Conducting Probe Atomic Force Microscopy: A
Transcription
Conducting Probe Atomic Force Microscopy: A
Research News Conducting Probe Atomic Force Microscopy: A Characterization Tool for Molecular Electronics By Tommie W. Kelley, Eric L. Granstrom, and C. Daniel Frisbie* 1. Introduction Recently, a number of new atomic force microscopy (AFM) techniques exploiting electrically conducting probes have been developed to measure electrostatic forces, charge distributions, voltage drops, capacitances, or resistances on sub-100 nm length scales. These new AFM adaptations, e.g., electric force microscopy,[1] scanning capacitance microscopy,[2] and scanning potentiometry,[3] hold great promise for electrical characterization of materials since high resolution topographic imaging and electrical measurements are achieved simultaneously, providing direct correlation of electrical properties with specific topographic features. Here we describe a variant of AFM in which conducting probes are used to measure current±voltage (I±V) relationships and resistances (conductances) of materials. We term this AFM technique ªconducting probe atomic force microscopyº (CP-AFM),[4] although others have suggested ªconducting AFMº[5] or ªscanning resistance microscopyº[6] for similar methods. Figure 1 shows a typical CP-AFM experiment in our laboratory in which the probed material is a semiconducting organic crystal contacted by a microfabricated Au wire on SiO2. The conducting probe is positioned with controlled load at desired points on the crystal and the resistance or I±V response between the probe and the wire is determined using external electronics. In our measurements, the probe is held stationary during the measurement and is used to image the sample in tapping mode before and after the I±V data are recorded. The aspects of CP-AFM that are most attractive for nanoscale electrical transport measurements are 1) the ability to image samples with high resolution before, during, or after the measurement, 2) the ability to record I±V relationships on samples that are highly resistive or ± [*] Dr. C. D. Frisbie, T. W. Kelley, E. L. Granstrom Department of Chemical Engineering and Materials Science University of Minnesota 421 Washington Avenue SE, Minneapolis, MN 55455 (USA) Adv. Mater. 1999, 11, No. 3 surrounded by insulating regions, and 3) straightforward interpretation of the tip position relative to the sample (i.e., a measured repulsive force indicates intimate tip±sample contact). These three characteristics make CP-AFM ideal for studying electrical transport in microfabricated semiconductor devices, nanoparticle assemblies, and individual molecules, for example. A deeper appreciation of these characteristics can be obtained by comparing CP-AFM to scanning tunneling microscopy (STM), which is a well established technique for probing electronic properties on nanometer length scales. Both CP-AFM and STM share the high spatial resolution imaging capability (STM, ~0.1 nm; CP-AFM, ~10 nm) that is critical in linking nanoscale structure to transport properties. An important distinction relates to the position of the tip. In CP-AFM the tip is placed in direct contact, under controlled load, with the material to be probed. This means that the measured I±V relationship may be profoundly influenced by the electronic properties of the tip±sample contact. In contrast, an STM tip is generally not in physical contact with the sample, so the I±V characteristic of the tunneling gap is determined by the sample electronic structure, not tip± sample contact properties. While reliance of STM on tunneling allows a powerful conductance spectroscopy that maps the electronic density of states of a material, the length scale over which one can probe transport in resistive materials is limited to typical tunneling distances (1± 10 nm). Also, since STM requires detection of a tunneling current to position the tip, it is not practical to use STM to characterize small structures surrounded by insulating regions. In CP-AFM, force feedback decouples probe positioning from conductivity of the sample, facilitating transport measurements over longer distances on samples with widely varying resistances. In addition, for some transport experiments it is important to know the precise location of the tip relative to the sample, and in this regard detection of a repulsive force in CP-AFM can be easier to interpret than a tunneling current in STM. The relative merit of the CP-AFM and STM approaches for electrical characterization certainly depends on specific goals and experimental constraints, and the two techniques should be Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999 0935-9648/99/0302-0261 $ 17.50+.50/0 261 Research News Fig. 1. Scheme of a typical point-contact CPAFM experiment in which a Au-coated AFM tip is used to probe the resistance of a thin crystal of the molecule sexithiophene (6T). During a measurement, current is recorded as a function of voltage applied between the positionable conducting probe and a fixed electrode. The inset shows the orientation of the 6T molecules with respect to the probe and substrate. viewed as complementary methods for probing transport in a variety of small-scale structures. In our work, we have used CP-AFM to probe transport in organic materials.[4] Heightened interest in molecule-based electronics has underscored the need for better understanding of conduction mechanisms in organic materials, particularly in thin film form. CP-AFM offers an ideal characterization strategy for organic thin films because, first, it allows direct correlation of electrical transport properties with specific, well-defined supramolecular structures or defects, and second, these films are often too resistive to be probed by STM. In this article, we outline previous CP-AFM studies and then highlight some of our recent CP-AFM measurements on extremely thin crystals of an organic semiconductor, as depicted in Figure 1. 2. Previous Work Previous CP-AFM studies have shown the ability to make two basic kinds of electrical measurements, stationary pointcontact measurements, and two-dimensional resistance maps. Figure 1 shows a point-contact measurement in which resistance (or I as a function of V) is measured between the stationary probe and a fixed contact. An important application of point-contact CP-AFM is ªspreading resistance profilingº (SRP) of dopant concentrations in conventional semiconductors.[7] Spreading resistance is the resistance associated with current crowding near a point contact and can be related to the dopant concentration in a material by comparison to a calibrated standard. Measurement of the spreading resistance as a function of point-contact location on a semiconductor device yields the spatial distribution of the dopant concentration. Several groups have shown in recent publications that CP-AFM (or ªnano-SRPº) allows determination of dopant concentration profiles with much higher resolution than is possible with conventional point probes commonly used in the semiconductor industry. Pointcontact CP-AFM measurements have also been used to measure the conductances of individual semiconductor nanoparticles,[8] Langmuir±Blodgett films,[9] adsorbed molecules on graphite,[5] and thin molecular crystals on Au.[4] 262 Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999 The second type of measurement, resistance mapping, involves simultaneous topographic imaging and resistance measurements. Resistance maps show the resistance between the scanning probe and a second, stationary contact as a function of probe position. Recently, Lieber and coworkers generated resistance maps of a single carbon nanotube contacted at one end by a microfabricated Au electrode.[10] Analysis of the maps revealed the resistance per unit length of nanotube as well as the contact resistance associated with the tip±tube and Au±tube junctions. A more general result of their study was that by using hard, conductive NbN coatings they were able to make reproducible electrical measurements while continuously scanning in contact. Canadian, French, and Chinese workers have also used resistance mapping to image local resistances on semiconductor,[11] metal,[12] and metal oxide[13] surfaces, respectively. Key to all CP-AFM measurements is the conducting probe. Reported conducting probes include heavily doped Si tips and conventional Si or Si3N4 tips coated with metal (e.g., Ag, Au, Pt, NbN) or B-doped diamond films. Thomson and Moreland made a detailed investigation of Ag-, Au-, and Ptcoated tips and doped Si tips, and achieved five orders of magnitude lower contact resistance to Au surfaces with metal-coated probes than with doped Si probes.[14] They also noted that shear-induced abrasion of the metalized tips was an important problem that could be mitigated by imaging samples in tapping mode instead of contact. Compressive and tensile forces on metal tips appear to be less damaging, as Stalder and Durig found that the yield strength of Au point contacts is more than one order of magnitude larger than the macroscopic yield strength of Au.[15] In our work, we have employed Au-coated Si probes (700 Au over a 70 Cr adhesion layer) because Au is easily deposited by vapor deposition and has a high work function, facilitating low resistance contacts to many organic materials. Au tips are generally not robust to continuous scanning in contact mode. Accordingly, we have devised an approach in which we image our samples in tapping, or intermittent contact mode, and make I±V measurements in stable contact at selected points. Imaging in tapping mode preserves the Au coating on the tip by eliminating the shear forces that tend to 0935-9648/99/0302-0262 $ 17.50+.50/0 Adv. Mater. 1999, 11, No. 3 Research News abrade the coating, and also has the advantage that we can characterize delicate samples that could not withstand continuous contact mode scanning. 3. Point-Contact I±V Measurements on Thin Molecular Crystals We have used CP-AFM to measure electrical resistances of very thin crystals of a p-type semiconducting thiophene oligomer, sexithiophene, or 6T.[4] The conductance of polycrystalline films of 6T has been studied extensively because of possible applications of this material in low cost thin film transistors. Previously, we found that very thin crystals of 6T may be grown on SiO2 by vacuum sublimation. The crystals are typically several micrometers in length and width and range from 2 to 16 nm in thickness. The 6T molecules are arranged in layers with the long axis of the molecule nearly perpendicular to the substrate as indicated in Figure 1. The thickness of one molecular layer (ML) of 6T is 2.3 nm, so the 2±16 nm thickness range corresponds to 1± 7 ML. Figure 2A shows an AFM topograph of a 2 ML thick 6T crystal contacted by a microfabricated Au wire on SiO2. This image was acquired in tapping mode using a Au-coated tip. We selected five points on the crystal, each an increasing distance from the wire, to make point-contact I±V measurements. These points are labeled in Figure 2A and the resulting I±V traces are shown in Figure 2B. Inspection of Figure 2B shows that the current increases monotonically with tip voltage over the entire 0±5 V range at each of the five probe locations. At a given tip voltage, current decreases with increasing distance of the probe from the wire, i.e., current at 5 V is less at point 2 than at point 1, as expected, since resistance of the crystal should increase with probe± wire separation. The nonlinearity of the I±V traces is not surprising since the precise I±V relationship is a function of any charge injection barriers at the tip±6T junction. These traces were acquired in air and were extremely reproducible. Repetitive measurements at each of the five points yielded the same curve to within 10 %. Importantly, imaging of the crystal after the measurements revealed no evidence of damage to the crystal. In Figure 2C we plot the resistance of the crystal at 5 V (i.e., the reciprocal of the I±V slope at 5 V) as a function of probe±wire separation. The dependence appears to be linear, and the line on the plot is the least squares fit. Linear dependence is somewhat surprising in light of the fact that we are probing a crystal that can be viewed as a layered sheet of molecules, and injected holes would be expected to spread Adv. Mater. 1999, 11, No. 3 Fig. 2. A) Topograph of a 6T crystal connected to a microfabricated Au wire on SiO2. This image was obtained in tapping mode with a Au-coated probe. The locations of five point-contact I±V measurements are labeled. B) Pointcontact I±V characteristics obtained by CP-AFM at points 1±5 labeled in (A). C) Resistance (reciprocal of I±V slope at 5 V) versus probe±wire separation distance. The line is a least squares fit. The intercept gives a contact resistance Rc = 82 MW. out from the tip into the sheet en route to the wire. Detailed modeling accounting for the distance dependence is in progress. The importance of these data is that they can be extrapolated to zero separation, yielding a contact resistance Rc of 82 MW due to the tip±6T and wire±6T junctions. Large contact resistances are typical for organic±metal junctions, and the measurements here demonstrate that CP-AFM may be used to measure these contact resistances directly and perhaps in future experiments to relate them to the number of molecular layers, specific crystal morphologies, or molecular orientations. 4. Resistance of a Grain Boundary Figure 3A shows another AFM topograph of a 6T crystal in contact with a Au wire. Point-contact I±V measurements were made at the four points labeled on the crystal. A grain boundary (GB) is visible between points 1 and 2, and the I±V Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999 0935-9648/99/0302-0263 $ 17.50+.50/0 263 Research News contacts is nearly constant for all measurements and is <50 MW, we conclude that the 25 GW ªcontact resistanceº associated with points 2, 3, and 4 is almost completely attributable to the resistance of the GB. Further studies are required to determine if this is a typical GB resistance for 6T. The key point is that we can use CP-AFM to measure the resistance of specific well-defined defects in molecular materials, such as GBs, which should ultimately give us better insight into the nature of transport in these materials. 5. Conclusion and Outlook The combination of high spatial resolution imaging and electrical characterization make CP-AFM a powerful characterization tool for relating transport properties to structure. We are particularly optimistic about the opportunities for CP-AFM in illuminating transport mechanisms in organic materials. In the future, we can expect CP-AFM methods to become more sophisticated. For example, it should be possible to integrate a second, independent ªgateº electrode on the probe tip or cantilever, which would allow field effect measurements on the nanoscale. One can also imagine creating conducting probes with thin tunneling barriers on their surfaces, facilitating Coulomb blockade experiments. Electro-optical measurements such as electroluminescence mapping also appear promising. All of these measurements would benefit from operation in a vacuum environment at variable temperatures. In general, CP-AFM is a valuable complement to the other scanning probe microscopies mentioned at the beginning of this article that reveal the electrical properties of materials with sub-100 nm resolution. Fig. 3. Estimation of the resistance of a grain boundary (GB) in 6T. A) A topograph of a 6T crystal connected to a microfabricated Au wire on SiO2. Two GBs are indicated with arrows. Point-contact measurements were made at points 1±4. The image was obtained in tapping mode with a au-coated probe. B) Point contact I±V characteristics obtained by CP-AFM at points 1 and 2 labeled in (A). The inset shows an expanded view of the I±V trace at point 2. C) Resistance (reciprocal of I±V slope at 5 V) versus probe±wire separation distance. The linear fit through points 2, 3, and 4 has been used to estimate the GB resistance (see text). Note the change of scale on the resistance axis. measurements taken at points 1 and 2 are dramatically different, as shown in Figure 3B. The current at 5 Vat point 2 is 105 times smaller than the current at point 1, indicating an enormous resistance associated with the GB. The resistance can be estimated by determining the nominal Rc on each side of the GB. Figure 3C shows the resistance (at 5 V) computed for each of the four probe locations indicated in Figure 3A. Note the discontinuity in the resistance axis in Figure 3C, which switches from MW to GW values. The resistance measured at point 1 is 50 MW and we can conclude that Rc on the near side (wire side) of the GB is therefore <50 MW. A linear extrapolation for the measurements at points 2, 3, and 4, which are on the far side of the GB, gives Rc = 25 GW. Assuming that the total Rc due to wire±6T and tip±6T 264 Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999 ± [1] H. Bluhm, A. Wadas, R. Wiesendanger, K.-P. Meyer, L. Szczesniak, Phys. Rev. B 1997, 55, 4. [2] Y. Martin, D. Abraham, H. Wickramasinghe, Appl. Phys. Lett. 1988, 52, 1103. [3] M. Hersam, A. Hoole, S. 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