JP2009242239A - Carbon film structure - Google Patents

Carbon film structure Download PDF

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JP2009242239A
JP2009242239A JP2009174129A JP2009174129A JP2009242239A JP 2009242239 A JP2009242239 A JP 2009242239A JP 2009174129 A JP2009174129 A JP 2009174129A JP 2009174129 A JP2009174129 A JP 2009174129A JP 2009242239 A JP2009242239 A JP 2009242239A
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carbon film
tip
carbon
stem
shape
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JP5121791B2 (en
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Hirooki O
宏興 王
Akio Hiraki
昭夫 平木
Hoki Haba
方紀 羽場
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Life Technology Research Institute Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain a carbon film remarkably excellent in IV characteristic. <P>SOLUTION: The structure of the carbon film is constituted so that a plurality of carbon film assembly units 12 are formed on a substrate 10. The carbon film assembly units 12 are provided with a stem-like carbon film 14 formed long and acicular, and a branched carbon film group 16 each formed to surround the stem-like carbon film 14 from the middle of the film to the lower part of the film. The stem-like carbon film 14 has the long acicular shape having a spiral stripe-like step part 18 toward the tip on the outer peripheral surface near the tip and having radius decreased toward the tip. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、先端が電界放射（フィールドエミッション）を行うのに適した鋭利な形状に成膜される炭素膜構造に関するものである。 The present invention relates to a carbon film structure whose tip is formed into a sharp shape suitable for performing field emission (field emission).

電界放射は電界集中により電子が真空に放射される現象であり、この電界放射を行うものとして例えばカーボンナノチューブが開発されてきている。カーボンナノチューブは、極めて細長く高アスペクト比のために電界放射特性に優れたもので電界電子放出素子を得ることができるとされている。電界放射特性（ＩＶ特性）とは、陽極と冷陰極との間に電圧Ｖを印加して冷陰極から電界放射する際の、電圧Ｖと電界放射電流（エミッション電流）Ｉとの関係を示す曲線により示される特性であり、電界放射を開始する電圧（閾値）や、上記曲線の傾きや形状で特徴づけられる。 Field emission is a phenomenon in which electrons are radiated to a vacuum due to electric field concentration, and for example, carbon nanotubes have been developed to perform this field emission. Carbon nanotubes are extremely thin and have a high aspect ratio, and are excellent in field emission characteristics, and it is said that a field electron emission device can be obtained. The field emission characteristic (IV characteristic) is a curve showing the relationship between the voltage V and the field emission current (emission current) I when the voltage V is applied between the anode and the cold cathode to emit the electric field from the cold cathode. This is a characteristic indicated by the voltage (threshold value) at which field emission is started, and the slope and shape of the curve.

このような冷陰極に蛍光体付きの陽極を対向配置し、冷陰極と陽極との間に電圧（陽陰極間電圧）を印加して冷陰極から電界放射により電子を放出させ、この放出した電子を蛍光体に加速衝突させて蛍光体を励起発光させる冷陰極蛍光ランプがある。   An anode with a phosphor is arranged opposite to such a cold cathode, and a voltage (a voltage between positive and negative electrodes) is applied between the cold cathode and the anode to emit electrons from the cold cathode by field emission. There is a cold cathode fluorescent lamp in which the phosphor is excited to collide with the phosphor and the phosphor is excited to emit light.

この蛍光体の発光には所定量の電子放出が必要である。この電子放出量を示すエミッション電流を縦軸に、陽陰極間電圧を横軸にして示す電流電圧（ＩＶ）特性曲線は冷陰極の電子放出性能を示している。   A predetermined amount of electron emission is required for light emission of the phosphor. A current-voltage (IV) characteristic curve showing the emission current indicating the electron emission amount on the vertical axis and the positive-cathode voltage on the horizontal axis shows the electron emission performance of the cold cathode.

カーボンナノチューブの場合、上記ＩＶ特性曲線の傾きが緩やかに立ち上がってくる。そのため、カーボンナノチューブでは蛍光体が発光を開始させるためのエミッション電流を得るのに必要な電圧Ｖは高くなる。   In the case of carbon nanotubes, the slope of the IV characteristic curve rises gently. Therefore, in the carbon nanotube, the voltage V necessary for obtaining an emission current for the phosphor to start light emission becomes high.

しかしながら、所望のエミッション電流を得るための印加電圧Ｖの値が大きいことはその電源設備が要求されたり、上記冷陰極蛍光ランプの製作に影響したりするなどの課題がある。そこで、より低い印加電圧Ｖで蛍光体を発光開始させることができるエミッション電流を得られるＩＶ特性を提供する冷陰極用の炭素膜の実現が望まれていた。
特開平１０−２２３１２８号公報 However, when the value of the applied voltage V for obtaining a desired emission current is large, there is a problem that the power supply facility is required or the manufacture of the cold cathode fluorescent lamp is affected. Therefore, it has been desired to realize a carbon film for a cold cathode that provides an IV characteristic capable of obtaining an emission current capable of starting emission of a phosphor with a lower applied voltage V.
JP-A-10-223128

本出願人は、上記に鑑み、鋭意研究を行い、カーボンナノチューブ等に代えて、半径が先端に向かうにつれて針状に小さくなる形状を備えたことにより、より低い印加電圧で所望するエミッション電流を得ることができるＩＶ特性に優れた針状炭素膜を開発することができた。本発明は、このような針状炭素膜の構造にさらに改良を重ねた結果、さらに、より低い印加電圧で所望するエミッション電流を得ることができるＩＶ特性に優れた炭素膜を提供することができるに至ったものである。   In view of the above, the present applicant has earnestly researched and obtained a desired emission current at a lower applied voltage by providing a shape that decreases in a needle shape as the radius goes to the tip instead of a carbon nanotube or the like. An acicular carbon film with excellent IV characteristics could be developed. As a result of further improving the structure of such a needle-like carbon film, the present invention can provide a carbon film excellent in IV characteristics that can obtain a desired emission current at a lower applied voltage. Has been reached.

本発明による炭素膜構造は、基板上に形成される炭素膜であって、この炭素膜は複数の炭素膜集合単位からなり、前記炭素膜集合単位は幹状炭素膜とこの幹状炭素膜の途中から炭素膜の下部にかけて前記幹状炭素膜を囲むように成膜された枝状炭素膜群とからなるものである。   The carbon film structure according to the present invention is a carbon film formed on a substrate, and the carbon film is composed of a plurality of carbon film aggregate units, and the carbon film aggregate unit is composed of a trunk carbon film and the trunk carbon film. The branched carbon film group is formed so as to surround the trunk-like carbon film from the middle to the lower part of the carbon film.

本発明は、好ましくは、その先端近傍の外周面周りに当該先端に向けて連続した筋状段差部を有する。   The present invention preferably has a stair-like stepped portion continuous toward the tip around the outer peripheral surface near the tip.

上記筋状段差部は、好ましくは、上記先端近傍の外周面周りを当該先端に向けて螺旋状になって連続している。   The streaky stepped portion is preferably continuous spirally around the outer peripheral surface near the tip toward the tip.

上記筋状段差部は、好ましくは、グラフェンシートが複数層重なって螺旋状となった内部中空の針状炭素膜単位が先端に向けて多数段に積み重なって構成され、各針状炭素膜単位の境界で螺旋状に形成されているものである。上記「筋状」とはその連続方向の幅や形状を特定して限定するものではなく、ＴＥＭ写真で観察した場合の表現の一例であり、少なくとも段差部に電界放射に有効な角張ったエミッションサイトとなる部分を有する。   The streaky stepped portion is preferably formed by stacking a plurality of graphene sheets in a spiral shape with a plurality of layers of inner hollow acicular carbon units stacked toward the tip, and each acicular carbon membrane unit It is formed in a spiral shape at the boundary. The above-mentioned “streaks” are not limited by specifying the width and shape in the continuous direction, but are an example of expression when observed with a TEM photograph, and at least a stepped portion is an angular emission site effective for field emission. The part which becomes.

上記「連続」とは完全に連続していることに限定されず、部分的に連続する場合を含むことができる。   The “continuous” is not limited to being completely continuous, but may include a case of being partially continuous.

この筋状段差部は上記炭素膜の外周面から螺旋状に膨出するような形態、あるいは突出するような形態、あるいは先端に向けて所定高さまで連続的に半径が小さくなっていき途中で不連続的に半径が小さくなりもしくは半径が大きくなるなどして、次いで連続的に半径が小さくなるという膜形成のペースが螺旋状に繰り替えされるような形態の筋状段差部である。結果として電界を集中させやすい構造の筋状段差部となっている。   The streaky stepped portion has a shape that bulges spirally from the outer peripheral surface of the carbon film, a shape that protrudes, or a radius that continuously decreases to a predetermined height toward the tip, and is not This is a streak-shaped stepped portion in such a manner that the pace of film formation in which the radius is continuously reduced and then the radius is continuously reduced is repeated spirally. As a result, a stair-like step portion having a structure in which the electric field is easily concentrated is obtained.

この針状炭素膜は、任意の位置から先端までの間で、半径が部分的に大きい部分が存在しても、全体として先端に向けて半径が小さくなる場合を含む。また、任意の位置から先端までの間の途中部分は真直ぐな場合に限定する必要はなく、途中部分において曲線状、折れ線状、等に変形していても、全体として先端に向けて半径が小さくなるとよい。上記任意の位置は、炭素膜の基部に限定するものではなく、途中の位置からでもよい。   This acicular carbon film includes a case where the radius decreases toward the tip as a whole even if a portion with a large radius exists between an arbitrary position and the tip. In addition, it is not necessary to limit the middle part between the arbitrary position and the tip when it is straight, and even if the middle part is deformed into a curved shape, a broken line shape, etc., the radius decreases toward the tip as a whole. It ’s good. The arbitrary position is not limited to the base portion of the carbon film, and may be from an intermediate position.

本発明による炭素膜構造では、その先端が基本構造として先細り形状を有した有効なエミッションサイト構造であるから、カーボンナノチューブのように先端に向けて半径が一定の炭素膜とは異なって、低い印加電圧で所望のエミッション電流を得ることができ、ＩＶ特性に優れた炭素膜構造である。   The carbon film structure according to the present invention is an effective emission site structure having a tapered shape at the tip thereof as a basic structure. Therefore, unlike a carbon film having a constant radius toward the tip, such as a carbon nanotube, a low application is applied. A desired emission current can be obtained with voltage, and the carbon film structure has excellent IV characteristics.

そして本発明による炭素膜構造では、上記基本構造に加えてその先端近傍の外周面に当該先端に向けて螺旋状の筋状段差部を備えたので、先端だけでなく、その筋状段差部も電界集中する有効なエミッションサイトとなって電界放射が行われるものであり、筋状段差部が無い針状炭素膜よりもよりさらに低い印加電圧で所望のエミッション電流を得ることができ、ＩＶ特性が格段に向上する。   In the carbon film structure according to the present invention, in addition to the basic structure, the outer peripheral surface in the vicinity of the tip is provided with a spiral streak step toward the tip. The field emission is performed as an effective emission site that concentrates the electric field, and a desired emission current can be obtained with a lower applied voltage than the needle-like carbon film having no streak-like step portion, and the IV characteristics are improved. Greatly improved.

本発明による炭素膜構造は、基板上に複数の炭素膜集合単位が形成されてなり、これら炭素膜集合単位は、幹状炭素膜と、この幹状炭素膜の膜中途から膜下部にかけて当該幹状炭素膜を囲むように成膜されている枝状炭素膜群とを備えると共に、上記幹状炭素膜は、グラフェンシートが多層に重なって内部中空となっていて、かつ、先端に向けて半径が小さくなる針状形状を備えることを特徴とするものである。   In the carbon film structure according to the present invention, a plurality of carbon film aggregate units are formed on a substrate. The carbon film aggregate unit includes a trunk carbon film and the trunk carbon film from the middle to the lower part of the trunk carbon film. A branched carbon film group formed so as to surround the carbon-like carbon film, and the stem-like carbon film has a graphene sheet stacked in multiple layers to be hollow inside, and has a radius toward the tip. It is characterized by having a needle-like shape in which becomes smaller.

上記幹状炭素膜は、好ましくは、その先端近傍の外周面周りに当該先端に向けて連続している筋状段差部を有する。   The stem-like carbon film preferably has a stair-like stepped portion continuous toward the tip around the outer peripheral surface near the tip.

本発明では、幹状炭素膜が先端に向けて半径が小さくなる形状を有するから、上記本発明第１と同様に、低い印加電圧で所望のエミッション電流を得ることができ、ＩＶ特性に優れた炭素膜である。   In the present invention, the stem-like carbon film has a shape with a radius that decreases toward the tip, so that a desired emission current can be obtained with a low applied voltage as in the first aspect of the present invention, and the IV characteristics are excellent. It is a carbon film.

そして、本発明では、この幹状炭素膜に加えて、さらに、針状炭素膜の膜中途から膜下部にかけて枝状炭素膜群が構成されているので、この枝状炭素膜群により、幹状炭素膜の姿勢が安定化し、電子を安定して放出することができる。   In the present invention, in addition to this stem-like carbon film, a branch-like carbon film group is formed from the middle of the needle-like carbon film to the lower part of the membrane. The posture of the carbon film is stabilized, and electrons can be stably emitted.

本発明ではまた、枝状炭素膜群を構成する針状炭素膜からも電子放出が行われ、全体の電界放射量が多くなり、電界放射型の照明ランプの電界電子放出源に用いた場合、高輝度の照明ランプを提供することができるようになる。   In the present invention, electrons are also emitted from the acicular carbon film constituting the branched carbon film group, and the total field emission amount is increased. When used as a field electron emission source of a field emission type illumination lamp, A high-intensity illumination lamp can be provided.

本発明ではさらに、基板上に成膜された場合、機械的に支持され、基板上に倒れ込みにくくなる結果、照明ランプの電子放出源としての安定性が向上することに加えて、幹状炭素膜の直径が細くても、電流を流し込むための基板との電気的コンタクトを枝状炭素膜群によりとることができる。   Furthermore, in the present invention, when the film is formed on the substrate, it is mechanically supported and is difficult to fall on the substrate. As a result, the stability as an electron emission source of the illumination lamp is improved, and the stem carbon film Even if the diameter of the substrate is small, the branch carbon film group can make electrical contact with the substrate through which current flows.

本発明では、好ましくは上記筋状段差部にシート状、ウォール状、針状等の炭素膜が成膜される。筋状段差部にシート状、ウォール状、針状等の炭素膜が成膜されている場合、単に筋状段差部だけの場合よりもさらにより低い印加電圧で所望のエミッション電流を得ることができ、さらによりＩＶ特性が向上する。   In the present invention, a carbon film such as a sheet shape, a wall shape, or a needle shape is preferably formed on the streaky stepped portion. When a carbon film such as a sheet shape, wall shape, or needle shape is formed on the streaky stepped portion, a desired emission current can be obtained with a lower applied voltage than when only a streaky stepped portion is formed. Further, the IV characteristics are further improved.

本発明によれば、カーボンナノチューブよりもＩＶ特性において格段に優れた炭素膜を得ることができる。   According to the present invention, it is possible to obtain a carbon film that is much better in IV characteristics than carbon nanotubes.

図１は実施の形態に係る炭素膜の構成を示す図である。FIG. 1 is a diagram showing a configuration of a carbon film according to an embodiment. 図２は実施の形態に係る炭素膜の平面視ＳＥＭ写真像である。FIG. 2 is a plan view SEM photograph image of the carbon film according to the embodiment. 図３は実施の形態に係る炭素膜の平面視ＳＥＭ写真像である。FIG. 3 is a plan-view SEM photograph image of the carbon film according to the embodiment. 図４は実施の形態に係る炭素膜のやや斜め方向から視たＳＥＭ写真像である。FIG. 4 is an SEM photograph image of the carbon film according to the embodiment viewed from a slightly oblique direction. 図５は実施の形態に係る炭素膜のやや斜め方向から視たＳＥＭ写真像である。FIG. 5 is a SEM photograph image of the carbon film according to the embodiment viewed from a slightly oblique direction. 図６は実施の形態に係る炭素膜のやや斜め方向から視たＳＥＭ写真像である。FIG. 6 is a SEM photograph image of the carbon film according to the embodiment viewed from a slightly oblique direction. 図７は実施の形態に係る炭素膜のやや斜め方向から視たＳＥＭ写真像である。FIG. 7 is a SEM photograph image of the carbon film according to the embodiment viewed from a slightly oblique direction. 図８は実施の形態に係る幹状炭素膜を撮影したＳＥＭ写真像である。FIG. 8 is a SEM photograph image obtained by photographing the stem-like carbon film according to the embodiment. 図９は実施の形態に係る幹状炭素膜の先端を撮影したＳＥＭ写真像である。FIG. 9 is an SEM photograph image obtained by photographing the tip of the stem-like carbon film according to the embodiment. 図１０は実施の形態に係る幹状炭素膜の先端近傍の一部のＴＥＭ写真像である。FIG. 10 is a TEM photographic image of a part near the tip of the stem-like carbon film according to the embodiment. 図１１は実施の形態に係る幹状炭素膜の先端近傍の全体を模式的に示す図である。FIG. 11 is a diagram schematically showing the entire vicinity of the tip of the stem-like carbon film according to the embodiment. 図１２はカーボンナノチューブ、針状炭素膜、筋状段差部付き針状炭素膜（幹状炭素膜）のＩＶ特性曲線を示す図である。FIG. 12 is a diagram showing IV characteristic curves of a carbon nanotube, a needle-like carbon film, and a needle-like carbon film (stem-like carbon film) with streak-like steps. 図１３は、炭素膜の製造装置の概略構成図である。FIG. 13 is a schematic configuration diagram of a carbon film manufacturing apparatus.

以下、添付した図面を参照して本発明の実施の形態に係る炭素膜を説明する。     Hereinafter, a carbon film according to an embodiment of the present invention will be described with reference to the accompanying drawings.

実施の形態の炭素膜の構造は、図１で示すように、基板１０上に複数の炭素膜集合単位１２が形成されて構成されている。これら炭素膜集合単位１２は、基板１０上に所定の間隔で形成されている。炭素膜集合単位１２は、先端に向け半径が小さくなる細長い針状の幹状炭素膜１４と、この幹状炭素膜１４の膜中途から膜下部にかけて当該幹状炭素膜１４を囲むように成膜されている枝状炭素膜群１６とから構成されている。幹状炭素膜は、図中の円部分を引き出して円Ｐで囲むように、先端近傍の外周面に当該先端に向けて連続状の筋状段差部１８を有した構成になっている。これら筋状段差部１８には膜中途から下部に向かうにつれ成長したシート状、ウォール状、針状等の炭素膜２０が成膜される。この筋状段差部１８は螺旋状になって幹状炭素膜１４の先端に向けて連続している。 As shown in FIG. 1, the structure of the carbon film according to the embodiment is configured by forming a plurality of carbon film aggregate units 12 on a substrate 10. These carbon film aggregate units 12 are formed on the substrate 10 at predetermined intervals. The carbon film aggregate unit 12 is formed so as to surround an elongated needle-like trunk-like carbon film 14 whose radius decreases toward the tip, and the trunk-like carbon film 14 from the middle of the trunk-like carbon film 14 to the lower part of the film. The branched carbon film group 16 is formed. The trunk-like carbon film has a configuration in which a continuous streak-shaped step portion 18 is provided on the outer peripheral surface in the vicinity of the tip so as to draw out a circle portion in the drawing and surround the circle P in the drawing toward the tip. A carbon film 20 having a sheet shape, a wall shape, a needle shape, or the like grown from the middle of the film toward the lower portion is formed on the streaky stepped portion 18. The streak-like stepped portion 18 has a spiral shape and continues toward the tip of the stem-like carbon film 14.

以上の構成を備えた実施の形態の炭素膜構造では、炭素膜集合単位１２で基板１０上に形成されていると共に、枝状炭素膜群１６が全体の基本構造となりその土台となる基本構造に対して幹状炭素膜１４が先端に向けて半径が小さくなる針状形状を有した構造で形成されているから、カーボンナノチューブのように先端に向けて半径が一定の炭素膜とは異なって、低い印加電圧で所望のエミッション電流を得ることができるＩＶ特性に優れた炭素膜構成である。   In the carbon film structure of the embodiment having the above-described configuration, the carbon film aggregate unit 12 is formed on the substrate 10, and the branched carbon film group 16 becomes the entire basic structure and the basic structure serving as the foundation thereof. On the other hand, since the stem-like carbon film 14 is formed in a structure having a needle-like shape with a radius decreasing toward the tip, unlike a carbon film having a constant radius toward the tip like a carbon nanotube, It is a carbon film configuration excellent in IV characteristics that can obtain a desired emission current with a low applied voltage.

また、炭素膜集合単位１２が間隔を隔てて配置されているので各炭素膜集合単位１２ごとの幹状炭素膜１４は互いの電子放出を阻害しないから、電子放出性能が向上する。   Further, since the carbon film aggregate units 12 are arranged at intervals, the stem-like carbon film 14 for each carbon film aggregate unit 12 does not inhibit the mutual electron emission, so that the electron emission performance is improved.

特に幹状炭素膜１４はグラフェンシートが多層に重なった内部中空で先端に向けて半径が小さくなる針形状を備え、その先端に向かう外周面に螺旋状の筋状段差部１８を備えているので、先端だけでなく、その筋状段差部１８でも電界放射が行われるものであり、筋状段差部１８が無い針状炭素膜の場合よりもよりさらに低い印加電圧で所望のエミッション電流を得ることができ、ＩＶ特性が格段に向上する。   In particular, the stem-like carbon film 14 has a hollow inner shape in which graphene sheets are stacked in multiple layers, has a needle shape with a radius decreasing toward the tip, and has a spiral streaky step 18 on the outer peripheral surface toward the tip. The field emission is performed not only at the tip but also at the streaky step portion 18, and a desired emission current can be obtained with a lower applied voltage than in the case of a needle-like carbon film without the streak step portion 18. And IV characteristics are remarkably improved.

さらに、筋状段差部１８には膜中途から下部に向かうにつれ成長したシート状、ウォール状、針状等の炭素膜２０が成膜されるので、これらも電界を集中させやすい構成であり、上記ＩＶ特性の向上に貢献することができる。   Further, since the sheet-like stepped portion 18 is formed with a carbon film 20 such as a sheet shape, a wall shape, and a needle shape that grows from the middle of the film toward the lower portion, these are also configured to easily concentrate the electric field. It can contribute to the improvement of IV characteristics.

さらに、枝状炭素膜群１６により、幹状炭素膜１４の姿勢が安定化しかつ電気的コンタクトも確保できるので、電子を長期にわたり安定放出させることができる。   Further, the branched carbon film group 16 stabilizes the posture of the stem-like carbon film 14 and can ensure electrical contact, so that electrons can be stably emitted over a long period of time.

以下、ＳＥＭ写真像等を参照して実施の形態の炭素膜の構造を詳細に説明する。   Hereinafter, the structure of the carbon film of the embodiment will be described in detail with reference to an SEM photograph image and the like.

[炭素膜構造]
図２から図９までに実施の形態の炭素膜を撮影した一連のＳＥＭ（走査型電子顕微鏡）写真像、図１０にＴＥＭ（透過型電子顕微鏡）写真像を示す。 [Carbon film structure]
2 to 9 show a series of SEM (scanning electron microscope) photographic images obtained by photographing the carbon film of the embodiment, and FIG. 10 shows a TEM (transmission electron microscope) photographic image.

図２に実施の形態に係る炭素膜の平面視ＳＥＭ写真像、図３にさらに拡大ＳＥＭ写真像を示す。これのＳＥＭ写真像中に多数の炭素膜集合単位１２が撮影されている。写真像中に大きさ単位が記入されている。図１では１０μｍ単位で、図２では１μｍ単位が記入されている。図１、図２ではこれら炭素膜集合単位１２は全体的にほぼ均等な間隔で成膜されている。炭素膜集合単位１２は直径が数μｍから１０数μｍ以上である。図２、図３の平面視のＳＥＭ写真像からは炭素膜集合単位１２を構成する幹状炭素膜１４と枝状炭素膜群１６のうち、枝状炭素膜群１６の平面形状を確認することができるが幹状炭素膜１４は針状であるからその形状を確認することはできない。   FIG. 2 shows a plan view SEM photograph image of the carbon film according to the embodiment, and FIG. 3 further shows an enlarged SEM photograph image. In this SEM photograph image, a large number of carbon film aggregate units 12 are photographed. The unit of measure is entered in the photographic image. In FIG. 1, a unit of 10 μm is entered, and in FIG. 2, a unit of 1 μm is entered. In FIG. 1 and FIG. 2, these carbon film aggregate units 12 are formed at almost equal intervals as a whole. The carbon film aggregate unit 12 has a diameter of several μm to 10 or more μm. 2 and 3, the planar shape of the branched carbon film group 16 among the trunk carbon film 14 and the branched carbon film group 16 constituting the carbon film aggregate unit 12 is confirmed from the SEM photographic images in plan view. However, since the stem-like carbon film 14 has a needle shape, its shape cannot be confirmed.

図４ないし図７に上記炭素膜集合単位１２のやや斜め方向から視たＳＥＭ写真像を示す。写真像中に大きさ単位が記入されている。図４では１０μｍ単位、図５では１０μｍ単位、図６では１μｍ単位、図７では１０μｍ単位で、それら単位が記入されている。これらＳＥＭ写真像から炭素膜集合単位１２の高さは幹状炭素膜１４を除いて１０数μｍから数１０μｍである。幹状炭素膜１４の周囲に枝状炭素膜群１６がまとわりついている状態を確認することができる。また、炭素膜集合単位１２が所定間隔で配置されていることを確認することができる。   4 to 7 show SEM photographic images of the carbon film aggregate unit 12 viewed from a slightly oblique direction. The unit of measure is entered in the photographic image. These units are entered in units of 10 μm in FIG. 4, in units of 10 μm in FIG. 5, in units of 1 μm in FIG. 6, and in units of 10 μm in FIG. From these SEM photographic images, the height of the carbon film aggregate unit 12 is from several tens of μm to several tens of μm excluding the stem-like carbon film 14. A state in which the branched carbon film group 16 is clinging around the trunk-like carbon film 14 can be confirmed. Further, it can be confirmed that the carbon film aggregate units 12 are arranged at a predetermined interval.

図８、図９に幹状炭素膜１４を撮影したＳＥＭ写真像を示す。写真像中に大きさ単位が記入されている。図８では１μｍ単位で、図９では１μｍ単位が記入されている。幹状炭素膜１４は先端に向けて半径が小さくなってエミッションサイトとして有効な先端形状を備えていることが示されている。幹状炭素膜１４は枝状炭素膜群１６から突出している状態を確認することができる。この幹状炭素膜１４は先端に向かうにつれてその半径が小さくなっていることを確認することができる。   8 and 9 show SEM photograph images of the trunk carbon film 14 taken. The unit of measure is entered in the photographic image. In FIG. 8, 1 μm unit is entered, and in FIG. 9, 1 μm unit is entered. It is shown that the stem-like carbon film 14 has a tip shape effective as an emission site with a radius decreasing toward the tip. The state in which the trunk-like carbon film 14 protrudes from the branch-like carbon film group 16 can be confirmed. It can be confirmed that the radius of the trunk-like carbon film 14 decreases toward the tip.

図１０に幹状炭素膜１４の先端近傍の一部のＴＥＭ写真像を示す。図１０の幹状炭素膜１４の先端近傍はＴＥＭ写真像の撮影の都合でその全体が示されていないが、図１１に幹状炭素膜１４の先端近傍の全体を模式的に示す。また、図１０のＴＥＭ写真像に示す幹状炭素膜１４の先端近傍の一部を図１１の円Ｑで囲む部分で簡略に拡大して示す。図１０で確認することができ、また図１１で示されているように、幹状炭素膜１４はその外周面回りを当該先端に向けて螺旋状となって形成された筋状段差部１８を有する。これら螺旋状になって連続する筋状段差部１８にはシート状、ウォール状、針状等の炭素膜２０が成膜されている。特に幹状炭素膜１４の膜途中から下部に向けてこのシート状、ウォール状、針状等の炭素膜２０が大きくなっており、これらは枝状炭素膜群１６を構成するものと考えられる。これら筋状段差部１８や炭素膜２０はエミッションサイトとして有効な形状を備える。   FIG. 10 shows a TEM photographic image of part of the vicinity of the tip of the stem-like carbon film 14. Although the whole of the vicinity of the tip of the stem-like carbon film 14 in FIG. 10 is not shown for convenience of taking a TEM photograph image, the whole of the vicinity of the tip of the stem-like carbon film 14 is schematically shown in FIG. Further, a part near the tip of the stem-like carbon film 14 shown in the TEM photographic image of FIG. 10 is simply enlarged and shown by a part surrounded by a circle Q of FIG. As can be seen in FIG. 10, and as shown in FIG. 11, the stem-like carbon film 14 has a stair-like step portion 18 formed in a spiral shape around its outer peripheral surface toward the tip. Have. A carbon film 20 having a sheet shape, a wall shape, a needle shape, or the like is formed on the streak-like stepped portions 18 that are continuous in a spiral shape. In particular, the sheet-like, wall-like, and needle-like carbon films 20 increase from the middle of the trunk-like carbon film 14 toward the lower part, and these are considered to constitute the branched carbon film group 16. These streaky step portions 18 and the carbon film 20 have a shape effective as an emission site.

図１１の円で囲む部分の拡大図において、幹状炭素膜１４はグラフェンシートが複数層重なって螺旋状となった内部中空の針状炭素膜単位…１９ｎ−１、１９ｎ，１９ｎ＋１…が先端に向けて多数段に積み重なって構成され、各針状炭素膜単位…１９ｎ−１、１９ｎ，１９ｎ＋１…の境界で螺旋状の筋状段差部１８が形成されている。この図１１で示すように筋状段差部１８はエミッションサイトとして有効な形状を有する。   In the enlarged view of the portion surrounded by a circle in FIG. 11, the stem-like carbon film 14 has a hollow inner needle-like carbon film unit 19n−1, 19n, 19n + 1. A spiral stair-like step 18 is formed at the boundary of each acicular carbon film unit... 19n-1, 19n, 19n + 1. As shown in FIG. 11, the streaky step 18 has a shape effective as an emission site.

[炭素膜のＩＶ特性]
図１２は上記炭素膜のＩＶ特性を示す図である。図１２においてＡは従来のカーボンナノチューブによるＩＶ特性曲線、Ｂは筋状段差部が無い針状炭素膜によるＩＶ特性曲線、Ｃは実施の形態の上記螺旋状の筋状段差部付きの炭素膜によるＩＶ特性曲線である。これらＩＶ特性曲線を比較して明らかであるように、いずれのＩＶ特性曲線も電界放射を開始する電圧（閾値）はさほど相違しないが、ＩＶ特性曲線の傾きや形状が大きく相違している。すなわち、カーボンナノチューブのＩＶ特性曲線Ａでは所望するエミッション電流を得るための印加電圧が大きい曲線であり、筋状段差部が無い針状炭素膜によるＩＶ特性曲線Ｂでは所望のエミッション電流を得る印加電圧はカーボンナノチューブの場合よりも低くなる曲線であり、実施の形態の上記螺旋状の筋状段差部付きの炭素膜によるＩＶ特性曲線Ｃでは所望するエミッション電流を得るための印加電圧が最も低く済む曲線である。したがって、ＩＶ特性曲線は実施の形態の炭素膜が最も良く、そのＩＶ特性が大きく向上した炭素膜であることが明らかである。 [IV characteristics of carbon film]
FIG. 12 is a diagram showing IV characteristics of the carbon film. In FIG. 12, A is an IV characteristic curve by a conventional carbon nanotube, B is an IV characteristic curve by a needle-like carbon film having no streak-like stepped portion, and C is by a carbon film with a spiral streaky step-like portion of the embodiment. It is an IV characteristic curve. As apparent from comparison of these IV characteristic curves, the voltage (threshold value) at which field emission starts is not very different in any IV characteristic curve, but the inclination and shape of the IV characteristic curve are greatly different. That is, in the IV characteristic curve A of the carbon nanotube, the applied voltage for obtaining a desired emission current is a large curve, and in the IV characteristic curve B of the acicular carbon film having no streaky step portion, the applied voltage for obtaining the desired emission current. Is a curve that is lower than in the case of carbon nanotubes, and in the IV characteristic curve C by the carbon film with the spiral streaky step portion of the embodiment, a curve that requires the lowest applied voltage to obtain a desired emission current is required. It is. Therefore, it is clear that the carbon film of the embodiment has the best IV characteristic curve, and the IV film has a greatly improved IV characteristic.

以上において、実施の形態の炭素膜構造においては、鋭利な先端を備えた幹状炭素膜により電界放射させる電子放出源として、電界放射電流の調整範囲が極めて広いため、各種のデバイス、装置等への応用範囲が大きく拡充させることができるものとなる。特に、カーボンナノチューブと同等程度に直径に対する高さの比率であるアスペクト比をもっているにもかかわらず、枝状炭素膜群により先端がゆらぎにくく、基板上に機械的に支持して高い安定性があり、基板との電気的コンタクトを確保することができ、カーボンナノチューブとは異なって密集が制約され電界集中が起きやすく電子放出特性に優れた炭素膜構造である。   As described above, in the carbon film structure of the embodiment, the field emission current adjustment range is extremely wide as an electron emission source that emits electric field by a stem-like carbon film having a sharp tip. The application range of can be greatly expanded. In particular, despite having an aspect ratio, which is the ratio of the height to the diameter, similar to that of carbon nanotubes, the tip of the branched carbon film group is less likely to fluctuate, and it is mechanically supported on the substrate and has high stability. Unlike carbon nanotubes, it is possible to ensure electrical contact with the substrate, and the carbon film structure is excellent in electron emission characteristics because it is densely constrained and electric field concentration tends to occur.

[炭素膜の製造]
図１３を参照して炭素膜の製造例を説明する。図１３は成膜装置の概略構成図である。 [Manufacture of carbon film]
A manufacturing example of the carbon film will be described with reference to FIG. FIG. 13 is a schematic configuration diagram of a film forming apparatus.

真空成膜室２１内に一対の平行平板電極２２，２４を対向配置する。真空成膜室２１はガス導入系２６と真空排気系２８とを備える。直流電源３０の負極側を上側の平行平板電極２２に接続し、直流電源３０の正極側を接地する。下側の平行平板電極２４を接地する。上側の平板電極２２をモリブデン材で構成する。上側の平板電極２２近傍にＳＵＳ３２を配置する。   A pair of parallel plate electrodes 22, 24 are arranged opposite to each other in the vacuum film forming chamber 21. The vacuum film formation chamber 21 includes a gas introduction system 26 and a vacuum exhaust system 28. The negative side of the DC power source 30 is connected to the upper parallel plate electrode 22 and the positive side of the DC power source 30 is grounded. The lower parallel plate electrode 24 is grounded. The upper plate electrode 22 is made of molybdenum material. An SUS 32 is disposed in the vicinity of the upper plate electrode 22.

真空成膜室２１に導入するガスは水素とメタンとの混合ガスである。下側の平行平板電極２４上に基板３４を搭載する。   The gas introduced into the vacuum film forming chamber 21 is a mixed gas of hydrogen and methane. A substrate 34 is mounted on the lower parallel plate electrode 24.

まず、真空成膜室２１を真空排気系２８で排気しガス導入系２６から水素ガスを導入しその内圧を３０ｔｏｒｒ程度に徐々に減圧し、真空成膜室２１内圧力を３０ｔｏｒｒにする。真空成膜室２１内圧が３０ｔｏｒｒになると、その圧力を５ないし２５分程度維持する。   First, the vacuum film formation chamber 21 is evacuated by the vacuum exhaust system 28, hydrogen gas is introduced from the gas introduction system 26, the internal pressure is gradually reduced to about 30 torr, and the internal pressure of the vacuum film formation chamber 21 is set to 30 torr. When the internal pressure of the vacuum film forming chamber 21 reaches 30 torr, the pressure is maintained for about 5 to 25 minutes.

この場合、直流電源３０の印加により、両平板電極２２，２４間にプラズマ３６を発生させ、電流を２．５Ａ程度にまで徐々に増加させ、真空成膜室２１内圧が３０ｔｏｒｒになるときには電流を２．５Ａに維持する。こうして基板３４上の酸化物を除去する。   In this case, the plasma 36 is generated between the plate electrodes 22 and 24 by the application of the DC power source 30 and the current is gradually increased to about 2.5 A. When the internal pressure of the vacuum film formation chamber 21 becomes 30 torr, the current is increased. Maintain at 2.5A. Thus, the oxide on the substrate 34 is removed.

次いで、真空成膜室１０内にガス導入系２６から水素ガスとメタンガスとの混合ガスを導入し真空成膜室２１内圧を７５ｔｏｒｒ程度にまで徐々に増大し、真空成膜室２１内圧が７５ｔｏｒｒになると、この内圧を２時間程度維持する。同時に直流電源３０により電流を２．５Ａから６Ａ程度にまで徐々に増加させ、６Ａに到達すると、その電流を２時間維持する。メタンガスに代えて他の炭素を含むガス、例えば、アセチレン、エチレン、プロパン、プロピレン等のガス、あるいは一酸化炭素、二酸化炭素、エタノールやアセトンの有機溶剤の蒸気を用いることができる。   Next, a mixed gas of hydrogen gas and methane gas is introduced into the vacuum film formation chamber 10 from the gas introduction system 26 to gradually increase the internal pressure of the vacuum film formation chamber 21 to about 75 torr, and the internal pressure of the vacuum film formation chamber 21 is increased to 75 torr. Then, this internal pressure is maintained for about 2 hours. At the same time, the current is gradually increased from 2.5 A to about 6 A by the DC power source 30 and when 6 A is reached, the current is maintained for 2 hours. Instead of methane gas, other carbon-containing gas, for example, gas such as acetylene, ethylene, propane, or propylene, or vapor of organic solvent such as carbon monoxide, carbon dioxide, ethanol, or acetone can be used.

その結果、基板３４上に発生するプラズマ３６により、基板温度が９００℃ないし１１５０℃程度となって、メタンガスが分解され、基板表面に上記説明した炭素膜が成膜される。   As a result, the plasma 36 generated on the substrate 34 brings the substrate temperature to about 900 ° C. to 1150 ° C., methane gas is decomposed, and the carbon film described above is formed on the substrate surface.

１０ 基板
１２ 炭素膜集合単位
１４ 幹状炭素膜
１６ 枝状炭素膜群
１８ 筋状段差部 DESCRIPTION OF SYMBOLS 10 Substrate 12 Carbon film assembly unit 14 Trunk carbon film 16 Branched carbon film group 18 Streaky step portion

Claims (5)

基板上に形成される炭素膜であって、この炭素膜は複数の炭素膜集合単位からなり、前記炭素膜集合単位は幹状炭素膜とこの幹状炭素膜の途中から炭素膜の下部にかけて前記幹状炭素膜を囲むように成膜された枝状炭素膜群とからなることを特徴とする炭素膜構造。 A carbon film formed on a substrate, the carbon film comprising a plurality of carbon film aggregate units, the carbon film aggregate unit being a trunk carbon film and the middle of the trunk carbon film from the middle of the carbon film to the bottom of the carbon film, A carbon film structure comprising a branch-like carbon film group formed so as to surround a trunk-like carbon film. 請求項１に記載の炭素膜構造において、前記幹状炭素膜は、グラフェンシートが多層に重なって内部中空となっていて、かつ、先端に向けて半径が小さくなる針状形状を備えることを特徴とする炭素膜構造。 2. The carbon film structure according to claim 1, wherein the stem-like carbon film has a needle-like shape in which a graphene sheet is overlapped in multiple layers to be hollow inside and a radius decreases toward a tip. And carbon film structure. 請求項１に記載の炭素膜構造において、前記幹状炭素膜は、その先端近傍の外周面周りに当該先端に向けて連続している筋状段差部を有することを特徴とする炭素膜構造。 2. The carbon film structure according to claim 1, wherein the stem-like carbon film has a stair-like stepped portion that is continuous toward the tip around an outer peripheral surface in the vicinity of the tip. 3. 請求項３に記載の炭素膜構造において、前記筋状段差部が、上記先端近傍の外周面周りを当該先端に向けて螺旋状になって連続していることを特徴とする炭素膜構造。 4. The carbon film structure according to claim 3, wherein the streaky stepped portion is continuous in a spiral shape around the outer peripheral surface in the vicinity of the tip toward the tip. 請求項４に記載の炭素膜構造において、前記筋状段差部はグラフェンシートが複数層重なって螺旋状となった内部中空の針状炭素膜単位が先端に向けて多数段に積み重なって構成され、各針状炭素膜単位の境界で螺旋状に形成されているものであることを特徴とする炭素膜。 The carbon film structure according to claim 4, wherein the streaky stepped portion is configured by stacking a plurality of graphene sheets in a spiral shape with a plurality of graphene sheets stacked in a spiral toward the tip. A carbon film characterized by being formed in a spiral shape at the boundary of each acicular carbon film unit.
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JP2007055856A (en) * 2005-08-25 2007-03-08 Dialight Japan Co Ltd Carbon film, electron releasing source, and electric field emission type illumination lamp
JP4565089B2 (en) * 2005-09-05 2010-10-20 株式会社ピュアロンジャパン Carbon film and field emission electron emission source

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JP2005190721A (en) * 2003-12-24 2005-07-14 Jfe Engineering Kk Carbon nanotube installation base
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JP2007055856A (en) * 2005-08-25 2007-03-08 Dialight Japan Co Ltd Carbon film, electron releasing source, and electric field emission type illumination lamp
JP4565089B2 (en) * 2005-09-05 2010-10-20 株式会社ピュアロンジャパン Carbon film and field emission electron emission source

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