High Resolution Imaging of Few-Layer Graphene by Near-Field Scanning Microwave Microscopy

Tamara Monti, Andrea Di Donato, Marco Farina Universit Politecnica delle Marche, Information Engineering Dept. (DII), Ancona, via Brecce Bianche 60131, Italy
Abstract In this work, we describe the application of an in-house system performing simultaneously Scanning Tunneling Microscopy (STM) and wide-band Near Field Scanning Microwave Microscopy (wide-band SMM) to a few-layer graphene sample. This sample is produced by mechanical exfoliation of bulk highly oriented graphite and deposited on a substrate of conductive glass. By introducing the time-domain conversion of frequency domain data, we show that it is possible to achieve nanometric resolution. Index Terms Microwave imaging, Microwave measurement, Nanotechnology, Nanomaterials, Scanning probe microscopy.

image. If the system is not sensitive enough, it is challenging to detect the sample presence. The best way to obtain a strong focusing of the microwave field, and the subsequent reduction in the sampling volume, is to exploit the rapid decaying of the signal flowing from a sharp tip. This explains the reason why the best resolution ever (atomic) has been achieved by a hybrid Scanning Tunneling Microscopy (STM) SMM technique [5]. In this work we tested different samples of few-layer graphene, deposited on Indium-Tin Oxide (ITO) coated glass, with our STM-based near-field scanning microwave microscope, performing wide-band frequency measurements. We achieved nanometric resolution, agreeing to previous results showing the thickness dependence of the microwave impedence. Such a high resolution power comes from the implementation of time-domain conversion of broadband frequency data. II. DETAILS OF STM-SMM SYSTEM A. Microscope head and connections We have modified two commercial instruments: an STM, an NT-MDT P-47 Solver, and a Vector Network Analyzer Agilent E8361A (VNA), used to perform ultrabroad band measurements of the microwave signal with high dynamic (bandwidth 70GHz). In Figure 1 we show a schematic of the hybrid STM/SMM head. A home-made program synchronizes the STM and the acquisition from the VNA. Basically, the sample is horizontally displaced by a piezo membrane (xy), and the reflection coefficient is read through an Ethernet connection. The VNA performs a frequency sweep over a sub-band of the 0-70 GHz capability. The STM controller keeps the sample/probe distance by changing the zposition of the piezo-membrane, and ensuring a predefined tunnel current. By reading the z-position, a simultaneous STM topographical map is obtained.

I. INTRODUCTION Near-Field Scanning Microwave Microscopy (NearField SMM) seems to be very promising as a nondestructive way to evaluate electromagnetic properties of materials at the nanoscale. For example, owing to the skin effect, this kind of analysis can be efficiently used to test bulk materials, even though a complex calibration procedure has to be followed [1]. Based on this physical property of microwave field, it was defined the concept of sampling volume. It is the volume under the probe containing a certain fraction of net energy of the microwave field [2]. The interaction between probe and sample is based on this energy that is mainly reactive. Such a volume always defines a region with dimensions much smaller than the used wavelength (sub-diffraction imaging). The reduction of this volume improves the spatial resolution of the microscope. The main limitation to the application of the SMM analysis to 1D and 2D carbon-based structures is the sensitivity of the instrument itself. Some authors tested the microwave impedance of few-layer graphene flakes and found that is thickness dependent [3], [4]. However, the images produced in the aforementioned works have poor resolution, both in planar and depth dimension. We believe that this is due to the specific interaction between probe and sample: in the case of graphene, the sample under test is only one-atom thick layer of carbon. Hence, since it behaves mostly as a dielectric in the direction perpendicular to the plane, an impinging microwave field gets slightly perturbed by the few layer sample. Such a perturbation is the source of the SMM

At the end of the scan, we have an STM topographic image, and several microwave images (usually more than 500) at different frequencies. They record the reflection coefficient for each position of the probe, during the scanning. The same software performs calibration and time-domain transform.
SMA center electrode
Metal Cyclinder SMA

III. RESULTS AND COMMENTS The presented results have been obtained using a welloptimized STM-SMM head: it integrates both measurements systems in a single chassis, following our original design but the STM performances are improved, to increase the sensitivity in tunnel current measurement. We have prepared few-layer graphene sample, following a simple procedure by exfoliation of the bulk Highly Oriented Pyrolitic Graphite (HOPG) [8]. As described above, our system is able to perform simultaneously STM and SMM imaging, related to the same area under investigation. In this way it is possible to have a tunnel current measurement, that gives topographic information of the sample surface. Among several factors, the tunnel current is influenced by the working function of the materials: the effect is that heights are reported with a systematic difference from true topography when imaging different materials in the same sample. In our case the problem is in the estimation of the height of the graphene layer that is immediately over the ITOcoated glass. Fig. 2 shows an STM image of one of these microflakes. We can clearly see a stair-like shape formed by overlapped graphite layers. Although the signal is very noisy, as we can see from the profile of Fig. 3, the last step is few nanometers high. So they exhibits graphene properties.

STM head Teflon DC blocking insulator STM tipsupport

Ipodermic needle

PlatinumIridium tip/probe XYZ piezo mover

Sample

Fig. 1. Schematic of our STM-SMM hybrid microscope head. The capacitive coupling of the microwave signal is performed in Teflon inside of the metallic cylinder.

B. Time domain conversion Our proposed calibration procedure of the system is thoroughly discussed in another paper [6], and the detailed description of our system can be found in [7]. To improve both the accuracy and sensitivity of our microscope, we apply a post-processing algorithm on both the real and imaginary part of S11. In this algorithm we calculate the time-domain signal by Fourier Transform. As a matter of fact, the time-domain image collects all the detail given by the (several) frequency domain images. In this case we need just to choose the most convenient time interval related to the first reflection due to the direct interaction with the sample. The proper time instant allows to exclude secondary reflections, also coming from the rest of the system, delayed in time. In other words, we obtain a sort of response to a virtual pulse. The time domain reflections are given by the virtual pulse response of the sample. The direct reflection from the sample gives a time-domain image of it. Any microwave image is inevitably the convolution of local and non-local interactions: consequently the interpretation of data becomes easier if seen under a time-domain point of view.

Fig. 2. STM image of a few-layer graphene micro-flake over ITO-coated glass substrate.

Fig. 5 shows the same image but after the time domain conversion, and picked up at a proper time instant.

Fig. 3. Profile related to the green line in the STM image (Fig.2). The ordinate scale is in nanometres. The zero is referred to the STM starting condition, due to the choosen set-point.

We perform microwave analysis sampling 512 points over a wide range of frequencies (15.35-16.35 GHz). The number of spatial sampling points are 256*256, obtained scanning row by row the sample by the probe. Fig. 4 shows the resulting microwave measurement on the flake described above. It is obtained from a filtering algorithm over the whole frequency range [9].

Fig. 5. SMM time-domain image of the previously described micro-flake. The size scales are the same of Fig.2 and 4.

The microwave images show an improved resolution with respect to STM one. They clearly draw graphene edges and highlight details otherwise invisible in STM. Of course, the quality of the tunneling image depends on the set-point in use, necessary to perform measurements over inhomogeneous materials without tip damage. Furthermore, in microwave images, the field looks concentrated in close proximity of nanometric edges.

Fig. 4. SMM frequency image of the previous described micro-flake. The size of the axis is in micrometers.

Fig. 6. STM detail of an edge of a second few-layer graphene micro-flake. The flake surface is topographically flat.

few-layer graphene sample. By using our in-house near-field scanning microwave microscope and through the time-domain conversion of the frequency domain data, we obtained nanometric resolution. It thus becomes possible to depict an accurate mapping of the qualitative microwave impedence of the sample under test. Near-field microwave analysis allows to observe interesting graphene features whose physical grounds are still to be clarified. REFERENCES
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By comparison between Fig. 6 and 7, the microwave field concentration seems to be independent from tunneling measurement, as the same surface region is found to be flat in STM image. This effect is not completely explained by the mere concentration of charges on edges, since it spreads over a wide area (more than 500 nm) nearby the boundary. Further investigation, also involving other metallic substrates, are ongoing. It is to be noticed that some edges seem to appear despite the presence of an overlapped layer, showing a kind of transparent view of buried structure (see the bottom part of the image in figures 4 and 5, where the layer starting in the middle of the image can be followed underneath the layer on the left). Again further investigations are ongoing to find a solid proof of this capability, also considering different nanometric structures, such as carbon nanotubes. It could be related to the sampling volume of our microscope. Time-domain analysis could help in better understanding observed phenomena. IV. CONCLUSION We have presented a near-field microwave analysis of a