JP2007027190A - Rectifier element - Google Patents
Rectifier element Download PDFInfo
- Publication number
- JP2007027190A JP2007027190A JP2005203190A JP2005203190A JP2007027190A JP 2007027190 A JP2007027190 A JP 2007027190A JP 2005203190 A JP2005203190 A JP 2005203190A JP 2005203190 A JP2005203190 A JP 2005203190A JP 2007027190 A JP2007027190 A JP 2007027190A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- swnt
- carbon nanotube
- aggregate
- bpp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
この発明は、カーボンナノチューブを利用した整流素子に関し、より詳細には、カーボンナノチューブと環状平面有機分子又はそれらの集合体の界面の整流作用を利用した整流素子に関する。 The present invention relates to a rectifying device using carbon nanotubes, and more particularly to a rectifying device using a rectifying action at the interface between a carbon nanotube and an annular planar organic molecule or an assembly thereof.
カーボンナノチューブは各種電子素子に利用されているが（例えば、特許文献１〜３等）、もっぱらその導電性が利用されているに過ぎない。
カーボンナノチューブを利用したナノ構造物の伝導度を測定するために、ナノメートルサイズのギャップ（ナノギャップ）が電極に必要とされている。そのため、電子ビームリソグラフィー、ブレークジャンクション、フリースタンディング炭素ナノワイヤー、電気化学的成長、カーボンナノチューブマスク、電気マイグレーションなどの手法で作製されたナノギャップ電極を用いてナノ構造の伝導度が報告されているが、対象物が10nm以下場合その対象物が実際に電極に安定的に接触しているかどうかを観察することは非常に困難である（非特許文献１）。例えば、直径10nm以下の微粒子が基板上に作製された数nmのギャップ間に置かれた場合には観察の手段がない。それは、SPMの探針はギャップ中に入ることができないし、SEMの分解能では観察するのに十分でないなどの理由による。ナノギャップ電極の結果によると、計測中に観察が不可能であるので、実際に分子が電極に接着しているかどうかも疑わしい。
Carbon nanotubes are used in various electronic devices (for example, Patent Documents 1 to 3), but their conductivity is only used.
In order to measure the conductivity of nanostructures using carbon nanotubes, a nanometer-sized gap (nanogap) is required in the electrode. Therefore, the conductivity of nanostructures has been reported using nanogap electrodes fabricated by techniques such as electron beam lithography, break junction, free-standing carbon nanowires, electrochemical growth, carbon nanotube mask, and electromigration. When the object is 10 nm or less, it is very difficult to observe whether the object is actually in stable contact with the electrode (Non-Patent Document 1). For example, there is no observation means when fine particles having a diameter of 10 nm or less are placed in a gap of several nm formed on a substrate. This is because the SPM probe cannot enter the gap, and the SEM resolution is not sufficient for observation. According to the results of the nanogap electrode, observation is impossible during measurement, so it is also doubtful whether molecules are actually attached to the electrode.
この問題を解決するために、点接触電流イメージング原子間力顕微鏡(PCI-AFM)を使うと原理的にコンタクトモード原子間力顕微鏡(AFM)での測定に比べて、走査時の試料や探針表面に与えるダメージが非常に少く、ポリマー（ワイヤー）などのソフトマテリアルが走査中に探針により掃きだされることが避けることや、ナノ領域での電気特性の変化を検出することができる（非特許文献２）。
更に、ナノ領域の測定のために有効な電極である単層カーボンナノチューブ（SWNT）を用いると、SWNT上の試料のAFM観察が容易となり、トポグラフィー像を観察しながら、分子ワイヤーの長軸方向へ沿った電流を測定することができる。そのために、SWNTとポルフィリン化合物との複合体を形成させ、SWNTを単離して測定することも行われている（非特許文献３）
また、ポルフィリン環を有する酸化還元物質をレドックス電位の異なる別の酸化還元物質と接合させた整流素子も提案されている（特許文献４）。
In order to solve this problem, the point contact current imaging atomic force microscope (PCI-AFM) is used in principle compared to the measurement with the contact mode atomic force microscope (AFM). The damage to the surface is very small, and soft materials such as polymers (wires) can be avoided from being swept away by the probe during scanning, and changes in electrical properties in the nano range can be detected (non- Patent Document 2).
Furthermore, using single-walled carbon nanotubes (SWNT), which is an effective electrode for nano-area measurements, makes it easy to observe AFM on samples on SWNTs, while observing the topographic image, and in the direction of the long axis of the molecular wire The current along can be measured. Therefore, a complex of SWNT and a porphyrin compound is formed, and SWNT is isolated and measured (Non-patent Document 3).
In addition, a rectifying element in which a redox substance having a porphyrin ring is joined to another redox substance having a different redox potential has been proposed (Patent Document 4).
本発明者らは、点接触電流イメージング原子間力顕微鏡(PCI-AFM)を用いて、SWNTとポルフィリン化合物との複合体（非特許文献３）を観察し、その電気特性を測定することにより、その構造や機能の解明を試みた。 By observing a complex of SWNT and a porphyrin compound (Non-patent Document 3) using a point contact current imaging atomic force microscope (PCI-AFM) and measuring the electrical characteristics thereof, I tried to elucidate its structure and function.
その結果、SWNTとポルフィリン化合物との複合体（非特許文献３）が整流作用を持つことを見出し、本発明を完成させるに至った。
本発明においては、カーボンナノチューブと環状平面有機分子又はそれらの集合体との界面において整流作用が起こり、整流作用は金属と有機分子の界面における金属の仕事関数のずれによるものと考えられる。
即ち、本発明は、（１）電極１、（２）１本の又は５本以内の束のカーボンナノチューブ、（３）分子量が４００〜１０００のπ電子を有する環状平面有機分子又はそれらの集合体、及び（４）電極２から成る整流作用を有する素子であって、該電極１が該カーボンナノチューブと接触し、該カーボンナノチューブ表面に該環状平面有機分子又はそれらの集合体が吸着され、該環状平面有機分子又はそれらの集合体が該電極２と接触してなる整流素子である。
As a result, it was found that a complex of SWNT and a porphyrin compound (Non-patent Document 3) has a rectifying action, and the present invention has been completed.
In the present invention, a rectification action occurs at the interface between the carbon nanotube and the cyclic planar organic molecule or the aggregate thereof, and the rectification action is considered to be due to a shift in the work function of the metal at the interface between the metal and the organic molecule.
That is, the present invention includes (1) an electrode 1, (2) one or five bundles of carbon nanotubes, (3) a cyclic planar organic molecule having a π electron having a molecular weight of 400 to 1000, or an aggregate thereof. And (4) a device having a rectifying action comprising the electrode 2, wherein the electrode 1 is in contact with the carbon nanotube, and the annular planar organic molecule or the aggregate thereof is adsorbed on the surface of the carbon nanotube, This is a rectifying device in which planar organic molecules or their aggregates are in contact with the electrode 2.
本発明は、SWNT上のポルフィリンの電気特性を初めて測定することに成功した結果完成された。SWNT上に環状平面有機分子又はそれらの集合体を配置した結果、得られた素子は、環状平面有機分子又はそれらの集合体（サイズ2-5 nm程度）がSWNTの上で整流デバイスとして機能する。
実際の素子においては、カーボンナノチューブで配線した上に、本発明の環状平面有機分子又はそれらの集合体を直接載せるだけで整流デバイスを構成することができる。
The present invention was completed as a result of the first successful measurement of the electrical properties of porphyrin on SWNT. As a result of arranging the planar planar organic molecules or their aggregates on SWNT, the resulting device has the planar planar organic molecules or their aggregates (size of about 2-5 nm) function as a rectifying device on SWNT. .
In an actual element, a rectifying device can be configured by directly placing the annular planar organic molecule of the present invention or an aggregate thereof on a wiring with carbon nanotubes.
本発明で用いるカーボンナノチューブは、単層カーボンナノチューブ（SWNT）、２層その他の多層カーボンナノチューブ、ツェッペリン型カーボンナノチューブ、カップナノスタック型カーボンナノチューブ、カーボンナノホーン等いかなる形状のものを用いることができるが、単層カーボンナノチューブ（SWNT）と２層その他の多層カーボンナノチューブが好ましく用いられる。
このカーボンナノチューブは一本で用いてもよいが２〜５本程度の束で用いてもよい。
The carbon nanotubes used in the present invention may be any shape such as single-walled carbon nanotubes (SWNT), double-walled multi-walled carbon nanotubes, zeppelin-type carbon nanotubes, cup nano-stacked carbon nanotubes, carbon nanohorns, Single-walled carbon nanotubes (SWNT) and double-walled or other multi-walled carbon nanotubes are preferably used.
These carbon nanotubes may be used alone or in bundles of about 2 to 5.
本発明の環状平面有機分子は、π電子を有する環状平面有機分子であって、ある程度分子量の大きなもの、例えば、分子量が４００〜１０００のものであり、例えば、ポルフィリン、フタロシアニン、フェニレンビニレン等又はこれらの置換体が挙げられる。これらは置換基として、アルキル基、アミノ基、ニトロ基、メルカプト基、カルボン基などを有していてもよい。 The cyclic planar organic molecule of the present invention is a cyclic planar organic molecule having π electrons and has a certain molecular weight, for example, a molecular weight of 400 to 1000, such as porphyrin, phthalocyanine, phenylene vinylene, or the like. The substitution body of this is mentioned. These may have an alkyl group, amino group, nitro group, mercapto group, carboxylic group and the like as a substituent.
このような環状平面有機分子の例として、以下のような化合物を挙げることができる。
本発明において環状平面有機分子の集合体とは、この環状平面有機分子が集合したもの及びこの環状平面有機分子を単位としてポリマー状に結合したものの両方をいう。
この環状平面有機分子は、π-πスタッキングによって平面同士を向き合って積み重なったものであってもよい。この場合には、その厚さが２〜４分子程度（０．５〜５ｎｍ程度）の集合体（塊状）を形成していてもよい。
また、この環状平面有機分子に不飽和結合（炭素−炭素の二重結合や三重結合）を有する置換基（ビニル基等）を置換基として付加し、この不飽和結合を介して重合することにより，分子量を増大させてもよい。このような重合体は塊状となりその径はやはりせいぜい約５ｎｍ程度である。
これらの分子は、金属と錯体を形成する配位子として機能するものであってもよく、この場合には、例えばＮｉ、Ｆｅ、Ｚｎ、Ａｌ等の遷移金属原子を有していてもよい。但し、この金属は本発明の環状平面有機分子に配位する場合に周期的連続体となっていないため、伝導体ではなく、本発明の整流素子の必須の要素にはなりえない。
In this invention, the aggregate | assembly of a cyclic | annular planar organic molecule means both the thing which this cyclic | annular planar organic molecule aggregated, and the thing couple | bonded in the polymer form by making this cyclic | annular planar organic molecule unit.
The cyclic planar organic molecules may be stacked with the planes facing each other by π-π stacking. In this case, aggregates (lumps) having a thickness of about 2 to 4 molecules (about 0.5 to 5 nm) may be formed.
Moreover, by adding a substituent (vinyl group, etc.) having an unsaturated bond (carbon-carbon double bond or triple bond) to the cyclic planar organic molecule as a substituent, and polymerizing through the unsaturated bond. , The molecular weight may be increased. Such a polymer is agglomerated and has a diameter of about 5 nm at most.
These molecules may function as a ligand that forms a complex with a metal. In this case, the molecule may have a transition metal atom such as Ni, Fe, Zn, or Al. However, since this metal is not a periodic continuum when coordinated to the cyclic planar organic molecule of the present invention, it is not a conductor and cannot be an essential element of the rectifying device of the present invention.
また、電極は導電性があれば特に限定されず、その材質がＰｔなどの金属、ドープシリコンなどの伝導性半導体等を用いることが出来る。 Further, the electrode is not particularly limited as long as it has conductivity, and the material thereof can be a metal such as Pt, a conductive semiconductor such as doped silicon, or the like.
本発明の素子においては、まず、一方の電極（電極１）とカーボンナノチューブとを接触させる。次に、このカーボンナノチューブに環状平面有機分子又はそれらの集合体を接触させる。カーボンナノチューブ溶液に環状平面有機分子の溶液を加えることにより、環状平面有機分子又はそれらの集合体をカーボンナノチューブの壁面に吸着させることができる。この環状平面有機分子又はそれらの集合体を電極２と接触させる。
このカーボンナノチューブと環状平面有機分子又はそれらの集合体との接触点は、カーボンナノチューブと電極１との接触点と離れていなくともよいが（例えば、カーボンナノチューブを挟んで反対側）、これらを十分は離すことによりカーボンナノチューブを単に電気伝導体として素子の配線として利用するものであってもよい。
このようにして構成した本発明の整流素子は電極１と電極２との間で整流作用を持つ。
In the element of the present invention, first, one electrode (electrode 1) is brought into contact with the carbon nanotube. Next, an annular planar organic molecule or an assembly thereof is brought into contact with the carbon nanotube. By adding a solution of an annular planar organic molecule to the carbon nanotube solution, the annular planar organic molecule or an aggregate thereof can be adsorbed on the wall surface of the carbon nanotube. This circular planar organic molecule or an assembly thereof is brought into contact with the electrode 2.
The contact points between the carbon nanotubes and the circular planar organic molecules or their aggregates do not have to be separated from the contact points between the carbon nanotubes and the electrode 1 (for example, on the opposite side of the carbon nanotubes). By separating the carbon nanotubes, the carbon nanotubes may be used simply as electrical conductors for the wiring of the device.
The rectifying element of the present invention configured as described above has a rectifying action between the electrode 1 and the electrode 2.
以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。
製造例１
まず、下式
メソ−β−無置換ジピロメタン0.25 g(1.71 mmol)をジクロルメタン（関東化学）200 mLに溶かし、トリフルオロ酢酸（和光純薬工業）65μLを滴下した。室温で撹拌しながら、ジクロルメタン(50mL)に溶かした1−ヘキサナール（和光純薬工業）0.17g(1.71 mmol)を30分かけて滴下した。5時間後、2,3−ジクロロ−5,6−ジシアノ−1,4−ベンゾキノン(アルドリッチ)(0.5g , 2.25 mmol)を加え、さらに室温で攪拌。30分後、トリエチルアミン（和光純薬工業）を3mL加え溶液を中和し、カラムクロマトグラフィーと再結晶で精製し、赤色針状結晶を得た（0.08g, 22%）。
得られた針状結晶を (0.07 g, 0.16 mmol)をクロロフォルム（関東化学）35 mLに溶かし、Methanol (3.5 mL)に溶かした酢酸亜鉛二水和物（Zn(Oac)2・2H2O関東化学）0.17g(0.8 mmol)を加え、室温で1.5時間攪拌した。カラムクロマトグラフィーと再結晶で精製し、暗赤色針状結晶(BPP-Zn)を得た (0.06g 72%)。
The following examples illustrate the invention but are not intended to limit the invention.
Production Example 1
First, the following formula
0.25 g (1.71 mmol) of meso-β-unsubstituted dipyrromethane was dissolved in 200 mL of dichloromethane (Kanto Chemical), and 65 μL of trifluoroacetic acid (Wako Pure Chemical Industries) was added dropwise. While stirring at room temperature, 0.17 g (1.71 mmol) of 1-hexanal (Wako Pure Chemical Industries) dissolved in dichloromethane (50 mL) was added dropwise over 30 minutes. After 5 hours, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (Aldrich) (0.5 g, 2.25 mmol) was added, and the mixture was further stirred at room temperature. After 30 minutes, 3 mL of triethylamine (Wako Pure Chemical Industries, Ltd.) was added to neutralize the solution, and purified by column chromatography and recrystallization to obtain red needle crystals (0.08 g, 22%).
Zinc acetate dihydrate (Zn (Oac) 2 · 2H 2 O Kanto) obtained by dissolving (0.07 g, 0.16 mmol) of the obtained acicular crystal in 35 mL of chloroform (Kanto Chemical) and dissolving in methanol (3.5 mL) Chemistry) 0.17 g (0.8 mmol) was added and stirred at room temperature for 1.5 hours. Purification by column chromatography and recrystallization gave dark red needles (BPP-Zn) (0.06 g 72%).
SWNT（シグマアルドリッチ社製）を上記暗赤色針状結晶(BPP-Zn)のジメチルフォルムアミド(DMF)溶液 (0.1 mM, 5mL)中に加え、30分超音波にかけた。その溶液を1000Gで遠心分離し上澄みを収集した。SWNT/BPP-Zn複合体をフィルター(0.5μm, MILIPORE)を使って集め、余剰なBPP-Znをトリクロロメタン100 mLで洗浄した。SWNT/BPP-ZnをDMF(2 mL)に加え、さらに30分超音波にかけた。SWNT/BPP-Zn複合体は非常に安定で、1ヶ月室温で放置しても全く析出しなかった。
得られた溶液をマイカ（基板）上にキャストし、表面をタッピングモードAFM（日本電子(株)製JSPM4200、カンチレバー加振周波数150kHz、電気測定時印加電圧は-1.5〜1.5V）で観察を行なった。
SWNT (manufactured by Sigma Aldrich) was added to the above dark red needle crystal (BPP-Zn) in dimethylformamide (DMF) solution (0.1 mM, 5 mL), and subjected to ultrasonic waves for 30 minutes. The solution was centrifuged at 1000 G and the supernatant was collected. SWNT / BPP-Zn complex was collected using a filter (0.5 μm, MILIPORE), and excess BPP-Zn was washed with 100 mL of trichloromethane. SWNT / BPP-Zn was added to DMF (2 mL) and further sonicated for 30 minutes. The SWNT / BPP-Zn composite was very stable and did not precipitate at all even after standing at room temperature for 1 month.
The obtained solution was cast on mica (substrate), and the surface was observed in tapping mode AFM (JSPM4200 manufactured by JEOL Ltd., cantilever excitation frequency 150 kHz, applied voltage during electrical measurement is -1.5 to 1.5 V). It was.
複合体のAFM像を図１に示す。SWNTとBPP-Zn集合体の複合体が高さ2.4〜4.5nmで観察された。過剰なBPP-Zn 分子の集合体が基板全体で観察された。図１からポルフィリンが、図２に示すようにSWNTの表面に非常に強力に吸着している様子が伺える。SWNTの直径は1.1〜1.5nmであるので、BPP-Zn 集合体の厚さは約1〜3 nmである。SWNTと基板の両方で観察された白い点がBPP-Zn分子数個の集まりである。図１の矢印(i)で示したようにSWNTのほとんどの部分がBPP-Znに覆われている。一方、図１の矢印(ii)で示したように、ところどころSWNTがむき出しになっている部分も観察されている。 An AFM image of the composite is shown in FIG. A complex of SWNT and BPP-Zn aggregates was observed at a height of 2.4-4.5 nm. Excess BPP-Zn molecule aggregates were observed throughout the substrate. It can be seen from FIG. 1 that porphyrin is adsorbed very strongly on the surface of SWNT as shown in FIG. Since the diameter of SWNT is 1.1 to 1.5 nm, the thickness of the BPP-Zn aggregate is about 1 to 3 nm. The white dots observed on both SWNTs and the substrate are a collection of several BPP-Zn molecules. As shown by the arrow (i) in FIG. 1, most of the SWNT is covered with BPP-Zn. On the other hand, as shown by the arrow (ii) in FIG. 1, some parts where SWNT is exposed are observed.
製造例１で得たSWNTとBPP-Zn集合体の複合体をその上に有する基板（マイカ）上の半分をカバーグラスで覆い、金電極を用いて熱蒸着法で金蒸着した。蒸着された金の厚さは約40nmであった。カバーグラスを慎重に取り去ることにより、真っ直ぐな壁面を有する金電極が得られた。その様子を図３に示す。 A half on the substrate (mica) having the composite of SWNT and BPP-Zn aggregate obtained in Production Example 1 was covered with a cover glass, and gold was deposited by a thermal evaporation method using a gold electrode. The thickness of the deposited gold was about 40 nm. By carefully removing the cover glass, a gold electrode having a straight wall surface was obtained. This is shown in FIG.
図４はPCI-AFMで得られたトポグラフィー像を示し、図５は各点における断面を示す。この断面の高さと形状から、点A'、D'、E'、G' （以下「Ｐ点」という。）では、高さ約3nmのBPP-Zn 集合体が高さ2.5nmの束になったSWNT(b-SWNT)に吸着している。単体のSWNT(s-SWNT)の平均直径は1.1nmであるので(Sigma Aldrichのプロダクトシートによる)、b-SWNTは2本のs-SWNTからなっている。BPP-Zn の高さは約0.35 nmであるので、このBPP-Zn 集合体は数個のBPP-Zn 分子が一箇所に集まったものであると考えられる。即ち、Ｐ点においては、図６（ａ）の模式図に示すように、カンチレバーはBPP-Znの塊を介してカーボンナノチューブに連結している。図６（ａ）は本発明の整流素子の構成を示す。
一方、点B'、C'、F'（以下「Ｎ点」という。）では、図６（ｂ）の模式図に示すように、カンチレバーは直接カーボンナノチューブに接している。
FIG. 4 shows a topography image obtained by PCI-AFM, and FIG. 5 shows a cross section at each point. Based on the height and shape of this cross section, BPP-Zn aggregates with a height of about 3 nm form bundles with a height of 2.5 nm at points A ′, D ′, E ′, and G ′ (hereinafter referred to as “P points”). Adsorbed to SWNT (b-SWNT). Since the average diameter of a single SWNT (s-SWNT) is 1.1 nm (according to the product sheet of Sigma Aldrich), b-SWNT consists of two s-SWNTs. Since the height of BPP-Zn is about 0.35 nm, this BPP-Zn aggregate is thought to be a collection of several BPP-Zn molecules in one place. That is, at the point P, as shown in the schematic diagram of FIG. 6A, the cantilever is connected to the carbon nanotube via the BPP-Zn mass. Fig.6 (a) shows the structure of the rectifier of this invention.
On the other hand, at points B ′, C ′, and F ′ (hereinafter referred to as “N point”), the cantilever is in direct contact with the carbon nanotube, as shown in the schematic diagram of FIG.
図４の128×128の各点において、I-V曲線（図６）を同時に得た。
PCI−AFMを用いたI-V 測定の手順を、図７（ａ）〜（ｃ）に示す。(a)タッピングモードAFMでトポグラフィー像を得る。(b)I-V曲線を測定するためカンチレバーの振動を停止する。(c)電気的に接触するためAFM端針を試料に押し付け、I-V曲線を測定する。ステップ (a)〜(c)を繰り返して、128×128点の各点のAFM像を得る。
PCI-AFM測定は原子間力顕微鏡(JEOL JSPM-4210)を2つのファンクションジェネレーターで拡張した装置を用いて行なった。シリコンにPtを蒸着した伝導性カンチレバーを電流測定に用いた。カンチレバーの力定数と共鳴周波数はそれぞれ4.5 N/m、150 kHzであった。この測定は湿気を避けるために窒素ガス雰囲気中で行なわれた。フォースカーブを解析した結果、I-V 測定がなされた際の試料とカンチレバーの間に働く力が13 nNであることがわかった。
バイアス電圧を基板上の金電極に与え、カンチレバーをアースした。その結果を図８に示す。
An IV curve (FIG. 6) was simultaneously obtained at each 128 × 128 point in FIG.
The procedure of IV measurement using PCI-AFM is shown in FIGS. (a) A topography image is obtained by tapping mode AFM. (b) Stop the cantilever vibration to measure the IV curve. (c) Press the AFM end needle against the sample for electrical contact and measure the IV curve. Steps (a) to (c) are repeated to obtain AFM images of 128 × 128 points.
PCI-AFM measurements were performed using an instrument that extended the atomic force microscope (JEOL JSPM-4210) with two function generators. A conductive cantilever with Pt deposited on silicon was used for current measurement. The force constant and resonance frequency of the cantilever were 4.5 N / m and 150 kHz, respectively. This measurement was performed in a nitrogen gas atmosphere to avoid moisture. As a result of analyzing the force curve, it was found that the force acting between the sample and the cantilever at the time of IV measurement was 13 nN.
A bias voltage was applied to the gold electrode on the substrate, and the cantilever was grounded. The result is shown in FIG.
Ｎ点（点B'、C'、F'）ではオーミックでない原点について対称なI-V曲線が裸のb-SWNTから得られた。Ｐ点（点A'、D'、E'、G'）では、原点について非対称なI-V 曲線がSWNT上のポルフィリンから得られた。N点における正バイアス時の電流量は負電圧時の電流量やN点における電流量よりはるかに小さかった。
一方、BPP-Zn 集合体を通る電流はPtとSWNTの接点を通る電流とは区別された。I-V 曲線（図８（ａ））を1.5Vで標準化したところ（図８（ｂ））、A'-F'から得られたすべての曲線がV<0で一致した。一方、V>0ではそれらは２種類に分別された。
Ｎ点から得られた曲線は、原点に対し対称な曲線である、それに対し、Ｐ点から得られた曲線は非対称な曲線であり、整流作用があることを示している。
At point N (points B ′, C ′, F ′), an IV curve symmetric about the non-ohmic origin was obtained from bare b-SWNT. At point P (points A ′, D ′, E ′, G ′), an IV curve asymmetric with respect to the origin was obtained from porphyrin on SWNT. The amount of current at positive bias at point N was much smaller than that at negative voltage and at point N.
On the other hand, the current through the BPP-Zn aggregate was distinguished from the current through the contact point of Pt and SWNT. When the IV curve (FIG. 8 (a)) was normalized to 1.5V (FIG. 8 (b)), all the curves obtained from A′-F ′ agreed with V <0. On the other hand, when V> 0, they were separated into two types.
The curve obtained from the N point is a symmetric curve with respect to the origin, whereas the curve obtained from the P point is an asymmetric curve, indicating that there is a rectifying action.
Claims (2)
The rectifying device according to claim 1, wherein the cyclic planar organic molecule is porphyrin, phthalocyanine, phenylene vinylene, or the like or a substitution product thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005203190A JP4992069B2 (en) | 2005-07-12 | 2005-07-12 | Rectifier element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005203190A JP4992069B2 (en) | 2005-07-12 | 2005-07-12 | Rectifier element |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2007027190A true JP2007027190A (en) | 2007-02-01 |
| JP2007027190A5 JP2007027190A5 (en) | 2008-07-03 |
| JP4992069B2 JP4992069B2 (en) | 2012-08-08 |
Family
ID=37787619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005203190A Active JP4992069B2 (en) | 2005-07-12 | 2005-07-12 | Rectifier element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4992069B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016015361A (en) * | 2014-07-01 | 2016-01-28 | 公立大学法人首都大学東京 | Semiconductor element manufacturing method and device, semiconductor element and thermoelectric transducer using the same |
| EP3702326A1 (en) | 2019-02-28 | 2020-09-02 | Fujitsu Limited | Compound, nanoribbon, and semiconductor device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016257A2 (en) * | 2000-08-24 | 2002-02-28 | William Marsh Rice University | Polymer-wrapped single wall carbon nanotubes |
| US20050040417A1 (en) * | 2002-12-17 | 2005-02-24 | Zhiyong Li | Nano optical sensors via molecular self-assembly |
| JP2005093990A (en) * | 2003-08-11 | 2005-04-07 | Mitsubishi Chemicals Corp | Organic electronic device using cooper porphyrin compound |
-
2005
- 2005-07-12 JP JP2005203190A patent/JP4992069B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016257A2 (en) * | 2000-08-24 | 2002-02-28 | William Marsh Rice University | Polymer-wrapped single wall carbon nanotubes |
| US20050040417A1 (en) * | 2002-12-17 | 2005-02-24 | Zhiyong Li | Nano optical sensors via molecular self-assembly |
| JP2005093990A (en) * | 2003-08-11 | 2005-04-07 | Mitsubishi Chemicals Corp | Organic electronic device using cooper porphyrin compound |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016015361A (en) * | 2014-07-01 | 2016-01-28 | 公立大学法人首都大学東京 | Semiconductor element manufacturing method and device, semiconductor element and thermoelectric transducer using the same |
| EP3702326A1 (en) | 2019-02-28 | 2020-09-02 | Fujitsu Limited | Compound, nanoribbon, and semiconductor device |
| US11401291B2 (en) | 2019-02-28 | 2022-08-02 | Fujitsu Limited | Compound, nanoribbon, and semiconductor device |
| US11702438B2 (en) | 2019-02-28 | 2023-07-18 | Fujitsu Limited | Compound, nanoribbon, and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4992069B2 (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7959779B2 (en) | Macroscopically manipulable nanoscale devices made from nanotube assemblies | |
| Bonifazi et al. | Microscopic and spectroscopic characterization of paintbrush-like single-walled carbon nanotubes | |
| Nakayama et al. | Development and application of multiple‐probe scanning probe microscopes | |
| Tanaka et al. | Porphyrin molecular nanodevices wired using single‐walled carbon nanotubes | |
| Pham et al. | Electronic interaction between nitrogen-doped graphene and porphyrin molecules | |
| Desbief et al. | Nanoscale investigation of the electrical properties in semiconductor polymer–carbon nanotube hybrid materials | |
| JPWO2006121155A1 (en) | Carbon nanotube composition, method for producing the same, array, and electronic device | |
| US20070152370A1 (en) | Method for surface imprinted films with carbon nanotubes | |
| Wang et al. | Ligand-induced dependence of charge transfer in nanotube–quantum dot heterostructures | |
| Hui et al. | Emerging scanning probe–based setups for advanced nanoelectronic research | |
| JP4992069B2 (en) | Rectifier element | |
| Jelken et al. | The Hidden Flower in WS2 Flakes: A Combined Nanomechanical and Tip-Enhanced Raman Exploration | |
| Magonov et al. | Advancing characterization of materials with atomic force microscopy-based electric techniques | |
| Wang et al. | Preferential growth of SnO2 triangular nanoparticles on ZnO nanobelts | |
| Xia et al. | KPFM and its Use to Characterize the CPD in Different Materials | |
| Li et al. | Bismuth triiodide sheet-assisted growth and enhanced field emission properties of cadmium sulfide nanowire array attached to a flexible CdS film | |
| Su et al. | Scanning Probe Microscopies for Characterizations of 2D Materials | |
| KR100866325B1 (en) | Probe for signal detection and electron emission, and method of manufacturing for same | |
| Taratula et al. | Highly aligned ribbon-shaped Pd nanoparticle assemblies by spontaneous organization | |
| Attanzio | Carbon nanostructures-quantum dot hybrids: self-assembly and photo-physical investigations of single-molecule heterostructures | |
| Tanaka et al. | Porphyrin molecules working as nanodevice on single-walled carbon nanotube wiring | |
| Jin | Synthesis, characterization and manipulation of Carbon nanotubes | |
| de Asis et al. | Carbon nanotube atomic force microscopy with applications to biology and electronics | |
| Berenguer-Murcia | Fullerene-Related Nanocarbons and Their Applications | |
| Li | Molecular crystallization directed by nanoparticles and nanopatterns |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080515 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080515 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111031 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111110 |
|
| 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: 20120402 |
|
| 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: 20120402 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |