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3.3.

Nanotubes

[Own knowledge, Dresselhaus, Dresselhaus and Avouris book, Poole-Owens, Enc. Nanoscience ch. 3]

3.3.1. History and structure 3.3.1.1. History The history of carbon nanotubes is interesting in that they were found before they were really found. - Standard reference: Iijima, Nature 354 (1991) 56. - However, several people had actually observed them before, and one of them had actually described it in some detail with clear figures in a regular publication: Oberline et al, J. Cryst. Mater. 32 (1976) 335. - But in the 1970’s nobody much cared for nanoscale stuff, and the work passed with little attention. The time was just not ripe - When Iijima refound the tubes, nobody remembered Endos results - Iijima also understood to make a lot of noise of his result
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Now Endo is also making noise, but too late for him...

3.3.1.2. Structure of single-walled tubes - Nanotubes typically look something like this in a TEM image:

A single-walled nanotube (SWNT) is formed by taking a sheet of graphene of some finite width w, and wrapping it up into a cylinder of fixed radius r and arbitrary length. - The circumference of the tube will be ≈ w +1.4 ˚ A, where the 1.4 ˚ A comes from the carbon-carbon bond length. - The wrapping up can be done in many ways. - To describe the tube structure, a special notation has been introduced. Consider the following figure:
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- Basic idea: select a rectangle in sheet which joins four crystallographically equivalent positions in the sheet. In this figure it is the rectangle OABB’. - Because it is a rectangle, the vector OA is enough to uniquely determine the way in which the sheet is wrapped up.
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a2) is needed to form the vector OA: Ch = OA = na1 + ma2 The angle between the unit vectors is exactly 60◦. 2).{z } ≤ aC −C ≤ 1 | . .49 ˚ A .The length of a single bond is in the range (1) graphite 1 41˚ A 44˚ A | . Introduction to Nanoscience. .{z } C60 (2) and all bonds in the same tube may not be of exactly the same length This defines fully the length of everything else in nanotubes..The unit cell in the tube length direction is given by OB .m) of the tube is the given by which combination of the graphite unit vectors (a1.The chiral index (n.The unit cell size a of graphene is more than the nearest-neighbour distance! It is √ a = 3aC −C = 2. 2005 (3) × 4 . m) = (4.The particular Ch shown in the figure is (n. .

θ = 30◦ b) zigzag tubes: m = 0. .Because of symmetry. In this way the following nanotube is generated: . 2005 (4) × 5 .The chiral angle θ is defined as the angle between the direction a1 and the vector Ch. θ = 0◦ c) chiral tubes: all the others. 0◦ < θ < 30◦. Introduction to Nanoscience. the non-equivalent indices are chosen such that n≥m which of course is just an arbitrary choise..Tells how far you have to move in the tube length direction to get back to a position crystallographically equivalent with the original one. .According to the wrapping up 3 types of nanotubes can be defined: a) armchair tubes: n = m.

2005 × 6 .Types a) and b) are considered achiral.5).5): The names “armchair” and “zigzag” are a bit silly. but can be understood if you look from the tube Introduction to Nanoscience.0). Here is examples of the three types. b) zigzag (9. a) armchair (5. c) chiral (10.

Then with considerable imagination you can see armchairs in the tube.Typical tubes are in the range (5. Here is a figure to help you out: . smaller tubes than this are not stable. with the pattern overall direction perpendicular to the tube length direction . m) to maybe (20. m).with the length direction upwards.The smallest tubes ever manufactured are something like (3.zigzag simply comes from having in the same view a zigzag pattern of bonds across the tube. . 2005 × 7 . Introduction to Nanoscience. m).

VTT/TKK] with a diameter of some 7 nm. 0) ! See /group/elena/tule/elena pres. 4 cm for a 1-nm wide object is quite an aspect ratio! 3. If this would be a zigzag tube this would correspond to about (90. and there appears to be no practical upper limit. and these were the ones Iijima originally found: Introduction to Nanoscience. Structure of multi-walled tubes The tubes described above were single-walled (SW or SWNT).3.. 2005 × 8 . But it is actually easier to manufacture multi-walled (MW or MWNT) nanotubes.The widest SW tube I have heard of is actually made in Finland [Esko Kauppinen.1.ppt . but using surface growth methods up to 4 cm long SW tubes have been made.The tube lengths are typically in the 100 nm to a few micron regime.3.

e.. i. .They are nested inside each other with an interlayer separation of ∼ 3.Each part of the MW tubes are single-walled tubes. with same kind of structure and chirality as a SW tube.Important special cases: double-walled tubes DWNT and triple-walled TWNT. just as in graphite Introduction to Nanoscience. 2005 × 9 . .4 ˚ A.

The closed ones are likely to be more stable.3.4.Which one they are will depend on how they were manufactured .. the inside is empty and can be quite large.As the TEM images clearly show. .2.MW tubes can easily be tens or hundreds of microns long 3. . 2005 × 10 . Manufacturing nanotubes Introduction to Nanoscience.The nanotube ends. 3.Interlayer interaction is the same weak vdW-interaction as in graphite .The chirality of one tube need not be correlated with that of others . but may be less interesting from an application point of view .3. Capped and uncapped nanotubes . both SW and MW. may be either open or closed with fullerene-like gaps (see figure above).1.Whether they have open and close caps affect the electronic properties of the tube also far from the opening.

It can be graphite or some gas containing carbon atoms. 2005 × 11 . . Fe or Co or Ni. but the most commonly used ones share some common charasteristics: . e. To obtain SW tubes there needs to be a catalyst involved which facilitates the growth.There are several ways to manufacture carbon nanotubes. Typically the catalyst particles are small metal nanoparticles. the tube would never grow long but just be a fullerene).6000 ◦ C) in a hot carbon gas or plasma .Without the catalyst the SW nanotube end does not stay open during growth.The tube growth occurs at high temperature (1000 . .There of course has to be a carbon source involved.e. but would close spontaneously (i. Detailed example: aerosol growth techniques of Esko Kauppinen et al (VTT Processes): Introduction to Nanoscience.g.MW tubes can grow by themselves.

Introduction to Nanoscience. 2005 × 12 .

2005 × 13 .End result (collected at top or on side surfaces): SW or MW nanotubes capped with the metal nanoparticles: .First a metal vapour is formed. .These nanotubes have a fairly narrow size distribution: Introduction to Nanoscience.Then it comes to contact with a carbon gas (CO2 or C2H5OH) where nanotubes grow out of the metal particles.. this then condenses to metal nanoclusters (a variety of gas phase condensation) .

6: Introduction to Nanoscience..which is thanks to the fact that the nanoparticle size distribution is narrow and that the ratio of the nanotube to the nanoparticle size is almost constant at 0. 2005 × 14 .

From this supersaturated C the tube growth then starts. though. and the tube grows outwards from the tube . . but the tube quality obtained is far from perfect: Introduction to Nanoscience. 2005 × 15 .The current best understanding of the growth is that the hot metal nanoparticles obtain a supersaturation of C at the surface and inside.Issue is still under intense debate and study.Growth can be modelled with atomistic simulations..

Sometimes also the term nanotube forest is used for this.A collection of nanotubes grown on a surface such that they stick out of it and are roughly perpendicular to each other is calles a nanotube mat.3. Introduction to Nanoscience. 2005 × 16 . ropes and paper . bundles.3. Nanotube mats.3.

2005 × 17 ..A collection of nanotubes aligned parallell to each other. and bonded to each other with the van der Waals interaction.A collection of nanotube bundles intertwined around each other is called a nanotube rope Introduction to Nanoscience. is called a nanotube bundle .

Nature 423 (2003) 703 CNT fibers of length 100 m is reported Introduction to Nanoscience. the terms rope and bundle may be used for the same things in different sources . Science 296 (2002) 884] a nanotube rope of similar length and width as a human hair is reported.In Dalton. see fig.g. that the terminology here is not quite stabilized yet. below.Nanotube ropes can be manufactured in macroscopic thicknesses and lengths . .Note. in [Zhu. however.E.. 2005 × 18 .

Finally. since fibres can be manufactured from nanotubes. .Known as nanotube paper or buckypaper. 2005 × 19 .Here is a figure of nanotube paper.The paper is black . taken on the lecturers office desk: 3.4. it is natural that one can also make paper out of them (paper is a flat network of fibers).3. Strength of nanotubes Introduction to Nanoscience. .

i..5 . steels with 0.One of the many interesting aspects of nanotubes is that they are very strong . .1. [http://www.g.Nanotubes are also special in that they can be bent a lot without them breaking. because of their narrow diamaters. Compare e.But these values should be viewed with some caution.Youngs modulus is very high: 1.On extreme bendings the carbon hexagons in the tube change shape. But even then they do not break.isr. Science 287 (2000) 637 ] Explain Youngs modulus. and these degrade the values from the above ones which are valid for high-quality tubes.html. . Introduction to Nanoscience. Compare e. however.To be more precise: . they are resilient against bending. experimental 63 GPa.Tensile strength: theoretical value up to 300 Gpa.5 GPa. In practice most tubes have defects in them. bulk Fe 211 GPa .25 TPa for SWNT [Krishnan. 2005 × 20 .g.For normal bulk materials a high Young’s modulus tends to indicate the material is also difficult to bend. PRB 58 (1998) 14013]. . in which case the tube may get a permanent kink in them. For carbon nanotubes this is not true. tensile strength .us/Downloads/niac pdf/chapter2.e.

or tubes surrounded e.This is a very significant problem and it is not clear whether it can be fully solved.Possible solution: introduce defects with covalent bonds between shells of a MW tube. by a polymer.. 2005 × 21 . . but a collection of tubes.But the major problem is again the van der Waals interaction between tubes: a single tube may be very strong. or between a tube and a surrounding. are usually much weaker because the interaction between tubes is so weak! . Introduction to Nanoscience. to make it stronger: . .Defects can be introduced with electron or ion irradiation or possibly during growth or with chemical methods.g.The strength values are valid for single (SW or MW) tubes.

2005 × 22 . Sammalkorpi] Introduction to Nanoscience.[Figures courtesy of M.

113. Krasheninnikov] 3. p.5. 2005 × 23 . Electronic properties [Louies article in Dresselhaus book.[Figure courtesy of A. See also Scientific American 283 (Dec 2000) p. 62] One of the most striking features of nanotubes is that they can be either semiconducting or metallic! Introduction to Nanoscience.3.

The reason to this is not quite trivial.Depends directly on chirality: .(n. . but here is a short summary (if you have not taken a course on solid state physics. i. parallel to the graphene sheets. is a semiconductor.Like graphite.. But sometimes the tube nevertheless has a band gap. n) (armchair) tubes are metals . 2005 × 24 . you probably can not follow this.(n. so then never mind): Introduction to Nanoscience. m) tubes with n − m divisible by 3 are very-small band gap semiconductors .All other are large-band gap semiconductors .e. electrons can move easily in the length direction of the tube.

but the more recent knowledge is interpreted to indicate that they are very good ballistic conductors. For some time it was believed that the electrons in a nanotube behave as a so called Luttinger liquid.Although the above features are well understood. otherwise it is semiconducting (in a tight-binding model).. the actual nature of electron transport in nanotubes is still under intense debate and study. . Introduction to Nanoscience. Comment on separating metallic and semiconducting nanotubes Electronic states in graphene States in reciprocal space in a nanotube.In a rolled-up graphene sheet (a nanotube) only certain k points of all the possible graphene points are allowed because there are periodic boundaries in the circumferential direction (analogous to the quantization of possible wavefunction in a 1D periodic array of atoms) . but curvature effects modify things from the tight-binding picture such that they actually are very small band gap semiconductors. the tube becomes metallic.If the allowed k states hit the K point.A single graphene sheet is an insulator with a band gap of zero at the K point in the Brillouin zone .This would give the rule that all tubes with (n − m) divisible by 3 would be metals. 2005 × 25 . left is metallic (allowed k lines hit K points) .

to be compared with the value for copper of 1 MA/cm2! 3. Kauppinen. . . 2005 × 26 .Nanotube transistors have been manufactured for some time. It is believed to be 1000 MA/cm2.g. Prosessorilehti.1. Wet dream of electron theorists.5.3.. there is strong interest in manufacturing nanotube devices. Marraskuu 2004 s. the current carrying capacity of tubes is enormous. 32-34].Figure of single-electron transistor manufactured at low-temperature laboratory at the Helsinki University of Technology: Introduction to Nanoscience. Nanotube devices [If you known Finnish see Hakonen. the Luttinger liquid question) and the huge current carrying capacity.Since ballistic conductance is very efficient. Nordlund. Two eigenmodes. ballistic conductor: uncorrelated electrons moving with no backscattering.Because of both fundamantal interest (e. best normal conductor possible. . .Luttinger liquid: ground state of correlated electrons in 1D..

. and have very promising properties. 2005 × 27 .The transistors have been shown to work. So far they usually have been made manually one at a time.But the big issue is how the nanotube devices can be manufactured reliably on a mass-production scale.There is lots of speculation like that they might even become the active component in conventional Si electronics .. Introduction to Nanoscience. which of course is completely out of the question for mass produced chips which may have literally billions of transistors each.

Growing nanotubes from one electrode to the next using electric-field directed growth . Nanotube chemistry .No clearly working solution has yet been demonstrated. it is interesting to insert things into carbon nanotubes Introduction to Nanoscience.Nanotube memories using several nanotubes at each memory component already exist (see e. 3. Endohedral nanotubes . .3. 2005 × 28 . rich field of nanotube chemistry exists 3. Scientific American 292 (2005) 64).Hence it is easy to get them to react with other atoms.Open-ended nanotubes have several unsaturated “dangling” C bonds at the end.g.3.6. chemists have already learnt how to attach things also to the side walls of nanotubes.As for fullerenes. .As for fullerenes. ..But even though graphene sheets are considered chemically inert. but there are some promising developments: .7.

nanotubes with fullerenes in them: Introduction to Nanoscience. Explain hydrogen economy Need to both get H in and out at the same temperatures as fuel cells operate. allowing for a straightforward path for ions to enter the tubes .. 2005 × 29 .e. achieving this is much harder than initially thought. But now most people who worked on that are rather pessimistic about this.A really funny kind of endohedral nanotubes: carbon peapods i. Also repeatability of research results problematic .Hydrogen storage in nanotubes was for a long time considered extremely promising in view of the forthcoming “hydrogen economy”.This is easier than for fullerenes since the nanotube ends can be open.

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g. One funny variety is carbon onions.staff. Introduction to Nanoscience. e.There are still many more kinds of pure carbon nanostructures than the ones mentioned here. Carbon onions [Florian Banharts work. http://www. 2005 × 31 .3. which is concentric shells of carbon spheres inside each other.4.uni-mainz.htm] .de/banhart/c-nanostructures/onions.

. 2005 × 32 .. [F. GER: Kohlenstoffzwiebeln. Banhart. SWE: Koll¨ ok.. Introduction to Nanoscience. 33-35 (1997)] Just don’t enter your grocery store and ask for them. ”Diamantbildung in Kohlenstoffzwiebeln”. Physikalische Bl¨ atter 53.If you think carbon onion sounds silly. think about the equivalents in your native tongue: FIN: Hiilisipuli.

Another is related to the carbon onions: long-term electron irradiation creates vacancies from the shells.It is also possible to manufacture nanosize diamonds . Thus the concentric C shells shrink.There are at least two distint ways of making them .3. Science 271 (1996) 1260].5. which then migrate outwards.They form during heavy ion irradiation. . 2005 × 33 . Nanodiamonds . creating a large pressure in the innermost shells which allow for diamond nucleation Introduction to Nanoscience. and thus also in naturally occuring minerals with radioactive heavy isotopes in them [Dalton.

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