Quantifying atom-scale dopant movement and electrical activation in Si:P monolayers.

Advanced hydrogen lithography techniques and low-temperature epitaxial overgrowth enable the patterning of highly phosphorus-doped silicon (Si:P) monolayers (ML) with atomic precision. This approach to device fabrication has made Si:P monolayer systems a testbed for multiqubit quantum computing architectures and atomically precise 2-D superlattice designs whose behaviors are directly tied to the deterministic placement of single dopants. However, dopant segregation, diffusion, surface roughening, and defect formation during the encapsulation overgrowth introduce large uncertainties to the exact dopant placement and activation ratio. In this study, we develop a unique method by combining dopant segregation/diffusion models with sputter profiling simulation to monitor and control, at the atomic scale, dopant movement using room-temperature grown locking layers (LLs). We explore the impact of LL growth rate, thickness, rapid thermal annealing, surface accumulation, and growth front roughness on dopant confinement, local crystalline quality, and electrical activation within Si:P 2-D systems. We demonstrate that dopant movement can be more efficiently suppressed by increasing the LL growth rate than by increasing the LL thickness. We find that the dopant segregation length can be suppressed below a single Si lattice constant by increasing the LL growth rates at room temperature while maintaining epitaxy. Although dopant diffusivity within the LL is found to remain high (on the order of 10-17 cm2 s-1) even below the hydrogen desorption temperature, we demonstrate that exceptionally sharp dopant confinement with high electrical quality within Si:P monolayers can be achieved by combining a high LL growth rate with low-temperature LL rapid thermal annealing. The method developed in this study provides a key tool for 2-D fabrication techniques that require precise dopant placement to suppress, quantify, and predict a single dopant's movement at the atomic scale.

Biofunctionalization of PEDOT films with laminin-derived peptides.

UNLABELLED: Poly(3,4-ethylenedioxythiophenes) (PEDOT) have been extensively explored as materials for biomedical implants such as biosensors, tissue engineering scaffolds and microelectronic devices. Considerable effort has been made to incorporate biologically active molecules into the conducting polymer films in order to improve their long term performance at the soft tissue interface of devices, and the development of functionalized conducting polymers that can be modified with biomolecules would offer important options for device improvement. Here we report surface modification, via straightforward protocols, of carboxylic-acid-functional PEDOT copolymer films with the nonapeptide, CDPGYIGSR, derived from the basement membrane protein laminin. Evaluation of the modified surfaces via XPS and toluidine blue O assay confirmed the presence of the peptide on the surface and electrochemical analysis demonstrated unaltered properties of the peptide-modified films. The efficacy of the peptide, along with the impact of a spacer molecule, for cell adhesion and differentiation was tested in cell culture assays employing the rat pheochromocytoma (PC12) cell line. Peptide-modified films comprising the longest poly(ethylene glycol) (PEG) spacer used in this study, a PEG with ten ethylene glycol repeats, demonstrated the best attachment and neurite outgrowth compared to films with peptides alone or those with a PEG spacer comprising three ethylene glycol units. The films with PEG10-CDPGYISGR covalently modified to the surface demonstrated 11.5% neurite expression with a mean neurite length of 90µm. This peptide immobilization technique provides an effective approach to biofunctionalize conducting polymer films. STATEMENT OF SIGNIFICANCE: For enhanced diagnosis and treatment, electronic devices that interface with living tissue with minimum shortcomings are critical. Towards these ends, conducting polymers have proven to be excellent materials for electrode-tissue interface for a variety of biomedical devices ranging from deep brain stimulators, cochlear implants, and microfabricated cortical electrodes. To improve the electrode-tissue interface, one strategy utilized by many researchers is incorporating relevant biological molecules within or on the conducting polymer thin films to provide a surface for cell attachment and/or provide biological cues for cell growth. The present study provides a facile means for generating PEDOT films grafted with a laminin peptide with or without a spacer molecule for enhanced cell attachment and neurite extension.

Study of the nanoscale morphology of polythiophene fibrils and a fullerene derivative.

Nanoscale blending of electron-donor and electron-acceptor materials in solution-processed bulk heterojunction organic photovoltaic devices is crucial for achieving high power conversion efficiency. We used a classic blend of poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM) as a model to observe the nanoscale morphology of the P3HT fibrils and PCBM nanoclusters in the mixture. Energy-filtered transmission electron microscopy (EFTEM) clearly revealed a nanoscopic phase separation. Randomly connected and/or nonconnected P3HT fibrous networks and PCBM domains, revealed by 2-dimensional micrographs, were observed by collecting electron energy loss spectra in the range of 19-30 eV. From EFTEM images, the average length and the diameter of P3HT fibrils were found to be approximately 70 ± 5 and 15 ± 2 nm, respectively. Combining the EFTEM, selected area electron diffraction, and X-ray diffraction results, the number and spacing of the ordered chains in P3HT fibrils were determined. There were 18 ± 3 repeating units of P3HT perpendicular to the fibril, ∼184 layers of π-π stacking along the fibril, and ∼9 layers of interchain stacking within the fibril. These conclusive observations provide insight into the number of molecules found in one instance of ordered-plane stacking. This information is useful for the calculation of charge transport in semicrystalline polymers. Using cross-section samples prepared with a focused ion beam technique, the vertical morphology of each phase was analyzed. By collecting 30 eV energy loss images, the phase separation in the P3HT/PCBM system was distinguishable. A higher P3HT concentration was observed at the top of the cell, near Al contact, which could possibly cause loss of carriers and recombination due to a mismatch in the P3HT and Al energy bands.