bOptimizing atomic force microscopy for characterization of diamond-protein interfaces

Atomic force microscopy (AFM) in contact mode and tapping mode is employed for high resolution studies of soft organic molecules (fetal bovine serum proteins) on hard inorganic diamond substrates in solution and air. Various effects in morphology and phase measurements related to the cantilever spring constant, amplitude of tip oscillations, surface approach, tip shape and condition are demonstrated and discussed based on the proposed schematic models. We show that both diamond and proteins can be mechanically modified by Si AFM cantilever. We propose how to choose suitable cantilever type, optimize scanning parameters, recognize and minimize various artifacts, and obtain reliable AFM data both in solution and in air to reveal microscopic characteristics of protein-diamond interfaces. We also suggest that monocrystalline diamond is well defined substrate that can be applicable for fundamental studies of molecules on surfaces in general

Impact of AFM-induced nano-pits in a-Si:H films on silicon crystal growth

Conductive tips in atomic force microscopy (AFM) can be used to localize field-enhanced metal-induced solid-phase crystallization (FE-MISPC) of amorphous silicon (a-Si:H) at room temperature down to nanoscale dimensions. In this article, the authors show that such local modifications can be used to selectively induce further localized growth of silicon nanocrystals. First, a-Si:H films by plasma-enhanced chemical vapor deposition on nickel/glass substrates are prepared. After the FE-MISPC process, yielding both conductive and non-conductive nano-pits in the films, the second silicon layer at the boundary condition of amorphous and microcrystalline growth is deposited. Comparing AFM morphology and current-sensing AFM data on the first and second layers, it is observed that the second deposition changes the morphology and increases the local conductivity of FE-MISPC-induced pits by up to an order of magnitude irrespective of their prior conductivity. This is attributed to the silicon nanocrystals (<100 nm) that tend to nucleate and grow inside the pits. This is also supported by micro-Raman spectroscopy

Guided assembly of nanoparticles on electrostatically charged nanocrystalline diamond thin films

We apply atomic force microscope for local electrostatic charging of oxygen-terminated nanocrystalline diamond (NCD) thin films deposited on silicon, to induce electrostatically driven self-assembly of colloidal alumina nanoparticles into micro-patterns. Considering possible capacitive, sp2 phase and spatial uniformity factors to charging, we employ films with sub-100 nm thickness and about 60% relative sp2 phase content, probe the spatial material uniformity by Raman and electron microscopy, and repeat experiments at various positions. We demonstrate that electrostatic potential contrast on the NCD films varies between 0.1 and 1.2 V and that the contrast of more than ±1 V (as detected by Kelvin force microscopy) is able to induce self-assembly of the nanoparticles via coulombic and polarization forces. This opens prospects for applications of diamond and its unique set of properties in self-assembly of nano-devices and nano-systems

Silicon-Vacancy Centers in Ultra-Thin Nanocrystalline Diamond Films

Color centers in diamond have shown excellent potential for applications in quantum information processing, photonics, and biology. Here we report the optoelectronic investigation of shallow silicon vacancy (SiV) color centers in ultra-thin (7–40 nm) nanocrystalline diamond (NCD) films with variable surface chemistry. We show that hydrogenated ultra-thin NCD films exhibit no or lowered SiV photoluminescence (PL) and relatively high negative surface photovoltage (SPV) which is ascribed to non-radiative electron transitions from SiV to surface-related traps. Higher SiV PL and low positive SPV of oxidized ultra-thin NCD films indicate an efficient excitation—emission PL process without significant electron escape, yet with some hole trapping in diamond surface states. Decreasing SPV magnitude and increasing SiV PL intensity with thickness, in both cases, is attributed to resonant energy transfer between shallow and bulk SiV. We also demonstrate that thermal treatments (annealing in air or in hydrogen gas), commonly applied to modify the surface chemistry of nanodiamonds, are also applicable to ultra-thin NCD films in terms of tuning their SiV PL and surface chemistry

Synthesis, structure, and opto-electronic properties of organic-based nanoscale heterojunctions

Enormous research effort has been put into optimizing organic-based opto-electronic systems for efficient generation of free charge carriers. This optimization is mainly due to typically high dissociation energy (0.1-1 eV) and short diffusion length (10 nm) of excitons in organic materials. Inherently, interplay of microscopic structural, chemical, and opto-electronic properties plays crucial role. We show that employing and combining advanced scanning probe techniques can provide us significant insight into the correlation of these properties. By adjusting parameters of contact- and tapping-mode atomic force microscopy (AFM), we perform morphologic and mechanical characterizations (nanoshaving) of organic layers, measure their electrical conductivity by current-sensing AFM, and deduce work functions and surface photovoltage (SPV) effects by Kelvin force microscopy using high spatial resolution. These data are further correlated with local material composition detected using micro-Raman spectroscopy and with other electronic transport data. We demonstrate benefits of this multi-dimensional characterizations on (i) bulk heterojunction of fully organic composite films, indicating differences in blend quality and component segregation leading to local shunts of photovoltaic cell, and (ii) thin-film heterojunction of polypyrrole (PPy) electropolymerized on hydrogen-terminated diamond, indicating covalent bonding and transfer of charge carriers from PPy to diamond

Enhanced Growth and Osteogenic Differentiation of Human Osteoblast-Like Cells on Boron-Doped Nanocrystalline Diamond Thin Films

Intrinsic nanocrystalline diamond (NCD) films have been proven to be promising substrates for the adhesion, growth and osteogenic differentiation of bone-derived cells. To understand the role of various degrees of doping (semiconducting to metallic-like), the NCD films were deposited on silicon substrates by a microwave plasma-enhanced CVD process and their boron doping was achieved by adding trimethylboron to the CH4:H2 gas mixture, the B∶C ratio was 133, 1000 and 6700 ppm. The room temperature electrical resistivity of the films decreased from >10 MΩ (undoped films) to 55 kΩ, 0.6 kΩ, and 0.3 kΩ (doped films with 133, 1000 and 6700 ppm of B, respectively). The increase in the number of human osteoblast-like MG 63 cells in 7-day-old cultures on NCD films was most apparent on the NCD films doped with 133 and 1000 ppm of B (153,000±14,000 and 152,000±10,000 cells/cm2, respectively, compared to 113,000±10,000 cells/cm2 on undoped NCD films). As measured by ELISA per mg of total protein, the cells on NCD with 133 and 1000 ppm of B also contained the highest concentrations of collagen I and alkaline phosphatase, respectively. On the NCD films with 6700 ppm of B, the cells contained the highest concentration of focal adhesion protein vinculin, and the highest amount of collagen I was adsorbed. The concentration of osteocalcin also increased with increasing level of B doping. The cell viability on all tested NCD films was almost 100%. Measurements of the concentration of ICAM-1, i.e. an immunoglobuline adhesion molecule binding inflammatory cells, suggested that the cells on the NCD films did not undergo significant immune activation. Thus, the potential of NCD films for bone tissue regeneration can be further enhanced and tailored by B doping and that B doping up to metallic-like levels is not detrimental for cells

Charge transport at polypyrrole diamond interface

Changes of surface potential and photo-current under illumination indicate exciton splitting at the polypyrrole-diamond interface and transport of holes to diamond

Surface-related 2D conductivity of nanocrystalline diamond in-plane nanowires

Diamond is an attractive material for nanoelectronics, biological interfaces and electrical transducers. Small device dimensions are highly demanded for higher sensitivity, parallelism, remote sensing and reduced costs. Recently we have demonstrated that directly grown nanocrystalline diamond micro-channels (down to 5 um widths) are feasible and fully operational as field-effect transistors using H-terminated surface conductivity