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Scanning tunneling spectroscopyScanning tunneling spectroscopy (STS) is a powerful experimental technique in scanning tunneling microscopy (STM) that uses a scanning tunneling microscope (STM) to probe the local density of electronic states (LDOS) and band gap of surfaces and materials on surfaces at the atomic scale [1]. Generally, STS involves observation of changes in constantcurrent topographs with tipsample bias, local measurement of the tunneling current versus tipsample bias (IV) curve, measurement of the tunneling conductance, dI / dV, or more than one of these. Since the tunneling current in a scanning tunneling microscope only flows in a region with diameter ~5Å, STS is unique in comparison with other surface spectroscopy techniques, which average over a larger surface region. The origins of STS are found in some of the earliest STM work of Gerd Binnig and Heinrich Rohrer, in which they observed changes in the appearance of some atoms in the (7 x 7) unit cell of the Si(111) – (7 x 7) surface with tipsample bias [2]. Additional recommended knowledge
Tunneling CurrentSince STS relies on the tunneling phenomena and measurement of the tunneling current or its derivative, understanding the expressions for the tunneling current is very important. Using the modified Bardeen transfer Hamiltonian method, which treats tunneling as a perturbation, the tunneling current (I) is found to be where is the Fermi distribution function, ρ_{s} and ρ_{T} are the density of states (DOS) in the sample and tip, respectively, and M_{μν} is the tunneling matrix element between the modified wavefunctions of the tip and the sample surface. The tunneling matrix element, describes the energy lowering due to the interaction between the two states. Here ψ and χ are the sample wavefunction modified by the tip potential and the tip wavefunction modified by sample potential, respectively [3]. For low temperatures and a constant tunneling matrix element, the tunneling current reduces to which is a convolution of the DOS of the tip and the sample [3]. Generally, STS experiments attempt to probe the sample DOS, but equation (3) shows that the tip DOS must be known for the measurement to have meaning. Equation (3) implies that under the gross assumption that the tip DOS is constant. For these ideal assumptions, the tunneling conductance is directly proportional to the sample DOS [3]. For higher bias voltages, the predictions of simple planar tunneling models using the WentzelKramers Brillouin (WKB) approximation are useful. In the WKB theory, the tunneling current is predicted to be where ρ_{s} and ρ_{t} are the density of states (DOS) in the sample and tip, respectively [2]. The energy and biasdependent electron tunneling transition probability, T, is given by where φ_{s} and φ_{t} are the respective work functions of the sample and tip and Z is the distance from the sample to the tip [2]. Experimental MethodsAcquiring standard STM topographs at many different tipsample biases and comparing the resulting topographic information is perhaps the most straightforward spectroscopic method [4]. The tipsample bias can also be changed on a linebyline basis during a single scan. This method creates two interleaved images at different biases [2]. Since only the states between the Fermi levels of the sample and the tip contribute to I, this method is quick way to determine whether there are any interesting biasdependent features on the surface. However, only limited information about the electronic structure can be extracted by this method, since the constant I topographs depend on the tip and sample DOS’s and the tunneling transmission probability, which depends on the tipsample spacing, as described in equation (5) [4]. By using modulation techniques, a constant current topograph and the spatially resolved dI / dV can be acquired simultaneously. A small, high frequency sinusoidal modulation voltage is superimposed on the d.c. tipsample bias. The a.c. component of the tunneling current is recorded using a lockin amplifier, and the component inphase with the tipsample bias modulation gives dI / dV directly. In practice, the modulation frequency is chosen slightly higher than the bandwidth of the STM feedback system [4]. This choice prevents the feedback control from compensating for the modulation by changing the tipsample spacing and minimizes the displacement current 90° outofphase with the applied bias modulation. Such effects arise from the capacitance between the tip and the sample, which grows as the modulation frequency increases [2]. In order to obtain IV curves simultaneously with a topograph, a sampleandhold circuit is used in the feedback loop for the z piezo signal. The sampleandhold circuit freezes the voltage applied to the z piezo, which freezes the tipsample distance, at the desired location allowing IV measurements without the feedback system responding [5]. The tipsample bias is swept between the specified values, and the tunneling current is recorded. After the spectra acquisition, the tipsample bias is returned to the scanning value, and the scan resumes. Using this method, the local electronic structure of semiconductors in the band gap can be probed [4]. There are two ways to record IV curves in the manner described above. In constantspacing scanning tunneling spectroscopy (CSSTS), the tip stops scanning at the desired location to obtain an IV curve. The tipsample spacing is adjusted to reach the desired initial current, which may be different from the initial current setpoint, at a specified tipsample bias. A sampleandhold amplifier freezes the z piezo feedback signal, which holds the tipsample spacing constant by preventing the feedback system from changing the bias applied to the z piezo [5]. The tipsample bias is swept through the specified values, and the tunneling current is recorded. Either numerical differentiation of I(V) or lockin detection as described above for modulation techniques can be used to find dI / dV. If lockin detection is used, then an a.c. modulation voltage is applied to the d.c. tipsample bias during the bias sweep and the a.c. component of the current inphase with the modulation voltage is recorded. In variablespacing scanning tunneling spectroscopy (VSSTS), the same steps occur as in CSSTS through turning off the feedback. As the tipsample bias is swept through the specified values, the tipsample spacing is decreased continuously as the magnitude of the bias is reduced [7]. Generally, a minimum tipsample spacing is specified to prevent the tip from crashing into the sample surface at 0V tipsample bias. Lockin detection and modulation techniques are used to find the conductivity, because the tunneling current is a function also of the varying tipsample spacing. Numerical differentiation of I(V) with respect to V would include the contributions from the varying tipsample spacing [6]. Introduced by Mårtensson and Feenstra to allow conductivity measurements over several orders of magnitude, VSSTS is useful for conductivity measurements on systems with large band gaps. Such measurements are necessary to properly define the band edges and examine the gap for states [7]. Currentimagingtunneling spectroscopy (CITS) is an STS technique where an IV curve is recorded at each pixel in the STM topograph [6]. Either variablespacing or constantspacing spectroscopy may be used to record the IV curves. The conductance, dI / dV, can be obtained by numerical differentiation of I with respect to V or acquired using lockin detection as described above. As a practical concern, the number of pixels in the scan or the scan area may be reduced to prevent piezo creep or thermal drift from moving the feature of study or the scan area during the duration of the scan. Since some CITS scans can last in excess of 12 hours, low drift and creep are absolutely necessary. Data InterpretationFrom the obtained IV curves, the band gap of the sample at the location of the IV measurement can be determined. By plotting the magnitude of I on a log scale versus the tipsample bias, the band gap can clearly be determined. Although determination of the band gap is possible from a linear plot of the IV curve, the log scale increases the sensitivity [6]. Alternatively, a plot of the conductance, dI / dV, versus the tipsample bias, V, allows one to locate the band edges that determine the band gap. The structure in the dI / dV, as a function of the tipsample bias, is associated with the DOS of the surface when the tipsample bias is less than the work functions of the tip and the sample. Usually, the WKB approximation for the tunneling current is used to interpret these measurements at low tipsample bias relative to the tip and sample work functions. The derivative of equation (5), I in the WKB approximation, is where ρ_{s} is the sample density of states, ρ_{t} is the tip density of states, and T is the tunneling transmission probability [2]. Although the tunneling transmission probability T is generally unknown, at a fixed location T increases smoothly and monotonically with the tipsample bias in the WKB approximation. Hence, structure in the dI / dV is usually assigned to features in the density of states in the first term of equation (7) [4]. Interpretation of dI / dV as a function of position is more complicated. Spatial variations in T show up in measurements of dI / dV as an inverted topographic background. When obtained in constant current mode, images of the spatial variation of dI / dV contain a convolution of topographic and electronic structure. An additional complication arises since dI / dV = I / V in the lowbias limit. Thus, dI / dV diverges as V approaches 0, preventing investigation of the local electronic structure near the Fermi level [4]. Since both the tunneling current, equation (5), and the conductance, equation (7), depend on the tip DOS and the tunneling transition probability, T, quantitative information about the sample DOS is very difficult to obtain. Additionally, the voltage dependence of T, which is usually unknown, can vary with position due to local fluctuations in the electronic structure of the surface [2]. For some cases, normalizing dI / dV by dividing by I / V can minimize the effect of the voltage dependence of T and the influence of the tipsample spacing. Using the WKB approximation, equations (5) and (7), we obtain [8]: Feenstra et al. argued that the dependencies of and on tipsample spacing and tipsample bias tend to cancel, since they appear as ratios [9]. This cancellation reduces the normalized conductance to the following form: where normalizes T to the DOS and describes the influence of the electric field in the tunneling gap on the decay length. Under the assumption that and vary slowly with tipsample bias, the features in reflect the sample DOS, ρ_{s} [2]. LimitationsWhile STS can provide spectroscopic information with amazing spatial resolution, there are some limitations. The STM and STS lack chemical sensitivity. Since the tipsample bias range in tunneling experiments is limited to , where φ is the apparent barrier height, STM and STS are only sample valence electron states. Elementspecific information is generally impossible to extract from STM and STS experiments, since the chemical bond formation greatly perturbs the valence states [4]. The shape of the tip is of critical importance for the spatial resolution of an STM scan and for the reliability of STS information. The tip density of states always affects information obtained by STS since the spectra are a convolution of the electronic structure of the tip and the sample [2]. In order to obtain an atomicresolution topographic image, the tip needs to be very sharp. Unfortunately, atomically sharp tips can have prominent, nonuniform electronic structure and produce very unreliable spectroscopy. Very blunt tips with poor spatial resolution are more likely to produce reliable spectroscopy [4]. Feenstra et al. developed an insitu tip treatment process to produce tips with flatter density of states and freeelectron metal behavior. The process uses field emission current to locally heat the end of the tip, leading to local melting and recrystalization that forms facets with low surface energy. For the tungsten (W) tips used, the result of this process is a tip with surface DOS similar to those of a freeelectron metal. This process produced tips giving reproducible tunneling spectra [3]. At finite temperatures, the thermal broadening of the electron energy distribution due to the Fermidistribution limits spectroscopic resolution. At T = 300K, , and the sample and tip energy distribution spread are both . Hence, the total energy deviation is [3]. Assuming the dispersion relation for simple metals, it follows from the uncertainty relation that where E_{F} is the Fermi energy, E_{0} is the bottom of the valence band, k_{F} is the Fermi wave vector, and r is the lateral resolution. Since spatial resolution depends on the tipsample spacing, smaller tipsample spacings and higher topographic resolution blur the features in tunneling spectra [3]. Despite these limitations, STS and STM provide the possibility for probing the local electronic structure of metals, semiconductors, and thin insulators on a scale unobtainable with other spectroscopic methods. Additionally, topographic and spectroscopic data can be recorded simultaneously. References
Literature


This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Scanning_tunneling_spectroscopy". A list of authors is available in Wikipedia. 