VOLUME 89, NUMBER 27 P H Y S I C A L R E V I E W L E T T E R S 30 DECEMBER 2002

Tuning of Nanotube Mechanical Resonances by Electric Field Pulling

S.T. Purcell,* P. Vincent, C. Journet, and Vu Thien BinhLaboratoire d’Emission Electronique, DPM UMR CNRS 5586, University Lyon-1, Villeurbanne, 69622, France

(Received 6 July 2002; published 20 December 2002)

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We show here that field emission (FE) can be used to directly observe the vibration resonances �R ofcarbon nanotubes (CNTs) and that the tension created by the applied field allows the tuning of theseresonances by up to a factor of 10. The resonances are observable by the changes they create in the FEpattern or the emitted FE current. The tuning is shown to be linear in voltage and to follow from thebasic physics of stretched strings. The method allows one to study the mechanical properties ofindividual multiwall carbon nanotubes within an ensemble and follow their evolution as the CNTsare modified. The tuning and detection should be useful for nanometric resonant devices.

DOI: 10.1103/PhysRevLett.89.276103 PACS numbers: 68.65.–k, 73.63.Fg, 79.70.+q

FIG. 1. Schema of the experimental field emission setup used

present on the Ni tip, the FE patterns specific to individ-ual ones are distinguishable. This is first because FE is an

to measure the resonances (distances: tip anode �2 mm, tipscreen �3 cm, and screen size �4 cm).

One of the important phenomena in nanomechanicsthat has been recently developed for carbon nanotubes(CNTs) is the excitation of their natural mechanicalresonances �R by an alternating electric field [1,2]. Themode forms and resonance response were directly ob-served by transmission electron microscopy. Besides giv-ing a measure of the Young’s modulus of an individualCNT, this has opened up applications in nanoresonantdevices such as sensors, oscillator circuits, and nanoba-lances [1,3]. In such applications it would be useful to tune�R electronically. In this Letter we first present a newsimple method to observe �R in a field emission micro-scope. We then show that �R varies simply linearlywith applied voltage which creates a longitudinal tensionon the CNT as in the tuning of a guitar string. �R wastuned at will by over 10 times its natural resonancefrequency. The basic theory of the resonance phenomenonis presented and shown to be in agreement with themeasurements.

A large number of multiwall carbon nanotubes(MWNTs) were grown directly by chemical vapor depo-sition on the end of a Ni base tip to obtain good mechani-cal and electrical connection. The MWNTs were straight,up to 40 �m in length, had radii in the 10–20 nm range,and were approximately aligned along the support tipaxis. The Ni base tip was mounted on a heating loopwhich was then inserted into the classic field emission(FE) configuration in ultrahigh vacuum (10�10 Torr).This sample was recently used to show the existence oflarge heating effects accompanying FE [4]. A schema ofthe FE system is depicted in Fig. 1 which also illustrateshow the �R of individual MWNTs were measured. FEelectron and ion microscopy (FEM and FIM) patterns ofseveral MWNTs were made to appear on the observationscreen when the correct voltages VA were applied to thetip. VA was varied from �500 to �900 V for electronemission and from �1900 to �2500 V for ion imagery byargon ions at 1� 10�4 Torr. Though many MWNTs were

0031-9007=02=89(27)=276103(4)$20.00

exponential function of field and hence is very selective toonly a few MWNTs that are most exposed to the appliedfield. Second, the radial projection geometry of FE meansthat even if several MWNTs emit, they are in generalprojected at different angles and can be distinguishedwith ease in the FE pattern. A variable digital functiongenerator displaying seven digits was then connected tothe excitation anodes, which is actually a quadrupole, andwhen a �R was found, the corresponding part of thepattern suddenly got larger and the FE current varied.�R was then measured against the applied voltage to thetip for many different modes and three different MWNTs.The majority of measurements were made in the moreconvenient FEM mode. Note that the resonance frequency

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VOLUME 89, NUMBER 27 P H Y S I C A L R E V I E W L E T T E R S 30 DECEMBER 2002

is the same as the driving frequency �S and not 2�S as ispossible in the TEM experiments [1,2]. This is becausethe driving of the large static charge induced by VA is atleast 100 times larger than that of the time varyinginduced charge. Different excitation amplitudes Vs wereused from 0.5 to 10 V. However the true amplitudes atMHz frequencies were observed to be much smallerbecause of the bandpass of the anode driving system.Several FEM patterns are shown in Fig. 2(a)–2(e) thatshow that this method allows the easy observation of theresonances of different MWNTs of the ensemble. Theirregular FEM patterns are due to imperfections in theMWNT apexes and the perturbing electrostatic fields ofnearby MWNTs. The patterns are formed by FE fromthree different MWNTs, denoted hereafter NT1, NT2,and NT3. As � is varied in the MHz range the individual

FIG. 2. VA 700 V. (a) FEM pattern out of resonance. Thepattern from NT1 is overexposed so that those of NT2 andNT3 are visible. The 4 cm microchannel plate (mcp) fills mostof the image. (b) NT1 in vertical resonance,m 2 (see below),� 0:9588 MHz. (c) NT1 in horizontal resonance, m 1,� 0:7399 MHz. (d) NT2 in resonance, � 0:6017 MHz.(e) NT3 in resonance, � 1:0463 MHz. (f) Total FE currentIFE��� as NT1 is scanned through resonance.

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patterns enlarge independently as the correspondingMWNT resonates at one of its �R’s. The increase inpattern size gives approximately the amplitude of theCNT end angle by projection. We found angles up to ashigh as 20�. This experiment then permits one to distin-guish absolutely if different features in a complex FEpattern are due to different CNTs. The FIM patterns ofNT1 were also observed against VA for four differentresonances. This experiment detects the modes of differ-ent polarizations with the same sensitivity which is notthe case in the TEM method. In Figs. 2(b) and 2(c) weshow two different modes for NT1 that have approxi-mately orthogonal directions. This is detectable in thisexperiment because one effectively observes the MWNTsendon. Several tens of resonances were found as � wasvaried from the lowest values of 0.3 up to 20 MHz, themaximum of our generator.

The response as a function of frequency can in prin-ciple be measured by the increase in the pattern size butfor now we have used the FE current, IFE��� that isemitted from the MWNT. This was measured simulta-neously to the observation of the patterns as it passesthrough resonance. IFE��� varies because the averageelectric field, hFi, at the apex of the MWNT varieswhen the MWNT is in resonance due to the changing ofthe physical position of the end of the MWNT and theresulting changes of the local average screening. Note thatthough IFE��� does not give immediately the true re-sponse function because it is a function of the environ-ment of the specific MWNT and is nonlinear in field, itdoes allow a good estimate of the width and form of theresonance. A typical IFE��� curve is shown in Fig. 2(f). Afeature of these measurements is that the MWNTs do notcome smoothly into resonance but most often snap on oroff vibration as the frequency is scanned. The qualityfactor Q defined here simply by ��=� for the centralpeak of this resonance is 2400. However the IFE��� curvesare most often asymmetric and the extracted values of Qvary widely for different modes, driving amplitude, andscan directions. Clearly a large number of measurementsare called for to understand the response function of theseMWNTs. We discuss possible mechanisms below. Themeasure in Fig. 2(f) shows that FE is a simple andsensitive current detection method of resonances whichcould be applied in nanomechanical device applications.

The result on which we concentrate in this paper isshown in Fig. 3 which is the dependence of �R on VA.Plots for three pairs of different modes at the lowestfrequencies found for NT1 are presented that show analmost perfect linear dependence on VA: that is, �R�VA� �R0 � pVA with �R0 0:3–1 MHz and p 1–2 kHz=V.The resonances are designated as (m; n) where m desig-nates the ‘‘type’’ of mode (see below) and n is the modeorder. Each type m designates a specific polarization ormovement of the MWNT apex and therefore a specificresonant waveform. �R�VA� doubles and the polarization

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FIG. 3. Dependence of a selection of �R ’s on VA for NT1 andNT2. Only one measure by FIM for NT(1,1) is shown thoughfour series corresponding to modes (1,1) to (4,1) were mea-sured. We find �R0 ’ 190 kHz and p ’ 0:91 kHz=V forNT1(1,1) FEM, and �R0 ’ 280 kHz and p ’ 1:01 kHz=V forNT1(1,1) FIM. They also displayed the same polarization, thusestablishing the correspondence between the two series.

VOLUME 89, NUMBER 27 P H Y S I C A L R E V I E W L E T T E R S 30 DECEMBER 2002

remained the same within each pair presented in thefigure on passing from n 1 to 2. The FE patterns form 1 and 2 were clearly orthogonal [see Figs. 2(b) and2(c)] and stronger than mode m 3. NT2 and NT3 alsohad two strong orthogonal resonances.We were not able toclearly identify higher frequency modes of NT1 withthose plotted here though at least 20 other series weremeasured up to 10 MHz. They all showed a linear depen-dence on VA with increasing �R0 and p at higher fre-quency resonances. The polarizations were often eitherthe same as for n 1 or 2 though other mode types werealso often observed. These many series are not plottedhere so as not to encumber the plot. Two plots of �R�VA�for NT2 are also included. �R0 and p are quite differentfrom NT1 for the same range of � showing that we canmeasure the characteristic constants of differentMWNTs. One plot of �R�VA� for NT1(1,1) measured byFIM is also plotted which is in the 2–3 MHz range. Notethat p is approximately the same in both the FIM andFEM for mode NT1(1,1) and in both cases they were thelowest frequency resonances found. Some disagreementbetween the two series can be expected because thehigh strains, particularly in the FIM mode, may createstatic bending effects that cause some nonlinearity inthe �R�VA� plots. Therefore this resonance was tunedfrom 0.64 to 3 MHz. Extrapolating back to �R0 0:2–0:3 MHz, this is a factor of 10.

The linear dependence of �R on VA can be understoodfrom the basic physics of a string stretched by a tension Tand that an electric field exerts a force � F2 on a surface

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where F is the electric field. We have �R�����T

p�

������F2

p

F �VA.� is the field amplification factor. This explainsthe linear dependence on VA. In more detail, T is createdonly by the longitudinal force at the MWNT cap given byT ��0=2�

RF2zz � dA where z is along the MWNT axis.

Depending on the shape of the cap, T is a fraction of T0 ��0=2��r

2F20 ���0=2��r�0VA�

2 where F0 and �0 arethe maximum values of F and � in the emission zoneand r is the radius of the MWNT. For a smooth hemi-spherical cap we used the field distributions given byDyke and Dolan [5] to calculate this fraction to be T 0:64T0. For an uneven cap as in our case it can be muchsmaller. We write formally:

T � ���0=2��re�0VA�2 �2V2A; (1)

where re is an effective radius of the emission zone.The equation for a rigid stretched string is [6]

@2y

@t2

T�L

@2y

@x2�EI�L

@4y

@x4; (2)

with �L the mass per unit length, E the Young’s modulus,and I � ��=4�r4 the ‘‘cross sectional area moment ofinertia,’’ neglecting the hollow inner tube diameter. Themethod for deriving the general waveform and resonancecondition can be found in many texts and is rather cum-bersome [6]. In our limit the tension term is larger thanthe rigidity, or T � �n�=L�EI. After some work thecondition is rather simple and in the desired form:

�R�VA� ’ �R0 � pVA; �R0 n

L2

������EI�L

s;

p n�2L

������1

�L

s:

(3)

The resonance is linear in n, the y offset depends onlyon the mechanical properties of the tube, and the tensionterm is linear in VA. Note that the form of �R0 here is notthe same as in rigid strings at zero tension [1] as a differ-ent mathematical limit applies. For these first measureswe have only rough estimates of L and r for the MWNTsso we prove here only that we have an order of magnitudeagreement with the formulas. We take r 10–25 nm,L 10–40 �m, E 1010–1012 Pa [7], and the densityof graphite 2:26 kg=m3. This gives a wide range of�R0 5� 103–2� 106 Hz into which the measurementsfall (0.2–0.4 MHz for m 1). In the second term theunknown is re. FE onset occurred at 500 V for which wemust have F0 � 3 V=nm to allow FE. This gives �0 ’7� 106 m�1. From the plots p � 1 kHz=V for n 1. Forthe range of L and r given above this gives re � 1–10 nmwhich is in the expected range.

From the above discussion it seems clear that we under-stand the basic mechanism of the resonance tuning. Oneaspect of the measurements that deserves mention is themultiplicity of different modes and mode types. These

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VOLUME 89, NUMBER 27 P H Y S I C A L R E V I E W L E T T E R S 30 DECEMBER 2002

modes are not the driving of a perfect MWNT in con-trolled directions but the excitation of the characteristicmodes of our nonhomogeneous MWNTs. Different polar-ization modes have already been observed by Wang et al.[8] and ascribed to the mechanical anisotropies in theirnanotubes. The large number of modes observed here maytherefore be due to a combination of the nonhomogeneityof our MWNTs, the close proximity of other MWNTswhich may also go into resonance, the symmetry break-ing electrostatic force of VA, and of course the excitationof higher order modes. Another interesting aspect is thetendency of the tubes to snap into and out of resonancereversibly while scanning � [see Fig. 2(f)]. One explana-tion is that from classical physics nonlinear driving cre-ates abrupt transitions in the frequency response function[6]. It is also possible that the vibrations may createreversible configurations in the MWNT structure as hasbeen observed and theoretically modeled [9] for singlewall CNTs. From a practical point of view, the abruptbreaks in IFE��� allow the detection of a change in the �Rmuch finer than predicted by the Q.

There are numerous ramifications of this work. This isa new and simple method to measure the mechanicalresonances of CNTs. This is a standard geometry for FEstudies used currently by hundreds of researchers world-wide. They need only to add a function generator to studythe mechanical properties of their CNTs. The techniqueallows a clear identification of different CNTs within acomplex FE pattern. The mechanical properties can befollowed as the CNTs evolve under FE which permitsrecrystallization, tube shortening, and narrowing byevaporation, deposition, ion bombardment, oxidation, etc.The FE current sensing can provide feedback signals fornanoresonating devices. It is easy to show that electricforce can create strains of up to �1%. Thus one can carryout stress-strain experiments to influence the microscopicand macroscopic structure of the CNTs and which inturn can be immediately followed by the resonanceexperiments.

The wide range electronic tuning can be used for nano-electromechanical systems, for example, for the tuning ofarrayed CNTs to have the same frequency or in resonantatomic force experiments. In this experiment the field wasapplied at the tube end. A transversal static field will alsocreate similar tuning for circuits in which the CNT isfixed at both ends. An exotic application comes from thefact that �R is sensitive to the area and field at the apex of

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the CNT. Therefore at high fields the addition of one atomto the cap of a smooth CNT will shift �R by �

�������������dA=A

pwhere dA is the ‘‘size’’ of the added atom. For a (10,10)single wall CNT of 30 end atoms this is �1%–2%. Thehigh Q resonances should easily detect the arrival ofsingle atoms. This is a sensitivity of the mechanicalresonance of the CNT up to 12 orders of magnitude lessatoms than reported for the nanobalance [1].

Finally, we have recently shown that FE permits thecontrolled heating of individual MWNTs up to 2000 K byJoule heating along the MWNTand quantitative measure-ments of the induced temperature and MWNT resistance[4]. This was done in the same FE setup used here. Inparallel with modelization [10] and microscopy studies ofthe MWNT dimensions one can estimate the electricaland thermal conductivities, " and #. It is therefore nowpossible to have access to ", #, and E for a single nano-tube, or other nanowires, in a single experimental setup atany stage in their evolution.

*Electronic address: purcell@dpm.univ-lyon1.fr[1] P. Poncharal, Z. L. Wang, D. Ugarte, and W. A. de Heer,

Science 283, 1513 (1999).[2] R. Gao, Z. L. Wang, Z. Bai, W. A. de Heer, L. Dai, and

M. Gao, Phys. Rev. Lett. 85, 622 (2000).[3] See D. Qian, G. J. Wagner, W. K. Liu, M.-F. Yu, and R. S.

Ruoff, Appl. Mech. Rev. 55, 495 (2002).[4] S.T. Purcell, P. Vincent, C. Journet, and Vu Thien Binh,

Phys. Rev. Lett., 88, 105502 (2002).[5] W. P. Dyke and W.W. Dolan, in Field Emission, edited by

L. Marton, Advances in Electronics and ElectronPhysics Vol. 8 (Academic Press, New York, 1956).

[6] L. Meirovitch, Elements of Vibration Analysis (McGraw-Hill, New York, 1986); C. Vallette, Mecanique de laCorde Vibrante (Hermes, Paris, 1993) (in French).

[7] M. M. J. Treacy, T.W. Ebbesen, and J. M. Gibson, Nature(London) 381, 678 (1996); J.-P. Salvetat, A. J. Kulik,J.-M. Bonard, G. Briggs, T. Stokli, K. Metenier,S. Bonnamy, F. Beguin, N. A. Burnham, and L. Forro,Adv. Mater. 11, 161 (1999).

[8] Z. L. Wang, R. P. Gao, P. Poncharal, W. A. de Heer, Z. R.Dai, and Z.W. Pan, Mater. Sci. Eng., C 16, 3 (2001).

[9] S. Iijima, C. Brabec, A. Maiti, and J. Bernholc, J. Chem.Phys. 104, 2089 (1995); B. I. Yakobson, C. J. Brabec, andJ. Bernholc, Phys. Rev. Lett. 76, 2511 (1996).

[10] P. Vincent, S. T. Purcell, C. Journet, and Vu Thien Binh,Phys. Rev. B 66, 075406 (2002).

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