JP4536456B2 - Plasma chemical vapor deposition method - Google Patents
Plasma chemical vapor deposition method Download PDFInfo
- Publication number
- JP4536456B2 JP4536456B2 JP2004238251A JP2004238251A JP4536456B2 JP 4536456 B2 JP4536456 B2 JP 4536456B2 JP 2004238251 A JP2004238251 A JP 2004238251A JP 2004238251 A JP2004238251 A JP 2004238251A JP 4536456 B2 JP4536456 B2 JP 4536456B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- plasma
- chemical vapor
- substrate
- vapor deposition
- 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.)
- Active
Links
Description
本発明は、化学気相堆積（CVD:chemical vapor deposition)法を応用して、基板上に形成対象物（例えばカーボンナノチューブ）を堆積成長させるためのプラズマ化学気相堆積装置及び該装置を用いるプラズマ化学気相堆積方法に関する。 The present invention applies a chemical vapor deposition (CVD) method, a plasma chemical vapor deposition apparatus for depositing and growing an object to be formed (for example, carbon nanotube) on a substrate, and a plasma using the apparatus. The present invention relates to a chemical vapor deposition method.
プラズマ化学気相堆積法は今日、炭素膜等の各種膜の形成に利用されている。カーボンナノチューブ（以下、「ＣＮＴ」と称することがある。）の形成にも利用が試みられている。プラズマ化学気相堆積法は比較的低温下で形成対象物を堆積形成でき、高温に耐えられない低融点のガラス等からなる基板等上にも形成対象物を堆積形成できる利点がある。 Plasma chemical vapor deposition is currently used to form various films such as carbon films. An attempt has been made to form carbon nanotubes (hereinafter sometimes referred to as “CNT”). The plasma chemical vapor deposition method has an advantage that an object to be formed can be deposited at a relatively low temperature, and the object to be formed can be deposited on a substrate made of a low melting point glass that cannot withstand high temperatures.
ここでカーボンナノチューブ（ＣＮＴ）を例にとってみると、ＣＮＴは、一般に直径が１〜数十ナノメートルであるのに対して長さはそれよりも百倍以上長い構造を有し、また機械的に堅牢であり、大きな電流を流すことができる。このことから、ＣＮＴは各種分野において利用が試みられており、今日では、電界電子放出型ディスプレイ（FED:Field Emission Display) における電子源材料として期待されている。 Taking carbon nanotubes (CNTs) as an example, CNTs are generally 1 to several tens of nanometers in diameter, while their length is 100 times longer than that, and they are mechanically robust. A large current can flow. For this reason, CNTs have been tried to be used in various fields, and today, CNTs are expected as electron source materials in field emission displays (FEDs).
ＣＮＴをＦＥＤの電子源として利用するには、電子を放出するＣＮＴ端部に強い電界を印加しなければならず、そのためには、ＣＮＴを基板上に垂直に或いはできるだけ垂直に配向させて立ち上がらせる必要がある。 In order to use CNT as an electron source of FED, a strong electric field must be applied to the end of the CNT that emits electrons, and for that purpose, the CNT is raised vertically or vertically as much as possible. There is a need.
ＣＮＴを用いたＦＥＤはすでに試作されているが、こうしたＣＮＴの基板上への配向の方法としては、一般的には、別途製造した微粒子粉末状のＣＮＴを溶液に分散させた後、該溶液をＦＥＤ製造に要求される大きい基板上に塗布し、該塗膜に電界を印加してＣＮＴを直立させる方法が採用されている。 FEDs using CNTs have already been prototyped. Generally, as a method for aligning such CNTs on a substrate, after separately dispersing finely divided particulate CNTs in a solution, the solution is used. A method of applying the CNTs upright by applying an electric field to the coating film on a large substrate required for FED production is employed.
しかし、この方法ではＣＮＴが基板上に均一に分布し難く、配向性の点でもあまり良くなく、そのため、かかるＣＮＴを用いたＦＥＤにおいては画像の明るさにムラがあり、また、電界電子放出のために大きな電圧を必要としている。 However, this method makes it difficult for CNTs to be uniformly distributed on the substrate and is not very good in terms of orientation. Therefore, in an FED using such CNTs, there is unevenness in image brightness, and field electron emission In order to require a large voltage.
そこで一方では、マイクロ波放電、高周波放電や直流（ＤＣ）放電によるプラズマ化学気相堆積（ＣＶＤ）法を利用して、ＣＮＴを基板上に直接、垂直配向性良く成長させることが試みられている。 Therefore, on the other hand, attempts have been made to grow CNTs directly on a substrate with good vertical alignment by utilizing plasma chemical vapor deposition (CVD) method using microwave discharge, high frequency discharge or direct current (DC) discharge. .
ＤＣ放電によるプラズマ化学気相堆積（ＣＶＤ）法を利用してＣＮＴを基板上に形成する方法では、熱フィラメントを併用し、該熱フィラメントから熱電子をＣＮＴ形成のためのプラズマ内へ供給して電離を促進する方法も提案されている（Journal of Vacuum
Science and Technology A, Vol.19, No.4, pp.1796-1799, 2001 参照）。
In a method of forming CNTs on a substrate using a plasma enhanced chemical vapor deposition (CVD) method using DC discharge, a hot filament is used in combination, and thermoelectrons are supplied from the hot filament into the plasma for CNT formation. A method of promoting ionization has also been proposed (Journal of Vacuum
Science and Technology A, Vol.19, No.4, pp.1796-1799, 2001).
また、特開２００３−１４７５３３号公報は、二つの電極のうち一方の電極を基板ホルダとして該電極上に基板を設置し、該両電極間に高周波電圧を印加してＣＮＴ形成のための高周波放電プラズマを形成するとともに該両電極間にグリッド電極を配置し、これにグリッド電圧を印加することで、ＣＮＴの垂直配向性を向上させることを開示している。
文献「Applied Physics Letters, Vol.76, No.13, pp.1776-1778, 2000」には、２．４５ＧＨｚのマイクロ波プラズマＣＶＤ装置において、基板に負電圧を印加して垂直配向したＣＮＴを作製する方法が提案されている。
Japanese Patent Laid-Open No. 2003-147533 discloses a high-frequency discharge for forming CNTs by setting a substrate on one of two electrodes as a substrate holder and applying a high-frequency voltage between the electrodes. It discloses that the vertical alignment of CNTs is improved by forming a plasma and arranging a grid electrode between the two electrodes and applying a grid voltage thereto.
In the document “Applied Physics Letters, Vol.76, No.13, pp.1776-1778, 2000”, in a 2.45 GHz microwave plasma CVD apparatus, a negative voltage is applied to the substrate to produce vertically aligned CNTs. A method has been proposed.
しかしながら、特開２００３−１４７５３３号公報に開示された方法では基板に十分な負の電圧が印加されず、ＣＮＴの良好な垂直配向性が期待できない。また、マイクロ波プラズマＣＶＤ法では、プラズマの大きさがマイクロ波の波長（約１２ｃｍ）で制限されているため、大きな面積の基板上にＣＮＴを成長させることは困難である。 However, in the method disclosed in Japanese Patent Application Laid-Open No. 2003-147533, a sufficient negative voltage is not applied to the substrate, and good vertical alignment of CNT cannot be expected. In the microwave plasma CVD method, since the size of plasma is limited by the wavelength of the microwave (about 12 cm), it is difficult to grow CNTs on a substrate with a large area.
ＤＣプラズマ法では、大きな面積の基板上へのＣＮＴの成長は可能であるが、一般的なＤＣプラズマ法によると、異常放電が起きやすく、安定した定常的なプラズマの維持が困難であり、それがＣＮＴの成長に影響を与えるという問題がある。 In the DC plasma method, it is possible to grow CNTs on a substrate having a large area. However, according to a general DC plasma method, abnormal discharge is likely to occur, and it is difficult to maintain a stable and steady plasma. Affects the growth of CNTs.
ＤＣプラズマ法において、前記のように熱フィラメントを併用すると、該熱フィラメントから熱電子をＣＮＴ形成のためのプラズマ内へ供給して電離を促進することができ、それだけ安定した定常的なプラズマが維持される。
しかし、このように熱フィラメントを併用する場合、熱フィラメントとして用いる金属が、ＣＮＴ成長のために真空容器内に導入された炭素を含むガスから分化した炭素と反応して炭化物を形成する。このため、ＣＮＴ成長中に熱フィラメントが変形し温度分布が不均一となってプラズマが不安定になったりする。
In the DC plasma method, when a hot filament is used together as described above, thermoelectrons can be supplied from the hot filament into the plasma for CNT formation to promote ionization, and a stable and steady plasma can be maintained. Is done.
However, when the hot filament is used in this way, the metal used as the hot filament reacts with carbon differentiated from the gas containing carbon introduced into the vacuum vessel for CNT growth to form carbide. For this reason, the hot filament is deformed during CNT growth, the temperature distribution becomes non-uniform, and the plasma becomes unstable.
また、炭化物は脆いため、ＣＮＴ成長中や基板の交換時にフィラメントが断線しやすくなり、このため、大面積基板上にＣＮＴを成長させるためにＣＶＤ装置内に長さの長いフィラメントを張ることが難しく、基板のＣＮＴ成長面積に限界がある。 In addition, since the carbide is brittle, the filament is likely to break during CNT growth or during substrate replacement. For this reason, it is difficult to stretch a long filament in a CVD apparatus in order to grow CNT on a large area substrate. There is a limit to the CNT growth area of the substrate.
高周波プラズマＣＶＤ法では、一般に利用される高周波（１３．５６ＭＨｚ）の波長は約２２ｍであるため放電プラズマは大面積化が可能であり、従ってＣＮＴ成長基板の大面積化が可能となるが、高周波放電プラズマによると、基板表面に形成されるシース中の電界の大きさが不十分であり、そのためＣＮＴを基板面に対し垂直に配向させて成長させることが困難である。 In the high-frequency plasma CVD method, since the wavelength of high-frequency (13.56 MHz) that is generally used is about 22 m, the discharge plasma can be increased in area, and thus the CNT growth substrate can be increased in area. According to the discharge plasma, the magnitude of the electric field in the sheath formed on the substrate surface is insufficient, so that it is difficult to grow by aligning CNTs perpendicular to the substrate surface.
以上、カーボンナノチューブの形成を例にとって説明したが、一般的に言っても、形成対象物を比較的大面積の基板上に該基板面に対し垂直配向性良好に立ち上がるように堆積成長させる場合には、かかるカーボンナノチューブ形成の場合と同様の問題が発生することがある。 As described above, the formation of carbon nanotubes has been described as an example. Generally speaking, however, the object to be formed is deposited and grown on a relatively large area substrate so as to stand up with good vertical alignment with respect to the substrate surface. May cause the same problem as in the case of such carbon nanotube formation.
そこで本発明は、参考までに言えば、形成対象物を比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積装置を提供することや、かかるプラズマ化学気相堆積装置の１例として、カーボンナノチューブを比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積装置を提供することも課題としているが、特に次のことを課題とする。 Therefore, for reference , the present invention provides a plasma chemical vapor deposition apparatus capable of depositing and growing an object to be formed on a relatively large area substrate so as to stand up with good vertical alignment with respect to the substrate surface. In addition, as an example of such a plasma chemical vapor deposition apparatus, a plasma chemical vapor deposition apparatus capable of depositing and growing carbon nanotubes on a substrate having a relatively large area so as to have good vertical alignment with respect to the substrate surface is provided. However, the following are the issues.
すなわち、本発明は、形成対象物を比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積方法を提供することを課題とする。
また本発明は、かかるプラズマ化学気相堆積方法の１例として、カーボンナノチューブを比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積方法を提供することを課題とする。
That is, an object of the present invention is to provide a plasma chemical vapor deposition method capable of depositing and growing an object to be formed on a substrate having a relatively large area so as to stand up with good vertical alignment with respect to the substrate surface.
In addition, as an example of such a plasma chemical vapor deposition method, the present invention provides a plasma chemical vapor deposition method in which carbon nanotubes can be deposited and grown on a substrate having a relatively large area so as to stand up with good vertical alignment with respect to the substrate surface. It is an object to provide a method.
本発明は前記課題を解決するため、次のプラズマ化学気相堆積装置及びプラズマ化学気相堆積方法を提供する。
（１）プラズマ化学気相堆積装置
真空容器と、該真空容器内に設置された第１、第２及び第３の三つの電極とを含み、該真空容器は、形成対象物の堆積成長のためのガスを該真空容器内に導入するために該ガスの供給装置に接続されるガス導入部及び該真空容器内から排気するために排気装置に接続される排気部を有しており、該第１及び第２の電極は該両電極間に直流電圧が印加される電極であり、該第１電極は前記形成対象物を堆積成長させるための基板の支持体を兼ねており、該第３電極は高周波電圧を印加される電極であり、該真空容器は接地電位に設定されるプラズマ化学気相堆積装置。
In order to solve the above problems, the present invention provides the following plasma chemical vapor deposition apparatus and plasma chemical vapor deposition method.
(1) Plasma chemical vapor deposition apparatus includes a vacuum vessel and three first, second and third electrodes installed in the vacuum vessel, and the vacuum vessel is used for deposition growth of an object to be formed. A gas introduction portion connected to the gas supply device for introducing the gas into the vacuum vessel and an exhaust portion connected to an exhaust device for exhausting from the vacuum vessel, The first and second electrodes are electrodes to which a DC voltage is applied between the two electrodes. The first electrode also serves as a substrate support for depositing and growing the object to be formed, and the third electrode Is an electrode to which a high-frequency voltage is applied, and the vacuum vessel is a plasma chemical vapor deposition apparatus in which the vacuum vessel is set to a ground potential.
（２）プラズマ化学気相堆積方法
上記（１）のプラズマ化学気相堆積装置において、前記第１電極上に前記形成対象物を堆積成長させるための基板を設置し、前記ガス導入部から前記真空容器内へ前記ガスを導入するとともに該真空容器内を前記排気部からの排気により前記形成対象物の堆積成長のためのガス圧に設定しつつ前記第１及び第２電極間に直流電圧を印加して該第１及び第２電極間に直流放電プラズマを形成する一方、前記第３電極に高周波電圧を印加して該第３電極と該第２電極間に高周波放電プラズマを発生させ、該高周波放電プラズマを前記第１及び第２の電極間に拡散させつつ前記基板上に前記形成対象物を堆積成長させるプラズマ化学気相堆積方法。
(2) Plasma chemical vapor deposition method In the plasma chemical vapor deposition apparatus of (1), a substrate for depositing and growing the object to be formed is placed on the first electrode, and the vacuum is introduced from the gas introduction part. The gas is introduced into the container, and a DC voltage is applied between the first and second electrodes while the inside of the vacuum container is set to a gas pressure for deposition growth of the object to be formed by exhausting from the exhaust part. A DC discharge plasma is formed between the first electrode and the second electrode, while a high frequency voltage is applied to the third electrode to generate a high frequency discharge plasma between the third electrode and the second electrode. A plasma chemical vapor deposition method for depositing and growing the object to be formed on the substrate while diffusing discharge plasma between the first and second electrodes.
本発明に係るプラズマ化学気相堆積装置及びプラズマ化学気相堆積方法によると、真空容器内に第１、第２及び第３の三つの電極が配置される。そして、基板が第１電極に設置され、該第１電極と第２電極との間に形成されるＤＣ放電プラズマのもとで、該基板上に形成対象物を堆積成長させることができる。このようにＤＣ放電プラズマを利用するので比較的大面積の基板上への形成対象物の堆積成長が可能であるとともに、高周波放電プラズマの場合より形成対象物を基板面に対する垂直配向性良好に成長させることができる。 According to the plasma chemical vapor deposition apparatus and the plasma chemical vapor deposition method according to the present invention, the first, second, and third electrodes are disposed in the vacuum vessel. Then, the substrate is placed on the first electrode, and an object to be formed can be deposited and grown on the substrate under DC discharge plasma formed between the first electrode and the second electrode. Since DC discharge plasma is used in this way, it is possible to deposit and grow an object to be formed on a substrate having a relatively large area, and the object to be formed grows better in the vertical alignment with respect to the substrate surface than in the case of high-frequency discharge plasma. Can be made.
また、第３電極に高周波電圧が印加されることで形成される高周波放電プラズマがＤＣ放電プラズマ内に拡散し、さらに言えば該高周波放電プラズマにおける電子がＤＣ放電プラズマ内に拡散し、該ＤＣ放電プラズマ中での電離が促進され、これにより安定した定常的なＤＣ放電プラズマが維持される。 Further, the high frequency discharge plasma formed by applying a high frequency voltage to the third electrode diffuses into the DC discharge plasma, and more specifically, electrons in the high frequency discharge plasma diffuse into the DC discharge plasma, and the DC discharge. Ionization in the plasma is promoted, thereby maintaining a stable and steady DC discharge plasma.
このように本発明に係るプラズマ化学気相堆積装置、プラズマ化学気相堆積方法によると、形成対象物の基板上への堆積成長にＤＣ放電プラズマを利用し、該ＤＣ放電プラズマを安定に維持するため高周波放電プラズマを支援用として利用するので、比較的大面積の基板上に形成対象物を該基板面に対する垂直配向性良好に立ち上がるように、安定して堆積成長させることができる。 As described above, according to the plasma chemical vapor deposition apparatus and the plasma chemical vapor deposition method according to the present invention, the DC discharge plasma is used for deposition growth on the substrate of the object to be formed, and the DC discharge plasma is stably maintained. Therefore, since the high-frequency discharge plasma is used for support, the object to be formed can be stably deposited and grown on the substrate having a relatively large area so as to stand up with good vertical alignment with respect to the substrate surface.
本発明に係るプラズマ化学気相堆積装置、プラズマ化学気相堆積方法のいずれにおいても、前記第３電極が前記第１及び第２の電極間領域の外側に配置されているとともに前記第２電極が接地電位に設定される場合を例示できる。
また、この場合、前記第３電極が前記第２電極を間にして前記第１電極とは反対側に配置される場合を例示できる。
この場合は、前記第２電極は、該第２電極及び前記第３電極間の領域から該第２電極及び前記第１電極間の領域へ貫通する孔を形成した電極（例えばメッシュ状電極、パンチングメタル状電極等）とすることが望ましい。
In any of the plasma chemical vapor deposition apparatus and the plasma chemical vapor deposition method according to the present invention, the third electrode is disposed outside the region between the first and second electrodes, and the second electrode is The case where it is set to the ground potential can be exemplified.
In this case, the third electrode may be disposed on the opposite side of the first electrode with the second electrode in between.
In this case, the second electrode is an electrode in which a hole penetrating from the region between the second electrode and the third electrode to the region between the second electrode and the first electrode (for example, a mesh electrode, punching) It is desirable to use a metal electrode or the like.
また、プラズマ密度増大のための磁石部材が前記三つの電極のうち少なくとも一つ又は（及び）前記真空容器内に設けられてもよい。 In addition, a magnet member for increasing the plasma density may be provided in at least one of the three electrodes or (and) the vacuum vessel.
本発明に係るプラズマ化学気相堆積装置、プラズマ化学気相堆積方法において、前記基板上への形成対象物は特に制限はないが、代表例としてカーボンナノチューブを挙げることができる。
すなわち、形成対象物の堆積成長のためのガスとしてカーボンナノチューブの堆積成長のためのガス（例えばメタンのような炭化水素を含むガス、或いは必要応じてさらに水素ガス）を採用することで、比較的大面積の基板上に、安定した定常プラズマを維持しながら該基板面に対する垂直配向性良好に立ち上がるカーボンナノチューブを形成することができる。
In the plasma chemical vapor deposition apparatus and the plasma chemical vapor deposition method according to the present invention, the object to be formed on the substrate is not particularly limited, but a carbon nanotube can be given as a representative example.
That is, by adopting a gas for deposition growth of carbon nanotubes (for example, a gas containing a hydrocarbon such as methane, or further a hydrogen gas if necessary) as a gas for the deposition growth of the formation target, Carbon nanotubes can be formed on a large-area substrate, with good vertical alignment with respect to the substrate surface, while maintaining stable steady plasma.
このようにして得られるカーボンナノチューブを成長させた基板は例えば電界電子放出型ディスプレイ（ＦＥＤ）の電子源として利用でき、本発明によると、５０インチ以上の大きさのＦＥＤの製造を可能にする電子源としての基板を提供することも可能である。 The substrate on which the carbon nanotubes thus obtained are grown can be used as an electron source of, for example, a field electron emission display (FED). According to the present invention, an electron capable of manufacturing an FED having a size of 50 inches or more can be used. It is also possible to provide a substrate as a source.
以上説明したように本発明によると、形成対象物を比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積装置を提供することができる。
また本発明によると、かかるプラズマ化学気相堆積装置の１例として、カーボンナノチューブを比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積装置を提供することができる。
As described above, according to the present invention, it is possible to provide a plasma enhanced chemical vapor deposition apparatus capable of depositing and growing an object to be formed on a substrate having a relatively large area so as to stand up with good vertical alignment with respect to the substrate surface. it can.
Further, according to the present invention, as an example of such a plasma enhanced chemical vapor deposition apparatus, a plasma chemical vapor phase capable of depositing and growing carbon nanotubes on a relatively large area substrate so as to stand up with good vertical alignment with respect to the substrate surface. A deposition apparatus can be provided.
さらに特に、本発明によると、形成対象物を比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積方法を提供することができる。
また本発明によると、かかるプラズマ化学気相堆積方法の１例として、カーボンナノチューブを比較的大面積の基板上に基板面に対する垂直配向性良好に立ち上がるように堆積成長させることができるプラズマ化学気相堆積方法を提供することができる。
More particularly, according to the present invention, it is possible to provide a plasma chemical vapor deposition method capable of depositing and growing an object to be formed on a substrate having a relatively large area so as to stand up with good vertical alignment with respect to the substrate surface.
Further, according to the present invention, as an example of such a plasma enhanced chemical vapor deposition method, a plasma chemical vapor phase capable of depositing and growing carbon nanotubes on a substrate having a relatively large area so as to stand up with good vertical alignment with respect to the substrate surface. A deposition method can be provided.
以下、本発明の実施の形態について図面を参照して説明する。
図１はプラズマ化学気相堆積装置の１例Ａの構成を概略的に示している。 図１に示す装置Ａは、真空容器１と、真空容器１内に設置された平板形の第１、第２及び第３の三つの電極２１、２２、２３を含んでいる。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 schematically shows a configuration of an example A of a plasma chemical vapor deposition apparatus . The apparatus A shown in FIG. 1 includes a vacuum vessel 1 and three plate-shaped first, second and third electrodes 21, 22 and 23 installed in the vacuum vessel 1.
真空容器１は接地されており、ガス導入部１１及び排気部１２を有している。ガス導入部１１にはガス供給装置３が接続され、排気部１２には排気装置４が接続される。ガス供給装置３は、形成対象物の堆積成長のためのガスを供給するものである。排気装置４は真空容器１内から排気して、容器１内を形成対象物の堆積成長のためのガス圧に維持するためのものである。 The vacuum vessel 1 is grounded and has a gas introduction part 11 and an exhaust part 12. The gas supply unit 3 is connected to the gas introduction unit 11, and the exhaust unit 4 is connected to the exhaust unit 12. The gas supply device 3 supplies a gas for deposition growth of the formation target. The evacuation device 4 is for evacuating from the inside of the vacuum vessel 1 and maintaining the inside of the vessel 1 at a gas pressure for deposition growth of the formation target.
第１電極２１は形成対象物を堆積成長させるための基板Ｓを支持する基板ホルダを兼ねている。第１、第２の電極２１、２２は対向配置されており、第１電極２１には直流電源ＰＷ１が接続されているとともに第２電極は容器１を介して接地されている。これら両電極２１、２２間には、形成対象物の形成にあたって直流電源ＰＷ１から負の直流電圧が印加される。 The first electrode 21 also serves as a substrate holder that supports the substrate S for depositing and growing an object to be formed. The first and second electrodes 21 and 22 are arranged to face each other. A DC power source PW1 is connected to the first electrode 21 and the second electrode is grounded via the container 1. A negative DC voltage is applied between the electrodes 21 and 22 from the DC power source PW1 in forming the object to be formed.
第３電極２３は、第２電極２２を間にして第１電極２１とは反対側に配置されており、これには高周波電源ＰＷ２が接続されている。形成対象物の形成にあたって電源ＰＷ２から電極２３に高周波電圧が印加される。 The third electrode 23 is disposed on the opposite side of the first electrode 21 with the second electrode 22 in between, and a high frequency power supply PW2 is connected thereto. A high frequency voltage is applied from the power source PW2 to the electrode 23 in forming the object to be formed.
第２電極２２は、電極２２、２３間の領域から電極２２、２１間の領域へ貫通する孔を形成した電極であり、ここではメッシュ板からなっている。 The 2nd electrode 22 is an electrode which formed the hole penetrated from the field between electrodes 22 and 23 to the field between electrodes 22 and 21, and consists of a mesh board here.
次に以上説明した装置Ａを用いて基板Ｓ上にカーボンナノチューブ（ＣＮＴ）を成長させる例について説明する。
先ず、図示省略の真空容器扉を開いて第１電極２１上に基板Ｓを設置し、該扉を閉じて容器１を気密に閉じる。
Next, an example in which carbon nanotubes (CNT) are grown on the substrate S using the apparatus A described above will be described.
First, a vacuum container door (not shown) is opened, the substrate S is placed on the first electrode 21, and the container 1 is closed in an airtight manner by closing the door.
次いで、ガス供給装置３からガス導入部１１を経て、水素ガスで例えば２０％程度に希釈したメタンガスを容器１内へ導入する一方、排気装置４を運転して容器１内をＣＮＴ形成のためのガス圧（１Ｐａ（パスカル）〜 １０ｋＰａ程度の範囲の所定のガス圧）に維持しつつ、電源ＰＷ１から電極２１に１００Ｖ以上、より好ましくは５００Ｖ以上の、基板上に比較的大きい電界を発生させ得る所定の負の直流（ＤＣ）電圧を印加するとともに、電極２３に電源ＰＷ２から１Ｗ／ｃｍ2 〜５０Ｗ／ｃｍ2 程度の範囲の所定の高周波電力を印加する。 Subsequently, methane gas diluted with hydrogen gas to about 20%, for example, is introduced into the container 1 from the gas supply device 3 via the gas introduction unit 11, while the exhaust device 4 is operated to form CNTs in the container 1. While maintaining the gas pressure (predetermined gas pressure in the range of 1 Pa (Pascal) to 10 kPa), a relatively large electric field of 100 V or more, more preferably 500 V or more can be generated from the power source PW1 to the electrode 21 on the substrate. It applies a predetermined negative current (DC) voltage, for applying a predetermined high-frequency power 1W / cm 2 ~50W / cm 2 in the range of about the electrode 23 from the power source PW2.
かくして電極２１、２２間にＤＣ放電プラズマＰ１が形成され、電極２２、２３間に交流放電プラズマＰ２が形成される。交流放電プラズマＰ２の一部が、より詳しく言えばそれにおける電子が中間電極２２の孔を通ってＤＣ放電プラズマＰ１中へ定常的に拡散し、それにより該ＤＣ放電プラズマにおける電離が促進され、該ＤＣ放電プラズマが安定して定常的に維持される。かかるＤＣ放電プラズマにより分解生成された炭素に基づいて基板Ｓ上にカーボンナノチューブが堆積成長する。 Thus, a DC discharge plasma P1 is formed between the electrodes 21 and 22, and an AC discharge plasma P2 is formed between the electrodes 22 and 23. A portion of the AC discharge plasma P2, more specifically, electrons therein steadily diffuse into the DC discharge plasma P1 through the holes in the intermediate electrode 22, thereby promoting ionization in the DC discharge plasma, The DC discharge plasma is stably and constantly maintained. Carbon nanotubes are deposited and grown on the substrate S based on the carbon decomposed and generated by the DC discharge plasma.
かかるＤＣ放電プラズマ中では、印加された電圧の大半がＤＣ放電プラズマＰ１と基板Ｓとの間のシースと呼ばれる部分にかかる。この部分の厚さは、例えば数百パスカル（数トール）のガス圧力の下では、１ｍｍ程度以下と薄く、したがって、極めて大きな電界の場となる。この電界により、電極（陰極）２１上の基板Ｓ上に成長するＣＮＴはプラズマの方向へと引っ張り上げられ、基板Ｓ面に対して垂直方向或いはそれに近い方向に配向しながら成長する。 In the DC discharge plasma, most of the applied voltage is applied to a portion called a sheath between the DC discharge plasma P1 and the substrate S. The thickness of this portion is as thin as about 1 mm or less under a gas pressure of, for example, several hundred Pascals (several torr), and therefore a very large electric field is generated. By this electric field, the CNT grown on the substrate S on the electrode (cathode) 21 is pulled up in the direction of the plasma, and grows while being oriented in the direction perpendicular to or near the substrate S surface.
また、基本的にはＤＣ放電プラズマＣＶＤによるカーボンナノチューブの形成であり、それだけ大きい基板面積に垂直配向性良好に立ち上がるカーボンナノチューブを成長させることができ、ひいては大面積のＣＮＴ−ＦＥＤの製造が可能になる。
なお、基板Ｓ上にＣＮＴを成長させるに先立って、必要に応じ基板面をプラズマ照射処理してもよい。
In addition, it is basically the formation of carbon nanotubes by DC discharge plasma CVD, and it is possible to grow carbon nanotubes with good vertical alignment on such a large substrate area, which in turn makes it possible to produce large-area CNT-FEDs Become.
Prior to growing the CNTs on the substrate S, the substrate surface may be subjected to plasma irradiation treatment as necessary.
ここで、真空容器内における放電の安定性を調べる実験を行ったのでそれについて説明する。この実験では、容器１内に圧力２０００Ｐａの水素を満たし、電源ＰＷ２から印加する高周波電力として１００Ｗ、２００Ｗ、３００Ｗの３種類を採用し、該各高周波電力のもとに電源ＰＷ１から電極２１へ印加する負のＤＣ電圧を変化させ、ＤＣ放電の安定性を調べた。結果を図２に示す。 Here, since the experiment which investigates the stability of the discharge in a vacuum vessel was conducted, it is demonstrated. In this experiment, the container 1 is filled with hydrogen at a pressure of 2000 Pa, and three types of high frequency power of 100 W, 200 W, and 300 W are applied from the power source PW2, and applied from the power source PW1 to the electrode 21 under the high frequency power. The stability of DC discharge was investigated by changing the negative DC voltage. The results are shown in FIG.
図２に示すように、高周波放電電力が大きいほど、ＤＣ放電プラズマが発生する放電開始の電圧が低く、また、安定したＤＣ放電維持のためのＤＣ電圧が高いことがわかる。よって、プラズマ化学気相堆積装置ＡによるＣＮＴの形成においては、前記のように電極２３に印加する高周波電力を大きくするとともに電極２１に印加するＤＣ電力も前記のように大きくし、それにより大面積の基板Ｓ上に垂直配向性良好にＣＮＴを形成できる。 As shown in FIG. 2, it can be seen that the higher the high-frequency discharge power, the lower the voltage at which discharge occurs in the DC discharge plasma, and the higher the DC voltage for maintaining stable DC discharge. Therefore, in the formation of CNTs by the plasma chemical vapor deposition apparatus A, the high frequency power applied to the electrode 23 is increased as described above, and the DC power applied to the electrode 21 is also increased as described above, thereby increasing the area. CNTs can be formed on the substrate S with good vertical alignment.
次に図１の装置Ａによる基板上へのＣＮＴ成長の実験例について説明する。ＣＮＴ形成に先立ち基板面はプラズマ照射処理した。
実験条件
(1) 基板 ：材質 鉄、 サイズ １ｃｍ×１ｃｍ×（厚さ）０．２ｍｍ
(2) プラズマ照射処理
使用ガス ：水素ガス
容器１内ガス圧 ：２０００Ｐａ
ＤＣ電圧 ：−３２０Ｖ
高周波周波数 ：１３．５６ＭＨｚ
高周波電力 ：３００Ｗ（高周波電力密度 １２Ｗ／ｃｍ2 ）
照射時間 ：１５分
(3) ＣＮＴ形成
使用ガス ：水素ガスで２０％に希釈したメタンガス
容器１内ガス圧 ：２０００Ｐａ
ＤＣ電圧 ：−４５０Ｖ
高周波周波数 ：１３．５６ＭＨｚ
高周波電力 ：３００Ｗ（高周波電力密度 １２Ｗ／ｃｍ2 ）
形成時間 ：１５分
Next, an experimental example of CNT growth on the substrate by the apparatus A of FIG. 1 will be described. Prior to the CNT formation, the substrate surface was subjected to plasma irradiation treatment.
Experimental conditions
(1) Substrate: Material Iron, Size 1cm x 1cm x (Thickness) 0.2mm
(2) Plasma irradiation treatment Gas used: Hydrogen gas Gas pressure in container 1: 2000 Pa
DC voltage: -320V
High frequency frequency: 13.56 MHz
High frequency power: 300 W (high frequency power density 12 W / cm 2 )
Irradiation time: 15 minutes
(3) CNT formation Gas used: Methane gas diluted to 20% with hydrogen gas Gas pressure in container 1: 2000 Pa
DC voltage: -450V
High frequency frequency: 13.56 MHz
High frequency power: 300 W (high frequency power density 12 W / cm 2 )
Formation time: 15 minutes
かくして得られたＣＮＴを走査型電子顕微鏡で観察したところ、図３に示すように、直径１００ナノメートル程度のＣＮＴが基板面から立ち上がるように配向成長していることを確認できた。以上、装置ＡによるＣＮＴの形成について説明してきたが、装置Ａは他の物質の堆積成長にも利用できる。 When the CNT thus obtained was observed with a scanning electron microscope, it was confirmed that CNTs having a diameter of about 100 nanometers were aligned and grown so as to rise from the substrate surface as shown in FIG. Although the formation of CNTs by the apparatus A has been described above, the apparatus A can also be used for the deposition growth of other substances.
いずれにしても、ＤＣ放電プラズマ及び（又は）高周波放電プラズマの密度を増大させるために電極及び（又は）真空容器内に磁石を設けてもよい。
図４、図５、図６はそれぞれ図１の装置において磁石を設ける場合の例を示している。 図４〜図６の各プラズマ化学気相堆積装置において図１の装置Ａと実質上同じ部品、部分には図１と同じ参照符号を付してある。
In any case, a magnet may be provided in the electrode and / or the vacuum vessel in order to increase the density of the DC discharge plasma and / or the high frequency discharge plasma.
4, 5, and 6 each show an example in which a magnet is provided in the apparatus of FIG. 1. In each plasma chemical vapor deposition apparatus of FIGS. 4 to 6, substantially the same components and parts as those of the apparatus A of FIG. 1 are denoted by the same reference numerals as those of FIG.
図４の装置Ｂでは、高周波電極２３に４個の磁石Ｍ１〜Ｍ４が配設され、磁石Ｍ１からＭ２へ、磁石Ｍ４からＭ３へ、それぞれ磁力線が形成される。
図５の装置Ｃでは、高周波放電プラズマＰ２の発生領域を挟む一対の磁石Ｍ５、Ｍ６が真空容器１内に配置されており、一方の磁石Ｍ５から他方の磁石Ｍ６へ磁力線が形成される。
図６の装置Ｄでは、電極２１の背後に磁石Ｍ７が、電極２３の背後に磁石Ｍ８が配置されており、磁石Ｍ８からＭ７へ磁力線が形成される。
なお、磁力線の向きは図４〜図６に示す向きに限定される必要はなく、例えばそれらとは反対の向きであってもよい。
In the apparatus B of FIG. 4, four magnets M1 to M4 are disposed on the high-frequency electrode 23, and magnetic lines of force are formed from the magnets M1 to M2 and from the magnets M4 to M3, respectively.
In the apparatus C of FIG. 5, a pair of magnets M5 and M6 sandwiching the generation region of the high-frequency discharge plasma P2 is disposed in the vacuum vessel 1, and magnetic lines of force are formed from one magnet M5 to the other magnet M6.
In the apparatus D of FIG. 6, the magnet M7 is disposed behind the electrode 21 and the magnet M8 is disposed behind the electrode 23, and magnetic lines of force are formed from the magnet M8 to M7.
The direction of the lines of magnetic force need not be limited to the direction shown in FIGS. 4 to 6, and may be the opposite direction, for example.
また、電極への電源の接続態様や、各電極の配置や形状は図１に示すものに限定されない。例えば、図７、図８、図９に示す装置Ｅ、Ｆ、Ｇのようにしてもよい。
図７〜図９の各プラズマ化学気相堆積装置において図１の装置Ａと実質上同じ部品、部分には図１と同じ参照符号を付してある。
Moreover, the connection aspect of the power supply to an electrode, and arrangement | positioning and shape of each electrode are not limited to what is shown in FIG. For example, the devices E, F, and G shown in FIGS. 7, 8, and 9 may be used.
In each of the plasma chemical vapor deposition apparatuses of FIGS. 7 to 9, substantially the same parts and portions as those of the apparatus A of FIG.
図７の装置Ｅでは、ＤＣ電圧を印加する電極（第１電極）２１とこれに対向する接地電極（第２電極）２２’との間に高周波電圧を印加する電極（第３電極）２３’を配置し、且つ、電極２２’は孔あきでない電極とされる一方、電極２３’は放電用の孔を形成した電極とされている。例えばこの孔により高周波ホローカソード放電を発生させ、プラズマ密度を増大させることもできる。
図８の装置Ｆ（真空容器は図示省略）では、ＤＣ電圧を印加する電極（第１電極）２１’が円柱状に形成されており、これに同心円的に筒状のメッシュ状接地電極（第２電極）２２”及び高周波印加電極（第３電極）２３”が配置されている。基板については、円筒形状の基板Ｓ’が電極２１’上に外嵌設置される。
図９の装置Ｇは、図７に示す装置Ｅにおいて、高周波印加電極（第３電極）２３’がＤＣ放電プラズマ生成領域を囲む筒状の電極２３ａ’に置き換えられている。
In the apparatus E of FIG. 7, an electrode (third electrode) 23 ′ for applying a high-frequency voltage between an electrode (first electrode) 21 for applying a DC voltage and a ground electrode (second electrode) 22 ′ opposed thereto. The electrode 22 ′ is a non-perforated electrode, while the electrode 23 ′ is an electrode having a discharge hole. For example, this hole can generate a high frequency hollow cathode discharge to increase the plasma density.
In the apparatus F of FIG. 8 (a vacuum vessel is not shown), an electrode (first electrode) 21 ′ for applying a DC voltage is formed in a columnar shape, and concentrically cylindrical mesh ground electrode (first electrode). Two electrodes) 22 "and a high-frequency applying electrode (third electrode) 23". As for the substrate, a cylindrical substrate S ′ is fitted on the electrode 21 ′.
In the apparatus G of FIG. 9, the high frequency application electrode (third electrode) 23 ′ is replaced with a cylindrical electrode 23a ′ surrounding the DC discharge plasma generation region in the apparatus E shown in FIG.
本発明は比較的大面積の基板上に形成対象物（例えばカーボンナノチューブ）を基板面に対する垂直配向性良好に堆積成長させることに利用でき、ひいてはカーボンナノチューブを電子源に利用した大面積の電界電子放出型ディスプレイの製造にも利用できる。 INDUSTRIAL APPLICABILITY The present invention can be used for depositing and growing an object to be formed (for example, carbon nanotube) on a substrate having a relatively large area with good vertical alignment with respect to the substrate surface. It can also be used to manufacture emissive displays.
Ａ プラズマ化学気相堆積装置
１ 真空容器
１１ ガス導入部
１２ 排気部
２１ 第１電極（ＤＣ電圧印加電極）
２２ 第２電極（接地電極）
２３ 第３電極（高周波電圧印加電極）
３ ガス供給装置
４ 排気装置
Ｓ 基板
ＰＷ１ ＤＣ電源
ＰＷ２ 高周波電源
Ｐ１ ＤＣ放電プラズマ
Ｐ２ 高周波放電プラズマ
Ｂ、Ｃ、Ｄ プラズマ化学気相堆積装置
Ｍ１〜Ｍ８ 磁石
Ｅ、Ｆ、Ｇ プラズマ化学気相堆積装置
２１’ＤＣ電圧印加電極
２２’、２２” 接地電極
２３’、２３”、２３ａ’ 高周波印加電極
Ｓ’ 基板
A Plasma chemical vapor deposition apparatus 1 Vacuum container 11 Gas introduction part 12 Exhaust part 21 1st electrode (DC voltage application electrode)
22 Second electrode (ground electrode)
23 Third electrode (high frequency voltage application electrode)
3 Gas supply device 4 Exhaust device S Substrate PW1 DC power supply PW2 High frequency power supply P1 DC discharge plasma P2 High frequency discharge plasma B, C, D Plasma chemical vapor deposition apparatus M1 to M8 Magnets E, F, G Plasma chemical vapor deposition apparatus 21 'DC voltage application electrode 22', 22 "ground electrode 23 ', 23", 23a' high frequency application electrode S 'substrate
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004238251A JP4536456B2 (en) | 2004-08-18 | 2004-08-18 | Plasma chemical vapor deposition method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004238251A JP4536456B2 (en) | 2004-08-18 | 2004-08-18 | Plasma chemical vapor deposition method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006057122A JP2006057122A (en) | 2006-03-02 |
| JP4536456B2 true JP4536456B2 (en) | 2010-09-01 |
Family
ID=36104846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004238251A Active JP4536456B2 (en) | 2004-08-18 | 2004-08-18 | Plasma chemical vapor deposition method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4536456B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5505786B2 (en) * | 2010-03-02 | 2014-05-28 | 日新電機株式会社 | Carbon nanotube structure manufacturing method and electron emission source using the same |
| JP5688996B2 (en) * | 2011-03-07 | 2015-03-25 | 株式会社神戸製鋼所 | Plasma source and film forming apparatus equipped with the plasma source |
| CN103493602B (en) * | 2011-07-14 | 2016-06-08 | 株式会社岛津制作所 | Plasma processing apparatus |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01147072A (en) * | 1987-12-04 | 1989-06-08 | Mitsubishi Electric Corp | Method and apparatus for forming thin film |
| JP2002313784A (en) * | 2001-04-12 | 2002-10-25 | Anelva Corp | Magnetron type parallel flat plate surface treating equipment |
| JP2003124192A (en) * | 2001-10-11 | 2003-04-25 | Tokyo Electron Ltd | Plasma processor |
| JP2003147533A (en) * | 2001-09-28 | 2003-05-21 | Hanyang Hak Won Co Ltd | Plasma enhanced chemical vapor deposition apparatus and method of producing carbon nanotube using the same |
-
2004
- 2004-08-18 JP JP2004238251A patent/JP4536456B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01147072A (en) * | 1987-12-04 | 1989-06-08 | Mitsubishi Electric Corp | Method and apparatus for forming thin film |
| JP2002313784A (en) * | 2001-04-12 | 2002-10-25 | Anelva Corp | Magnetron type parallel flat plate surface treating equipment |
| JP2003147533A (en) * | 2001-09-28 | 2003-05-21 | Hanyang Hak Won Co Ltd | Plasma enhanced chemical vapor deposition apparatus and method of producing carbon nanotube using the same |
| JP2003124192A (en) * | 2001-10-11 | 2003-04-25 | Tokyo Electron Ltd | Plasma processor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006057122A (en) | 2006-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100928409B1 (en) | Devices and Processes for Carbon Nanotube Growth | |
| US8992880B2 (en) | Method of manufacturing onion-like carbon | |
| KR20040090448A (en) | Method of manufacturing electron-emitting source | |
| JP3837451B2 (en) | Method for producing carbon nanotube | |
| JP4536456B2 (en) | Plasma chemical vapor deposition method | |
| Wang et al. | Macroscopic field emission properties of aligned carbon nanotubes array and randomly oriented carbon nanotubes layer | |
| Yap et al. | Formation of vertically aligned carbon nanotubes by dual-RF-plasma chemical vapor deposition | |
| JP4853861B2 (en) | Method and apparatus for forming carbon nanostructure | |
| Zheng et al. | Nitrogen-doped few-layer graphene grown vertically on a Cu substrate via C60/nitrogen microwave plasma and its field emission properties | |
| US20090078561A1 (en) | Apparatus and Methods for Growing Nanofibres and Nanotips | |
| JP5032042B2 (en) | Plasma CVD apparatus and film forming method | |
| Ren et al. | Large arrays of well-aligned carbon nanotubes | |
| Kyung et al. | Improvement of field emission from screen-printed carbon nanotubes by He∕(N2, Ar) atmospheric pressure plasma treatment | |
| US20050266764A1 (en) | Method of stabilizing field emitter | |
| Kyung et al. | The effect of atmospheric pressure plasma treatment on the field emission characteristics of screen printed carbon nanotubes | |
| JP2002069756A (en) | Apparatus and method for forming carbon nanofiber | |
| JP4707336B2 (en) | Manufacturing method of electron source using carbon nanofiber | |
| JP2005255492A (en) | Apparatus and method of manufacturing carbon nano-structure | |
| JP2009067663A (en) | Method of growing carbon nanotube on carbon fiber sheet and carbon nanotube emitter | |
| KR20010088087A (en) | Selective deposition method of carbon nanotubes | |
| Kyung et al. | Growth and field-emission properties of multiwalled carbon nanotubes synthesized by a pin-to-plate-type atmospheric pressure plasma enhanced chemical vapor deposition | |
| Han et al. | High field-emission current of carbon nanotubes grown on TiN-coated Ta substrate for electron emitters in a microwave power amplifier | |
| JP5264055B2 (en) | Field emission chip | |
| KR100543959B1 (en) | Method for conducting field emission using shell-shaped carbon nano particle | |
| JP2004006283A (en) | Plasma generation device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051122 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070130 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090602 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100302 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100427 |
|
| 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: 20100608 |
|
| 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: 20100616 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130625 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| 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 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |