A tunneling spectroscopy technique to measure the energy level of an electronic state in a completely nonconducting surface is demonstrated. Spectroscopy is performed by electrostatic force detection of single-electron tunneling between a scanning probe and the state as a function of an applied voltage. An electronic state near the surface of a SiO2 film is found 5.5±0.2eV below the conduction band edge. A random telegraph signal, caused by sporadic back-and-forth single-electron tunneling, is observed as the probe Fermi level passes through the state energy.
Single-electron tunneling events between a metal probe and an insulator surface are measured by frequency detection electrostatic force microscopy. Single-electron tunneling events typically cause 1–10Hz shifts in the 300kHz resonance frequency of the oscillating force probe. The frequency shifts appear only within a sub-2nm tip–sample gap and their magnitude is roughly uniform under fixed experimental conditions. An electrostatic model of the probe–sample system yields results consistent with the measurements.
Diborane (B 2 H 6 ) is a promising molecular precursor for atomic precision p-type doping of silicon that has recently been experimentally demonstrated [S ̌kereňet al. Nat. Electron. 2020]. We use density functional theory (DFT) calculations to determine the reaction pathway for diborane dissociating into a species that will incorporate as electrically active substitutional boron after adsorbing onto the Si(100)-2×1 surface. Our calculations indicate that diborane must overcome an energy barrier to adsorb, explaining the experimentally observed low sticking coefficient (<1 × 10 −4 at room temperature) and suggesting that heating can be used to increase the adsorption rate. Upon sticking, diborane has an ≈50% chance of splitting into two BH 3 fragments versus merely losing hydrogen to form a dimer such as B 2 H 4 . As boron dimers are likely electrically inactive, whether this latter reaction occurs is shown to be predictive of the incorporation rate. The dissociation process proceeds with significant energy barriers, necessitating the use of high temperatures for incorporation. Using the barriers calculated from DFT, we parameterize a Kinetic Monte Carlo model that predicts the incorporation statistics of boron as a function of the initial depassivation geometry, dose, and anneal temperature. Our results suggest that the dimer nature of diborane inherently limits its doping density as an acceptor precursor and furthermore that heating the boron dimers to split before exposure to silicon can lead to poor selectivity on hydrogen and halogen resists. This suggests that, while diborane works as an atomic precision acceptor precursor, other non-dimerized acceptor precursors may lead to higher incorporation rates at lower temperatures.
Sub-10 nm resolution can be obtained in scanning capacitance microscopy (SCM) if the probe tip is approximately of the same size. Such resolution is observed, although infrequently, with present commercially available probes. To acquire routine sub-10 nm resolution, a solid Pt metal probe has been developed with a sub-10 nm tip radius. The probe is demonstrated by SCM imaging on a cross-sectioned 70 nm gatelength field-effect transistor (FET), a shallow implant (n+/p, 24 nm junction depth), and an epitaxial staircase (p, ∼75 nm steps). Sub-10 nm resolution is demonstrated on the FET device over the abrupt meeting between a silicon-on-insulator oxide layer and a neighboring Si region. Comparable resolution is observed on the implant structure, and quantitative SCM dopant profiling is performed on it with sub-10 nm accuracy. Finally, the epitaxial staircase structure is quantitatively profiled demonstrating the accuracy obtained in quantitative profiling with the tips.
Occupation of individual electron states near the surface of a SiO2 film is controlled by reversible single-electron tunneling to or from a metallic electrostatic force microscope probe. By switching the polarity of an applied dc bias between the probe and the sample to adjust the Fermi energy of the probe with respect to states near the dielectric surface, individual electrons are repeatably manipulated in and out of the sample. The single-electron charging and discharging is detected by frequency detection electrostatic force microscopy.
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