NANO LETTERS

Nanomechanical Resonance Tuning and Phase Effects in Optical Near-Field Interaction

T. Taubner, F. Keilmann, and R. Hillenbrand*
Max-Planck-Institut fur Biochemie, 82152 Martinsried, Germany
Received June 2, 2004; Revised Manuscript Received July 13, 2004

2004 Vol. 4, No. 9 1669-1672

ABSTRACT
We use scattering-type apertureless near-field optical microscopy to demonstrate distance-controlled spectral resonance and phase shifts of a single near-field coupled system. In our experiment a metal tip optically interacts with a SiC surface at continuously varied nanometric distances. For illumination we use mid-infrared wavelengths (10 m) where phonon polaritons in SiC resonantly enhance the near-field interaction. The phase of the scattered light increases and the resonance peak red shifts with decreasing gap width, in accordance with theoretical modeling.

The resonant interaction of light with nanoparticles leads to enhanced local optical fields and to enhanced light scattering. Mostly metallic nanoparticles have been studied, with resonances in the visible spectrum caused by surface plasmon polaritons.1 Polar dielectric particles exhibit analoguous midinfrared resonances caused by surface phonon polaritons.2 The recent interest in plasmon-enhanced fields arises from enhanced nonlinear optical effects3 and from enhanced Raman scattering,4-8 giving even single-molecule sensitivity.5,6 Both basic understanding and potential applications of confined light such as in nanoscale optical circuits (plasmon nanophotonics)9 demand a detailed insight into optical interactions at nanoscale distance. This requires knowledge and even control10 of the oscillation phases in the system. However, spectroscopic characterization of single plasmon-resonant particles11 or of coupled particle pairs12-14 has mostly dealt with measuring intensity spectra only, thus omitting information on the phase lag between driving field and polariton oscillations. Phase-sensitive measurements were reported on plasmon-resonant particles,15,16 however, without separating amplitude and phase information. The nanoscale near-field interaction of two or more metal particles, which is supposed to provide outstanding field enhancement,6 has been calculated to shift the plasmon resonance,17,18 as experimentally verified by the preparation of different samples with varied interparticle distances.12,13,19 To avoid fabrication irreproducibilities in size and shape of the particles, we study here mechanically controlled resonance shifts in both amplitude and phase of one single resonant scattering system composed of two near-field
* Corresponding author. E-mail: hillenbr@biochem.mpg.de; Fax: +49 89 8578 2641. 10.1021/nl0491677 CCC: $27.50 Published on Web 08/05/2004 2004 American Chemical Society

Figure 1. Resonant scattering system consisting of a small sphere in variable distance from a surface (a), realized by a scatteringtype SNOM with interferometric detection (b). Each approach curve is recorded for two positions of the reference mirror separated by /8, to compute amplitude s and phase of the backscattered light.

interacting elements whose separation z is continuously adjusted on a nm scale (Figure 1a). A convenient experimental system for this purpose is a scattering-type, amplitude-and-phase sensing, near-field optical microscope (s-SNOM, Figure 1b),20 as it allows to control the near-field interaction between two elements, the probing tip and the sample, simply by continuously adjusting the tipsample distance z with subnanometer accuracy. The s-SNOM employs light scattering at the sharp tip of a probing needle, such that the probing light field confined at the tip apex extends only about one tip radius a , in any direction.21,22 Therefore, the characteristic length scale for near-field coupling is about a 20 nm, much smaller than the wavelength (10 m) used for illumination. The near-field coupling can be approximated by a simple sphere-plane model system as sketched in Figure 1a.23,24 Calculations for a plasmon-resonant sphere-plane system predict that the near-field coupling causes resonance shifts in the scattered

signal when changing the distance z between sphere and sample.25-27 In this letter, we show first experimental evidence of such resonance shifts, but at mid-infrared frequencies where near-field interaction is resonantly enhanced by phonon polaritons in a SiC sample.24 This phonon-enhanced near-field interaction has the advantage of a sharp resonance and a high field enhancement, due to the weaker damping of phonon polaritons compared to plasmon polaritons. The basis of the infrared s-SNOM is a tapping-mode AFM that uses a cantilevered, commercial Pt-coated tip (Mikromasch, www.spmtips.com). The tip oscillates at its mechanical resonance frequency 30 kHz with amplitude z ) 20 nm. It is illuminated by sharply focused infrared light from a CO2 laser, with the incident field Ei polarized in the x-z plane (Figure 1b).24,28-30 The backscattered light is analyzed with a homodyne-mode Michelson interferometer to record both amplitude s and phase of the complexvalued near-field interaction of tip and sample, ) sei ) Esca/Ei, where Esca denotes the scattered field.20 The nonlinear distance dependence of the near-field interaction (eq 1 below) is utilized to suppress a large, unavoidable background scattering b caused by parts of the tip shaft and the sample, in the following way.31 The tip oscillation at frequency modulates the distance z and induces harmonics in but not in b, so that by demodulating the detector signal at a harmonic frequency n (ng2) we extract a background-free nth Fourier coefficient of the near-field interaction, n ) sn ein. We study the distance-dependence of the phonon-enhanced near-field interaction, in amplitude and phase, between tip and SiC sample (polytype 4H, N-doped with n 2 1018 cm-3) at the mid-infrared resonance near ) 10.6 m.24 To compare with a nonresonant sample material, we also study a 20 nm thick Au film partly covering the SiC sample. When the sample approaches the tip (Figure 2a,b) the amplitude signal s2 increases strongly, for both sample materials, on a length scale of the tip radius a 20 nm, a behavior typical for s-SNOM.20,32 Due to the phonon-enhanced near-field interaction, the signal of SiC exceeds that of Au by a factor of 3. At large distance z the amplitude s2 decreases below the noise level, confirming that background signals are efficiently suppressed.23,33 The phase 2 develops very differently for both materials, changing strongly for SiC but remaining nearly constant for Au. Accordingly, a polar plot of the complex phasor 2 vs z (Figure 2c), where the polar angle represents the optical phase, exhibits a linear approach trajectory for Au, while for SiC the phasor performs an impressive quarter-circle rotation over just 10 nm preceding contact. On this scale of about /1000, phase changes by propagation of light between tip and sample can be neglected, so the strong phase changes result from a localized nearfield interaction. For further insight we investigate the spectral dependence by taking approach trajectories 2(z) at different frequencies f in the resonance region, between 893 and 951 cm-1. We observe a variety of trajectories shown in Figure 3. At each of the probing frequencies, the phasor 2 performs an anticlockwise rotation as z decreases. The
1670

Figure 2. Mechanical (a) and infrared (b,c) s-SNOM response during tip-sample approach. (a) Tapping amplitude z vs tipsample distance z. Contact (z ) 0) is defined by a beginning decrease of z. (b) Simultaneously recorded amplitude s2 and phase 2 signals at f ) 1/ ) 939 cm-1 of SiC (full curves) and Au (dotted curves), normalized to the complex-valued scattering signal 2 ) s2ei2 of Au at contact. (c) Data from (b) in polar display, resulting in approach trajectories of complex phasors 2(z) ) s2ei2; data points taken every 0.8 nm, contact points marked by asterisks.

phase at contact (marked by asterisk) increases continuously from 35 at 893 cm-1 to 270 at 951 cm-1. The angular range 2 covered by each trajectory also increases with frequency. We note that the demodulation process enhances the phase signal yielding phase shifts of more than 180, an effect analyzed before.20,31
Nano Lett., Vol. 4, No. 9, 2004

Figure 3. Approach trajectories of the complex near-field interaction 2 ) s2ei2 on SiC normalized and displayed as in Figure 2c, at different frequencies covering the infrared polaritonic near-field resonance.

To illustrate that the phase effects have their physical origin in a resonance shift, we extract amplitude and phase spectra at different z from measured approach trajectories such as shown in Figure 3. We reduce noise by averaging the data within height intervals z ) 9(5, 24(5, 40(5, 55(5 nm, and additionally average over five consecutive trajectories. For clarity, the resulting amplitude spectra (Figure 4a) are normalized to their peak values and separated by an offset of 0.5. The amplitude spectra clearly reveal a resonance maximum that shifts to lower frequencies with decreasing distance. From the amplitude data we estimate a red shift of about 9 cm-1 when decreasing distance z by 45 nm (corresponding to /220), from z ) 55 nm to 9 nm. The spectral phase data show first evidence that the resonance maximum is accompanied by a strongly rising phase, as for any resonance with weak damping. At smaller distances the phase 2 exhibits higher values but begins rising at lower frequencies, in accordance with the red shifting of the amplitude maximum s2. Thus, at any fixed frequency the phase increase during approach, i.e., the anticlockwise rotation of the complex phasor 2 in Figures 2 and 3 is caused by the red shifting of the resonance. The distance-dependent resonance shift can be explained by strong near-field coupling between the two entities, tip and sample. However, a quantitative theory of the scattering of a realistic, elongated tip in near-field interaction with a surface is complicated.34 To obtain a qualitative theroretical description, we approximate the tip by a small sphere and treat the scattering of the sphere-sample system (Figure 1a) by a dipolar, nonretarded near-field interaction.23,28,30 This model has well accounted for (i) the increased scattering amplitude s observed when the sample approaches the tip on a scale z a,20 (ii) material specific s-SNOM contrast,33 and (iii) the spectral behavior of phonon-enhanced near-field interaction.24 The calculation yields an analytic expression for the scattered field Esca ReffEi where
Nano Lett., Vol. 4, No. 9, 2004

Figure 4. Experimental (a) and calculated (b,c) infrared spectra 2 ) s2ei2 and ) sei of SiC, for different distances z of the probing tip. Amplitude spectra are normalized and vertically offset, solid lines are guides to the eye. The vertical lines (dashed) mark the position of amplitude maxima, the arrows indicate the red shifting on approach.

Reff ) R(1 + )/(1 - R/(16(a + z)3))

(1)

is the effective polarizability of the system consisting of the tip dipole and its mirror dipole in the sample. z is the distance between the sphere and sample, R is the polarizability of the tip with radius a, and is the samples surface response function ) ( - 1)/( + 1) with the samples dielectric function . The near-field interaction becomes resonantly enhanced due to a dielectric resonance in the samples surface response function , at ) -1. As the complex near-field interaction is ) sei Reff, a nonzero phase ) arg(Reff) arises from a nonvanishing imaginary part of . The dielectric function of undoped SiC is described by a single-phonon oscillator.35 Free carriers in the sample are taken into account by adding a Drude-term, altogether yielding (f) ) 6.49 + 3.23/(1 - f 2/f02 - if/f02) - ne2/( 0meff(f 2 + if/)), with f0 ) 788 cm-1, ) 6.8 cm-1, meff ) 2.88 10-31 kg, and ) 10-14 s. Calculating (Figure 4c) for different sphere-sample distances z clearly exhibits a resonance showing the amplitude maximum accompanied by a rising phase . Both curves shift to lower frequencies with decreasing z, revealing the
1671

red shifting of a resonance by near-field interaction that is in agreement with exact multipole calculation reported in ref 27. To compare the experimental data with the dipolar model we have to take into account the demodulation procedure. Since we measure 2 we calculate the 2nd Fourier coefficient of the predicted time course (z(t)), assuming a sinusoidal motion of the probing Pt sphere (radius a ) 2.5 z) between z and z + 2z with z ) 20 nm. Comparing and 2 (Figures 4b,c) directly illustrates the effect of the demodulation process on the spectral behavior: While the demodulation slightly shifts the resonance, it clearly sustains the essential effect, that of a distance-dependent spectral shift of the resonance, which qualitatively agrees with our experimental data. Quantitative differences between theory and experiment regarding spectral position and width of the resonances probably come from uncertainties in dielectric and damping contributions of SiC literature data, a nonlocal dielectric response,36 and neglecting the actual tip geometry. By comparing the shift between calculated and experimentally estimated amplitude maxima we find growing discrepancies with decreasing distance z. Further, the experimental phase spectrum at z ) 9 nm shows a particularly strong deviation from the dipolar model calculation. We take these deviations as an experimental indication of enhanced multipole excitations at small distances, predicted by Porto et al.27 for a plasmon-resonant system. However, the dipole model clearly demonstrates the essential effect of a distancedependent spectral shift of the resonance which compares qualitatively with the experimental data. This identifies the physical origin of the resonance shift as due to the strong near-field coupling at nanoscopic distances. In conclusion, our results on phonon-resonant tip-sample coupling represent the first experimental verification of a distance-controlled optical resonance shift of a single nearfield-coupled system. In particular, we observe strong phase effects induced by nanometric distance changes and explain them as a monochromatic signature of a resonance shift. The phase changes and spectral resonance shifts demonstrated in this letter are restricted neither to phonon polaritons nor to the sphere-plane system investigated but should occur with any polaritonic excitation and in various geometrical configurations. Phase changes on approach may be a convenient means to detect optically resonant materials with a single-wavelength s-SNOM. Tuning the resonance of a nanosystem by adjusting nanometric distances between its constituents could enable the control of local optical phases, and thus the manipulation of the coherent superposition of light within complex nanoassemblies. This could be applied to control optical transport in nanocircuits, or to achieve strongly enhanced optical fields essential for second harmonic generation or surface-enhanced spectroscopies, such as surface-enhanced Raman scattering (SERS) and surfaceenhanced infrared absorption (SEIRA).

Acknowledgment. We thank R. Guckenberger and N. Ocelic for stimulating discussions. Supported by DFG and BMBF. References
(1) Kreibig, U.; Vollmer, M. Optical properties of metal clusters; Springer-Verlag: Berlin, Heidelberg, 1995. (2) Bohren, C. F.; Huffmann, D. R. Absorption and Scattering of Light by Small Particles; Wiley-Interscience: New York, 1983. (3) Smolyaninov, I. I.; Zayats, A. V.; Davis, C. C. Optics Lett. 1997, 22, 1592-1594. (4) Nie, S.; Emory, S. R. Science 1997, 275, 1102-1106. (5) Kneipp, K.; Wang, Y.; Kneipp, H.; Perelman, L. T.; Itzkan, I.; Dasari, R. R.; Feld, M. S. Phys. ReV. Lett. 1997, 78, 1667-1670. (6) Xu, H.; Bjerneld, E. J.; Kall, M.; Borjesson, L. Phys. ReV. Lett. 1999, 83, 4357-4360. (7) Stockle, R. M.; Suh, Y. D.; Deckert, V.; Zenobi, R. Chem. Phys. Lett. 2000, 318, 131-136. (8) Hayazawa, N.; Inouye, Y.; Sekkat, Z.; Kawata, S. J. Chem. Phys. 2002, 117, 1296-1301. (9) Salerno, M.; Krenn, J. R.; Lamprecht, B.; Schnider, G.; Ditlbacher, H.; Felidj, N.; Leitner, A.; Aussenegg, F. R. Optoelectron. ReV. 2002, 10, 217-224. (10) Stockmann, M. I.; Faleev, S. V.; Bergmann, D. J. Phys. ReV. Lett. 2002, 88, 67402-1-67402-4. (11) Klar, T.; Perner, M.; Grosse, S.; Plessen, G. v.; Spirkl, W.; Feldmann, J. Phys. ReV. Lett. 1998, 80, 4249-4252. (12) Su, K.-H.; Wei, Q.-H.; Zhang, X.; Mock, J. J.; Smith, D. R.; Schultz, S. Nano Lett. 2003, 3, 1087-1090. (13) Fromm, D. P.; Sundaramurthy, A.; Schuck, P. J.; Kino, G.; Moerner, W. E. Nano Lett. 2004, 4, 957-961. (14) Prikulis, J.; Svedberg, F.; Kall, M.; Enger, J.; Ramser, K.; Goksor, M.; Hanstorp, D. Nano Lett. 2004, 4, 115-118. (15) Prikulis, J.; Xu, H.; Gunnarsson, L.; Kall, M.; Olin, H. J. Appl. Phys. 2002, 92, 6211-6214. (16) Mikhailovsky, A. A.; Petruska, M. A.; Li, K.; Stockman, M. I.; Klimov, V. I. Phys. ReV. B 2004, 69, 085401. (17) Aravind, P. K.; Nitzan, A.; Metiu, H. Surf. Sci. 1981, 110, 189204. (18) Weeber, J. C.; Girard, C.; Krenn, J. R.; Dereux, A.; Goudonnet, J. P. J. Appl. Phys. 1999, 86, 2576-2583. (19) Rechberger, W.; Hohenau, A.; Leitner, A.; Krenn, J. R.; Lamprecht, B.; Aussenegg, F. R. Optics Commun. 2003, 220, 137-141. (20) Hillenbrand, R.; Keilmann, F. Phys. ReV. Lett. 2000, 85, 3029-3032. (21) Martin, O. J. F.; Girard, C. Appl. Phys. Lett. 1997, 70, 705-707. (22) Novotny, L.; Sanchez, E. J.; Xie, X. S. Ultramicroscopy 1998, 71, 21-29. (23) Knoll, B.; Keilmann, F. Optics Commun. 2000, 182, 321-328. (24) Hillenbrand, R.; Taubner, T.; Keilmann, F. Nature 2002, 418, 159162. (25) Aravind, P. K.; Metiu, H. J. Phys. Chem. 1982, 86, 5076-5084. (26) Aravind, P. K.; Metiu, H. Surf. Sci. 1983, 124, 506-528. (27) Porto, J. A.; Johansson, P.; Apell, S. P.; Lopez-Rios, T. Phys. ReV. B 2003, 67, 85409-1-85409-9. (28) Knoll, B.; Keilmann, F. Nature 1999, 399, 134-137. (29) Taubner, T.; Hillenbrand, R.; Keilmann, F. J. Microscopy 2003, 210, 311-314. (30) Knoll, B.; Keilmann, F. Appl. Phys. Lett. 2000, 77, 3980-3982. (31) Hillenbrand, R.; Knoll, B.; Keilmann, F. J. Microscopy 2001, 202, 77-83. (32) Knoll, B.; Keilmann, F. J. Microscopy 1999, 194, 512-515. (33) Hillenbrand, R.; Keilmann, F. Appl. Phys. Lett. 2002, 80, 25-27. (34) Porto, J. A.; Carminati, R.; Greffet, J. J. J. Appl. Phys. 2000, 88, 4845-4850. (35) Engelbrecht, F.; Helbig, R. Phys. ReV. B 1993, 48, 15698-15707. (36) Korzeniewski, G. E.; Maniv, T.; Metiu, H. J. Chem. Phys. 1982, 76, 1564-1573.

NL0491677

1672

Nano Lett., Vol. 4, No. 9, 2004