JP3911564B2 - Boron nitride nanocomposite structure and manufacturing method thereof - Google Patents
Boron nitride nanocomposite structure and manufacturing method thereof Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 30
- 229910052582 BN Inorganic materials 0.000 title claims description 26
- 239000002114 nanocomposite Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- QLJWDUVBSPJCTP-UHFFFAOYSA-N [N].B(O)(O)O Chemical compound [N].B(O)(O)O QLJWDUVBSPJCTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910003472 fullerene Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000619 electron energy-loss spectrum Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- -1 boron nitride compound Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
この出願の発明は、窒化ホウ素ナノ複合構造物とその製造方法に関するもので、さらに詳しくは、中空の竹状形態を有する茎状部の外表面に、非晶質物質が充填された粒子状部あるいは中空のチューブ状の枝状部が直接結晶成長している、特異な形態を有する窒化ホウ素ナノ複合構造物とその製造方法に関するものである。
【０００２】
【従来の技術】
近年、炭素ナノチューブが発見されて以来多くの一次元（１Ｄ）ナノスケール物質が合成されてきた。そして、これらの一次元ナノスケール物質については中空のナノチューブと固いナノワイヤー（もしくはナノロッド）の二つの主要なものに分類することができる。例えば、炭素（Ｃ）や、窒化ホウ素（ＢＮ）のナノチューブ構造物、珪素（Ｓｉ）とゲルマニウム（Ｇｅ）のナノワイヤー、炭化珪素（ＳｉＣ）、窒化珪素（Ｓｉ3Ｎ4）、窒化ガリウム（ＧａＮ）のナノロッド等が知られている。ところで、一次元ナノスケール物質を他の物質で被覆した複合ナノ構造物もまた新規な三次元化合物の製造や、低温領域の電子発生体としての応用等の広範な分野への適用の可能性を秘めている。
【０００３】
このような三次元のナノ構造物技術の展開は、その新規な機能による適用分野の拡大の観点で注目されるところであるが、近年では、特異な三次元ナノ構造物の構造も報告されている。この構造は、幹から多数の枝が出た様な樹状形態をした構造であって、タングステン酸化物と炭素とによって調製された特異なものである（文献１）。
【０００４】
しかしながら、この報告された構造では、樹状形態の各々は良好に結晶化されたＷＯXの主要な茎状部および単斜晶系のＷ18Ｏ49の分枝部から構成されているが、分枝部がもろくて簡単に崩壊するために、このような特異な構造を実用分野に適用することは困難であるという問題があった。また、タングステン酸化物の場合以外には、特異な構造の三次元複合ナノ構造物であって、しかもその構造において崩壊や脱落が生じ難い一次元ナノスケール物質を他の物質で被覆した複合ナノ構造物は実現されていない。
【０００５】
【文献１】
Y.Q.Zhu, et al,Chem. Phys. Lett.,309(1999)327
【０００６】
【発明が解決しようとする課題】
一方、窒化ホウ素は、商業的にも重要な非酸化物セラミックの一つであり、耐熱性に優れ、化学的も安定であることから、耐熱材料や構造材料への利用等の広範な用途に有用であることが知られているが、この窒化ホウ素の複合ナノ構造物は半導体装置等の電子デバイスの応用等が期待されるものであって、その三次元構造の新しい展開によって、新規機能の実現や実用分野への適用の拡大が見込まれているものである。
【０００７】
そこで、この出願の発明は、上記のとおりの既報の特異構造等の従来技術の問題点を解消して、これまでに知られていない特異な三次元構造を窒化ホウ素ナノ複合構造物として実現することを課題としている。
【０００８】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、第１には、中空の竹状形態を有する茎状部の外表面に、非晶質物質が充填された粒子状部あるいは中空のチューブ状の枝状部が直接結晶成長していることを特徴とする窒化ホウ素ナノ複合構造物を提供する。
【０００９】
また、この出願の発明は、第２には、上記の窒化ホウ素ナノ複合構造物の製造方法であって、酸素含有のホウ素窒素化合物を１７００℃以上に加熱し、発生したガスをポリアクリルニトリル系炭素繊維と接触させて加熱を継続することを特徴とする窒化ホウ素ナノ複合構造物の製造方法を提供し、第３には、ホウ素窒素化合物が窒化ホウ素（ＢＮ）粉末であって、酸素含有量が５ｗｔ％〜２０ｗｔ％の範囲であることを特徴とする方法を、第４には、ホウ素窒素化合物が水酸化ホウ素窒素（Ｂ 4 Ｎ 3 Ｏ 2 Ｈ）であることを特徴とする方法を提供する。
【００１０】
【発明の実施の形態】
この出願の発明は上記のとおりの特徴をもつものであるが、以下にその実施の形態について説明する。
【００１１】
なによりもまず、この主願の発明において基本とされていることは、これまでに知られていない新規な、特異な形態を有する窒化ホウ素ナノ複合構造物が提供されることである。このものは、茎状部の外表面に複数の粒子状部または枝状部が直接結晶成長していること、つまり、その構造は、茎状部の外表面に多数の粒子状または枝状の付着物が付着して根粒状またはモミの木の枝葉状に類した形態を有している。そして、前記茎状部位は結節部と内部に中空部を有する竹形状もしくは瘤部を有する線状形態をなしていて、粒子状物は形状が多面体形状であり、枝状物の形状はチューブ形状をしている。この窒化ホウ素ナノ複合構造物では、茎状部と付着物との固着は高い安定性を有している。実際に、この出願の発明の窒化ホウ素ナノ複合構造物では、たとえば１５分間の超音波の照射においても茎状部と付着物との固着が維持されることが確認されている。
【００１２】
微細な構造について観察すると、たとえば図１（ａ）（ｂ）（ｃ）の走査型電子顕微鏡：ＳＥＭ像、図２（ａ）の高分解能電子顕微鏡：ＨＲＴＥＭ像並びに図２（ｂ）（ｃ）の電子エネルギー損失スペクトル：ＥＥＬＳ、そして図３（ａ）（ｂ）の走査型電子顕微鏡：ＳＥＭ像から以下のことがわかる。
【００１３】
すなわち、前記の根粒状のものについては、たとえば HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87///&N0001=23&N0552=9&N0553=000003" \t "tjitemdrw" 図１（ａ）に示すように、２時間以上（〜４時間）加熱し沈積させると竹形状をした茎状部の表面に多面体の粒子のクラスターが形成され根粒状形態をなしている。また、粒子状の付着物は、 HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87///&N0001=23&N0552=9&N0553=000003" \t "tjitemdrw" 図１（ｂ）に示されるように、確かに多面体物質であり、 HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87///&N0001=23&N0552=9&N0553=000003" \t "tjitemdrw" 図１（ｃ）において、茎状部位が付着物質で被覆されていることが確認できる。更には、 HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87///&N0001=23&N0552=9&N0553=000004" \t "tjitemdrw" 図２に示す様に、粒子状付着物質が窒化ホウ素のフラーレンケージに内部が非晶質物質で充填されたものであり、外側のフラーレンケージがホウ素と窒素の元素で窒素に対するホウ素の原子比率が１．０に近いものからなっていて、カプセル化している非晶質の化合物はホウ素および窒素だけでなく他の珪素、カルシウム、酸素の元素が含まれている。一方、モミの木の枝葉状のものについては、図３（ａ）に示す様に、茎状部に多くのナノ分枝が付着した形態をなしている。そして HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87///&N0001=23&N0552=9&N0553=000005" \t "tjitemdrw" 図３（ｂ）に示す様に、当該窒化ホウ素ナノ複合構造物の多くのものが、茎状部は直径が約２００ｎｍであり、分枝は直径が約５０ｎｍで長さが数百ｎｍである。また、窒化ホウ素ナノチューブ（ＢＮ−ＮＴｓ）である分枝の端部には前述の多面体の粒子が付着しているものもあり、該部位はホウ素、窒素、酸素、珪素、カルシウムの類似の化合物である。
【００１４】
たとえば以上のような、この出願の発明の窒化ホウ素ナノ複合構造物の製造には、好適には、化学的気体沈積（ＣＶＤ）方法を用いることができる。たとえば、この出願の発明の製造方法では、酸素含有のホウ素窒素化合物を１７００℃以上に加熱し、発生したガスをポリアクリルニトリル系炭素繊維と接触させて加熱を継続することにより窒化ホウ素ナノ複合構造物を製造する。
【００１５】
この場合のホウ素窒素化合物としては、たとえば窒化ホウ素（ＢＮ）粉末であって、酸素含有量が５ｗｔ％〜２０ｗｔ％の範囲であるや、水酸化ホウ素窒素（Ｂ 4 Ｎ 3 Ｏ 2 Ｈ）であるものが好適なものとして例示される。
【００１６】
実際に、たとえば実施例として説明すると、先駆物質として酸素量が約１０ｗｔ％の窒化ホウ素（ＢＮ）粉末または酸素含有量が約２７ｗｔ％の水酸化ホウ素窒素（Ｂ4Ｎ3Ｏ2Ｈ）を用いて、温度を１７００℃以上で加熱し、発生したガスの気流をポリアクリルニトリル（ＰＡＮ）系の炭素繊維に触れるようにして少なくとも２時間以上加熱を継続することにより、この出願の発明の特異な形態を有する窒化ホウ素ナノ構造物が生成される。生成物については、前記のとおり、図１（ａ）（ｂ）（ｃ）、図２（ａ）（ｂ）（ｃ）、並びに図３（ａ）（ｂ）について説明したものが得られている。
【００１７】
もちろん、以上の例に限定されることはない。また、製造に用いられる装置はこの発明の方法の条件のもとで化学的気相成長（ＣＶＤ）方法に使用できる限りにおいて限定されることはない。またポリアクリルニトリル（ＰＡＮ）系の炭素繊維には主たる不純物として少しの珪素（たとえば０．１ｗｔ％）とカルシウム（たとえば０．０３ｗｔ％）を含有していてもよい。
【００１８】
【発明の効果】
この出願の発明によれば、容易に崩壊し難い、一次元ナノスケール物質を他の物質で被覆した新規な窒化ホウ素ナノ複合構造物を提供することができる。このものは、半導体装置への応用の高い潜在力を秘めているだけでなく、窒化ホウ素が化学的反応に不活性であるのでその内部にカプセル化された物質のための保護物質として用いることもできる等、広範な分野への応用が期待される。
【図面の簡単な説明】
【図１】この出願の発明の窒化ホウ素ナノ複合構造物の根粒形状に類する形態を示す写真である。
（ａ）竹形状の茎状部の表面に粒子状の付着物が付着した状態を示す走査型電子顕微鏡（ＳＥＭ）像
（ｂ）粒子状付着物が多面体の粒子であることを示すＳＥＭ像
（ｃ）茎状部が粒子状付着物で完全に被覆されていることを示すＳＥＭ像
【図２】根粒状形態の粒子状付着物の高分解能電子顕微鏡（ＨＲＴＥＭ）および電子エネルギー損失スペクトル（ＥＥＬＳ）である。
（ａ）粒子状付着物がフラーレンケージと内部が非晶質物質で充填されていることを示すＨＲＴＥＭ像
（ｂ）外殻が化学量論的窒化ホウ素化合物であることを示すＥＥＬＳ
（ｃ）非晶質含有物がＢ、Ｎ、Ｏ、Ｓｉ、Ｃａの化合物であることを示すＥＥＬＳ
【図３】窒化ホウ素ナノ複合構造物がモミの木の枝葉状に類する形態を示す写真である。
（ａ）付着物がナノ分枝の集合体であることを示すＳＥＭ像
（ｂ）形態が主要な茎状部とナノチューブ分枝からなることを示すＳＥＭ像[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to a boron nitride nanocomposite structure and a method for producing the same, and more specifically, a particulate part in which an amorphous substance is filled on the outer surface of a stem part having a hollow bamboo-like form. Alternatively, the present invention relates to a boron nitride nanocomposite structure having a peculiar form in which hollow tube-shaped branch portions are directly crystal-grown and a method for producing the same.
[0002]
[Prior art]
In recent years, many one-dimensional (1D) nanoscale materials have been synthesized since the discovery of carbon nanotubes. These one-dimensional nanoscale materials can be classified into two main types: hollow nanotubes and solid nanowires (or nanorods). For example, carbon (C), boron nitride (BN) nanotube structures, silicon (Si) and germanium (Ge) nanowires, silicon carbide (SiC), silicon nitride (Si 3 N 4 ), gallium nitride (GaN) ) Nanorods and the like are known. By the way, composite nanostructures in which one-dimensional nanoscale materials are coated with other materials also have the potential to be applied in a wide range of fields, such as the production of new three-dimensional compounds and their application as low-temperature electron generators. Hidden.
[0003]
The development of such three-dimensional nanostructure technology is drawing attention from the viewpoint of expanding the field of application due to its new functions, but in recent years, the structure of unique three-dimensional nanostructures has also been reported. . This structure is a dendritic structure in which a large number of branches come out from the trunk, and is a unique structure prepared from tungsten oxide and carbon (Reference 1).
[0004]
However, in this reported structure, each of the dendritic forms is composed of well-crystallized WO X main stems and monoclinic W 18 O 49 branches, Since the branch part is fragile and easily collapses, there is a problem that it is difficult to apply such a unique structure to a practical field. In addition to the case of tungsten oxide, it is a three-dimensional composite nanostructure with a unique structure, and a composite nanostructure in which a one-dimensional nanoscale material that does not easily collapse or drop off is coated with another substance. Things are not realized.
[0005]
[Reference 1]
YQZhu, et al, Chem. Phys. Lett., 309 (1999) 327
[0006]
[Problems to be solved by the invention]
Boron nitride, on the other hand, is one of the commercially important non-oxide ceramics and has excellent heat resistance and chemical stability, so it can be used in a wide range of applications such as heat resistant materials and structural materials. Although it is known to be useful, this boron nitride composite nanostructure is expected to be applied to electronic devices such as semiconductor devices, etc. Realization and expansion of application to practical fields are expected.
[0007]
Therefore, the invention of this application solves the problems of the prior art such as the previously reported unique structure as described above, and realizes a unique three-dimensional structure that has not been known so far as a boron nitride nanocomposite structure. It is an issue.
[0008]
[Means for Solving the Problems]
In order to solve the above problems, the invention of this application is as follows. First, a particulate portion or a hollow tube in which an outer surface of a stem-like portion having a hollow bamboo-like shape is filled with an amorphous substance. Provided is a boron nitride nanocomposite structure characterized by direct crystal growth of a branch-like portion .
[0009]
In addition, the invention of this application is, secondly, a method for producing the boron nitride nanocomposite structure, wherein the oxygen-containing boron nitrogen compound is heated to 1700 ° C. or higher, and the generated gas is converted into a polyacrylonitrile-based material. Provided is a method for producing a boron nitride nanocomposite structure in which heating is continued in contact with carbon fibers. Third, the boron nitrogen compound is boron nitride (BN) powder, and the oxygen content Is provided in the range of 5 wt% to 20 wt%, and fourth, a method is characterized in that the boron nitrogen compound is boron hydroxide nitrogen (B 4 N 3 O 2 H) To do.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The invention of this application has the features as described above, and an embodiment thereof will be described below.
[0011]
First of all, what is fundamental in the invention of this main application is to provide a new and unique boron nitride nanocomposite structure that has not been known so far. This is because a plurality of particles or branches are directly grown on the outer surface of the stem , that is, the structure is a large number of particles or branches on the outer surface of the stem . It has a form similar to roots or fir tree branches and leaves attached to the deposits. The stem-shaped part has a nodule part and a bamboo form having a hollow part inside or a linear form having a knob part, the particulate matter has a polyhedral shape, and the branch shape has a tube shape I am doing. In this boron nitride nanocomposite structure, the sticking between the stem and the deposit has high stability. Actually, in the boron nitride nanocomposite structure of the invention of this application, for example, it has been confirmed that the adhesion between the stem-like portion and the attached matter is maintained even when irradiated with ultrasonic waves for 15 minutes.
[0012]
When the fine structure is observed, for example, the scanning electron microscope of FIGS. 1A, 1B and 1C: SEM image, the high-resolution electron microscope of FIG. 2A: the HRTEM image, and FIGS. 2B and 2C. From the electron energy loss spectrum: EELS, and the scanning electron microscope: SEM images of FIGS.
[0013]
That is, for the above-mentioned root-granularity, for example, HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87 /// & N0001 = 23 & N0552 = 9 & N0553 = 000003 "\ t" tjitemdrw "As shown in Fig. 1 (a), when heated and deposited for more than 2 hours (~ 4 hours), the polyhedron on the surface of the bamboo-shaped stem A cluster of particles is formed to form a root granular form. In addition, the particulate deposit is HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87/// & N0001 = 23 & N0552 = 9 & N0553 = 000003 "\ t" tjitemdrw "As shown in Fig. 1 (b), it is indeed a polyhedral substance, HYPERLINK" http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw ?? .ipdl N0000 = 234 & N0500 = 4E # N /;> 9 = 6: 87 /// Te & N0001 = 23 & N0552 = 9 & N0553 = 000003 "\ t" tjitemdrw " FIG. 1 (c) smell, with pedicle sites adhered substances It can be confirmed that it is covered. Furthermore, HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87///&N0001=23&N0552=9&N0553= 000004 "\ t" tjitemdrw "As shown in Fig. 2, the particulate adhering substance is a boron nitride fullerene cage filled with amorphous material inside, and the outer fullerene cage is composed of boron and nitrogen elements. The atomic ratio of boron to nitrogen is close to 1.0, and the encapsulated amorphous compound contains not only boron and nitrogen but also other silicon, calcium, and oxygen elements. On the other hand, as shown in FIG. 3A, fir tree branches and leaves are in the form of many nano branches attached to the stem. And HYPERLINK "http://www6.ipdl.ncipi.go.jp/Tokujitu/tjitemdrw.ipdl?N0000=234&N0500=4E#N/;>9=?6:87///&N0001=23&N0552=9&N0553=000005" \ t "tjitemdrw" As shown in FIG. 3 (b), many of the boron nitride nanocomposites have a stem-like diameter of about 200 nm and a branch having a diameter of about 50 nm and a length. It is several hundred nm. In addition, there is a boron nitride nanotube (BN-NTs) in which the above-mentioned polyhedral particles are attached to the end of the branch, and this part is a similar compound of boron, nitrogen, oxygen, silicon, and calcium. is there.
[0014]
For example, a chemical gas deposition (CVD) method can be preferably used for manufacturing the boron nitride nanocomposite structure of the present invention as described above. For example, in the manufacturing method of the invention of this application, a boron nitride nanocomposite structure is obtained by heating an oxygen-containing boron-nitrogen compound to 1700 ° C. or higher, contacting the generated gas with polyacrylonitrile-based carbon fiber, and continuing heating. Manufacturing things.
[0015]
The boron nitrogen compound in this case is, for example, boron nitride (BN) powder, and the oxygen content is in the range of 5 wt% to 20 wt%, or boron hydroxide nitrogen (B 4 N 3 O 2 H). Are illustrated as preferred.
[0016]
Actually, for example, as an example, boron nitride (BN) powder having an oxygen content of about 10 wt% or boron hydroxide nitrogen (B 4 N 3 O 2 H) having an oxygen content of about 27 wt% is used as a precursor. Then, heating is continued at a temperature of 1700 ° C. or higher, and heating is continued for at least 2 hours so that the generated gas stream comes into contact with the polyacrylonitrile (PAN) -based carbon fiber. Boron nitride nanostructures having a morphology are produced. As described above, the products described in FIGS. 1 (a), (b), (c), FIGS. 2 (a), (b), (c), and FIGS. 3 (a), (b) are obtained. Yes.
[0017]
Of course, it is not limited to the above example. Further, the apparatus used for the production is not limited as long as it can be used for the chemical vapor deposition (CVD) method under the conditions of the method of the present invention. The polyacrylonitrile (PAN) -based carbon fiber may contain a small amount of silicon (for example, 0.1 wt%) and calcium (for example, 0.03 wt%) as main impurities.
[0018]
【The invention's effect】
According to the invention of this application, it is possible to provide a novel boron nitride nanocomposite structure in which a one-dimensional nanoscale material that is not easily disintegrated is coated with another material. Not only does this have a high potential for application to semiconductor devices, but boron nitride is inert to chemical reactions, so it can also be used as a protective material for substances encapsulated inside it. It can be applied to a wide range of fields.
[Brief description of the drawings]
FIG. 1 is a photograph showing a form similar to a nodule shape of a boron nitride nanocomposite structure of the invention of this application.
(A) Scanning electron microscope (SEM) image showing a state where particulate deposits are attached to the surface of the bamboo-shaped stem-like portion (b) SEM image showing that the particulate deposits are polyhedral particles ( c) SEM image showing that the stem is completely covered with particulate deposits. FIG. 2 High resolution electron microscope (HRTEM) and electron energy loss spectrum (EELS) of particulate deposits in root granular form. It is.
(A) HRTEM image showing that particulate deposit is filled with fullerene cage and amorphous substance inside (b) EELS showing that outer shell is stoichiometric boron nitride compound
(C) EELS indicating that the amorphous material is a compound of B, N, O, Si, Ca
FIG. 3 is a photograph showing a form in which a boron nitride nanocomposite structure is similar to fir tree branches and leaves.
(A) SEM image showing that the deposit is an assembly of nano-branches (b) SEM image showing that the morphology consists of main stems and nanotube branches
Claims (4)
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