JP2002115071A - Method for depositing graphite nanofiber thin film by thermal cvd method - Google Patents
Method for depositing graphite nanofiber thin film by thermal cvd methodInfo
- Publication number
- JP2002115071A JP2002115071A JP2000307962A JP2000307962A JP2002115071A JP 2002115071 A JP2002115071 A JP 2002115071A JP 2000307962 A JP2000307962 A JP 2000307962A JP 2000307962 A JP2000307962 A JP 2000307962A JP 2002115071 A JP2002115071 A JP 2002115071A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- thin film
- graphite nanofiber
- carbon
- forming
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱ＣＶＤ法による
グラファイトナノファイバー薄膜形成方法に関し、特
に、特定の厚さの金属薄膜を下地層として有する基板を
用いて、熱ＣＶＤ法によりグラファイトナノファイバー
薄膜を形成する方法に関する。この方法は、平面ディス
プレー（電界放出型ディスプレー）やＣＲＴの電子管球
の代りに使用される電子発光素子を製作するために利用
され得る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a graphite nanofiber thin film by a thermal CVD method, and more particularly, to a method of forming a graphite nanofiber thin film by a thermal CVD method using a substrate having a metal thin film having a specific thickness as an underlayer. To a method of forming This method can be used to fabricate an electroluminescent device used in place of a flat display (field emission display) or an electron tube of a CRT.
【０００２】[0002]
【従来の技術】従来から、加熱することなしに電子を放
出させる電子放出源である冷陰極源として、円錐状の陰
極チップ（Ｗ、Ｍｏ、Ｓｉ等からなるチップ）を電極基
板上に形成したものが提案されている。この陰極チップ
の場合、例えば、Ｍｏチップを用いて作製したエミッタ
であってディスプレイ用途のものは、現在１００Ｖ／μ
ｍの電界で駆動し得るに過ぎない。2. Description of the Related Art Conventionally, a conical cathode tip (a tip made of W, Mo, Si or the like) is formed on an electrode substrate as a cold cathode source which is an electron emission source for emitting electrons without heating. Things have been suggested. In the case of this cathode chip, for example, an emitter manufactured using a Mo chip and used for a display is currently 100 V / μm.
It can only be driven by an electric field of m.
【０００３】上記したように、陰極材料として、Ｓｉや
Ｍｏ等が検討されてきたが、近年、カーボンナノチュー
ブを陰極材料に用いることが検討されている。カーボン
ナノチューブは、炭素６員環を主構造としたらせん構造
で形成された内部が空洞の円筒形状をもち、極めて微細
な、同心円状に円筒が配置された多重構造の黒鉛繊維で
ある。このカーボンナノチューブは、電子放出特性、耐
熱性、化学的安定性等の性能において、他の金属材料よ
りも優れている。カーボンナノチューブは、通常、アー
ク放電法、レーザー蒸発法、プラズマＣＶＤ法等により
作製されている。As described above, Si, Mo, and the like have been studied as cathode materials. In recent years, the use of carbon nanotubes as cathode materials has been studied. A carbon nanotube is a graphite fiber having a helical structure having a carbon 6-membered ring as a main structure, having a hollow cylindrical shape inside, and having an extremely fine, multi-layered structure in which cylinders are arranged concentrically. This carbon nanotube is superior to other metal materials in performances such as electron emission characteristics, heat resistance, and chemical stability. Carbon nanotubes are usually produced by an arc discharge method, a laser evaporation method, a plasma CVD method, or the like.
【０００４】本発明者らは、高電子放出密度、低電界電
子放出性能を有する陰極材料について、鋭意研究・開発
を進めてきたが、炭素含有ガスと水素ガスとを用いて熱
ＣＶＤ法により成膜せしめる過程で、従来報告されてい
ない構造を有するグラファイトナノファイバーを見出
し、このグラファイトナノファイバーに優れた電子放出
特性があることから、平成１２年２月４日付及び１２年
３月２８日付で、それぞれ、特願２０００−２８００１
号及び２０００−８９４６８号として特許出願した。こ
のグラファイトナノファイバーは、上記カーボンナノチ
ューブと違って、グラフェンシートが小さな断片に切れ
て積層した中実であり、例えば、截頭円錐形状を有する
結晶が積層されてなる円柱状構造を有し、その中心に貫
通空隙が存在し、この空隙は中空であるか又はアモルフ
ァスカーボンで充填されているものである。得られたグ
ラファイトナノファイバーは、直径が１０ｎｍ〜６００
ｎｍであり、直径が１０ｎｍ未満であるものは、今のと
ころ合成できておらず、また、６００ｎｍを超えるもの
は電子放出性能が劣る。このようなグラファイトナノフ
ァイバーは、高電子放出特性、低電界電子放出性能等の
ような優れた電子放出特性を有する陰極材料として有用
である。The present inventors have intensively studied and developed a cathode material having a high electron emission density and a low field electron emission performance. However, the cathode material was formed by a thermal CVD method using a carbon-containing gas and a hydrogen gas. In the process of forming a film, a graphite nanofiber having a structure which has not been reported was found, and since the graphite nanofiber has excellent electron emission characteristics, it was found on February 4, 2000 and March 28, 2000 that: See Japanese Patent Application 2000-28001
No. and 2000-89468. Unlike the carbon nanotubes, the graphite nanofiber is a solid in which a graphene sheet is cut into small pieces and stacked, and has, for example, a columnar structure in which crystals having a truncated cone shape are stacked. There is a through cavity at the center, which is hollow or filled with amorphous carbon. The obtained graphite nanofiber has a diameter of 10 nm to 600 nm.
Those having a diameter of 10 nm and a diameter of less than 10 nm have not been synthesized so far, and those having a diameter of more than 600 nm have poor electron emission performance. Such a graphite nanofiber is useful as a cathode material having excellent electron emission characteristics such as high electron emission characteristics and low field electron emission performance.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記し
たような従来のカーボンナノチューブを冷陰極源（電子
放出源）として利用しようとする場合、カーボンナノチ
ューブからの電子放出がその先端又は欠陥箇所から生じ
るために、ＣＲＴ用電子源のように高い電流密度が要求
される電子放出源としては、今のところ応用できないと
いう問題がある。However, when trying to use the above-mentioned conventional carbon nanotube as a cold cathode source (electron emission source), electron emission from the carbon nanotube occurs from its tip or from a defect. In addition, there is a problem that it cannot be applied as an electron emission source requiring a high current density, such as a CRT electron source.
【０００６】本発明者らは、上記したような熱ＣＶＤ法
によるグラファイトナノファイバー薄膜の形成に関する
技術では、被処理基板上の所定の箇所に効率よくグラフ
ァイトナノファイバー薄膜を形成せしめることが困難で
あることから、グラファイトナノファイバー薄膜を所定
の箇所に選択的に形成させ得る方法を見出したが、この
形成方法を実施する場合、グラファイトナノファイバー
薄膜を形成せしめる下地層の金属薄膜と基板との間の密
着性がやや劣り、金属薄膜が基板から剥がれてしまうこ
とがある。The present inventors have found that it is difficult to efficiently form a graphite nanofiber thin film at a predetermined position on a substrate to be processed by the technique relating to the formation of a graphite nanofiber thin film by the thermal CVD method as described above. From this fact, a method was found in which a graphite nanofiber thin film could be selectively formed at a predetermined location.However, when this forming method was implemented, the distance between the metal thin film of the base layer for forming the graphite nanofiber thin film and the substrate was reduced Adhesion may be slightly poor, and the metal thin film may peel off from the substrate.
【０００７】本発明は、上記問題点を解消するものであ
り、高電子放出密度、低電界電子放出性能を達成するこ
とのできる陰極材料として、炭素系電子放出源となり得
るグラファイトナノファイバー薄膜を形成する際に、下
地層の金属薄膜の密着性を向上せしめることを課題とす
る。The present invention solves the above-mentioned problems, and forms a graphite nanofiber thin film that can serve as a carbon-based electron emission source as a cathode material that can achieve high electron emission density and low field electron emission performance. In this case, it is an object to improve the adhesion of the metal thin film of the underlayer.
【０００８】[0008]
【課題を解決するための手段】本発明のグラファイトナ
ノファイバー薄膜形成方法は、ガラス基板又はＳｉ基板
上に、下地層として、Ｆｅ、Ｃｏ又はこれらの金属の少
なくとも１種を含んだ合金の触媒金属薄膜を１０〜５０
ｎｍの厚さで所定のパターンに形成せしめた基板を被処
理基板とし、該被処理基板を真空下熱処理した後、熱Ｃ
ＶＤ法により、炭素含有ガス及び水素ガスを用いて、該
被処理基板上のパターン部分のみにグラファイトナノフ
ァイバーを均一に成長せしめることからなり、これによ
り該下地層の基板への密着性を向上せしめることができ
る。触媒金属とは、その金属の上にグラファイトナノフ
ァイバー薄膜を形成することができる金属を意味する。
触媒金属薄膜の厚さが上記範囲内にあると触媒金属薄膜
は剥がれ難くなる。しかし、膜厚が１０ｎｍ未満である
と、グラファイトナノファイバーを作製することはでき
るけれども、成長速度が遅すぎるので実用的ではなく、
また、膜厚が５０ｎｍを超えると、触媒金属薄膜が剥が
れやすくなる傾向があるため好ましくない。According to a method of forming a graphite nanofiber thin film of the present invention, a catalyst metal of Fe, Co or an alloy containing at least one of these metals is provided as an underlayer on a glass substrate or a Si substrate. 10-50 thin films
A substrate formed in a predetermined pattern with a thickness of nm is used as a substrate to be processed.
The VD method uses a carbon-containing gas and a hydrogen gas to uniformly grow graphite nanofibers only in a pattern portion on the substrate to be processed, thereby improving the adhesion of the underlayer to the substrate. be able to. The catalyst metal means a metal capable of forming a graphite nanofiber thin film on the metal.
When the thickness of the catalyst metal thin film is within the above range, the catalyst metal thin film is difficult to peel off. However, if the film thickness is less than 10 nm, graphite nanofibers can be produced, but the growth rate is too slow, which is not practical.
On the other hand, if the thickness exceeds 50 nm, the catalytic metal thin film tends to peel off, which is not preferable.
【０００９】また、本発明のグラファイトナノファイバ
ー薄膜形成方法は、ガラス基板又はＳｉ基板上に、下地
層として、Ｆｅ、Ｃｏ又はこれらの金属の少なくとも１
種を含んだ合金の触媒金属薄膜を１０〜５０ｎｍの厚さ
で所定のパターンに形成せしめた基板を被処理基板とし
て用い、真空排気した真空チャンバー内に載置された該
被処理基板を赤外線ランプで加熱して該被処理基板を真
空下熱処理し、次いで、炭素含有ガス及び水素ガスを真
空チャンバー内へ導入し、真空チャンバー内の圧力をほ
ぼ１気圧に維持して、該被処理基板上のパターン部分の
みに熱ＣＶＤ法によりグラファイトナノファイバーを均
一に成長せしめることからなる。Further, in the method of forming a graphite nanofiber thin film according to the present invention, as a base layer, at least one of Fe, Co or at least one of these metals is formed on a glass substrate or a Si substrate.
Using a substrate on which a catalyst metal thin film of an alloy containing seeds is formed in a predetermined pattern with a thickness of 10 to 50 nm as a substrate to be processed, the substrate to be processed placed in a vacuum chamber evacuated is an infrared lamp. And heat-treats the substrate under vacuum in a vacuum. Then, a carbon-containing gas and a hydrogen gas are introduced into the vacuum chamber, and the pressure in the vacuum chamber is maintained at approximately 1 atm. It consists of uniformly growing graphite nanofibers only in the pattern portion by the thermal CVD method.
【００１０】前記被処理基板として、ガラス基板又はＳ
ｉ基板上に、非触媒金属の薄膜を所定のパターンに形成
せしめた後、該非触媒金属パターンの上にＦｅ、Ｃｏ又
はこれらの金属の少なくとも１種を含んだ合金の触媒金
属薄膜を１０〜５０ｎｍの厚さで所定のパターンに形成
せしめた２層構造の下地層を有する基板を用いてもよ
い。非触媒金属とは、その金属の上にグラファイトナノ
ファイバー薄膜を形成することができないような金属を
意味する。As the substrate to be processed, a glass substrate or S
After a non-catalytic metal thin film is formed in a predetermined pattern on an i-substrate, a catalytic metal thin film of Fe, Co or an alloy containing at least one of these metals is formed on the non-catalytic metal pattern by 10 to 50 nm. A substrate having an underlayer of a two-layer structure formed in a predetermined pattern with a thickness of may be used. By non-catalytic metal is meant a metal on which a graphite nanofiber thin film cannot be formed.
【００１１】前記熱処理を行う温度は４００℃以上、基
板の耐熱温度以下であることが好ましい。熱処理温度が
４００℃未満だと下地層の基板への密着性が向上せず、
また、２層構造の下地層では触媒金属と非触媒金属との
界面での合金化が起こらないので両層の密着性も向上し
ない。また、基板の耐熱温度を超えると基板が変形して
しまうという問題がある。It is preferable that the temperature at which the heat treatment is performed is not lower than 400 ° C. and not higher than the heat resistant temperature of the substrate. If the heat treatment temperature is less than 400 ° C., the adhesion of the underlayer to the substrate does not improve,
Further, in the two-layer underlayer, alloying does not occur at the interface between the catalytic metal and the non-catalytic metal, so that the adhesion between the two layers is not improved. Further, when the temperature exceeds the heat resistant temperature of the substrate, there is a problem that the substrate is deformed.
【００１２】前記炭素含有ガスと水素ガスとの混合比
は、容量基準で、炭素含有ガス／水素ガス＝０．１〜１
０であることが好ましい。混合比が０．１未満である
と、グラファイトナノファイバー薄膜を効率よく形成す
ることが難しく、また、１０を超えると、炭素含有ガス
濃度が濃すぎてグラファイトナノファイバー薄膜の形成
プロセスを制御することが実質的に難しいという問題が
ある。なお、水素ガスは、気相反応における希釈及び触
媒作用のために使用されるものである。The mixing ratio of the carbon-containing gas and the hydrogen gas is, based on volume, carbon-containing gas / hydrogen gas = 0.1 to 1
It is preferably 0. If the mixing ratio is less than 0.1, it is difficult to efficiently form the graphite nanofiber thin film, and if it exceeds 10, the carbon-containing gas concentration is too high to control the process of forming the graphite nanofiber thin film. There is a problem that is substantially difficult. The hydrogen gas is used for dilution and catalysis in a gas phase reaction.
【００１３】前記熱ＣＶＤ法を実施する温度は４５０〜
６５０℃であることが好ましい。４５０℃未満である
と、原料ガスとしての炭素含有ガスがほとんど分解され
ないので、グラファイトナノファイバーの成長速度が極
めて遅くなり経済的でないという問題がある。また、温
度が高いほど成長速度は速くなるが、６５０℃を超える
とグラファイトナノファイバー薄膜の形成プロセスを制
御することが実質的に難しくなるという問題がある。The temperature at which the thermal CVD method is performed is 450 to
Preferably it is 650 ° C. If the temperature is lower than 450 ° C., the carbon-containing gas as a raw material gas is hardly decomposed, so that there is a problem that the growth rate of the graphite nanofiber becomes extremely slow and it is not economical. In addition, the growth rate increases as the temperature increases, but if it exceeds 650 ° C., there is a problem that it is substantially difficult to control the process of forming the graphite nanofiber thin film.
【００１４】前記炭素含有ガスとしては、例えば、一酸
化炭素、二酸化炭素、又はメタンのような低級炭化水素
等の炭素含有ガスを用いることができ、一酸化炭素又は
二酸化炭素が好ましい。As the carbon-containing gas, for example, a carbon-containing gas such as carbon monoxide, carbon dioxide, or a lower hydrocarbon such as methane can be used, and carbon monoxide or carbon dioxide is preferable.
【００１５】また、前記下地層の金属薄膜を所定のパタ
ーンに形成せしめ、所望により真空熱処理を行った後、
該下地層の触媒金属薄膜の表面をウエットエッチング法
等によりエッチングして、その表面状態を粗くし、次い
で、熱ＣＶＤ法を行うことが好ましく、これによりグラ
ファイトナノファイバーの成長が極めて良好になる。After forming the metal thin film of the underlayer in a predetermined pattern and performing a vacuum heat treatment as required,
It is preferable to roughen the surface state by etching the surface of the catalyst metal thin film of the underlayer by wet etching or the like, and then to perform a thermal CVD method, whereby the growth of the graphite nanofiber becomes extremely good.
【００１６】[0016]
【発明の実施の形態】本発明の方法によれば、グラファ
イトナノファイバー薄膜は、上記したように、下地層と
して、Ｆｅ、Ｃｏ、又はこれらの金属の少なくとも１種
を含んだ合金の触媒金属薄膜を１０〜５０ｎｍの厚さで
所定のパターンに形成せしめたガラス基板若しくはＳｉ
基板を用いるか、又は、下地層として、好ましくはＮ
ｉ、Ｃｕ等のような非触媒金属の薄膜を所定のパターン
に形成せしめ、次いで、該非触媒金属パターンの上にＦ
ｅ、Ｃｏ、又はこれらの金属の少なくとも１種を含んだ
合金の触媒金属薄膜を１０〜５０ｎｍの厚さで所定のパ
ターンに形成せしめたガラス基板又はＳｉ基板を用い、
これを所定の温度で真空下熱処理し、次いで、熱ＣＶＤ
法により、例えば、一酸化炭素、二酸化炭素等のような
炭素含有ガス及び水素ガスを用いて、該下地層の触媒金
属薄膜パターン上にのみグラファイトナノファイバーを
成長せしめることによって作製される。下地層の触媒金
属薄膜を特定の厚さとすることにより、下地層と基板と
の間や、触媒金属薄膜と非触媒金属薄膜との間の密着性
が向上する。DETAILED DESCRIPTION OF THE INVENTION According to the method of the present invention, as described above, a graphite nanofiber thin film is formed as a catalyst metal thin film of Fe, Co, or an alloy containing at least one of these metals as an underlayer. A glass substrate or Si formed in a predetermined pattern with a thickness of 10 to 50 nm
Either a substrate is used or an underlayer is preferably N 2
A thin film of a non-catalytic metal such as i, Cu, etc. is formed in a predetermined pattern, and then a thin film of F is formed on the non-catalytic metal pattern.
e, Co, or a glass substrate or a Si substrate formed by forming a catalyst metal thin film of an alloy containing at least one of these metals in a predetermined pattern with a thickness of 10 to 50 nm,
This is heat-treated in a vacuum at a predetermined temperature, and then thermal CVD
According to the method, it is produced by growing a graphite nanofiber only on the catalytic metal thin film pattern of the base layer using a carbon-containing gas such as carbon monoxide, carbon dioxide and the like, and a hydrogen gas. By setting the thickness of the catalyst metal thin film of the underlayer to a specific thickness, the adhesion between the underlayer and the substrate or between the catalyst metal thin film and the non-catalytic metal thin film is improved.
【００１７】被処理基板上への金属薄膜パターン下地層
の形成法は特に制限されないが、例えば、スパッタ法、
ＣＶＤ法、蒸着法（例えば、ＥＢ蒸着法）等を用いて、
通常の条件下で、基板上の所定の箇所にパターンを形成
・付着せしめることにより行われ得る。あるいはまた、
基板表面上に公知の感光性樹脂液を塗布して行うフォト
リソグラフ工程によって、印刷工程によって、又はメッ
キ工程等によって、基板表面の所定の箇所に前記金属薄
膜パターンが施された基板を得、この金属薄膜が施され
た箇所に上記のようにして熱ＣＶＤ法によりグラファイ
トナノファイバーを均一に成長させ、成膜してもよい。
前記パターンの形状は特に制限されるわけではなく、直
線でも、曲線でも、点線でも、又はその他の任意形状の
ものでもよい。The method of forming the metal thin film pattern underlayer on the substrate to be processed is not particularly limited.
Using a CVD method, an evaporation method (for example, an EB evaporation method) or the like,
This can be performed by forming and attaching a pattern to a predetermined location on the substrate under normal conditions. Alternatively,
By a photolithographic process performed by applying a known photosensitive resin liquid on the substrate surface, by a printing process, or by a plating process, etc., a substrate having the metal thin film pattern applied to a predetermined portion of the substrate surface is obtained. The graphite nanofibers may be uniformly grown and formed into a film by the thermal CVD method at the place where the metal thin film is applied as described above.
The shape of the pattern is not particularly limited, and may be a straight line, a curve, a dotted line, or any other shape.
【００１８】本発明のグラファイトナノファイバー薄膜
形成方法では、まず、上記したような下地層パターンを
備えた被処理基板を装着した基板ホルダーを、赤外線ラ
ンプを備えた熱ＣＶＤ装置の真空チャンバー内に配設し
た支柱上に載置し、該チャンバー内を、通常、０．１〜
０．０１Ｔｏｒｒになるまで真空排気を行う。その状態
で、真空チャンバーの上方部分に、被処理基板に対向し
て設けられた複数の赤外線ランプを付勢して４００℃以
上、基板の耐熱温度以下の温度で１〜３０分間熱処理す
る。その後、炭素含有ガスと水素ガスとの混合ガスを、
所定の容量比で、好ましくは炭素含有ガス／水素ガス＝
０．１〜１０で該チャンバー内に導入し、ガス置換を行
う。その際、上記赤外線ランプを用いて該基板を加熱
し、好ましくは４５０℃〜６５０℃の温度で、該基板上
の触媒金属パターン上にのみグラファイトナノファイバ
ーを均一に成長せしめて、グラファイトナノファイバー
薄膜を形成する。このようにして得られるグラファイト
ナノファイバーは、直径１０〜１００ｎｍ程度である。
該混合ガスは、真空チャンバー内への導入前に予め加熱
しておけば、短時間で成膜温度まで上昇することができ
ると共に、このような加熱手段を設けることにより、成
膜速度を調節することもできる。In the method of forming a graphite nanofiber thin film according to the present invention, first, a substrate holder on which a substrate to be processed having the above-described underlayer pattern is mounted is placed in a vacuum chamber of a thermal CVD apparatus equipped with an infrared lamp. Placed on a support provided, and the inside of the chamber is usually 0.1 to
Vacuum exhaust is performed until the pressure becomes 0.01 Torr. In this state, a plurality of infrared lamps provided to face the substrate to be processed are energized in the upper part of the vacuum chamber, and heat treatment is performed at a temperature of 400 ° C. or more and a heat-resistant temperature of the substrate for 1 to 30 minutes. Then, the mixed gas of the carbon-containing gas and the hydrogen gas is
At a given volume ratio, preferably carbon-containing gas / hydrogen gas =
The gas is introduced into the chamber at 0.1 to 10 to perform gas replacement. At this time, the substrate is heated using the infrared lamp, and preferably at a temperature of 450 ° C. to 650 ° C., the graphite nanofibers are uniformly grown only on the catalyst metal pattern on the substrate, and the graphite nanofiber thin film is formed. To form The graphite nanofiber thus obtained has a diameter of about 10 to 100 nm.
If the mixed gas is heated in advance before being introduced into the vacuum chamber, the temperature can be raised to the film forming temperature in a short time, and the film forming speed is adjusted by providing such a heating means. You can also.
【００１９】上記したようにして得られたグラファイト
ナノファイバーの場合、炭素系電子放出源からの電界電
子放出特性について、高性能化することが可能になる。
すなわち、従来のカーボンナノチューブと同程度の低印
加電圧で、ＣＲＴ用電子源に使用できる程度まで十分な
高電流密度の電子放出が可能になる。In the case of the graphite nanofiber obtained as described above, it is possible to improve the field electron emission characteristics from the carbon-based electron emission source.
In other words, it is possible to emit electrons at a sufficiently high current density at a voltage as low as that of a conventional carbon nanotube, so as to be used for a CRT electron source.
【００２０】本発明のグラファイトナノファイバー薄膜
形成方法を実施するための熱ＣＶＤ装置としては、特に
制限されるわけではないが、例えば、添付図面の図１及
び２に示すような構成を有する装置を使用することがで
きる。The thermal CVD apparatus for carrying out the method for forming a graphite nanofiber thin film of the present invention is not particularly limited. For example, an apparatus having a structure as shown in FIGS. Can be used.
【００２１】本発明の方法を実施するために用いられる
熱ＣＶＤ装置の一つの例は、特願２０００−８９４６８
号に記載された装置である。この装置は、図１に示すよ
うに、成膜室を構成するステンレス製の真空チャンバー
１内に水素ガスと共に原料ガスを導入し、基板ホルダー
２に装着した被処理基板３上にグラファイトナノファイ
バーの薄膜を形成するための装置であって、基板ホルダ
ー２に対向する真空チャンバー１の上部壁面に石英のよ
うな耐熱性ガラスからなる赤外線透過窓４を設け、この
赤外線透過窓４の外側に、基板加熱用の赤外線ヒーター
５を設け、赤外線ヒーター５により基板３を加熱した状
態で、グラファイトナノファイバー薄膜を基板上に形成
することができるように構成されている。薄膜形成の際
の真空チャンバー内の圧力は、ほぼ１気圧に維持され
る。また、下地層の金属薄膜パターンが形成された被処
理基板３の熱処理は、前記真空チャンバー１内で真空下
で行われ得る。One example of a thermal CVD apparatus used to carry out the method of the present invention is disclosed in Japanese Patent Application No. 2000-89468.
It is the device described in the item. As shown in FIG. 1, this apparatus introduces a raw material gas together with a hydrogen gas into a stainless steel vacuum chamber 1 constituting a film forming chamber, and forms a graphite nanofiber on a substrate 3 to be processed mounted on a substrate holder 2. An apparatus for forming a thin film, wherein an infrared transmitting window 4 made of heat-resistant glass such as quartz is provided on an upper wall surface of a vacuum chamber 1 facing a substrate holder 2, and a substrate is provided outside the infrared transmitting window 4. The infrared heater 5 for heating is provided, and the graphite nanofiber thin film can be formed on the substrate while the substrate 3 is heated by the infrared heater 5. The pressure in the vacuum chamber during the formation of the thin film is maintained at approximately 1 atm. The heat treatment of the substrate 3 on which the metal thin film pattern of the underlayer is formed may be performed in the vacuum chamber 1 under vacuum.
【００２２】真空チャンバー１は、バルブ６を介して真
空ポンプ７に接続され、真空チャンバー１内を排気でき
るようになっており、真空チャンバー１には、真空計８
が取り付けられ、チャンバー内の圧力をモニターできる
ようになっている。The vacuum chamber 1 is connected to a vacuum pump 7 via a valve 6 so that the inside of the vacuum chamber 1 can be evacuated.
Is attached so that the pressure in the chamber can be monitored.
【００２３】真空チャンバー１にはまた、ガス供給系９
が接続されている。このガス供給系９は、バルブ１０ａ
からガス流量調節器１０ｂ及び圧力調整器１０ｃを介し
て、一酸化炭素ガス等の原料ガスボンベ１０ｄにガス配
管にて直列に連なっている原料ガス供給系と、バルブ１
１ａからガス流量調節器１１ｂ及び圧力調整器１１ｃを
介して、水素ガスボンベ１１ｄにガス配管にて直列に連
なっている水素ガス供給系とを並列に備え、原料ガス供
給系と水素ガス供給系とはバルブ１０ａ、１１ａと真空
チャンバー１との間で合流し、真空チャンバー内に炭素
含有ガス及び水素ガスの混合ガスが供給されるようにな
っている。なお、混合ガスは赤外線ヒーター５で加熱さ
れることなく被処理基板３上に到達されるようにする。The vacuum chamber 1 also has a gas supply system 9.
Is connected. The gas supply system 9 includes a valve 10a
A source gas supply system connected in series to a source gas cylinder 10d of carbon monoxide gas or the like via a gas pipe via a gas flow controller 10b and a pressure controller 10c;
1a, a hydrogen gas supply system serially connected to a hydrogen gas cylinder 11d by a gas pipe via a gas flow controller 11b and a pressure regulator 11c is provided in parallel, and the raw material gas supply system and the hydrogen gas supply system It merges between the valves 10a and 11a and the vacuum chamber 1, and a mixed gas of a carbon-containing gas and a hydrogen gas is supplied into the vacuum chamber. The mixed gas is allowed to reach the target substrate 3 without being heated by the infrared heater 5.
【００２４】上記真空チャンバー１の外側には真空チャ
ンバーを冷却する冷却手段１２が設けられ、真空チャン
バー１の内壁は絶縁体１３で被覆され、赤外線透過窓４
は耐熱ガラスで構成され、また、基板ホルダー２には抵
抗加熱式ヒーター１４が設けられていてもよい。A cooling means 12 for cooling the vacuum chamber is provided outside the vacuum chamber 1, and the inner wall of the vacuum chamber 1 is covered with an insulator 13,
Is made of heat-resistant glass, and the substrate holder 2 may be provided with a resistance heater 14.
【００２５】また、本発明の方法を実施するために用い
られる別の熱ＣＶＤ装置は、図２に示すように、成膜室
を構成するステンレス等の金属製の真空チャンバー２１
とロードロック室２２とを備えたものである。この真空
チャンバー２１内には被処理基板２３の装着された基板
ホルダー２４を載置するための支柱２５が任意の数で設
けられ、ロードロック室２２内には、搬送ロボット２６
が設けられている。また、該ロードロック室２２には、
真空ポンプ２７が接続され、さらに、真空計２９が取り
付けられて、室内の真空度を測定し、モニターできるよ
うになっている。被処理基板２３の装着された基板ホル
ダー２４は、搬送ロボット２６によって基板貯蔵室から
ロードロック室２２に搬送される。次いで、ロードロッ
ク室２２内を所定の真空度（０．０１Ｔｏｒｒ程度）に
なるまで真空排気した後、ゲートバルブ３０を開けて、
所定の真空度に真空排気された真空チャンバー２１内に
被処理基板２３の装着された基板ホルダー２４を搬送
し、支柱２５上に載置する。そして、搬送ロボット２６
がロードロック室２２へ戻されると、ゲートバルブ３０
を閉じる。上記では被処理基板２３の装着された基板ホ
ルダー２４を搬送する基板ホルダー搬送であったが、被
処理基板２３を搬送して、真空チャンバー２１内の支柱
２５上に固定して設けられている基板ホルダー２４上に
該基板を載置する基板搬送でもよい。As shown in FIG. 2, another thermal CVD apparatus used to carry out the method of the present invention is a vacuum chamber 21 made of a metal such as stainless steel which constitutes a film forming chamber.
And a load lock chamber 22. Arbitrary columns 25 for mounting a substrate holder 24 on which a substrate 23 is mounted are provided in the vacuum chamber 21, and a transfer robot 26 is provided in the load lock chamber 22.
Is provided. Also, in the load lock chamber 22,
A vacuum pump 27 is connected, and a vacuum gauge 29 is further attached so that the degree of vacuum in the room can be measured and monitored. The substrate holder 24 on which the substrate 23 is mounted is transferred from the substrate storage chamber to the load lock chamber 22 by the transfer robot 26. Next, after evacuating the inside of the load lock chamber 22 to a predetermined degree of vacuum (about 0.01 Torr), the gate valve 30 is opened,
The substrate holder 24 on which the substrate to be processed 23 is mounted is transported into the vacuum chamber 21 evacuated to a predetermined degree of vacuum, and is placed on the support 25. And the transfer robot 26
Is returned to the load lock chamber 22, the gate valve 30
Close. In the above description, the substrate holder is transported to transport the substrate holder 24 on which the substrate 23 to be processed is mounted. However, the substrate 23 transported to the substrate 23 and fixed on the support 25 in the vacuum chamber 21 is provided. The substrate may be transferred to place the substrate on the holder 24.
【００２６】真空チャンバー２１の上方壁面には、被処
理基板２３と対向して、石英のような耐熱ガラスからな
る赤外線透過窓３１が設けられ、この窓の外側に所定の
配列を有してなる複数の赤外線ランプ３２が取り付けら
れ、被処理基板２３を均一に加熱できるように構成され
ている。An infrared transmission window 31 made of heat-resistant glass such as quartz is provided on the upper wall surface of the vacuum chamber 21 so as to face the substrate 23 to be processed, and has a predetermined arrangement outside the window. A plurality of infrared lamps 32 are attached, and are configured to uniformly heat the substrate 23 to be processed.
【００２７】真空チャンバー２１には、バルブ３３を介
して真空ポンプ３４が接続され、真空チャンバー内を真
空排気できるように構成されている。また、真空ポンプ
３４をバイパスする配管２８がバルブ３９を介在させて
設けられている。更に、真空チャンバー２１には、任意
の箇所に真空計３５が取り付けられ、真空チャンバー内
の真空度を測定し、モニターできるようになっている。
真空計３５は、このような排気系の任意の箇所に接続さ
れていてもよい。なお、下地層の金属薄膜のパターンが
形成された被処理基板２３の真空下熱処理は、前記真空
チャンバー２１内で行われ得る。A vacuum pump 34 is connected to the vacuum chamber 21 via a valve 33 so that the inside of the vacuum chamber can be evacuated. Further, a pipe 28 that bypasses the vacuum pump 34 is provided with a valve 39 interposed. Further, a vacuum gauge 35 is attached to the vacuum chamber 21 at an arbitrary position so that the degree of vacuum in the vacuum chamber can be measured and monitored.
The vacuum gauge 35 may be connected to any part of such an exhaust system. The heat treatment under vacuum of the substrate 23 on which the pattern of the metal thin film of the underlayer is formed may be performed in the vacuum chamber 21.
【００２８】また、真空チャンバー２１にはガス供給系
３６が接続されている。このガス供給系３６は、バルブ
３７ａからガス流量調節器３７ｂ、圧力調整器３７ｃ及
びバルブ３７ｄを介して、一酸化炭素等の原料ガスボン
ベ３７ｅにガス配管にて直列に連なっている原料ガス供
給系と、バルブ３８ａからガス流量調節器３８ｂ、圧力
調整器３８ｃ及びバルブ３８ｄを介して、水素ガスボン
ベ３８ｅにガス配管にて直列に連なっている水素ガス供
給系とを並列に備えている。原料ガス供給系と水素ガス
供給系とは、バルブ３７ａ、３８ａと真空チャンバー２
１との間で合流し、真空チャンバー２１内に炭素含有ガ
ス及び水素ガスの混合ガスを供給するように構成されて
いる。混合ガスの導入は、被処理基板２３又は基板ホル
ダー２４の載置位置よりも下方であって、該基板をその
外側の近傍で囲繞するように設けられたガス噴射ノズル
手段を介して行われる。ガス供給系３６に接続された該
ガス噴射ノズル手段は、内部にガス流路を備えると共
に、その上面に、該内部ガス流路に連通する複数のガス
噴射口が列設されているものであって、真空チャンバー
内に、ガスを均一に噴射し得るものであれば、その形状
は問わない。このガス噴射ノズル手段は、真空チャンバ
ー２１内の底壁及び／又は側壁面に面接触して配設され
ていることが好ましい。該ガス噴射ノズル手段の冷却の
ためである。このようなガス噴射ノズル手段を設けるこ
とにより、混合ガスは、複数のガス噴射口から上方に向
かって噴射されると、被処理基板２３の上方全体にわた
って均一に拡散し、次いで、下方に向かって均等に降下
し、被処理基板全体にわたって一様に到達する。かくし
て均一な膜厚分布が達成できる。なお、真空チャンバー
２１内に配設されているガス噴射ノズル手段は、Ｃｕ等
のような熱伝導率の高い金属製であることが好ましい。Further, a gas supply system 36 is connected to the vacuum chamber 21. The gas supply system 36 is connected to a source gas supply system connected in series to a source gas cylinder 37e of carbon monoxide or the like by a gas pipe via a valve 37a, a gas flow controller 37b, a pressure regulator 37c, and a valve 37d. , A hydrogen gas supply system connected in series to a hydrogen gas cylinder 38e via a gas pipe via a gas flow controller 38b, a pressure controller 38c, and a valve 38d from the valve 38a. The source gas supply system and the hydrogen gas supply system are provided with valves 37a, 38a and vacuum chamber 2
1 and is configured to supply a mixed gas of a carbon-containing gas and a hydrogen gas into the vacuum chamber 21. The introduction of the mixed gas is performed through gas injection nozzle means provided below the position where the substrate 23 or the substrate holder 24 is placed and surrounding the substrate near the outside thereof. The gas injection nozzle means connected to the gas supply system 36 has a gas flow path inside, and a plurality of gas injection ports communicating with the internal gas flow path are arranged on the upper surface thereof. Any shape can be used as long as the gas can be uniformly injected into the vacuum chamber. It is preferable that the gas injection nozzle means be disposed in surface contact with the bottom wall and / or the side wall surface in the vacuum chamber 21. This is for cooling the gas injection nozzle means. By providing such a gas injection nozzle means, when the mixed gas is injected upward from the plurality of gas injection ports, the mixed gas is uniformly diffused over the entire substrate 23 to be processed, and then downward. It descends uniformly and reaches uniformly over the whole substrate to be processed. Thus, a uniform film thickness distribution can be achieved. The gas injection nozzle means provided in the vacuum chamber 21 is preferably made of a metal having a high thermal conductivity such as Cu.
【００２９】さらに、真空チャンバー２１の内壁は、鏡
面研磨仕上げされていてもよく、また、内壁にアルミナ
等の絶縁体が溶射により被覆されていてもよい。これ
は、生成するグラファイトナノファイバーが壁面に付着
しないようにするためである。また、真空チャンバー壁
面へのグラファイトナノファイバーの付着を防止するた
めに、壁面を冷却する手段として、チャンバー外周に、
冷却媒体、例えば冷却水を流す冷却管等を設けてもよ
い。さらに、真空チャンバー２１内に導入される混合ガ
スを予め加熱するための加熱機構を設けてもよい。Further, the inner wall of the vacuum chamber 21 may be mirror-polished, or the inner wall may be coated with an insulator such as alumina by thermal spraying. This is to prevent the generated graphite nanofiber from adhering to the wall surface. In addition, in order to prevent graphite nanofibers from adhering to the vacuum chamber wall surface, as a means for cooling the wall surface, on the outer periphery of the chamber,
A cooling medium, for example, a cooling pipe through which cooling water flows may be provided. Further, a heating mechanism for preheating the mixed gas introduced into the vacuum chamber 21 may be provided.
【００３０】[0030]
【実施例】上記構成を有する熱ＣＶＤ装置のうち、図２
に示す装置を用いて行うグラファイトナノファイバー薄
膜形成方法について、以下、実施例により説明する。 （実施例１）ＥＢ蒸着法により、ガラス基板上の所定の
箇所（所定形状のパターン部分）のみにＮｉを１００ｎ
ｍの厚さで蒸着し、このＮｉ薄膜パターン上にＦｅを１
０、２０、５０、１００ｎｍの４種類の厚さで蒸着し
た。次いで、Ｎｉ薄膜及びＦｅ薄膜からなる２層がパタ
ーン蒸着された基板２３を基板ホルダー２４上に装着し
たものを、基板貯蔵室から搬送ロボット２６により、熱
ＣＶＤ装置の真空チャンバー２１内の基板ホルダー用支
柱２５上に載置した。真空ポンプ３４を作動すると共
に、バルブ３３ａ、３３ｂを開状態にし、真空チャンバ
ー内の圧力を真空計３５で測定しながら、０．０５Ｔｏ
ｒｒ程度になるまで真空排気を行った。赤外線ランプ３
２を付勢して基板温度を５００℃にし、この温度で５分
間にわたって真空下熱処理を行った。その後、一酸化炭
素ガスボンベ３７ｅと水素ガスボンベ３８ｅとの元栓を
開き、圧力調整器３７ｃ、３８ｃにより約１気圧（絶対
圧力）に調整し、そしてバルブ３７ａ、３８ａを開き、
ガス流量調節器３７ｂ、３８ｂにより、一酸化炭素ガス
と水素ガスとの混合ガス（容量比で、ＣＯ：Ｈ2＝３
０：７０）を約１０００ｓｃｃｍ程度に調整して、真空
チャンバー２１内に、被処理基板ホルダー２４の下方か
ら、ガス噴射ノズル手段を介して導入し、ガス置換を行
った。この時、バルブ３３ａ、３３ｂを閉状態にし、真
空ポンプ３４を停止してバイパス配管２８のバルブ３９
を開状態にしておき、真空チャンバー２１内がほぼ大気
圧（７６０Ｔｏｒｒ）となるようにした。この場合、赤
外線ランプ３２を付勢して被処理基板２３を５００℃に
加熱した状態で混合ガスを導入した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG.
Hereinafter, a method for forming a graphite nanofiber thin film using the apparatus described in (1) will be described with reference to examples. (Example 1) 100 n of Ni was deposited only on a predetermined portion (pattern portion of a predetermined shape) on a glass substrate by EB vapor deposition.
m on the Ni thin film pattern.
Evaporation was performed in four thicknesses of 0, 20, 50, and 100 nm. Next, the substrate 23 on which the two layers composed of the Ni thin film and the Fe thin film are pattern-deposited is mounted on the substrate holder 24, and is transferred from the substrate storage room by the transfer robot 26 to the substrate holder in the vacuum chamber 21 of the thermal CVD apparatus. It was placed on the support 25. While operating the vacuum pump 34, the valves 33a and 33b are opened, and while measuring the pressure in the vacuum chamber with the vacuum gauge 35, 0.05 To
Evacuation was performed until the pressure reached about rr. Infrared lamp 3
2 was energized to bring the substrate temperature to 500 ° C., and a heat treatment under vacuum was performed at this temperature for 5 minutes. Thereafter, the main stoppers of the carbon monoxide gas cylinder 37e and the hydrogen gas cylinder 38e are opened, the pressure is adjusted to about 1 atm (absolute pressure) by the pressure regulators 37c, 38c, and the valves 37a, 38a are opened.
By the gas flow controllers 37b and 38b, a mixed gas of carbon monoxide gas and hydrogen gas (CO: H 2 = 3 by volume ratio)
0:70) was adjusted to about 1000 sccm, and introduced into the vacuum chamber 21 from below the substrate holder 24 to be processed through gas injection nozzle means to perform gas replacement. At this time, the valves 33a and 33b are closed, the vacuum pump 34 is stopped, and the valve 39 of the bypass pipe 28 is closed.
Was kept in an open state, so that the inside of the vacuum chamber 21 was almost at atmospheric pressure (760 Torr). In this case, the mixed gas was introduced in a state where the substrate 23 was heated to 500 ° C. by energizing the infrared lamp 32.
【００３１】本実施例では、真空チャンバー２１内の圧
力が大気圧になった後、赤外線ランプ３２を付勢して被
処理基板２３を５００℃に加熱し、この温度で２０分間
にわたって、熱ＣＶＤ法により該基板上でグラファイト
ナノファイバーの成長反応を行った。一酸化炭素ガスが
被処理基板２３上に達すると、一酸化炭素が解離し、被
処理基板上に蒸着されたＦｅ薄膜パターンの上にのみグ
ラファイトナノファイバー薄膜が形成した。成長反応の
終了した基板を真空チャンバー２１から取り出して、Ｆ
ｅ薄膜パターンの膜厚が１０、２０、５０ｎｍの３種類
の場合に得られたグラファイトナノファイバー薄膜につ
いて、走査型電子顕微鏡（ＳＥＭ、×４００００）によ
り成膜状態を観測したところ、図３〜図５に示すよう
に、多数のグラファイトナノファイバーがカールした状
態で成長していることが分かる。膜厚が５０ｎｍ以下で
あれば、このＦｅ薄膜パターンは剥がれることはなかっ
たが、１００ｎｍの場合にはこのＦｅ薄膜パターンの剥
がれが生じた。In this embodiment, after the pressure in the vacuum chamber 21 reaches the atmospheric pressure, the substrate 23 to be processed 23 is heated to 500 ° C. by energizing the infrared lamp 32, and the thermal CVD is performed at this temperature for 20 minutes. A growth reaction of graphite nanofibers was performed on the substrate by the method. When the carbon monoxide gas reached the target substrate 23, the carbon monoxide was dissociated, and a graphite nanofiber thin film was formed only on the Fe thin film pattern deposited on the target substrate. The substrate after the growth reaction is taken out of the vacuum chamber 21 and
e For the graphite nanofiber thin films obtained when the thickness of the thin film pattern was 10, 20, and 50 nm, the film formation state was observed with a scanning electron microscope (SEM, × 40000). As shown in FIG. 5, it can be seen that many graphite nanofibers are growing in a curled state. When the film thickness was 50 nm or less, the Fe thin film pattern did not peel off, but when the film thickness was 100 nm, the Fe thin film pattern peeled off.
【００３２】このようにして得られたグラファイトナノ
ファイバー薄膜からなる電子放出源の特性を測定したと
ころ、印加電界が１Ｖ／μｍに達したところで、電子放
出の開始が確認され、その後印加電界を大きくするに従
って電子放出量が増加し、５Ｖ／μｍで約１００ｍＡ／
ｃｍ2に達した。 （実施例２）実施例１のＥＢ蒸着法をスパッタ法に変え
て、下地層を形成し、実施例１と同様の手順に従ってグ
ラファイトナノファイバー薄膜を形成した。成長反応の
終了した基板について、得られたグラファイトナノファ
イバー薄膜を実施例１の場合と同様に観測したところ、
同様の結果が得られた。 （実施例３）実施例１で用いた基板の代わりに、ガラス
基板上の所定の箇所のみにＦｅを１０、２０、５０、１
００ｎｍの４種類の厚さでパターン蒸着してなる１層の
下地層を有する基板を用いて、実施例１と同様の手順に
従ってグラファイトナノファイバー薄膜を形成した。成
長反応の終了した基板について、得られたグラファイト
ナノファイバー薄膜を実施例１の場合と同様に観測した
ところ、同様の結果が得られた。When the characteristics of the electron emission source comprising the graphite nanofiber thin film thus obtained were measured, when the applied electric field reached 1 V / μm, the start of electron emission was confirmed. The electron emission amount increases as the voltage increases, and about 100 mA /
It reached cm 2. (Example 2) An EB vapor deposition method of Example 1 was changed to a sputtering method, an underlayer was formed, and a graphite nanofiber thin film was formed in the same procedure as in Example 1. When the obtained graphite nanofiber thin film was observed for the substrate after the growth reaction in the same manner as in Example 1,
Similar results were obtained. (Embodiment 3) Instead of the substrate used in Embodiment 1, Fe, 10, 20, 50, 1 were added only to predetermined portions on the glass substrate.
A graphite nanofiber thin film was formed according to the same procedure as in Example 1 using a substrate having one underlayer formed by pattern evaporation with four thicknesses of 00 nm. When the obtained graphite nanofiber thin film was observed in the same manner as in Example 1 for the substrate after the growth reaction, similar results were obtained.
【００３３】上記実施例では、ガラス基板上に、Ｎｉ薄
膜及び特定の膜厚を有するＦｅ薄膜からなる２層構造の
下地層パターン、又は、特定の膜厚を有するＦｅ薄膜か
らなる１層構造の下地層パターンを形成し、該パターン
部分のみにグラファイトナノファイバー薄膜を形成した
例について説明したが、Ｎｉ以外のＣｕ等の非触媒金属
の薄膜パターン、Ｆｅ以外の触媒金属の特定の膜厚を有
する薄膜パターンの場合も、さらには、Ｓｉ基板上に下
地層の金属薄膜をパターン形成した場合も、同様の結果
が得られた。In the above embodiment, a two-layer underlayer pattern composed of a Ni thin film and a Fe thin film having a specific thickness or a one-layer structure composed of an Fe thin film having a specific thickness is formed on a glass substrate. The example in which the underlayer pattern is formed and the graphite nanofiber thin film is formed only in the pattern portion has been described, but the non-catalytic metal thin film pattern such as Cu other than Ni has a specific thickness of the catalyst metal other than Fe. Similar results were obtained in the case of the thin film pattern and also in the case where the metal thin film of the underlayer was formed on the Si substrate.
【００３４】[0034]
【発明の効果】本発明の方法によれば、１０〜５０ｎｍ
の厚さの触媒金属薄膜パターンの１層構造からなる下地
層を有するガラス基板若しくはＳｉ基板、又は、非触媒
金属薄膜パターンと１０〜５０ｎｍの厚さの触媒金属薄
膜パターンとの２層構造からなる下地層を有するガラス
基板若しくはＳｉ基板を用いて、これを真空下熱処理
し、次いで、熱ＣＶＤ法を行うことによって該基板上に
グラファイトナノファイバー薄膜を形成しており、それ
によって下地層と基板との間の密着性や、触媒金属と非
触媒金属との界面での合金化による両者間の密着性が向
上する。そのため、この方法を利用することにより、高
電子放出密度、低電界電子放出性能の達成を可能にする
炭素系電子放出源（冷陰極源）を作製し、提供すること
ができ、さらに、この炭素系電子放出源を有する、発光
体の所望部分の発光を可能とする表示素子を提供するこ
ともできる。According to the method of the present invention, 10 to 50 nm
Glass substrate or Si substrate having an underlayer consisting of a one-layer structure of a catalyst metal thin film pattern having a thickness of, or a two-layer structure of a non-catalytic metal thin film pattern and a catalyst metal thin film pattern having a thickness of 10 to 50 nm. Using a glass substrate or an Si substrate having an underlayer, heat-treating this under vacuum, and then performing a thermal CVD method to form a graphite nanofiber thin film on the substrate, whereby the underlayer, the substrate, And the adhesion between the catalyst metal and the non-catalyst metal due to alloying at the interface is improved. Therefore, by using this method, a carbon-based electron emission source (cold cathode source) capable of achieving high electron emission density and low field electron emission performance can be manufactured and provided. A display element having a system electron emission source and capable of emitting light at a desired portion of a light-emitting body can also be provided.
【図１】 本発明の方法を実施するための成膜装置の一
例を示す概略構成図。FIG. 1 is a schematic configuration diagram showing an example of a film forming apparatus for performing a method of the present invention.
【図２】 本発明の方法を実施するための成膜装置の別
の例を示す概略構成図。FIG. 2 is a schematic configuration diagram showing another example of a film forming apparatus for performing the method of the present invention.
【図３】 本発明の方法で得られたグラファイトナノフ
ァイバー（Ｆｅ薄膜の厚さ：１０ｎｍ）対するＳＥＭに
よる顕微鏡写真（×４００００）。FIG. 3 is an SEM micrograph (× 40000) of a graphite nanofiber (Fe thin film thickness: 10 nm) obtained by the method of the present invention.
【図４】 本発明の方法で得られたグラファイトナノフ
ァイバー（Ｆｅ薄膜の厚さ：２０ｎｍ）に対するＳＥＭ
による顕微鏡写真（×４００００）。FIG. 4 is an SEM for a graphite nanofiber (Fe thin film thickness: 20 nm) obtained by the method of the present invention.
(× 40000).
【図５】 本発明の方法で得られたグラファイトナノフ
ァイバー（Ｆｅ薄膜の厚さ：５０ｎｍ）に対するＳＥＭ
による顕微鏡写真（×４００００）。FIG. 5 is an SEM for graphite nanofibers (thickness of Fe thin film: 50 nm) obtained by the method of the present invention.
(× 40000).
１ 真空チャンバー ２ 基板ホルダ
ー ３ 被処理基板 ４ 赤外線透過
窓 ５ 赤外線ヒーター ６ バルブ ７ 真空ポンプ ８ 真空計 ９ ガス供給系 １０ａ、１１ａ
バルブ １０ｂ、１１ｂ ガス流量調節器 １０ｃ、１１ｃ
圧力調整器 １０ｄ、１１ｄ ガスボンベ １２ 冷却手段 １３ 絶縁体 １４ 抵抗加熱
式ヒーター ２１ 真空チャンバー ２２ ロードロ
ック室 ２３ 被処理基板 ２４ 基板ホル
ダー ２５ 支柱 ２６ 搬送ロボ
ット ２７ 真空ポンプ ２９ 真空計 ３０ ゲートバルブ ３１ 赤外線透
過窓 ３２ 赤外線ランプ ３３ａ、３３ｂ
バルブ ３４ 真空ポンプ ３５ バルブ ３６ ガス供給系 ３７ａ、３８ａ
バルブ ３７ｂ、３８ｂ ガス流量調節器 ３７ｃ、３８ｃ
圧力調整器 ３７ｄ、３８ｄ バルブ ３７ｅ、３８ｅ
ガスボンベ ３９ バルブDESCRIPTION OF SYMBOLS 1 Vacuum chamber 2 Substrate holder 3 Substrate to be processed 4 Infrared transmission window 5 Infrared heater 6 Valve 7 Vacuum pump 8 Vacuum gauge 9 Gas supply system 10a, 11a
Valve 10b, 11b Gas flow controller 10c, 11c
Pressure regulator 10d, 11d Gas cylinder 12 Cooling means 13 Insulator 14 Resistance heating heater 21 Vacuum chamber 22 Load lock chamber 23 Substrate to be processed 24 Substrate holder 25 Post 26 Transfer robot 27 Vacuum pump 29 Vacuum gauge 30 Gate valve 31 Infrared transmission window 32 infrared lamps 33a, 33b
Valve 34 Vacuum pump 35 Valve 36 Gas supply system 37a, 38a
Valve 37b, 38b Gas flow controller 37c, 38c
Pressure regulator 37d, 38d Valve 37e, 38e
Gas cylinder 39 valve
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｊ 9/02 Ｈ０１Ｊ 9/02 Ｂ Ｆターム(参考） 4G046 CA01 CA02 CB08 CC06 4K030 AA14 AA17 BA27 BB12 BB14 CA04 CA06 CA17 DA02 DA04 FA10 JA06 JA09 JA10 KA24 4L037 CS04 FA03 FA05 FA20 PA03 PA06 PA17 PA18 PA28 UA02Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme coat II (Reference) H01J 9/02 H01J 9/02 B F Term (Reference) 4G046 CA01 CA02 CB08 CC06 4K030 AA14 AA17 BA27 BB12 BB14 CA04 CA06 CA17 DA02 DA04 FA10 JA06 JA09 JA10 KA24 4L037 CS04 FA03 FA05 FA20 PA03 PA06 PA17 PA18 PA28 UA02
Claims (8)
して、Ｆｅ、Ｃｏ又はこれらの金属の少なくとも１種を
含んだ合金の触媒金属薄膜を１０〜５０ｎｍの厚さで所
定のパターンに形成せしめた基板を被処理基板とし、該
被処理基板を真空下熱処理した後、熱ＣＶＤ法により、
炭素含有ガス及び水素ガスを用いて、該被処理基板上の
パターン部分のみにグラファイトナノファイバーを均一
に成長せしめ、グラファイトナノファイバー薄膜を得る
ことを特徴とするグラファイトナノファイバー薄膜形成
方法。1. A catalyst metal thin film of Fe, Co or an alloy containing at least one of these metals is formed in a predetermined pattern with a thickness of 10 to 50 nm as an underlayer on a glass substrate or a Si substrate. The substrate to be processed is used as a substrate to be processed, and after the substrate to be processed is heat-treated under vacuum,
A method for forming a graphite nanofiber thin film, wherein a graphite nanofiber thin film is obtained by uniformly growing a graphite nanofiber only on a pattern portion on the substrate to be processed using a carbon-containing gas and a hydrogen gas.
して、Ｆｅ、Ｃｏ又はこれらの金属の少なくとも１種を
含んだ合金の触媒金属薄膜を１０〜５０ｎｍの厚さで所
定のパターンに形成せしめた基板を被処理基板として用
い、真空排気した真空チャンバー内に載置された該被処
理基板を赤外線ランプで加熱して該被処理基板を真空下
熱処理し、次いで、炭素含有ガス及び水素ガスを真空チ
ャンバー内へ導入し、真空チャンバー内の圧力をほぼ１
気圧に維持して、該被処理基板上のパターン部分のみに
熱ＣＶＤ法によりグラファイトナノファイバーを均一に
成長せしめ、グラファイトナノファイバー薄膜を得るこ
とを特徴とするグラファイトナノファイバー薄膜形成方
法。2. A catalyst metal thin film of Fe, Co or an alloy containing at least one of these metals is formed in a predetermined pattern with a thickness of 10 to 50 nm as a base layer on a glass substrate or a Si substrate. Using the substrate as a substrate to be processed, the substrate to be processed placed in a vacuum chamber evacuated is heated by an infrared lamp to heat-treat the substrate to be processed under vacuum, and then a carbon-containing gas and a hydrogen gas are discharged. Introduce into the vacuum chamber and reduce the pressure in the vacuum chamber to approximately 1
A method of forming a graphite nanofiber thin film, wherein a graphite nanofiber thin film is obtained by uniformly growing graphite nanofibers only in a pattern portion on the substrate to be processed by a thermal CVD method while maintaining the pressure.
Ｓｉ基板上に、非触媒金属の薄膜を所定のパターンに形
成せしめた後、該非触媒金属パターンの上にＦｅ、Ｃｏ
又はこれらの金属の少なくとも１種を含んだ合金の触媒
金属薄膜を１０〜５０ｎｍの厚さで所定のパターンに形
成せしめた２層構造の下地層を有する基板を用いること
を特徴とする請求項１又は２記載のグラファイトナノフ
ァイバー薄膜形成方法。3. A non-catalytic metal thin film is formed in a predetermined pattern on a glass substrate or a Si substrate as the substrate to be processed, and then Fe, Co is deposited on the non-catalytic metal pattern.
A substrate having a two-layered underlayer in which a catalyst metal thin film of an alloy containing at least one of these metals is formed in a predetermined pattern with a thickness of 10 to 50 nm is used. Or the method of forming a graphite nanofiber thin film according to 2.
基板の耐熱温度以下であることを特徴とする請求項１〜
３のいずれかに記載のグラファイトナノファイバー薄膜
形成方法。4. The temperature for performing the heat treatment is 400 ° C. or higher,
The temperature is lower than the heat-resistant temperature of the substrate.
4. The method for forming a graphite nanofiber thin film according to any one of 3.
が、容量基準で、炭素含有ガス／水素ガス＝０．１〜１
０であることを特徴とする請求項１〜４のいずれかに記
載のグラファイトナノファイバー薄膜形成方法。5. The mixing ratio of the carbon-containing gas and the hydrogen gas is such that the carbon-containing gas / hydrogen gas is 0.1 to 1 on a volume basis.
The method for forming a graphite nanofiber thin film according to any one of claims 1 to 4, wherein the value is 0.
５０℃であることを特徴とする請求項１〜５のいずれか
に記載のグラファイトナノファイバー薄膜形成方法。6. The temperature for performing the thermal CVD method is 450 to 6
The method for forming a graphite nanofiber thin film according to any one of claims 1 to 5, wherein the temperature is 50 ° C.
化炭素であることを特徴とする請求項１〜６のいずれか
に記載のグラファイトナノファイバー薄膜形成方法。7. The method for forming a graphite nanofiber thin film according to claim 1, wherein the carbon-containing gas is carbon monoxide or carbon dioxide.
た後、該下地層の触媒金属薄膜の表面をエッチングし
て、その表面状態を粗くし、次いで、熱ＣＶＤ法を行う
ことを特徴とする請求項１〜７のいずれかに記載のグラ
ファイトナノファイバー薄膜形成方法。8. After forming the underlayer and performing heat treatment, the surface of the catalyst metal thin film of the underlayer is etched to roughen the surface state, and then thermal CVD is performed. The method for forming a graphite nanofiber thin film according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000307962A JP4644347B2 (en) | 2000-10-06 | 2000-10-06 | Method for forming graphite nanofiber thin film by thermal CVD |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000307962A JP4644347B2 (en) | 2000-10-06 | 2000-10-06 | Method for forming graphite nanofiber thin film by thermal CVD |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002115071A true JP2002115071A (en) | 2002-04-19 |
| JP4644347B2 JP4644347B2 (en) | 2011-03-02 |
Family
ID=18788369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000307962A Expired - Lifetime JP4644347B2 (en) | 2000-10-06 | 2000-10-06 | Method for forming graphite nanofiber thin film by thermal CVD |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4644347B2 (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060920A (en) * | 2003-07-31 | 2005-03-10 | Semiconductor Energy Lab Co Ltd | Method for manufacturing ultrafine carbon fiber and field emission element |
| JPWO2005047180A1 (en) * | 2003-11-17 | 2007-05-31 | コニカミノルタホールディングス株式会社 | Nanostructured carbon material manufacturing method, nanostructured carbon material formed by the manufacturing method, and substrate having the nanostructured carbon material |
| US7417320B2 (en) | 2004-08-31 | 2008-08-26 | Fujitsu Limited | Substrate structure and manufacturing method of the same |
| JP2008214688A (en) * | 2007-03-02 | 2008-09-18 | Ulvac Japan Ltd | Thermal cvd system and film deposition method |
| US7582507B2 (en) | 2002-08-02 | 2009-09-01 | Nec Corporation | Catalyst support substrate, method for growing carbon nanotubes using the same, and the transistor using carbon nanotubes |
| JP2012519141A (en) * | 2009-02-27 | 2012-08-23 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Low temperature CNT growth using gas preheating method |
| KR101252333B1 (en) * | 2009-04-02 | 2013-04-08 | 서울대학교산학협력단 | A controllable fabrication method of graphene sheets using the thermal plasma chemical vapor deposition method |
| US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
| KR101423037B1 (en) * | 2009-07-14 | 2014-08-13 | 그래핀스퀘어 주식회사 | Preparing method of graphene sheet, graphene laminate, preparing method of transformation-affordable graphene sheet, transformation-affordable graphene sheet and device using the same |
| US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
| US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| US8969225B2 (en) | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
| US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
| US10138128B2 (en) | 2009-03-03 | 2018-11-27 | Applied Nanostructured Solutions, Llc | System and method for surface treatment and barrier coating of fibers for in situ CNT growth |
| US10532947B2 (en) | 2014-10-08 | 2020-01-14 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
| US10579106B2 (en) | 2015-07-21 | 2020-03-03 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
| US11174197B2 (en) | 2016-04-08 | 2021-11-16 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
| US11472734B2 (en) | 2015-12-11 | 2022-10-18 | Corning Incorporated | Fusion-formable glass-based articles including a metal oxide concentration gradient |
| US11492291B2 (en) | 2012-02-29 | 2022-11-08 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
| US11613103B2 (en) | 2015-07-21 | 2023-03-28 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
| US11878941B2 (en) | 2014-06-19 | 2024-01-23 | Corning Incorporated | Glasses having non-frangible stress profiles |
| US11963320B2 (en) | 2022-10-06 | 2024-04-16 | Corning Incorporated | Glass-based articles including a stress profile comprising two regions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3953276B2 (en) * | 2000-02-04 | 2007-08-08 | 株式会社アルバック | Graphite nanofiber, electron emission source and manufacturing method thereof, display element having the electron emission source, and lithium ion secondary battery |
| JP4500407B2 (en) * | 2000-03-28 | 2010-07-14 | 株式会社アルバック | Graphite nano-fiber deposition method and apparatus |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3441923B2 (en) * | 1997-06-18 | 2003-09-02 | キヤノン株式会社 | Manufacturing method of carbon nanotube |
| JP3363759B2 (en) * | 1997-11-07 | 2003-01-08 | キヤノン株式会社 | Carbon nanotube device and method of manufacturing the same |
-
2000
- 2000-10-06 JP JP2000307962A patent/JP4644347B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3953276B2 (en) * | 2000-02-04 | 2007-08-08 | 株式会社アルバック | Graphite nanofiber, electron emission source and manufacturing method thereof, display element having the electron emission source, and lithium ion secondary battery |
| JP4500407B2 (en) * | 2000-03-28 | 2010-07-14 | 株式会社アルバック | Graphite nano-fiber deposition method and apparatus |
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7582507B2 (en) | 2002-08-02 | 2009-09-01 | Nec Corporation | Catalyst support substrate, method for growing carbon nanotubes using the same, and the transistor using carbon nanotubes |
| JP4489527B2 (en) * | 2003-07-31 | 2010-06-23 | 株式会社半導体エネルギー研究所 | Method for producing carbon fiber |
| JP2005060920A (en) * | 2003-07-31 | 2005-03-10 | Semiconductor Energy Lab Co Ltd | Method for manufacturing ultrafine carbon fiber and field emission element |
| JPWO2005047180A1 (en) * | 2003-11-17 | 2007-05-31 | コニカミノルタホールディングス株式会社 | Nanostructured carbon material manufacturing method, nanostructured carbon material formed by the manufacturing method, and substrate having the nanostructured carbon material |
| JP5002960B2 (en) * | 2003-11-17 | 2012-08-15 | コニカミノルタホールディングス株式会社 | Nanostructured carbon material manufacturing method, nanostructured carbon material formed by the manufacturing method, and substrate having the nanostructured carbon material |
| US7417320B2 (en) | 2004-08-31 | 2008-08-26 | Fujitsu Limited | Substrate structure and manufacturing method of the same |
| US9573812B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
| US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US9574300B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| JP2008214688A (en) * | 2007-03-02 | 2008-09-18 | Ulvac Japan Ltd | Thermal cvd system and film deposition method |
| JP2012519141A (en) * | 2009-02-27 | 2012-08-23 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Low temperature CNT growth using gas preheating method |
| US10138128B2 (en) | 2009-03-03 | 2018-11-27 | Applied Nanostructured Solutions, Llc | System and method for surface treatment and barrier coating of fibers for in situ CNT growth |
| KR101252333B1 (en) * | 2009-04-02 | 2013-04-08 | 서울대학교산학협력단 | A controllable fabrication method of graphene sheets using the thermal plasma chemical vapor deposition method |
| KR101423037B1 (en) * | 2009-07-14 | 2014-08-13 | 그래핀스퀘어 주식회사 | Preparing method of graphene sheet, graphene laminate, preparing method of transformation-affordable graphene sheet, transformation-affordable graphene sheet and device using the same |
| US8969225B2 (en) | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
| US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
| US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
| US11492291B2 (en) | 2012-02-29 | 2022-11-08 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
| US11878941B2 (en) | 2014-06-19 | 2024-01-23 | Corning Incorporated | Glasses having non-frangible stress profiles |
| US11459270B2 (en) | 2014-10-08 | 2022-10-04 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
| US10532947B2 (en) | 2014-10-08 | 2020-01-14 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
| US11220456B2 (en) | 2014-10-08 | 2022-01-11 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
| US11465937B2 (en) | 2014-10-08 | 2022-10-11 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
| US11267228B2 (en) | 2015-07-21 | 2022-03-08 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
| US11613103B2 (en) | 2015-07-21 | 2023-03-28 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
| US10579106B2 (en) | 2015-07-21 | 2020-03-03 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
| US11472734B2 (en) | 2015-12-11 | 2022-10-18 | Corning Incorporated | Fusion-formable glass-based articles including a metal oxide concentration gradient |
| US11878936B2 (en) | 2015-12-11 | 2024-01-23 | Corning Incorporated | Fusion-formable glass-based articles including a metal oxide concentration gradient |
| US11279652B2 (en) | 2016-04-08 | 2022-03-22 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
| US11174197B2 (en) | 2016-04-08 | 2021-11-16 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
| US11691913B2 (en) | 2016-04-08 | 2023-07-04 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
| US11963320B2 (en) | 2022-10-06 | 2024-04-16 | Corning Incorporated | Glass-based articles including a stress profile comprising two regions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4644347B2 (en) | 2011-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2002115071A (en) | Method for depositing graphite nanofiber thin film by thermal cvd method | |
| EP1134304B1 (en) | Method of vertically aligning carbon nanotubes on substrates using thermal chemical vapor deposition with dc bias | |
| EP1885909B1 (en) | Nanostructure production methods | |
| US8163647B2 (en) | Method for growing carbon nanotubes, and electronic device having structure of ohmic connection to carbon element cylindrical structure body and production method thereof | |
| JP5014600B2 (en) | Method for growing oriented carbon nanotubes | |
| US7479052B2 (en) | Method of growing carbon nanotubes and method of manufacturing field emission device using the same | |
| CN1302079A (en) | Field emission display device by using vertical arranged carbon nanometer tube | |
| KR20010085509A (en) | Process for controlled growth of carbon nanotubes | |
| JP2004523460A (en) | Method and apparatus for producing carbon nanotubes | |
| JP2001032071A (en) | Thermochemical vapor phase vapor deposition apparatus and low-temperature synthesis of carbon nanotube using the same | |
| JP2003286017A (en) | Method for transferring aligned carbon nanotube film | |
| JP2001048512A (en) | Preparation of perpendicularly oriented carbon nanotube | |
| JP2001167721A (en) | Electric field discharge display element and manufacturing method of the same | |
| JP4156879B2 (en) | A method for producing carbon fiber. | |
| JP4881504B2 (en) | Selective formation method of graphite nanofiber thin film by thermal CVD method | |
| JP4644346B2 (en) | Method for forming graphite nanofiber thin film by thermal CVD | |
| JP2006306704A (en) | Method of forming carbon film and carbon film | |
| JP4714328B2 (en) | Method for controlling the diameter of graphite nanofibers | |
| JP2969503B2 (en) | How to make carbonaceous fiber | |
| JP4644345B2 (en) | Method for forming graphite nanofiber thin film by thermal CVD | |
| RU2753399C1 (en) | Method for creating quantum dots for element base of radio engineering | |
| JP4059795B2 (en) | Carbon nanotube growth method | |
| US20200102647A1 (en) | Multilayer stack for the growth of carbon nanotubes by chemical vapor deposition | |
| JP2001240403A (en) | Carbon material, method for manufacturing the same, and electron discharging element | |
| KR20010029763A (en) | Method for manufacturing field emission display device using carbon nanotube |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20070517 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20070517 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071005 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100118 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101124 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101206 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4644347 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131210 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |