Solution Chemistry to Control Boron-Containing Monolayers on Silicon: Reactions of Boric Acid and 4-Fluorophenylboronic Acid with H- and Cl-terminated Si(100).

The reactions of boric acid and 4-fluorophenylboronic acid with H- and Cl-terminated Si(100) surfaces in solution were investigated. X-ray photoelectron spectroscopy (XPS) studies reveal that both molecules react preferentially with Cl-Si(100) and not with H-Si(100) at identical conditions. On Cl-Si(100), the reactions introduce boron onto the surface, forming a Si-O-B structure. The quantification of boron surface coverage demonstrates that the 4-fluorophenylboronic acid leads to ∼2.8 times higher boron coverage compared to that of boric acid on Cl-Si(100). Consistent with these observations, density functional theory studies show that the reaction of boric acid and 4-fluorophenylboronic acid is more favorable with the Cl- versus H-terminated surface and that on Cl-Si(100) the reaction with 4-fluorophenylboronic acid is ∼55.3 kJ/mol more thermodynamically favorable than the reaction with boric acid. The computational studies were also used to demonstrate the propensity of the overall approach to form high-coverage monolayers on these surfaces, with implications for selective-area boron-based monolayer doping.

Reaction of Hydrazine with Solution- and Vacuum-Prepared Selectively Terminated Si(100) Surfaces: Pathways to the Formation of Direct Si-N Bonds.

The reactivity of liquid hydrazine (N2H4) with respect to H-, Cl-, and Br-terminated Si(100) surfaces was investigated to uncover the principles of nitrogen incorporation into the interface. This process has important implications in a wide variety of applications, including semiconductor surface passivation and functionalization, nitride growth, and many others. The use of hydrazine as a precursor allows for reactions that exclude carbon and oxygen, the primary sources of contamination in processing. In this work, the reactivity of N2H4 with H- and Cl-terminated surfaces prepared by traditional solvent-based methods and with a Br-terminated Si(100) prepared in ultrahigh vacuum was compared. The reactions were studied with X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy, and the observations were supported by computational investigations. The H-terminated surface led to the highest level of nitrogen incorporation; however, the process proceeds with increasing surface roughness, suggesting possible etching or replacement reactions. In the case of Cl-terminated (predominantly dichloride) and Br-terminated (monobromide) surfaces, the amount of nitrogen incorporation on both surfaces after the reaction with hydrazine was very similar despite the differences in preparation, initial structure, and chemical composition. Density functional theory was used to propose the possible surface structures and to analyze surface reactivity.

Reaction of BCl3 with H- and Cl-terminated Si(1 0 0) as a pathway for selective, monolayer doping through wet chemistry.

The reaction of boron trichloride with the H and Cl-terminated Si(100) surfaces was investigated to understand the interaction of this molecule with the surface for designing wet-chemistry based silicon surface doping processes using a carbon- and oxygen-free precursor. The process was followed with X-ray photoelectron spectroscopy (XPS). Within the reaction conditions investigated, the reaction is highly effective on Cl-Si(100) for temperatures below 70°C, at which point both surfaces react with BCl3. The XPS investigation followed the formation of a B 1s peak at 193.5 eV corresponding to (B-O)x species. Even the briefest exposure to ambient conditions lead to hydroxylation of surface borochloride species. However, the Si 2p signature at 102 eV allowed for a confirmation of the formation of a direct Si-B bond. Density functional theory was utilized to supplement the analysis and identify possible major surface species resulting from these reactions. This work provides a new pathway to obtain a functionalized silicon surface with a direct Si-B bond that can potentially be exploited as a means of selective, ultra-shallow, and supersaturated doping.

Strain-tunable Berry curvature in quasi-two-dimensional chromium telluride.

Magnetic transition metal chalcogenides form an emerging platform for exploring spin-orbit driven Berry phase phenomena owing to the nontrivial interplay between topology and magnetism. Here we show that the anomalous Hall effect in pristine Cr2Te3 thin films manifests a unique temperature-dependent sign reversal at nonzero magnetization, resulting from the momentum-space Berry curvature as established by first-principles simulations. The sign change is strain tunable, enabled by the sharp and well-defined substrate/film interface in the quasi-two-dimensional Cr2Te3 epitaxial films, revealed by scanning transmission electron microscopy and depth-sensitive polarized neutron reflectometry. This Berry phase effect further introduces hump-shaped Hall peaks in pristine Cr2Te3 near the coercive field during the magnetization switching process, owing to the presence of strain-modulated magnetic layers/domains. The versatile interface tunability of Berry curvature in Cr2Te3 thin films offers new opportunities for topological electronics.

B-Doped δ-Layers and Nanowires from Area-Selective Deposition of BCl3 on Si(100).

Atomically precise, δ-doped structures forming electronic devices in Si have been routinely fabricated in recent years by using depassivation lithography in a scanning tunneling microscope (STM). While H-based precursor/monatomic resist chemistries for incorporation of donor atoms have dominated these efforts, the use of halogen-based chemistries offers a promising path toward atomic-scale manufacturing of acceptor-based devices. Here, B-doped δ-layers were fabricated in Si(100) by using BCl3 as an acceptor dopant precursor in ultrahigh vacuum. Additionally, we demonstrate compatibility of BCl3 with both H and Cl monatomic resists to achieve area-selective deposition on Si. In comparison to bare Si, BCl3 adsorption selectivity ratios for H- and Cl-passivated Si were determined by secondary ion mass spectrometry depth profiling (SIMS) to be 310(10):1 and 1529(5):1, respectively. STM imaging revealed that BCl3 adsorbed readily on bare Si at room temperature, with SIMS measurements indicating a peak B concentration greater than 1.2(1) × 1021 cm-3 with a total areal dose of 1.85(1) × 1014 cm-2 resulting from a 30 langmuir BCl3 dose at 150 °C. In addition, SIMS showed a δ-layer thickness of ∼0.5 nm. Hall bar measurements of a similar sample were performed at 3.0 K, revealing a sheet resistance of ρ□ = 1.9099(4) kΩ â–¡-1, a hole carrier concentration of p = 1.90(2) × 1014 cm-2, and a hole mobility of µ = 38.0(4) cm2 V-1 s-1 without performing an incorporation anneal. Finally, 15 nm wide B δ-doped nanowires were fabricated from BCl3 and were found to exhibit ohmic conduction. This validates the use of BCl3 as a dopant precursor for atomic-precision fabrication of acceptor-doped devices in Si and enables development of simultaneous n- and p-type doped bipolar devices.