JP4829634B2 - Method for forming catalyst and method for producing carbon film using the same - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 68
- 229910052799 carbon Inorganic materials 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title description 14
- 239000000758 substrate Substances 0.000 claims description 97
- 238000000137 annealing Methods 0.000 claims description 50
- 239000010419 fine particle Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 230000001737 promoting effect Effects 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 2
- 230000005684 electric field Effects 0.000 description 63
- 239000002041 carbon nanotube Substances 0.000 description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 27
- 239000002245 particle Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 21
- 238000009826 distribution Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
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- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 239000002121 nanofiber Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Description
本発明は、カーボンナノファイバ等の炭素膜を成長させるのに好適な触媒を形成する方法およびその触媒を用いた炭素膜の製造方法に関する。 The present invention relates to a method for forming a catalyst suitable for growing a carbon film such as carbon nanofiber, and a method for producing a carbon film using the catalyst.
電子放出材料にカーボンナノファイバ等の炭素膜を用いることが行われている（例えば、特許文献１参照。）。このような炭素膜、例えば、カーボンナノチューブを製造する方法としては、例えば、熱エネルギが付与されている雰囲気中に、基板上に炭素の成膜を促進する物質である触媒金属を配置し、この触媒金属に炭素を含むガスを接触させることによりそのガスを分解して炭素膜を成膜する熱ＣＶＤ法が提案されている。 A carbon film such as carbon nanofiber is used as an electron emission material (for example, refer to Patent Document 1). As a method for producing such a carbon film, for example, a carbon nanotube, for example, a catalyst metal which is a substance that promotes carbon film formation is placed on a substrate in an atmosphere to which thermal energy is applied. A thermal CVD method has been proposed in which a gas containing carbon is brought into contact with a catalytic metal to decompose the gas to form a carbon film.
このような熱ＣＶＤ法で基板上に、カーボンナノチューブを高密度に均一に形成するためには、触媒となる金属を、できるだけ粒径の揃った微粒子にして基板上に均一な密度で分散させる必要がある。
そこで、本発明は、炭素膜の成長を促進する触媒を、高い密度で均一に形成できる方法およびそれを用いた炭素膜の製造方法を提供することを解決すべき課題としている。 Therefore, the present invention has an object to be solved by providing a method for uniformly forming a catalyst for promoting the growth of a carbon film at a high density and a method for producing a carbon film using the same.
本発明の触媒の形成方法は、炭素膜の成長を促進する作用を有する触媒金属膜を成長させた基板に、熱エネルギおよび電気的エネルギを付与して前記触媒金属膜を微粒子化する触媒の形成方法であって、
前記電気的エネルギの付与を、前記基板に対する電圧の印加により行ない、
前記電圧が、放電現象が発生しない電圧であることを特徴とするものである。
Forming a catalyst of the present invention, formation of the catalyst fine particles on a substrate to grow the catalytic metal film, by applying thermal energy and electrical energy of the catalytic metal film having the effect of promoting the growth of the carbon film A method,
Applying the electrical energy by applying a voltage to the substrate;
The voltage is a voltage that does not cause a discharge phenomenon .
触媒金属には、例えば、鉄、コバルト、ニッケル等の金属がある。 Examples of the catalyst metal include metals such as iron, cobalt, and nickel.
本発明によると、熱エネルギを付与して膜状の触媒金属を微粒子化するに際して、電気的エネルギを付与して行うので、触媒金属の微粒子の粒径および分布密度を均一に制御することができる。 According to the present invention, since the thermal energy is applied to form the catalyst metal in the form of a fine particle, the electric energy is applied so that the particle size and distribution density of the catalyst metal fine particles can be uniformly controlled. .
したがって、この触媒金属の微粒子を起点として炭素膜を製造することにより、均一な径でかつ均一な長さの炭素膜を成長させて製造することが可能となる。 Therefore, by producing a carbon film starting from the catalyst metal fine particles, it is possible to grow and produce a carbon film having a uniform diameter and a uniform length.
熱エネルギを付与する態様としては、アニール処理であるのが好ましい。 As an aspect for applying thermal energy, an annealing process is preferable.
この印加電圧は、負電圧、正電圧のいずれでもよい。 This applied voltage may be either a negative voltage or a positive voltage.
電圧の印加は、少なくとも膜状の触媒金属が微粒子化するまでの期間に亘って行なうのが好ましい。 The voltage application is preferably performed over at least a period until the film-like catalyst metal is finely divided.
基板は、触媒金属膜の下層に、アルミニウムなどの下地金属膜を形成したものであってもよい。 The substrate may be one in which a base metal film such as aluminum is formed below the catalyst metal film.
炭素膜には、カーボンナノチューブ、カーボンナノホーン、カーボンナノコーン、カーボンナノバンブ、グラファイトナノファイバを含むことができる。 The carbon film can include carbon nanotubes, carbon nanohorns, carbon nanocones, carbon nanobumps, and graphite nanofibers.
炭素を含むガスには、例えば、アセチレン、エチレン、メタン、プロパン、プロピレン等がある。また、常温・常圧下においては気体でなくともカーボンファイバの成膜条件（圧力・温度など）において気体であれば良く、メタノールやエタノールをはじめとするアルコール類やアセトンやベンゼンなどの有機溶剤などを用いることができる。 Examples of the gas containing carbon include acetylene, ethylene, methane, propane, and propylene. Also, at normal temperature and normal pressure, it is not necessary to use gas as long as the carbon fiber film formation conditions (pressure, temperature, etc.) are sufficient, such as alcohols such as methanol and ethanol, and organic solvents such as acetone and benzene. Can be used.
本発明によれば、触媒金属を、粒径および分布密度が均一な微粒子にすることが可能となる。 According to the present invention, the catalyst metal can be made into fine particles having a uniform particle size and distribution density.
かかる微粒子の触媒金属を用いるとともに、電気的エネルギを付与して炭素膜の成膜をアシストすることにより、炭素膜の成膜効率が向上し、かつ成膜速度、膜厚および膜質の制御が可能となる。 By using such fine particulate catalyst metal and applying electric energy to assist the formation of the carbon film, the film formation efficiency of the carbon film can be improved, and the film formation speed, film thickness and film quality can be controlled. It becomes.
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触媒の形成方法およびそれを用いた炭素膜の製造方法を説明する。 Hereinafter, a method for forming a catalyst according to an embodiment of the present invention and a method for manufacturing a carbon film using the same will be described with reference to the accompanying drawings.
図１は、本発明方法の実施に用いる製造装置の一例である熱ＣＶＤ装置を示す概略構成図である。 FIG. 1 is a schematic configuration diagram showing a thermal CVD apparatus which is an example of a manufacturing apparatus used for carrying out the method of the present invention.
同図において、２０は石英管チャンバである。石英管チャンバ２０の内部には一対の平行平板電極２２，２４が対向配置されている。下側の平行平板電極２４は、アルミナ２４ａに、電極２４ｂおよび耐熱性の絶縁材としての石英板３４が埋設されている。 In the figure, 20 is a quartz tube chamber. Inside the quartz tube chamber 20, a pair of parallel plate electrodes 22, 24 are arranged to face each other. In the lower parallel plate electrode 24, an electrode 24b and a quartz plate 34 as a heat-resistant insulating material are embedded in alumina 24a.
２６はガス導入管、２８は排気管、３０は電気炉、３２は直流電源である。 26 is a gas introduction pipe, 28 is an exhaust pipe, 30 is an electric furnace, and 32 is a DC power source.
直流電源３２の負極側が下側平行平板電極２４に接続され、直流電源３２の正極側は接地されている。上側平行平板電極２２は接地されている。 The negative side of the DC power source 32 is connected to the lower parallel plate electrode 24, and the positive side of the DC power source 32 is grounded. The upper parallel plate electrode 22 is grounded.
下側平行平板電極２４のアルミナ２４ａ上にはシリコンウエハ、石英ガラス、等からなる基板１０が搭載されている。 On the alumina 24a of the lower parallel plate electrode 24, a substrate 10 made of silicon wafer, quartz glass, or the like is mounted.
基板１０と電極２４との間に絶縁部材である石英板３４を挟み込むことにより基板１０を電極２４から電気的に絶縁した状態におき、この絶縁状態で基板１０に異常放電を発生させずに高電界、例えば基板１０と電極２２との距離を短く設定したり、および／あるいは直流電源３２の電圧を高く設定したりして高電界、を印加することができるようになっている。 A quartz plate 34, which is an insulating member, is sandwiched between the substrate 10 and the electrode 24 so that the substrate 10 is electrically insulated from the electrode 24. A high electric field can be applied by setting the electric field, for example, the distance between the substrate 10 and the electrode 22 short, and / or setting the voltage of the DC power supply 32 high.
この実施形態の触媒の形成方法は、炭素膜の成長を促進する作用を有する触媒金属膜を、電子ビーム物理蒸着（ＥＢ−ＰＶＤ）法、スパッタリング法等によって成長させた基板１０を、上記熱ＣＶＤ装置を用いて熱エネルギおよび電気的エネルギを付与して触媒金属膜を微粒子化するものである。 In the catalyst forming method of this embodiment, a substrate 10 on which a catalytic metal film having an action of promoting the growth of a carbon film is grown by an electron beam physical vapor deposition (EB-PVD) method, a sputtering method or the like is used. A catalyst metal film is made into fine particles by applying thermal energy and electrical energy using an apparatus.
熱エネルギの付与は、真空中（減圧下）における電気炉３０による加熱処理、すなわち、熱アニール処理として行なわれる。 The application of thermal energy is performed as a heat treatment by the electric furnace 30 in a vacuum (under reduced pressure), that is, a thermal annealing treatment.
電気的エネルギの付与は、一対の平行平板電極２２，２４間に、直流電源３２によって電圧を印加することにより行なわれる。 The application of electrical energy is performed by applying a voltage between the pair of parallel plate electrodes 22 and 24 by a DC power source 32.
この実施形態では、一方の電極２４に直流電源３２の負極側を接続し、該直流電源３２の正極側を接地するとともに、他方の電極２２を接地する。 In this embodiment, the negative electrode side of the DC power source 32 is connected to one electrode 24, the positive electrode side of the DC power source 32 is grounded, and the other electrode 22 is grounded.
一方、電極２４上に、触媒金属膜を成長させた基板１０を搭載して該基板１０に負電圧を印加しておく。この場合、上記雰囲気内にはプラズマ等の放電が発生しない条件とする。そのため、減圧圧力、雰囲気温度、印加電圧値が調整される。 On the other hand, a substrate 10 on which a catalytic metal film is grown is mounted on the electrode 24, and a negative voltage is applied to the substrate 10. In this case, the atmosphere is set to a condition in which discharge of plasma or the like does not occur. Therefore, the reduced pressure, the ambient temperature, and the applied voltage value are adjusted.
直流電源３２からの基板１０に印加する電圧のモードとしてはパルス波形の電圧印加モード、直流電圧の印加モードのいずれでもよく、プラズマが発生しない電圧以下であればよい。 The mode of the voltage applied to the substrate 10 from the DC power supply 32 may be either a voltage application mode of a pulse waveform or a DC voltage application mode, as long as the voltage does not generate plasma.
この実施形態の触媒の形成方法は、触媒金属膜を成長させた基板を、熱ＣＶＤ装置を用いて真空中で熱アニール処理する際に、直流電源によって基板１０に電界を印加するものであり、これによって、触媒金属を微粒子化できるとともに、後述の実施例で示すように、金属触媒の微粒子の粒径および分布密度を均一に制御することができるものである。 The method for forming a catalyst of this embodiment is to apply an electric field to the substrate 10 by a DC power source when a substrate on which a catalytic metal film is grown is subjected to a thermal annealing process in a vacuum using a thermal CVD apparatus. As a result, the catalyst metal can be made into fine particles and the particle size and distribution density of the fine particles of the metal catalyst can be uniformly controlled as shown in Examples described later.
次に、この実施形態の炭素膜の製造法について説明する。 Next, a method for manufacturing the carbon film of this embodiment will be described.
この実施形態の炭素膜の製造方法は、触媒の形成工程と炭素膜の成膜工程とを備えており、上記触媒の形成方法によって、触媒が形成された基板を用いて、熱ＣＶＤ法によって炭素膜を成膜するものであって、その際に、電気的エネルギを付与して炭素膜の成膜をアシストするものである。 The method for producing a carbon film of this embodiment includes a catalyst forming step and a carbon film forming step, and carbon is formed by thermal CVD using a substrate on which the catalyst is formed by the catalyst forming method. A film is formed, and at that time, electric energy is applied to assist the formation of the carbon film.
電気的エネルギの付与は、触媒の形成方法と同様に、上記熱ＣＤＶ装置において、一対の平行平板電極２２，２４間に、直流電源３２によって電圧を印加することにより行なわれる。 The application of electrical energy is performed by applying a voltage between the pair of parallel plate electrodes 22 and 24 by the DC power source 32 in the thermal CDV apparatus, as in the catalyst formation method.
この実施形態では、電界を印加しながら行なう上記熱アニール処理、すなわち、上記触媒の形成に引き続いて、炭素膜の成膜を行なうものであり、電気炉３０で加熱しながら減圧下で、アセチレン、エチレン、メタン、プロパン、プロピレン、一酸化炭素等の炭素を含むガスを導入する。 In this embodiment, the thermal annealing treatment performed while applying an electric field, that is, the formation of the catalyst is followed by the formation of a carbon film, and the acetylene, A gas containing carbon such as ethylene, methane, propane, propylene and carbon monoxide is introduced.
同時に、触媒形成のときと同様に、平行平板電極２２，２４間に、直流電源３２によって電圧を印加するものである。 At the same time, as in the catalyst formation, a voltage is applied between the parallel plate electrodes 22 and 24 by the DC power source 32.
この場合、プラズマ等の放電が発生しないように、減圧圧力、温度、印加電圧値が調整される。 In this case, the reduced pressure, temperature, and applied voltage value are adjusted so that discharge of plasma or the like does not occur.
以上の過程により、上記ガスを、基板１０上の微粒子化した触媒金属に接触させてガスを分解することにより基板１０上に炭素膜を成膜することができる。 Through the above process, a carbon film can be formed on the substrate 10 by bringing the gas into contact with the finely divided catalyst metal on the substrate 10 to decompose the gas.
なお、上記ガスに加えて、ヘリウム、アルゴン、水素等のキャリアガスあるいは希釈ガスを導入しても構わない。 In addition to the above gas, a carrier gas such as helium, argon, hydrogen, or a dilution gas may be introduced.
以上の製造においては、熱エネルギが付与された雰囲気内に直流電源３２からプラズマ等の放電が発生しない条件下で基板１０に負電圧を印加することにより、後述の実施例で示すように、触媒金属の触媒性能が向上し、成膜速度、膜厚、膜質が向上する。 In the above manufacturing, a negative voltage is applied to the substrate 10 under a condition in which no discharge of plasma or the like is generated from the DC power source 32 in an atmosphere to which thermal energy is applied. The catalytic performance of the metal is improved, and the film formation speed, film thickness, and film quality are improved.
なお、本発明の他の実施形態として、負電圧に代えて、正電圧を印加してもよい。 As another embodiment of the present invention, a positive voltage may be applied instead of the negative voltage.
以下、触媒の形成方法およびそれを用いた炭素膜の製造方法の具体例を説明する。 Hereinafter, specific examples of a method for forming a catalyst and a method for producing a carbon film using the catalyst will be described.
図２は、触媒の形成工程およびそれに引き続く炭素膜の成膜工程における時間と温度との関係を示す図である。 FIG. 2 is a diagram showing the relationship between time and temperature in the catalyst formation step and the subsequent carbon film formation step.
同図において、横軸が時間（分）を、縦軸が温度（℃）をそれぞれ示しており、第１段階が、触媒の形成工程を示し、第２段階が、炭素膜の成膜工程をそれぞれ示している。 In the figure, the horizontal axis indicates time (minutes) and the vertical axis indicates temperature (° C.), the first stage indicates the catalyst formation process, and the second stage indicates the carbon film formation process. Each is shown.
触媒の形成工程では、電界を印加しつつ、触媒金属膜を成長させた基板に対して熱アニール処理を実施するものであり、石英管チャンバ２０を、例えば、１０-3Ｐａ程度の真空を保った状態で基板１０全体を、例えば、７００℃程度の温度にまで徐々に昇温しその温度に達するとその状態に放置する。熱アニールの工程時間は、例えば、３０分間であるが、この工程時間は３０分間に限定されず、必要に応じて任意の工程時間に設定することができる。 In the catalyst formation process, thermal annealing is performed on the substrate on which the catalytic metal film is grown while applying an electric field, and the quartz tube chamber 20 is maintained at a vacuum of, for example, about 10 −3 Pa. In this state, the entire substrate 10 is gradually heated to a temperature of about 700 ° C., for example, and when that temperature is reached, it is left in that state. The process time of thermal annealing is, for example, 30 minutes, but this process time is not limited to 30 minutes, and can be set to an arbitrary process time as necessary.
熱処理はこの工程時間において基板１０の加熱温度を室温から７００℃に昇温する。加熱雰囲気は好ましくは真空であるが、真空中に限定されない。電界を印加しながら上記熱アニールを行なうことにより、基板１０上の触媒金属は膜状から粒径および分布密度が均一な微粒子状になる。 In the heat treatment, the heating temperature of the substrate 10 is raised from room temperature to 700 ° C. during this process time. The heating atmosphere is preferably a vacuum, but is not limited to a vacuum. By performing the thermal annealing while applying an electric field, the catalytic metal on the substrate 10 is changed from a film shape into fine particles having a uniform particle size and distribution density.
この触媒形成における電界印加の効果を確認するために、シリコン基板上に、鉄触媒の膜を、例えば、１０Åの膜厚に成膜した複数のサンプル基板を準備し、上記熱ＣＶＤ装置によって、図２のＡ２で示すように触媒形成の工程（第１段階）のみを行い、その際に、比較例として電極２４に印加される負電圧が０（ゼロ）Ｖでサンプル基板に電界が印加されない電界非印加モードと、実施例として電極２４に３００Ｖの負電圧が印加されてサンプル基板に電界が印加される電界印加モードとで触媒形成をそれぞれ行なった。 In order to confirm the effect of electric field application in this catalyst formation, a plurality of sample substrates each having an iron catalyst film formed on a silicon substrate to a film thickness of, for example, 10 mm are prepared. As shown by A2 in FIG. 2, only the catalyst formation step (first stage) is performed, and at that time, as a comparative example, the negative voltage applied to the electrode 24 is 0 (zero) V and no electric field is applied to the sample substrate. Catalyst formation was performed in the non-application mode and in the electric field application mode in which a negative voltage of 300 V was applied to the electrode 24 and an electric field was applied to the sample substrate as an example.
サンプル基板は、１０×１０ｍｍ角であり、２５０μｍ径の円形ドットが縦横の辺に２５０μｍの等間隔に並んだメタルマスクを使用し、電子ビーム物理蒸着法によって、鉄触媒膜を成膜した。 The sample substrate was a 10 × 10 mm square, and an iron catalyst film was formed by electron beam physical vapor deposition using a metal mask in which 250 μm diameter circular dots were arranged at equal intervals of 250 μm on the vertical and horizontal sides.
以上のようにして電界非印加モードで熱アニール処理して得られた比較例としてのサンプル基板および電界印加モードで熱アニール処理して得られた実施例としてのサンプル基板の表面を、ＡＦＭ（原子力間顕微鏡）で評価した。 As described above, the surface of the sample substrate as a comparative example obtained by the thermal annealing treatment in the electric field non-application mode and the sample substrate as the embodiment obtained by the thermal annealing treatment in the electric field application mode are represented by AFM (nuclear power). Evaluation).
なお、説明の簡略化のために電界非印加で熱アニールした比較例としてのサンプル基板１０を単に熱アニール基板、電界印加で熱アニールした実施例としてのサンプル基板を特に電界印加熱アニール基板と称する。 For the sake of simplification, the sample substrate 10 as a comparative example thermally annealed without application of an electric field is simply referred to as a thermal annealing substrate, and the sample substrate as an example subjected to thermal annealing with application of an electric field is particularly referred to as an electric field applied thermal annealing substrate. .
図３（ａ）は熱アニール基板のＡＦＭ写真像を、また、図３（ｂ）は電界印加熱アニール基板のＡＦＭ写真像を示す。 FIG. 3A shows an AFM photographic image of the thermal annealing substrate, and FIG. 3B shows an AFM photographic image of the electric field applied thermal annealing substrate.
図３（ａ）で示すように熱アニール基板上には幅３０ｎｍ程度、高さ１５ｎｍ程度の粗大な凸部が約１００ｎｍの粗い間隔で生成されていることを観察することができる。 As shown in FIG. 3A, it can be observed that coarse protrusions having a width of about 30 nm and a height of about 15 nm are generated on the thermal annealing substrate at a rough interval of about 100 nm.
また、図３（ｂ）で示すように電界印加熱アニール基板上には幅１０〜２０ｎｍ、高さ５〜１０ｎｍ程度の比較的小さい凸部が１０〜５０ｎｍの比較的密な間隔で細かく分散されて生成されていることを観察することができる。 Further, as shown in FIG. 3B, relatively small convex portions having a width of about 10 to 20 nm and a height of about 5 to 10 nm are finely dispersed at a relatively dense interval of 10 to 50 nm on the electric field applied thermal annealing substrate. Can be observed.
図３（ａ）（ｂ）を対比して判るように、電界印加熱アニール基板では、熱アニール基板と比較して、細かく分散した凸部が触媒の微粒子として１０倍以上の頻度で存在していることを確認することができる。このように電界印加熱アニール基板においては、電界印加効果によって、触媒金属の微粒子化が促進され、触媒の微粒子が多く生成され、触媒金属の触媒性能が向上する。 As can be seen by comparing FIGS. 3 (a) and 3 (b), in the electric field applied thermal annealing substrate, the finely dispersed convex portions are present as catalyst fine particles 10 times or more as compared with the thermal annealing substrate. Can be confirmed. As described above, in the electric field applied thermal annealing substrate, the effect of electric field application promotes the formation of fine particles of the catalyst metal, generates a large amount of fine particles of the catalyst, and improves the catalytic performance of the catalyst metal.
次に、シリコン基板上に、アルミニウムの下地膜と鉄触媒の膜とを、電子ビーム物理蒸着法によって、例えば、１００Åと２０Åの膜厚でそれぞれ成膜した複数のサンプル基板を準備し、電界非印加モードと電界印加モードとで熱アニール処理して触媒形成を行ない、得られたサンプル基板の表面をＦＥ−ＳＥＭおよびＡＦＭを用いて評価した。 Next, a plurality of sample substrates are prepared by depositing an aluminum base film and an iron catalyst film on a silicon substrate by electron beam physical vapor deposition, for example, with a thickness of 100 mm and 20 mm, respectively. A catalyst was formed by thermal annealing in the application mode and the electric field application mode, and the surface of the obtained sample substrate was evaluated using FE-SEM and AFM.
図４（ａ）は熱アニール基板のＳＥＭ写真像であり、図４（ｂ）は電界印加熱アニール基板のＳＥＭ写真像である。 FIG. 4A is an SEM photographic image of the thermal annealing substrate, and FIG. 4B is an SEM photographic image of the electric field applied thermal annealing substrate.
図４（ａ）では１辺が３０ｎｍ程度の多角形状に微粒子化した触媒を多く確認することができる。図４（ｂ）では直径が２０ｎｍ以下の丸みを帯びた形状の触媒を確認することができる。 In FIG. 4A, a large number of catalysts finely divided into polygonal shapes having a side of about 30 nm can be confirmed. In FIG. 4B, a round catalyst having a diameter of 20 nm or less can be confirmed.
この触媒の形状を、図５（ａ）（ｂ）のＡＦＭ写真像によりさらに詳細に示す。図５（ａ）は図４（ａ）に対応する写真像であり、この写真像から電界非印加モードで熱アニールした場合、図中点線で代表的に選択して囲む数個の触媒微粒子の粒径は直径１０ｎｍ以下〜８０ｎｍ以上の大きさの分布幅を持っている。図５（ｂ）は図４（ｂ）に対応する写真像であり、この写真像から、電界印加モードで熱アニールした場合、図中点線で代表的に選択して囲む数個の触媒微粒子の粒径は直径２０〜５０ｎｍ程度で揃っていることが判る。 The shape of this catalyst is shown in more detail by the AFM photographic images of FIGS. 5 (a) and 5 (b). FIG. 5 (a) is a photographic image corresponding to FIG. 4 (a). When thermal annealing is performed from this photographic image in the electric field non-application mode, several catalyst fine particles typically selected and surrounded by dotted lines in the figure are shown. The particle diameter has a distribution width of a diameter of 10 nm or less to 80 nm or more. FIG. 5 (b) is a photographic image corresponding to FIG. 4 (b). From this photographic image, when thermal annealing is performed in the electric field application mode, several catalyst fine particles that are typically selected and surrounded by dotted lines in the figure are shown. It can be seen that the particle diameters are approximately 20 to 50 nm in diameter.
上記ＡＦＭ写真像に基づいて粒度分布を解析した結果を、図６および図７に示す。 The results of analyzing the particle size distribution based on the AFM photographic image are shown in FIGS.
図６（ａ），（ｂ）は、図５（ａ），（ｂ）にそれぞれ対応するものであり、熱アニール基板および電界印加熱アニール基板の触媒微粒子の粒径に対する個数を示すものであり、横軸は粒径の範囲を、縦軸はその粒径の範囲に属する微粒子の個数をそれぞれ示している。 6 (a) and 6 (b) correspond to FIGS. 5 (a) and 5 (b), respectively, and indicate the number of catalyst fine particles with respect to the particle diameter of the thermal annealing substrate and the electric field application thermal annealing substrate. The horizontal axis represents the particle size range, and the vertical axis represents the number of fine particles belonging to the particle size range.
これらの図に示すように、電界印加モードで熱アニールした電界印加熱アニール基板の触媒微粒子の粒径の分布範囲は、１１ｎｍ〜５０ｎｍであるのに対して、電界非印加モードで熱アニールした熱アニール基板の触媒微粒子の粒径の分布範囲は、０ｎｍ〜１００ｎｍと大きくなっている。 As shown in these drawings, the particle size distribution range of the catalyst fine particles of the electric field applied thermal annealing substrate thermally annealed in the electric field application mode is 11 nm to 50 nm, whereas the heat annealed in the electric field non application mode. The distribution range of the particle size of the catalyst fine particles on the annealed substrate is as large as 0 nm to 100 nm.
すなわち、電界印加熱アニール基板の触媒微粒子の粒径の分布幅は、４０ｎｍ以内であるのに対して、熱アニール基板の触媒微粒子の粒径の分布幅は、１００ｎｍ以内と広く、熱アニール基板の触媒微粒子の粒径は、電界印加熱アニール基板の触媒微粒子の粒径に比べて、広い範囲に分布していることが判る。 That is, the distribution width of the particle size of the catalyst fine particles of the electric field applied thermal annealing substrate is within 40 nm, while the distribution width of the particle size of the catalyst fine particles of the thermal annealing substrate is as wide as 100 nm. It can be seen that the particle diameters of the catalyst fine particles are distributed over a wider range than the particle diameters of the catalyst fine particles of the electric field applied thermal annealing substrate.
更に、電界印加モードで熱アニールした電界印加熱アニール基板の触媒微粒子は、３１ｎｍ〜４０ｎｍの粒径のものが６割以上を占めるのに対して、電界非印加モードで熱アニールした熱アニール基板の触媒微粒子は、最も個数が多い５１ｎｍ〜６０ｎｍの粒径のものでも２割程度に留まり、幅広く分布している、すなわち、粒径のばらつきが大きいことが判る。 Further, the catalyst fine particles of the electric field applied thermal annealing substrate thermally annealed in the electric field application mode account for 60% or more of those having a particle diameter of 31 nm to 40 nm, whereas the thermal annealing substrate thermally annealed in the electric field non-application mode. It can be seen that the catalyst fine particles having the largest number of particles having a particle diameter of 51 nm to 60 nm remain at about 20% and are widely distributed, that is, the variation in particle diameter is large.
上記のように電界印加熱アニール基板の触媒微粒子は、その粒径が、３１ｎｍ〜４０ｎｍの範囲、すなわち、１０ｎｍの分布幅に収まるものが６割以上を占めている。 As described above, the fine particles of the catalyst applied to the electric field applied thermal annealing substrate occupy 60% or more of the particles having a particle diameter falling within the range of 31 nm to 40 nm, that is, within the distribution width of 10 nm.
このように電界印加熱アニール基板は、電界を印加しない熱アニール基板に比べて、触媒微粒子の粒径および分布密度が均一であることが判る。 Thus, it can be seen that the electric field applied thermal annealing substrate has a uniform particle size and distribution density of the catalyst fine particles as compared with the thermal annealing substrate to which no electric field is applied.
次に、図２における第１段階（触媒形成工程）および第２段階（成膜工程）を備える炭素膜の製造工程について説明する。 Next, a carbon film manufacturing process including the first stage (catalyst forming process) and the second stage (film forming process) in FIG. 2 will be described.
この炭素膜の製造工程においては、Ａ１に示すように、第１段階の触媒形成工程に引き続いて、触媒形成工程で基板１０上に生成した触媒の微粒子をカーボンナノチューブの成長起点としてカーボンナノチューブを成長させて成膜するものである。 In this carbon film production process, as shown in A1, following the first stage catalyst formation process, the carbon nanotubes are grown using the catalyst fine particles produced on the substrate 10 in the catalyst formation process as the carbon nanotube growth starting point. To form a film.
この成膜工程においては、電界を印加しつつ、例えば、チャンバ内圧力２００Ｐａで、例えば、７００℃の温度で炭素を含むガスとして例えばＣ2Ｈ2（アセチレンガス）を所要の流量、例えば１００ＳＣＣＭ以下の流量で導入し、そのガス雰囲気内でその温度をさらに約３０分間程度維持して化学的気相蒸着（ＣＶＤ）により成膜を行う。 In this film forming process, for example, C 2 H 2 (acetylene gas) is used as a gas containing carbon at a pressure of, for example, 700 ° C., for example, at a temperature of 700 ° C. while applying an electric field. The film is formed by chemical vapor deposition (CVD) while maintaining the temperature for about 30 minutes in the gas atmosphere.
成膜後は、冷却（自然冷却、強制冷却）する。成膜工程では触媒の微粒子にアセチレンガスが接触して分解され、その触媒の微粒子を成長起点としてカーボンナノチューブが基板１０上に成長する。 After film formation, cooling (natural cooling, forced cooling) is performed. In the film forming process, acetylene gas comes into contact with the fine particles of the catalyst to be decomposed, and carbon nanotubes grow on the substrate 10 using the fine particles of the catalyst as a growth starting point.
次に、上述の図３（ａ）に示される比較例としての電界非印加モードで形成されたサンプル基板および図３（ｂ）に示される実施例としての電界印加モードで形成されたサンプル基板について、電界非印加モードおよび電界印加モードでそれぞれカーボンナノチューブを製造し、ＳＥＭによって評価した。なお、このカーボンナノチューブの成膜条件は、触媒金属が膜厚１０Åの鉄触媒、原料ガスがＨｅ希釈の２０％のＣ2Ｈ2（アセチレンガス）、成膜温度が７００℃、ガス流量が１００ＳＣＣＭ、成膜圧力２００Ｐａ、成膜時間が３０分である。 Next, the sample substrate formed in the electric field non-application mode as the comparative example shown in FIG. 3A and the sample substrate formed in the electric field application mode as the embodiment shown in FIG. Carbon nanotubes were produced in the non-electric field application mode and the electric field application mode, respectively, and evaluated by SEM. The film formation conditions for the carbon nanotube are as follows: the catalyst metal is an iron catalyst having a thickness of 10 mm, the source gas is He diluted 20% C 2 H 2 (acetylene gas), the film formation temperature is 700 ° C., and the gas flow rate is 100 SCCM. The film forming pressure is 200 Pa and the film forming time is 30 minutes.
図７は電界非印加モードで製造した比較例としてのカーボンナノチューブ束の側面のＳＥＭ写真像である。図７（ａ）のＳＥＭ写真像からは基板上に直径２５０μｍ、高さ７０μｍのカーボンナノチューブ束が製造されていることを確認することができる。また、図７（ａ）の矩形枠部分を拡大して示す図７（ｂ）のＳＥＭ写真像からカーボンナノチューブ束を構成するカーボンナノチューブが粗な間隔で個々に成長していることを確認することができる。 FIG. 7 is an SEM photographic image of the side surface of a carbon nanotube bundle as a comparative example manufactured in the electric field non-application mode. From the SEM photograph image of FIG. 7A, it can be confirmed that a carbon nanotube bundle having a diameter of 250 μm and a height of 70 μm is manufactured on the substrate. Also, confirm that the carbon nanotubes constituting the carbon nanotube bundle are individually grown at rough intervals from the SEM photograph image of FIG. 7B showing the rectangular frame portion of FIG. Can do.
図８は電界印加モードで製造した実施例としてのカーボンナノチューブ束の側面のＳＥＭ写真像である。図８（ａ）のＳＥＭ写真像からは基板上に直径２５０μｍ、高さ２９０μｍのカーボンナノチューブ束が製造されていることを確認することができ、図８（ａ）の矩形枠部分を拡大して示す図８（ｂ）のＳＥＭ写真像からはカーボンナノチューブ束を構成するカーボンナノチューブが密な間隔でほぼ均一に成長していることを確認することができる。 FIG. 8 is a SEM photograph image of the side surface of the carbon nanotube bundle as an example manufactured in the electric field application mode. From the SEM photograph image of FIG. 8A, it can be confirmed that a carbon nanotube bundle having a diameter of 250 μm and a height of 290 μm is produced on the substrate, and the rectangular frame portion of FIG. From the SEM photographic image shown in FIG. 8B, it can be confirmed that the carbon nanotubes constituting the carbon nanotube bundle are grown almost uniformly at close intervals.
図７と図８の両ＳＥＭ写真像を比較して明らかであるように電界印加モードで製造されたカーボンナノチューブは、電界非印加モードで製造されたカーボンナノチューブよりも、垂直配向性および成長密度が飛躍的に増加し、成膜速度および膜厚が向上していることが判る。 As is clear from comparison between the SEM photographic images of FIGS. 7 and 8, the carbon nanotubes produced in the electric field application mode have a higher vertical alignment and growth density than the carbon nanotubes produced in the electric field non-application mode. It can be seen that the film formation rate and film thickness are improved dramatically.
次に、上述の図４（ａ）に示される比較例としての電界非印加モードで形成されたサンプル基板および図４（ｂ）に示される実施例としての電界印加モードで形成されたサンプル基板について、電界非印加モードおよび電界印加モードでそれぞれカーボンナノチューブを製造し、得られた基板をそれぞれ電子エミッタとして発光特性を評価した。なお、このカーボンナノチューブの成膜条件は、触媒が膜厚１００Åのアルミニウムの下地膜と膜厚２０Åの鉄触媒、原料ガスがＨｅ希釈の２０％のＣ2Ｈ2（アセチレンガス）、成膜温度が７００℃、ガス流量が１００ＳＣＣＭ、成膜圧力２００Ｐａ、成膜時間が３０分である。 Next, the sample substrate formed in the electric field non-application mode as the comparative example shown in FIG. 4A and the sample substrate formed in the electric field application mode as the embodiment shown in FIG. 4B. Carbon nanotubes were produced in the electric field non-application mode and electric field application mode, respectively, and the emission characteristics were evaluated using the obtained substrates as electron emitters. The carbon nanotube film forming conditions are as follows: the catalyst is an aluminum base film with a film thickness of 100 mm and the iron catalyst with a film thickness of 20 mm, the source gas is 20% C 2 H 2 (acetylene gas) diluted with He, and the film forming temperature. Is 700 ° C., the gas flow rate is 100 SCCM, the deposition pressure is 200 Pa, and the deposition time is 30 minutes.
図９（ａ）（ｂ）はそれぞれ熱アニール基板と電界印加熱アニール基板とをそれぞれ電子エミッタとし、これら基板上にそれぞれ成長したカーボンナノチューブから電界電子放出された電子の衝突により発光している各蛍光体基板の写真である。 9 (a) and 9 (b), each of the thermal annealing substrate and the electric field applied thermal annealing substrate is used as an electron emitter, and light is emitted by collision of electrons emitted from the carbon nanotubes grown on these substrates. It is a photograph of a phosphor substrate.
図９（ａ）（ｂ）を比較して、図９（ａ）の蛍光体基板の発光点数よりも図９（ｂ）の蛍光体基板の発光点数が多いことを確認することができる。 9A and 9B, it can be confirmed that the number of light emission points of the phosphor substrate of FIG. 9B is larger than the number of light emission points of the phosphor substrate of FIG. 9A.
上述のように、１０×１０ｍｍ角のサンプル基板に、２５０μｍ径の円形ドットが縦横の辺に２５０μｍの等間隔に並んだメタルマスクを使用して触媒膜を成膜したので、図９に示される１０×１０ｍｍ角の蛍光体基板の１辺には、カーボンナノチューブの束が、２０個形成されることになる。 As described above, a catalyst film is formed on a 10 × 10 mm square sample substrate using a metal mask in which 250 μm diameter circular dots are arranged at equal intervals of 250 μm on the vertical and horizontal sides, as shown in FIG. 20 bundles of carbon nanotubes are formed on one side of the 10 × 10 mm square phosphor substrate.
したがって、図９（ａ）の熱アニール基板による場合、蛍光体基板上の発光点数はカーボンナノチューブ束１本当たり１〜２点であると考えられる。一方、図９（ｂ）の電界印加熱アニール基板による場合、蛍光体基板上の発光点数はカーボンナノチューブ束１本当たり５〜６点であると考えられる。 Therefore, in the case of the thermal annealing substrate of FIG. 9A, the number of emission points on the phosphor substrate is considered to be 1 to 2 points per one carbon nanotube bundle. On the other hand, in the case of using the electric field applied thermal annealing substrate of FIG.
このように電界印加モードで製造された図９（ｂ）の電界印加熱アニール基板は、電界非印加モードで製造された図９（ａ）の熱アニール基板よりも、膜質が向上してエミッション特性が向上していることが判る。 The electric field applied thermal annealing substrate of FIG. 9B manufactured in the electric field application mode as described above has improved film quality and emission characteristics as compared with the thermal annealing substrate of FIG. 9A manufactured in the electric field non-application mode. It can be seen that is improved.
なお、図９（ａ）（ｂ）それぞれの写真中に見られる蛍光体基板上で特に明るく発光している発光点（図中矢印）は基板を測定治具に固定する際に受けた傷（凹凸箇所）や基板端部での電界集中による電界電子放出によると考えられる。 9A and 9B, the light emitting points (arrows in the figure) that emit light particularly brightly on the phosphor substrate seen in the respective photographs are scratches ( This is thought to be due to field electron emission due to electric field concentration at the uneven portion) or at the edge of the substrate.
上述の実施形態では、微粒子化した触媒金属を用いて熱ＣＶＤ法によって、カーボンナノチューブを製造したけれども、本発明の他の実施形態として、微粒子化した触媒金属を用いてプラズマＣＶＤや他の方法でカーボンナノチューブや他の炭素膜を製造してもよい。 In the above embodiment, carbon nanotubes are produced by thermal CVD using finely divided catalytic metal. However, as another embodiment of the present invention, plasma CVD or other methods using finely divided catalytic metal are used. Carbon nanotubes and other carbon films may be manufactured.
本発明は、上述した実施の形態に限定されるものではなく、特許請求の範囲に記載した範囲内で、種々な変更ないしは変形を含むものである。 The present invention is not limited to the above-described embodiment, and includes various changes or modifications within the scope described in the claims.
１０ 基板
１２ カーボンナノチューブ（炭素膜）
２０ 石英管チャンバ
２２，２４ 平行平板電極
２４ａ アルミナ
２４ｂ 電極
２６ ガス導入管
２８ 排気管
３０ 電気炉
３２ 直流電源
３４ 石英板
10 Substrate 12 Carbon nanotube (carbon film)
20 Quartz tube chambers 22, 24 Parallel plate electrode 24a Alumina 24b Electrode 26 Gas introduction tube 28 Exhaust tube 30 Electric furnace 32 DC power supply 34 Quartz plate
Claims (3)
前記電気的エネルギの付与を、前記基板に対する電圧の印加により行ない、前記電圧が、放電現象が発生しない電圧であることを特徴とする触媒の形成方法。 A method for forming a catalyst in which thermal energy and electrical energy are applied to a substrate on which a catalytic metal film having an action of promoting the growth of a carbon film is applied to make the catalytic metal film fine particles,
The method for forming a catalyst, wherein the electrical energy is applied by applying a voltage to the substrate, and the voltage is a voltage that does not cause a discharge phenomenon.
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