Nanoscale

Cite this: DOI: 10.1039/c1nr10491h www.rsc.org/nanoscale

Dynamic Article Links <

View Online

COMMUNICATION

Disentangling time in a near-eld approach to scanning probe microscopy

Marco Farina,*a Agnese Lucesoli,a Tiziana Pietrangelo,b Andrea di Donato,a Silvia Fabiani,a Giuseppe Venanzoni,a Davide Mencarelli,a Tullio Rozzia and Antonio Morinia
Downloaded by Universita di Chieti -Pescara on 01 August 2011 Published on 01 August 2011 on http://pubs.rsc.org | doi:10.1039/C1NR10491H

Received 13th May 2011, Accepted 29th June 2011 DOI: 10.1039/c1nr10491h

Microwave microscopy has recently attracted intensive effort, owing to its capability to provide quantitative information about the local composition and the electromagnetic response of a sample. Nonetheless, the interpretation of microwave images remains a challenge as the electromagnetic waves interact with the sample and the surrounding in a multitude of ways following different paths: microwave images are a convolution of all contributions. In this work we show that examining the time evolution of the electromagnetic waves allows us to disentangle each contribution, providing images with striking quality and unexplored scenarios for near-eld microscopy. Scanning probe microscopes constitute a broad class of devices sharing a common feature: a probe performs a scan in close proximity to the sample surface. Depending on the type of probe, the system records variations of some physical parameters arising from the short range interaction between the sample surface and the probe.1 In the seminal work by Ash and Nicholls in 1972 (ref. 2) microwaves were proposed as a possible interaction medium; at rst glance the use of electromagnetic waves looks constrained by the diffraction limit (or Abbes limit) relating the resolution of an imaging system to the wavelength, which is centimetric for microwaves. However in microscopy this limit is circumvented by exploiting the near-eld (or evanescent eld) of a probe or of an antenna.2 Near-eld decays exponentially from the source and is therefore an excellent way to probe a sample at a very high resolution. In the aforementioned paper the authors achieved a resolution of l/60 with a signal at 10 GHz, but more recent works have achieved atomic resolution. A complete review of the state-of-the-art may be found in ref. 3. Microwave microscopy however has many unpaired potentialities, not yet fully exploited, owing to its capability to perform local quantitative measurements of electromagnetic properties such as
a  Politecnica delle Marche, Via Brecce Bianche, 60131 DIBET, Universita Ancona, Italy. E-mail: m.farina@univpm.it; Tel: +390712204837 b  G. dAnnunzio, Via dei Dept. of Neuroscience and Imaging, Universita Vestini, I-66100 Chieti, Italy. E-mail: tiziana@unich.it; Tel: +3908713554554 Electronic supplementary information (ESI) available: Materials and methods, Fig. S1S7, Table 1, and Videos S1S4. See DOI: 10.1039/c1nr10491h

dielectric constant and conductivity.46 Broadband measurements of these parameters would open the possibility to perform local microwave spectroscopy. The latter might be especially attractive for biological applications as many cellular structures have polar properties, giving rise to phonon excitation when irradiated by the timevarying electromagnetic eld: basically the applied electric eld slightly deforms the structure in a periodic manner and vibration resonances can occur, possibly in the microwave, millimetre and submillimetre wave range.79 Yet, local microwave spectroscopy could be an intriguing tool for the characterization of quantum-mechanical properties of structures such as carbon nanotubes or nanoribbons.10 We should mention that microwaves were also used as a powerful approach to perform the scanning tunneling microscopy on nonconducting samples, by exploiting the harmonics generated by the non-linear tunnel junction11 and achieving atomic resolution. The simplest way to generate decaying elds is to use a sharp tip, kept in close proximity to the sample to be investigated, since the electromagnetic eld diverges in proximity to an ideal metal edge; an alternative widely used approach is to use an aperture. However in both cases the microwave source acts at the same time as an antenna, radiating in the complex environment of the microscope. Focusing on the tip approach, it is apparent how the latter is unable to selectively illuminate only the desired area under its sharp vertex, because it is basically an antenna exciting any sort of electromagnetic wave and interacting with all the regions of the microscope and of the sample. Any microwave image will be inevitably the convolution of all those interactions; consequently the interpretation of data and the accurate modeling of the source/sample/microscope interaction are still open issues limiting the scope of this powerful technique. To date, the philosophy adopted to partially overcome this major problem has been to create resonant structures involving the tip whose interaction with the sample is modeled mostly as a capacitanceand to work at specic frequencies where all the surrounding interactions can be safely modeled as an unwanted parasitic capacitance to be removed. Of course, this approach is sound only insofar as a microwave signal is generated at a single specic frequencythe resonant frequencythus losing many of the attractive possibilities offered by this kind of microscopy. A more holistic approach which is being investigated by many researchers, including ourselves (see ESI, Materials and methods, where some hints about our calibration solution are reported), involves the idea of calibration, namely a multi-step procedure exploiting the measurement of a set of known samples (or loads, also called standards) over an arbitrary
Nanoscale

This journal is The Royal Society of Chemistry 2011

View Online

frequency range; this allows the evaluation of the error network modeling any electromagnetic interaction between parts of the microscope and its analytical removal from the raw measurement.5 However even this idea is faced with several open issues, among others: (1) one has to be able to create samples which are well characterized over a frequency range and whose measurement can be easily repeated. (2) When changing samples as in ref. 5, it is very difcult to ensure that no modication in the part modeling the microscope (the error network) has occurred. (3) The surrounding can change or move with time and with temperature, and those modications cannot be neglected when working on the nanometric scale. (4) Dening the error network may be difcult, as the tip and the sample interact in a complicated way (multimodal interaction). In this work we propose to follow a completely different strand, namely to introduce the concept of time-domain in near-eld microscopy: the idea is to simply perform an inverse Fourier-transform of the microwave data, typically the reection coefcient (the ratio between complex amplitudes of reected and incident signals) measured at one edge of the tip over a given frequency range. In this way we obtain a description of how the reected signal changes with time, mimicking a kind of measurement known as Time-Domain Reectometry, used in ground penetrating radar or in signal integrity applications. Much like what happens with the diffraction limit, even in this case we are faced with an apparent limit, related to the slowness of the microwave signals when compared to the time-scale involved in microscopy: if we sweep the signal frequency between 0 and fmax, the inverse Fourier-transform would provide the response to a pulse having time width 1/fmax, typically in the order of tens of picoseconds, really an eternity when compared to the time required for the light to travel across 1 nmin air just 3 attoseconds. Actually, the interaction with matter introduces quite longer delays, but still the time-scales apparently do not match, and this is why the time-domain is never used in this framework. Nonetheless in this work we show how time can still be conveniently used. Let us consider a microwave probe: assumejust to simplify calculationsit is 1.5 cm long (it would include some part of a microwave connector). The microwave signal would travel along the probe much like along a transmission line: the total back and forth travel path of the wave involved in the measurement of the reection coefcient would be 3 cm; in air, the signal would cover this distance in 100 picoseconds. Now the interaction between the probe and the sample will induce some additional delays: the simplest model of the probe-to-sample interaction is a capacitance, and a transmission line terminated on a capacitance is equivalent to a longer open line (for a given frequency). Variations of this capacitance appear as variations of the delay, reecting both changes in topography and surface composition. The point is that we can appreciate such variations in the pulse obtained by the inverse Fourier-transform, in spite of the frequency limit. What actually limits our capability is the system dynamics and the noise, namely how well we can detect small changes in the reconstructed (reected) pulse. Actually, this application of time does not even require the above assumptions (long transmission line and signal bandwidth comparable to the travel time); this is evident when considering a single tone, where the small change in the phase of the reection coefcient is a measure of the same time-delay. In this framework the time domain is consequently just a convenient expedient to present data, simplifying understanding. In the limit case of a homogeneous sample, for example, differences in time will map differences in topography; the
Nanoscale

additional intriguing information is provided by the penetration of microwaves under the sample surface. A further advantage is that the reection coefcient in time is a real quantity, while in frequency it is a complex one: in the latter case, informative images will either appear in amplitude or phase plot when changing the frequency, and sometimes information spreads between the two, with a deterioration of quality. However the major issue of near eld microscopy is that near eld and far eld interactions generally coexist; in fact the waves radiated by the probe reach the sample following multiple paths, some of them interacting with the surrounding (the shield, the microscope body, etc.). This is the key point where operating in the time-domain provides a solution. In fact, while frequency-domain images are a convolution of all the contributions, in time they can be at least partially disentangled, as the distance between the probe and the sample is in the nanometre range while the distance between the probe and parts of the microscope is in the centimetre range. The time-domain transform provides a set of synthetic echoes and, in some intuitive sense, the rst echo comes from the nearest interaction, namely the informative part of the sample. At different times, depending on the actual bandwidth of the excitation, we will receive the echoes from parasitic paths. Some of them come from a non-local interaction with the sample itselfbringing for example images about its tiltingand some from the surroundings. Hence, after converting data in the time-domain, it is possible to focus on a specic interaction (see ESI, Fig. S1). Most importantly, the whole procedure is a post-processing that can be done off-line on existing data, not requiring modications to the instrument. In order to prove this concept we have developed an ultra-wideband microwave microscope (Fig. 1; see ESI, Video S1 showing the setup) exploiting a Scanning Tunneling Microscope (STM) and a Vector Network Analyzer, the latter being used to perform measurements of the microwave signal (up to 70 GHz) with high dynamics. However it should be stressed that ultra-wideband is not strictly necessary to implement our time-domain microscopy, as shown in the Materials and methods section (see ESI, e.g. Fig. S5): we just need to measure the reection coefcient over a nite set of frequencies in order to take at least some of the advantages from a virtual time-pulse. In our system the STM current is recorded simultaneously and is used in the feedback chain in order to maintain the tip-to-sample distance, while providing at the same time an STM topographical image of the sample being characterized. Hence, the conductive platinumiridium STM tip, fed by a capacitively coupled coaxial line, is also used as the microwave source. The choice of the STM in this system has some advantages: among others, the STM tip is naturally a good microwave probe, the STM is intrinsically contact-less, and STM by itself easily allows atomic resolution. The major drawback is the need for a conducting sample; however Guckenberger et al. in ref. 12 demonstrated the possibility to partially overcome this STM limitation by exploiting a thin water lm present on the sample surface and its peculiar high lateral conductivity. Fig. 2 shows an equivalent circuit that we propose for the head: a set of transmission lines, modeling non-local interactions and enclosure resonances, the coaxial probe and the local tip-to-sample interaction, modeled as a capacitor (in this case 0.7 fF). Number and parameters of lines are adjusted to t experimental data, and Fig. 2(b) reports the comparison between measured data and the model. In order to demonstrate the concept, we have transformed the reection coefcient in time and evaluated the difference between
This journal is The Royal Society of Chemistry 2011

Downloaded by Universita di Chieti -Pescara on 01 August 2011 Published on 01 August 2011 on http://pubs.rsc.org | doi:10.1039/C1NR10491H

View Online

Downloaded by Universita di Chieti -Pescara on 01 August 2011 Published on 01 August 2011 on http://pubs.rsc.org | doi:10.1039/C1NR10491H

Fig. 1 Broadband setup (top) and details of the STM/SMM tip (bottom).

Fig. 2 Model (a) and comparison between theoretical and measured data (b). Parameters are given in Table S1 (in the ESI, Materials and methods). TL are transmission lines.

data obtained by modifying the tip-to-sample capacitance from 0.7 to 0.701 and then to 0.702 fFmodeling a change in a feature of the sample (topography or composition)a further plot shows the difference produced by modifying the rst transmission line length by just 0.001 degrees from the nominal value of 104 at 10 GHz. This models a slight change in the non-local interaction (a distance of 83 nm for a wave traveling in air). Fig. 3 shows the corresponding time-plots; it is evident that there are two timeframes: one where the local interaction dominates and the other where mostly the non-local effects dominate: local and non-local interactions are distinguishable. This technique has been applied to a number of samples; Fig. 4 reports as an example a specimen of Highly Oriented Pyrolitic Graphite (HOPG). The total scanning area is 10 10 mm2, and the height of the smallest features is in the order of few nanometres. In particular Fig. 4 on the left shows the time-domain image from the microwave microscopy, while on the right we see the plot of the STM topography recorded simultaneously. The time-domain image has not been processed for further improvement, while the STM image showed also a relevant plane tilt (of the order of 1 mm) that was removed in post-processing. The STM image quality was limited by the quality of the tip (obtained by wire cutting) and by microphonic noise induced by the microwave cable. The microwave image, on the other hand, shows a high quality, taking advantage of the underlying multi-frequency measurement, and is likely to be displaying also some of the sub-surface HOPG layers. Further pictures, also showing
This journal is The Royal Society of Chemistry 2011

spectroscopic barrier-height images, are in Fig. S4 (ESI, Materials and methods, Additional data). Fig. 5 shows a similar comparison for mouse myotube C2C12 xed in paraformaldehyde on the HOPG substrate (see ESI, Materials and methods; also shown in Fig. S6, a zoom); the right image is the STM (Set Point: 1 pA, bias voltage: 8 V), while the left image is the simultaneous microwave scan (X band) at a time instant.

Fig. 3 Differences in the time-domain reection coefcient: there are time-frames where the local interaction dominates (left rectangle, near time) and where a non-local interaction, mediated by the far-eld, dominates (right rectangle, far time).

Nanoscale

View Online

Downloaded by Universita di Chieti -Pescara on 01 August 2011 Published on 01 August 2011 on http://pubs.rsc.org | doi:10.1039/C1NR10491H

Fig. 4 HOPG in the time-domain microwave microscopy (left; max. frequency 20.5 GHz) and the simultaneous STM image (right; height in nanometres).

Fig. 5 Comparison for myotubes xed with paraformaldehyde on the HOPG substrate. Left: time-domain microwave image; right: simultaneous STM.

Note that this scan is quite challenging for our STM head, as 1 pA is the minimum current allowed. The microwave image highlights details partially hidden in the STM scan, in particular over the border of the cell membrane; note that microwaves seem to discriminate well the region between cells, having different reectivities. Images show part of the connective structures around the bers and some details of the membranes. This is even more evident in living C2C12 cells (Fig. S7 in the ESI, Materials and methods, area 35 35 mm2). It is also useful to follow the time evolution in Videos S3, S4 and S5 (ESI) showing, respectively, the reected signal changes in time for the HOPG, the xed and the living C2C12. In conclusion, our work proves that the time-domain approach discloses unexpected developments for the near-eld microscopy.

grateful to G. Scoles (Princeton University) for valuable discussions on the subject. We also thank R. Castagna for reviewing the paper and L. Palma for running measurements reported in S3.

Notes and references

1 G. Binning, F. Quate and C. Gerber, Atomic force microscope, Phys. Rev. Lett., 1986, 56, 930933. 2 E. A. Ash and G. Nicholls, Super-resolution aperture scanning microscope, Nature, 1972, 237, 510512. 3 S. Kalinin and A. Gruverman, Scanning Probe Microscopy, Springer, New York, 2007. 4 A. Imtiaz and S. M. Anlage, A novel STM-assisted microwave microscope with capacitance and loss imaging capability, Ultramicroscopy, 2003, 94, 209212. 5 D. Karbassi, et al., Quantitative scanning near-eld microwave microscopy for thin lm dielectric constant measurement, Rev. Sci. Instrum., 2008, 79, 094706. 6 A. Tselev, S. M. Anlage, Z. Ma and J. Melngailis, Broadband dielectric microwave microscopy on mm length scales, Rev. Sci. Instrum., 2007, 78, 044701. 7 C. K. Sun, T. M. Liu and H. P. Chen, US Pat., 2009/0237067A1, 2009.

Acknowledgements
We thank C. Franzini-Armstrong (University of Pennsylvania) for the suggestions during the preparation of the manuscript. We are
Nanoscale

This journal is The Royal Society of Chemistry 2011

View Online

8 F. H. Westheimer, Why nature chose phosphates, Science, 1987, 235, 11731178. 9 D. L. Woolard, et al., Submillimeter-wave phonon modes in DNA macromolecules, Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top., 2002, 65, 051903. 10 V. V. Talanov, et al., Few-layer graphene characterization by neareld scanning microwave microscopy, ACS Nano, 2010, 4, 38313833.

11 S. L. Stranick and P. S. Weiss, Alternating current scanning tunnelling microscopy and nonlinear spectroscopy, J. Phys. Chem., 1994, 98, 17621764. 12 R. Guckenberger, et al., Scanning tunnelling microscopy of insulators and biological specimens based on lateral conductivity of ultrathin water lms, Science, 1994, 266, 1538 1540.

Downloaded by Universita di Chieti -Pescara on 01 August 2011 Published on 01 August 2011 on http://pubs.rsc.org | doi:10.1039/C1NR10491H

This journal is The Royal Society of Chemistry 2011

Nanoscale