Surface Functionalization toward Biosensing via Free-Standing Si-OH Bonds on Nonoxidized Silicon Surfaces.

Usually hydroxyl groups present on top of oxidized silicon served as binding centers for a silanization reaction toward surface functionalization. In this study, we developed a novel surface functionalization strategy where hydroxyl functionalization on nonoxidized silicon surfaces are obtained. These surfaces were stable for several weeks even in ambient air at room temperature. This high stability indicates a strong spatial isolation of the hydroxyl groups because they keenly tend to undergo a condensation reaction, forming silicon oxide. To prove the applicability of the obtained hydroxylated silicon surface, we further modified the hydroxyl groups with a commonly used silane molecule, (3-aminopropyl)triethoxysilane (APTES). The functional amino groups of the APTES layer bonded to the surface were subsequently altered by N-maleoyl-ß-alanin to generate a surface highly specific for the immobilization of thiol-containing biomolecules (like thiolated single-stranded DNA or cysteine-tagged proteins). All modification steps have been investigated by IR spectroscopic ellipsometry measurements.

Unravelling the low-temperature metastable state in perovskite solar cells by noise spectroscopy.

The hybrid perovskite methylammonium lead iodide CH3NH3PbI3 recently revealed its potential for the manufacturing of low-cost and efficient photovoltaic cells. However, many questions remain unanswered regarding the physics of the charge carrier conduction. In this respect, it is known that two structural phase transitions, occurring at temperatures near 160 and 310 K, could profoundly change the electronic properties of the photovoltaic material, but, up to now, a clear experimental evidence has not been reported. In order to shed light on this topic, the low-temperature phase transition of perovskite solar cells has been thoroughly investigated by using electric noise spectroscopy. Here it is shown that the dynamics of fluctuations detect the existence of a metastable state in a crossover region between the room-temperature tetragonal and the low-temperature orthorhombic phases of the perovskite compound. Besides the presence of a noise peak at this transition, a saturation of the fluctuation amplitudes is observed induced by the external DC current or, equivalently, by light exposure. This noise saturation effect is independent on temperature, and may represent an important aspect to consider for a detailed explanation of the mechanisms of operation in perovskite solar cells.

Electrochemical functionalization of Au by aminobenzene and 2-aminotoluene.

Au surfaces are functionalized by aminobenzene (AB) and 2-aminotoluene (AT) using the electrochemical reduction of diazotized 1,4-diaminobenzene and 2,5-diaminotoluene. The IR spectroscopic measurements reveal the successful modification of Au surfaces by AB and AT. Both types of layers show similar thicknesses as obtained by microgravimetric measurements via electrochemical quartz crystal microbalance (EQCM). However, the faradaic efficiency for the grafting of AT onto an EQCM-Au sensor was 6% compared to 41% for the grafting of AB. This behavior points to a steric hindrance during the binding of AT to the EQCM surface induced by the additional methyl group present in the toluene derivative. The AB and AT functionalized surfaces have been further modified by the amidation reaction of EDC/NHS activated 4-nitrobenzoic acid. This model system reveals that the amidation reaction is slightly hindered in case of the AT layer due to the presence of the methyl group close to the amino group. This behavior leads to a four times less amount of amide bonds at the AT compared to AB modified Au surfaces as obtained from IR spectroscopic measurements.

Vibrational and electronic characterization of ethynyl derivatives grafted onto hydrogenated Si(111) surfaces.

Covalent grafting of ethynyl derivatives (-C triple bond C-H, -C triple bond C-CH3, -C triple bond C-aryl) onto H-terminated Si(111) surfaces was performed by a one-step anodic treatment in Grignard electrolytes. The electrochemical grafting of such ethynyl derivatives, which tends to form ultrathin polymeric layers, can be controlled by the current and charge flow passing through the Si electrode. The prepared ultrathin layers cover the Si surface and had a thickness up to 20 nm, as investigated by the scanning electron microscopy (SEM) technique. Exchanging Cl for Br in the ethynyl Grignard reagent leads to very thin layers, even under the same electrochemical conditions. However, for all ethynyl derivatives, high-resolution synchrotron X-ray photoelectron spectroscopy (SXPS) investigations reveal the incorporation of halogen atoms in the organic layers obtained. Moreover, it was observed that the larger the end group of the ethynyl derivative, the thinner the thickness of the ultrathin polymeric layers as measured by both SXPS and SEM techniques after low and high current flow respectively. For the first time, these new types of ultrathin organic layers on Si surfaces were investigated using infrared spectroscopic ellipsometry (IRSE). The different possible reaction pathways are discussed.

Anisotropy in hydrogen-passivated and organically modified nanoporous silicon surfaces studied by polarization dependent IR spectroscopy.

Infrared spectroscopic ellipsometry (IRSE) was applied for characterization of porous silicon (PSi) electrochemically prepared in acidic fluoride solution. When no formation of SiO2 was involved in the preparation, an anisotropic distribution of PSi bonds with the terminating molecules was achieved. On the contrary, oxidation of PSi samples during the preparation led to an isotropic structure. IR spectra obtained from organically functionalized PSi surfaces suggested that the morphology of the organic layer on PSi was anisotropic for electrochemical grafting of methyl but not nitrobenzene. Comparison between the IRSE spectra obtained from PSi and Si(111) surfaces and application of optical models supported these observations.

Smoothing and passivation of special Si(111) substrates: studied by SPV, PL, AFM and SEM measurements.

Surface sensitive techniques, the field-modulated surface photovoltage, photoluminescence measurements, atomic force microscopy and scanning electron microscopy, were employed to yield detailed information on the influence of wet-chemical treatments on the preparation induced microroughness and electronic properties of wet-chemically passivated Si(111) substrates with special surface morphology. Stepped substrates with evenly distributed atomically flat terraces were prepared and passivated by thin oxide layers, which were used as a starting point for the subsequent H-termination after long storage in air. It was shown that their surface morphology and electronic properties do not degrade. Applying this preparation method to solar cell substrates with randomly distributed Si(111) pyramids, we achieved significantly lower densities of surface states and reduced recombination loss at a-Si:H/c-Si interfaces, compared with conventional pretreatments. The surface microroughness, the density of rechargeable states and the resulting recombination loss on a-Si:H/c-Si heterojunctions were found to be mainly influenced by two steps of surface pretreatment: firstly, the wet-chemical smoothing procedure of structured substrates and, secondly, the removal of native and wet-chemical oxides during the final etching in HF- or NH(4)F-containing solutions.

Time-resolved synchrotron XPS monitoring of irradiation-induced nitrobenzene reduction for chemical lithography.

The irradiation-induced reduction of electrochemically grafted nitrobenzene films on Si(111) was monitored by high-resolution photoelectron spectroscopy. The experiments were performed using synchrotron soft X-ray irradiation at the BESSY II synchrotron facility. The evolution of different chemical species was monitored as a function of time. Careful fitting of the Si2p, C1s, N1s, and O1s core level spectra allowed us to follow this process in detail and to determine the constants of growth and decay of the specific components. The chemical changes were caused by the X-ray irradiation-induced secondary electron current through the aryl layer. A minor fraction (approximately 25%) of the initial nitro groups was split off and desorbed. The bulk of the NO2 groups was reduced to species in an amino-like chemical environment. A desorption of carbon fragments was not observed, and benzene ring specific shakeup satellites indicated that the aromatic ring structure remained intact. Irradiation-induced line-shape changes suggest a polymerization via -NH- bridges, which were formed after the irradiation-induced N-O bond splitting. A significant part of the released oxygen appeared to contribute to an oxidation of the silicon substrate at the Si(111)/benzene interface. The irradiation-induced aryl layer modification can be exploited for chemical lithography (i.e., a lateral structuring of functionalized silicon surfaces).

Analysis of biosensors by chemically specific optical techniques. Chemiluminescence-imaging and infrared spectroscopic mapping ellipsometry.

The standard methods currently used to read out microarrays are fluorescent and chemiluminescent imaging techniques. These methods require labeling of a component with a marker and, usually, only the concentration of the marker molecule is detected. A label-free imaging method that also enables quantitative spectroscopic analysis of the composition and component interaction would be of great advantage. In this article it is shown for the first time that IR mapping ellipsometry enables label-free imaging of a biochip before and after incubation with peptide solution. The measurements prove that IR ellipsometry is a sensitive tool for laterally resolved identification of the different materials and determination of the composition of a biochip. The lateral resolution required was achieved by using radiation from an infrared synchrotron beamline.