a high image quality of a display, it is essential that a current intensity per pixel is temporally stable.
However, in the conventional electron source, the current value of each electron source has a large time variation, so that it is necessary to overcome this point. For this reason, by increasing the number of electron sources per unit area, it is possible to suppress variations in the characteristics of individual electron sources, and also to increase the electron emission efficiency by reducing the radius of curvature of the tip of each electron source. It is an important technical issue. An object of the present invention is to solve the above-mentioned problems and to provide an electron-emitting device in which current intensity is temporally stable.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、カーボ
ンナノチューブの電子源と引き出し電極とを備え、該引
き出し電極によって該電子源から電子を引き出し放出さ
せる機能を有する電子放出素子において、絶縁基板上に
金属薄膜を介して細孔を有する陽極酸化膜が設けられ、
該細孔中に金属触媒が埋め込まれ、該金属触媒を起点と
して成長したカーボンナノチューブを有し、該細孔の開
口部に電子引き出し電極が設けられた構造を有すること
を特徴とする電子放出素子が提供される。カーボンナノ
チューブは、その先端の曲率半径が小さく、また化学的
安定性が高いため、電流強度安定性に優れる。本発明の
電子放出素子によれば、電子源の数密度を高めるととも
にカーボンナノチューブの持つ優れた特徴を十分に活か
し、電流強度安定性の改善を図ることができる。 According to the present invention, a carburetor is provided.
And an extraction electrode.
Electrons are extracted from the electron source by the extraction electrode and emitted.
Electron-emitting device with the function of
An anodized film having pores is provided via a metal thin film,
A metal catalyst is embedded in the pores, and the metal catalyst is used as a starting point.
With carbon nanotubes grown by
Having a structure with an electron extraction electrode at the mouth
An electron-emitting device is provided. Carbon nano
The tube has a small radius of curvature at its tip and
Since the stability is high, the current strength stability is excellent. Of the present invention
According to the electron-emitting device, the number density of the electron
Fully utilize the excellent features of carbon nanotubes
Thus, the current strength stability can be improved.
【０００５】請求項２に記載の発明は、ディスプレイ装
置に用いられる請求項１に記載の電子放出素子である。
カーボンナノチューブを用いた電子放出素子は電流強度
安定性に優れるため、ディスプレイ装置に使用したとき
にディスプレイの薄膜化、高画像化を図ることができ
る。The invention according to claim 2 is the electron-emitting device according to claim 1 used for a display device.
Since the electron-emitting device using carbon nanotubes has excellent current intensity stability, the display can be made thinner and have a higher image quality when used in a display device.
【０００６】請求項３に記載の発明は、陽極酸化膜の細
孔中に電子源を有することを特徴とする請求項１または
２に記載の電子放出素子である。電子源の数密度が高い
ため、電流強度安定性に優れる。According to a third aspect of the present invention, there is provided the electron-emitting device according to the first or second aspect, wherein an electron source is provided in pores of the anodic oxide film. Since the number density of the electron source is high, the current intensity stability is excellent.
【０００７】請求項４に記載の発明は、絶縁基板上に金
属薄膜を介して陽極酸化膜が形成され、該陽極酸化膜中
に細孔を有し、該細孔中にカーボンナノチューブが形成
され、該細孔の開口部に電子引き出し電極が設けられた
構造を有する請求項３に記載の電子放出素子である。ま
た、請求項５に記載の発明は、複数の陽極酸化膜の細孔
が規則正しく配列した構造を有する請求項４に記載の電
子放出素子である。これらの構造を有する電子放出素子
は、電子源の数密度を高めるとともにカーボンナノチュ
ーブの持つ優れた特徴を十分に活かし、電流強度安定性
の改善を図ることができる。According to a fourth aspect of the present invention, an anodic oxide film is formed on an insulating substrate via a metal thin film, the anodic oxide film has pores, and carbon nanotubes are formed in the pores. 4. The electron-emitting device according to claim 3, wherein the electron-emitting device has a structure in which an electron extraction electrode is provided in an opening of the pore. The invention according to claim 5 is the electron-emitting device according to claim 4, which has a structure in which pores of a plurality of anodic oxide films are regularly arranged. The electron-emitting device having these structures can improve the current intensity stability by increasing the number density of the electron source and fully utilizing the excellent characteristics of the carbon nanotube.
【０００８】また本発明によれば、絶縁基板上に金属膜
を介して細孔を有する陽極酸化膜を形成する工程と、前
記陽極酸化膜の細孔中に金属触媒を析出させる工程と、
該金属触媒の触媒作用により前記陽極酸化膜の細孔中に
カーボンナノチュ−ブを成長させる工程とを有すること
を特徴とする電子放出素子の製造方法が提供される。こ
のような方法によればカーボンナノチューブを規則正し
く配列させ、かつ、その先端の方向を揃えることができ
る。 According to the present invention, a metal film is formed on an insulating substrate.
Forming an anodic oxide film having pores through
Depositing a metal catalyst in the pores of the anodized film,
Due to the catalytic action of the metal catalyst, pores in the anodic oxide film
Having a step of growing carbon nanotubes.
A method for manufacturing an electron-emitting device is provided. According to such a method, the carbon nanotubes can be regularly arranged, and the directions of the tips can be aligned.
【０００９】本発明において、１０００℃以上１２００
℃以下の温度でカーボンナノチュ−ブを形成することが
好ましい。このような方法によれば、陽極酸化膜細孔中
に配置するのに適したサイズのカーボンナノチューブを
形成することができる。[0009] In the present invention , 1000 ° C or more and 1200
It is possible to form carbon nanotubes at temperatures below
Preferred . According to such a method, carbon nanotubes having a size suitable for being disposed in the pores of the anodic oxide film can be formed.
【００１０】[0010]
【発明の実施形態】本発明の電子放出素子は、ディスプ
レイ装置、陰極線管、エミッター、ランプ、電子銃等に
対して適用できるが、以下、ディスプレイ装置を代表例
に挙げて説明する。いずれに用いられる場合も電子源の
構造は実質的に同一である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The electron-emitting device of the present invention can be applied to a display device, a cathode ray tube, an emitter, a lamp, an electron gun and the like. Hereinafter, the display device will be described as a representative example. In each case, the structure of the electron source is substantially the same.
【００１１】図１に本発明の電子放出素子の一例につい
て断面図を示す。断面構造は、ガラス基板上にアルミニ
ウム層を介し、アルミナ層を有する構造となっており、
アルミナ層にはアルミニウム層まで到達する細孔が設け
られている。それぞれの細孔には、金属触媒を起点とし
て成長したカーボンナノチューブが存在する。このカー
ボンナノチューブにはアルミニウム基板を通して電力が
供給され、電子源として機能する。FIG. 1 is a sectional view showing an example of the electron-emitting device of the present invention. The cross-sectional structure is a structure having an alumina layer on a glass substrate with an aluminum layer interposed,
The alumina layer has pores reaching the aluminum layer. Each of the pores has a carbon nanotube grown from a metal catalyst as a starting point. Electric power is supplied to the carbon nanotubes through an aluminum substrate, and functions as an electron source.
【００１２】本発明に用いられる金属触媒として、例え
ば、ニッケル、コバルト、鉄等を用いることができる。As the metal catalyst used in the present invention, for example, nickel, cobalt, iron and the like can be used.
【００１３】本発明におけるカーボンナノチューブと
は、円筒状に巻いたグラファイト層が入れ子状になった
もので、太さが数十ｎｍ以下のものをいう。チューブ状
の形態を有することはＴＥＭ観察により確認されてい
る。先端部分の曲率半径は１０ｎｍ程度である。一般
に、冷陰極電子源の先端部は、曲率半径を小さくして強
電解をその部分に集中させ、電子放出効率を高める必要
がある。このため、従来技術においては先端を尖らせる
工程が不可欠となり、高度な技術とノウハウが必要とさ
れていた。これに対し、カーボンナノチューブは前述の
ようにもともと先端の曲率半径が小さいため、このよう
な工程を特に設ける必要がなく、簡便な工程で電子放出
効率の高く電流強度安定性の優れた電子源を作製するこ
とができる。また、カーボンナノチューブは耐酸化性、
耐イオン衝撃性に優れ、残留ガスのイオン化による電子
源のダメージを抑制できるため、この点からも電流強度
安定性の改良に寄与する。さらに、カーボンナノチュー
ブはサイズが極微小なため、電子源間隔を狭くした構造
とするのに好適である。後述するように、陽極酸化膜の
細孔中にカーボンナノチューブを形成させる等の簡便な
手法により電子源の数密度を高めることができる。これ
により、個々の電子源の特性のばらつきを抑え、一画素
あたりの電流強度の安定性を改善することができる。In the present invention, the carbon nanotubes are formed by nesting a graphite layer wound in a cylindrical shape and having a thickness of several tens nm or less. It has been confirmed by TEM observation that it has a tubular shape. The radius of curvature at the tip is about 10 nm. Generally, at the tip of a cold cathode electron source, it is necessary to reduce the radius of curvature so that strong electrolysis is concentrated on the portion, thereby increasing the electron emission efficiency. For this reason, in the prior art, a step of sharpening the tip became indispensable, and advanced technology and know-how were required. On the other hand, carbon nanotubes originally have a small radius of curvature as described above, so there is no need to provide such a step, and an electron source with high electron emission efficiency and excellent current intensity stability can be provided in a simple step. Can be made. In addition, carbon nanotubes have oxidation resistance,
Since it is excellent in ion impact resistance and can suppress damage to the electron source due to ionization of the residual gas, this also contributes to improvement of current intensity stability. Further, since the carbon nanotube has an extremely small size, it is suitable for a structure in which the interval between electron sources is narrowed. As described later, the number density of the electron sources can be increased by a simple method such as forming carbon nanotubes in the pores of the anodic oxide film. This makes it possible to suppress variations in the characteristics of the individual electron sources and improve the stability of the current intensity per pixel.
【００１４】カーボンナノチューブにはこのような利点
があるものの、その形成方法に関し、以下のような問題
点があった。すなわち、従来法により形成した場合、そ
れぞれの先端の方向が不揃いになりやすく、また、束ね
て方向をある程度揃えることができても、適度な間隔を
おいて規則正しく配置することが難しく、このために個
々のカーボンナノチューブに十分な電圧を印加できるよ
うな構造にすることが困難であった。Although carbon nanotubes have such advantages, there are the following problems in the method of forming them. That is, when formed by the conventional method, the directions of the respective tips are likely to be irregular, and even if the directions can be bundled and aligned to some extent, it is difficult to arrange regularly at appropriate intervals. It has been difficult to make the structure such that a sufficient voltage can be applied to each carbon nanotube.
【００１５】これに対し、本発明では、アルミニウム等
の金属を陽極酸化処理することにより規則正しく配列し
た細孔を形成し、該細孔中に金属触媒を埋め込み、ここ
を起点としてカーボンナノチューブを成長させるという
手法をとることにより、上記問題点を解決した。In contrast, in the present invention, a metal such as aluminum is anodized to form regularly arranged pores, a metal catalyst is buried in the pores, and carbon nanotubes are grown from these starting points. The above problem was solved by adopting the technique described above.
【００１６】本発明の電子放出素子は、例えば以下のよ
うな方法で製造される。まずアルミニウムの陽極酸化処
理を行う。これにより約４０ｎｍのアルミナの規則正し
い蜂の巣構造が形成され、それぞれの六角セルの中央に
は１５ｎｍ程度の直径の細孔が設けられる（図２）。細
孔の大きさや間隔は、電解液の種類、印加電圧、温度等
の処理条件により変動させることもできる。このアルミ
ナ層に対して異方性エッチングを行い、細孔の底を導電
性のアルミニウム基板に到達させる。次に、アルミサッ
シに使われる電解着色技術を用いて金属触媒を析出させ
る。電解着色を行う際の金属塩溶液としては、硫酸塩、
ホウ酸塩等の溶液が使用できる。溶液中には電解に直接
関与しない支持電解質、錯化剤などを添加しても良い。
このようにして埋め込まれた触媒の作用により、炭化水
素ガスを炭化させ、一定の方向と間隔をもったカーボン
ナノチューブをアルミニウム基板上に成長させる。つづ
いて各画素に対応した素子分離のための間隙を作り、グ
リッドを斜め蒸着法で作り各素子毎の配線を設けること
により、極微小な電子源を有する電子放出素子を作製す
ることができる。The electron-emitting device of the present invention is manufactured, for example, by the following method. First, anodizing treatment of aluminum is performed. This forms a regular honeycomb structure of alumina of about 40 nm, and pores having a diameter of about 15 nm are provided at the center of each hexagonal cell (FIG. 2). The size and spacing of the pores can also be varied by processing conditions such as the type of electrolyte, applied voltage, and temperature. Anisotropic etching is performed on the alumina layer so that the bottoms of the pores reach the conductive aluminum substrate. Next, a metal catalyst is deposited using the electrolytic coloring technique used for aluminum sashes. As the metal salt solution for performing the electrolytic coloring, sulfate,
Solutions such as borates can be used. A supporting electrolyte, a complexing agent or the like which does not directly participate in the electrolysis may be added to the solution.
By the action of the catalyst embedded in this way, the hydrocarbon gas is carbonized, and carbon nanotubes having a certain direction and an interval are grown on the aluminum substrate. Subsequently, by forming a gap for element isolation corresponding to each pixel, forming a grid by an oblique vapor deposition method, and providing wiring for each element, an electron-emitting element having a very small electron source can be manufactured.
【００１７】[0017]
（実施例１） 本発明の電子放出素子を以下のようにし
て作製した。まず、平坦なガラス基板上にアルミニウム
膜を形成した。形成の方法は、蒸着、貼り合わせのいず
れの方法によっても良い。次に表面を洗浄した。洗浄
は、脱脂、水洗、アルカリエッチング、酸による中和、
水洗の手順により行った。酸で中和する理由は、水洗だ
けではアルカリ液が残存しやすく、スマット（黒い粉状
のもの）ができてしまうためである。(Example 1) An electron-emitting device of the present invention was manufactured as follows. First, an aluminum film was formed on a flat glass substrate. The method of formation may be any of vapor deposition and bonding. Next, the surface was cleaned. Washing includes degreasing, water washing, alkali etching, acid neutralization,
The washing was performed according to a washing procedure. The reason for neutralization with an acid is that rinsing with water alone tends to leave an alkaline solution, resulting in smut (black powder).
【００１８】次に、アルミニウム膜の陽極酸化処理（硫
酸アルマイト）を行った。前記のようにして洗浄した基
板を、１０％濃度の硫酸中に浸しこれを陽極とした。対
極にもアルミニウム材を用い、直流１５Ｖにて通電し
た。電流密度１５０A/m2で２０分間通電したところ、約
９μｍの厚さの皮膜が得られた。Next, an anodic oxidation treatment (alumite sulfate) of the aluminum film was performed. The substrate washed as described above was immersed in 10% sulfuric acid and used as an anode. An aluminum material was also used as a counter electrode, and electricity was supplied at DC 15V. When a current was applied at a current density of 150 A / m 2 for 20 minutes, a film having a thickness of about 9 μm was obtained.
【００１９】処理後、ＲＩＥ（反応性イオンエッチン
グ）の異方性エッチングにより、陽極酸化処理時に形成
された細孔の底部をアルミニウム基板まで到達させた。After the treatment, the bottom of the pores formed during the anodizing treatment reached the aluminum substrate by anisotropic etching of RIE (reactive ion etching).
【００２０】次に、前記細孔内に金属触媒を析出させる
ため電解着色を行った。電解液として硫酸ニッケル液
（ｐＨ＝５）を用いた。前述のように陽極酸化処理した
基板を電解液に浸漬し、カーボンを対極として電圧１０
Ｖ、５０Ｈｚの交流で１分間通電し、陽極酸化皮膜細孔
中にニッケルの金属を析出させた。析出量は通電時間、
電圧、溶液濃度等により制御できる。Next, electrolytic coloring was performed to precipitate a metal catalyst in the pores. A nickel sulfate solution (pH = 5) was used as an electrolyte. The substrate, which has been anodized as described above, is immersed in an electrolytic solution, and a voltage of 10
A current of V, 50 Hz was applied for 1 minute to deposit nickel metal in the pores of the anodic oxide film. The amount of deposition is
It can be controlled by voltage, solution concentration, etc.
【００２１】以上のようにしてニッケル金属触媒を細孔
中に埋め込んだ後、カーボンナノチューブを図３に示す
ような装置を用いＣＶＤ法により成長させた。アルミナ
基板を図３中の管状炉の中央部に置き、メタンガスを
０．０５l/min、水素を０．２l/minで供給しながら炉内
の真空度を１００Ｔｏｒｒに保ち、１１５０℃で５分間
加熱処理した。水素を用いた理由は、カーボンナノチュ
ーブ以外の相であるアモルファスカーボンの生成を抑え
るためである。なお、反応時間を制御するため不活性ガ
スを加えることもできる。カーボンナノチューブは約１
０００℃以上で形成されるが、アルミナの細孔の直径に
適した１０ｎｍ程度の直径を持つものは１１５０℃で多
く形成された。なお、１２００℃をこえる温度で加熱し
た場合には直径がミクロンオーダーとなってしまい、好
ましくない。After the nickel metal catalyst was embedded in the pores as described above, carbon nanotubes were grown by a CVD method using an apparatus as shown in FIG. The alumina substrate was placed at the center of the tubular furnace shown in FIG. 3 and heated at 1150 ° C. for 5 minutes while maintaining a vacuum of 100 Torr while supplying methane gas at 0.05 l / min and hydrogen at 0.2 l / min. Processed. The reason for using hydrogen is to suppress the generation of amorphous carbon, which is a phase other than carbon nanotubes. Note that an inert gas can be added to control the reaction time. About 1 carbon nanotube
Although formed at 000 ° C. or higher, those having a diameter of about 10 nm suitable for the diameter of the pores of alumina were often formed at 1150 ° C. If the heating is performed at a temperature exceeding 1200 ° C., the diameter is on the order of microns, which is not preferable.
【００２２】つづいて、ディスプレイ用の冷陰極電子源
とするため、引出し電極であるグリッドの取り付けを行
い、各画素を分別するために素子分離を行った。素子分
離は、マスクをして異方性エッチングによりアルミニウ
ム層を支持基板であるガラスまでエッチングすることに
よって行い、一つの画素に対応する電子源の素子寸法が
１μｍ×１μｍとなるようにした。その面積中には、約
２５００個ものカーボンナノチューブが入っていること
になる。Subsequently, a grid, which is an extraction electrode, was attached in order to provide a cold cathode electron source for a display, and element separation was performed to separate each pixel. Element separation was performed by etching the aluminum layer to glass as a supporting substrate by anisotropic etching using a mask so that the element size of the electron source corresponding to one pixel was 1 μm × 1 μm. In the area, about 2500 carbon nanotubes are contained.
【００２３】以上のようにして本発明の電子放出素子を
作製した。この電子放出素子を評価したところ、従来の
シリコンやモリブデンを用いリソグラフィー技術で微細
加工したものと比較して電流強度の時間的安定度が約５
０倍に改善されていることが確認された。The electron-emitting device of the present invention was manufactured as described above. When this electron-emitting device was evaluated, the temporal stability of the current intensity was about 5 times that of a conventional device which was finely processed by lithography using silicon or molybdenum.
It was confirmed that it was improved to 0 times.
【００２４】（実施例２）実施例１では図１のように細
孔内にカ−ボンナノチューブが収まる構造としたが、カ
ーボンナノチューブをさらに成長させ、細孔から先端が
突き出る形としても良い。(Embodiment 2) In Embodiment 1, as shown in FIG. 1, the structure is such that the carbon nanotubes are accommodated in the pores. However, the carbon nanotubes may be further grown so that the tips protrude from the pores.
【００２５】実施例１に示した電子放出素子の製造方法
において、カ−ボンナノチューブをＣＶＤ法により作製
する際、成長時間を１５分としたところ、先端が細孔か
ら突き出る形状となった。なお、１５分をこえてさらに
長時間成長させた場合にはナノチューブが屈曲する現象
が起こった。成長時間の設定には十分注意する必要があ
る。In the method of manufacturing the electron-emitting device shown in Example 1, when the carbon nanotubes were produced by the CVD method, the growth time was set to 15 minutes. In the case where the growth was continued for more than 15 minutes, the nanotube was bent. Care must be taken in setting the growth time.
【００２６】引き出し電極となるグリッドは、ブラウン
管のマスクに使用されているタイプの金属メッシュを用
いることにより容易に設けることができた。また、カー
ボンナノチューブとグリッドの間には絶縁性スペーサー
を設けた。その他については実施例１と同様にして電子
放出素子を作製した。The grid serving as the extraction electrode could be easily provided by using a metal mesh of the type used for the mask of the cathode ray tube. An insulating spacer was provided between the carbon nanotube and the grid. Otherwise, an electron-emitting device was manufactured in the same manner as in Example 1.
【００２７】[0027]
【発明の効果】シリコンやモリブデン等を用いた従来の
冷陰極電子源では、微小加工技術の制約上、電子源の間
隔を１μｍ程度とするのが限界であった。これに対し本
発明では、陽極酸化膜が有する細孔の中に電子源となる
カーボンナノチューブを形成するという手法により、電
子源の間隔を４０ｎｍ程度にすることができる。これに
より、電子源の数密度が従来の数千倍となり、電流強度
の時間的安定度が約５０倍となる。In the conventional cold cathode electron source using silicon, molybdenum or the like, the limit of the interval between the electron sources was about 1 μm due to the restriction of the micromachining technology. On the other hand, in the present invention, the interval between the electron sources can be reduced to about 40 nm by the method of forming the carbon nanotubes serving as the electron sources in the pores of the anodic oxide film. As a result, the number density of the electron source becomes several thousand times the conventional one, and the temporal stability of the current intensity becomes about 50 times.
【００２８】また、カーボンナノチューブは耐酸化性、
耐イオン衝撃性に優れ、残留ガスのイオン化による電子
源のダメージを抑制できることから、電子放出素子の真
空度に対する制約を緩和できるというメリットもある。Also, carbon nanotubes have oxidation resistance,
Since it has excellent ion impact resistance and can suppress damage to the electron source due to ionization of the residual gas, there is also an advantage that the restriction on the degree of vacuum of the electron-emitting device can be relaxed.
【００２９】さらに、本発明によれば精密なリソグラフ
ィー技術が不要なため、プロセスの簡便化を図ることが
できる。Further, according to the present invention, since a precise lithography technique is not required, the process can be simplified.
【図１】本発明の電子源アレイの断面図である。FIG. 1 is a sectional view of an electron source array according to the present invention.
【図２】陽極酸化皮膜の立体構造を示した図である。FIG. 2 is a diagram showing a three-dimensional structure of an anodized film.
【図３】ＣＶＤ法によりカーボンナノチューブを成長さ
せるために用いる装置を示した図である。FIG. 3 is a view showing an apparatus used for growing carbon nanotubes by a CVD method.
１ グリッド ２ カーボンナノチューブ ３ アルミニウム ４ 蛍光板 ５ 金属触媒 ６ 素子分離のための間隙 ７ 細孔 ８ 六角セル ９ アルミナ １０ 電気管状炉 １１ 金属触媒入りアルミナ基板 Reference Signs List 1 grid 2 carbon nanotube 3 aluminum 4 fluorescent plate 5 metal catalyst 6 gap for element separation 7 pore 8 hexagonal cell 9 alumina 10 electric tubular furnace 11 alumina substrate with metal catalyst
フロントページの続き (56)参考文献 特開 平５−211029（ＪＰ，Ａ) 特開 平４−36922（ＪＰ，Ａ) Ｗａｌｔ Ａ．ｄｅ Ｈｅｅｒ，”Ａ Ｃａｒｂｏｎ Ｎａｎｏｔｕｂｅ Ｆ ｉｅｌｄ−Ｅｍｉｓｓｉｏｎ Ｅｌｅｃ ｔｒｏｎ Ｓｏｕｒｃｅ”，ＳＣＩＥＮ ＣＥ，1995年11月，第270巻，第5239号, ｐ．1179−1180 Ｔａｋａｓｈｉ，Ｋｙｏｔａｎｉ，" Ｆｏｒｍａｔｉｏｎ ｏｆ Ｕｌｔｒａ ｆｉｎｅ Ｃａｒｂｏｎ Ｔｕｂｅｓ ｂｙ Ｕｓｉｎｇ ａｎ Ａｎｏｄｉｃ Ａｌｕｍｉｎｕｍ Ｏｘｉｄｅ Ｆｉ ｌｍ ａｓ ａ Ｔｅｍｐｌａｔｅ”, ＣＨＥＭＩＳＴＲＹ ｏｆ ＭＡＴＥＲ ＩＡＬＳ，1995年８月，第７巻，第８ 号，ｐ．1427−1428 遠藤守信，”カーボンナノチューブの 生成、構造と物性”，表面，1994年，第 32巻，第５号，ｐ．277−283 (58)調査した分野(Int.Cl.7，ＤＢ名) H01J 1/30,9/02,29/04,31/12 C01B 31/02 101 ＷＰＩ（ＤＩＡＬＯＧ) ＪＩＣＳＴファイル（ＪＯＩＳ)Continuation of front page (56) References JP-A-5-211029 (JP, A) JP-A-4-36922 (JP, A) De Heer, "A Carbon Nanotube Field-Emission Electron Source", SCIENCE, November 1995, Vol. 270, No. 5239, p. 1177-1180 Takashi, Kyotani, "Formation of Ultra fine Carbon Tubes by Using an Anodical Aluminum Oxide Film as a Template", Vol. 1427-1428 Morinobu Endo, "Formation, Structure and Properties of Carbon Nanotubes", Surface, 1994, Vol. 32, No. 5, p. 277-283 (58) Field surveyed (Int. Cl. 7 , DB name) H01J 1/30, 9/02, 29/04, 31/12 C01B 31/02 101 WPI (DIALOG) JICST file (JOIS)
Claims (3)
し電極とを備え、該引き出し電極によって該電子源から
電子を引き出し放出させる機能を有する電子放出素子に
おいて、絶縁基板上に金属薄膜を介して細孔を有する陽
極酸化膜が設けられ、該細孔中に金属触媒が埋め込ま
れ、該金属触媒を起点として成長したカーボンナノチュ
ーブを有し、該細孔の開口部に電子引き出し電極が設け
られた構造を有することを特徴とする電子放出素子。 An electron-emitting device comprising a carbon nanotube electron source and an extraction electrode, and having a function of extracting and emitting electrons from the electron source by the extraction electrode, wherein pores are formed on an insulating substrate via a metal thin film. Positive sun
An extremely oxidized film is provided, and a metal catalyst is embedded in the pores.
Carbon nanotubes grown from the metal catalyst.
And an electron extraction electrode is provided in the opening of the pore.
An electron-emitting device having a structure as described above.
る陽極酸化膜を形成する工程と、前記陽極酸化膜の細孔
中に金属触媒を析出させる工程と、該金属触媒の触媒作
用により前記陽極酸化膜の細孔中にカーボンナノチュ−
ブを成長させる工程とを有することを特徴とする電子放
出素子の製造方法。 2. It has pores on an insulating substrate via a metal film.
Forming an anodic oxide film, and pores of the anodic oxide film.
Depositing a metal catalyst in the catalyst;
Carbon nanotubes in the pores of the anodic oxide film by use.
And a step of growing an electron beam.
Manufacturing method of output element.
出させる際、電解着色技術を用いることを特徴とする請
求項２に記載の電子放出素子の製造方法。 3. A metal catalyst is deposited in pores of the anodic oxide film.
The service is characterized by using electrolytic coloring technology.
3. The method for manufacturing an electron-emitting device according to claim 2.
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| JP16150696A JP3008852B2 (en) | 1996-06-21 | 1996-06-21 | Electron emitting device and method of manufacturing the same |
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|---|---|---|---|
| JP16150696A JP3008852B2 (en) | 1996-06-21 | 1996-06-21 | Electron emitting device and method of manufacturing the same |
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| JP3008852B2 true JP3008852B2 (en) | 2000-02-14 |
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