Improvement of CZTSSe film quality and superstrate solar cell performance through optimized post-deposition annealing.

Improving the performance of kesterite solar cells requires high-quality, defect-free CZTS(Se) films with a reduced number of secondary phases and impurities. Post-annealing of the CZTS films at high temperatures in a sulfur or selenium atmosphere is commonly used to improve the quality of the absorbing material. However, annealing at high-temperatures can promote material decomposition, mainly due to the loss of volatile elements such as tin or sulfur. In this work, we investigate how the additional step of sulfurization at reduced temperatures affects the quality and performance of CZTSSe based solar cells. A comprehensive structural analysis using conventional and high resolution XRD as well as Raman spectroscopy revealed that the highest CZTSSe material quality with the lowest structural disorder and defect densities was obtained from the CZTS films pre-sulfurized at 420 °C. Furthermore, we demonstrate the possibility of using Sb2Se3 as a buffer layer in the superstrate configuration of CZTSSe solar cells, which is possible alternative to replace commonly employed toxic CdS as a buffer layer. We show that the additional low-temperature selenization process and the successful use of Sb2Se3 as a buffer layer could improve the performance of CZTSSe-based solar cells by up to 3.48%, with an average efficiency of 3.1%.

The direct growth of planar and vertical graphene on Si(100) via microwave plasma chemical vapor deposition: synthesis conditions effects.

In the present research, graphene was synthesized directly on a Si(100) substrate via combining direct microwave plasma-enhanced chemical vapor deposition and protective enclosure. The graphene flake orientation was controlled using suitable synthesis conditions. We revealed that high processing temperatures and plasma powers promote vertical graphene growth. The main related physical mechanisms were raised temperature gradients, thermal stress, ion bombardment, and elevated electric field effects. Lowering the synthesis temperature and plasma power resulted in planar graphene growth. An elevated synthesis temperature and long deposition time decreased the graphene layer number as the carbon desorption rate increased with temperature. Dominating defect types and their relationships to the graphene growth conditions were revealed. Planar graphene n-type self-doping was found due to substrate-based charge transfer. In the case of vertical graphene, the increased contact area between graphene and air resulted in the adsorption of more molecules, resulting in no doping or p-type doping.

Separation of anthropogenic radionuclides from aqueous environment using raw and modified biosorbents.

In this study, two types of biosorbents were used to remove 137Cs and plutonium isotopes from aqueous solutions - moss (Ptilium crista - castrensis) and oak sawdust (Quercus robur), both in the form of natural and modified state. Sorbent modification significantly increases the sorbent surface area (for moss sorbents - from 4.0 to 47.2 m2/g, and for sawdust sorbents - from 1.1 to 26.3 m2/g), pore volume (from 10-3 to 10-2), concentration and amount of basic cations and anions, as well as active functional groups on the sorbent surface. The main functional groups on the surface of natural sorbents modified with iron hydroxide interacting with analytes are carboxyl and hydroxyl groups. For carbonized sawdust and its subsequent activation with concentrated HCl, in addition to carboxyl and hydroxyl groups, acetyl groups also become active. Carbonated sawdust treated with HCl showed the highest average removal efficiency and sorption capacity for radiocesium and plutonium isotopes in laboratory column experiments - for 137Cs ∼78.6% and ∼196.6 Bq/g and for 239+240Pu ∼83% and ∼41.5 Bq/g, respectively. The moss and moss modified with iron hydroxide also showed good properties of adsorbing plutonium isotopes in field (in-situ) experiments. The best results on the sorption of 137Cs in field experiments were shown by carbonated sawdust activated with HCl, and for isotopes of plutonium - the raw moss and moss modified with iron hydroxide. The results of the study showed that sorbents can be used not only for purification of water from plutonium isotopes but allow the operational sampling and more accurate measurement of radiocesium and plutonium isotopes in the fresh water reservoirs by the dynamic flow method.

Interaction of Amyloid-ß-(1-42) Peptide and Its Aggregates with Lipid/Water Interfaces Probed by Vibrational Sum-Frequency Generation Spectroscopy.

In this study, we use surface-sensitive vibrational sum-frequency generation (VSFG) spectroscopy to investigate the interaction between model lipid monolayers and Aß(1-42) in its monomeric and aggregated states. Combining VSFG with atomic force microscopy (AFM) and thioflavin T (ThT) fluorescence measurements, we found that only small aggregates with probably a ß-hairpin-like structure adsorbed to the zwitterionic lipid monolayer (DOPC). In contrast, larger aggregates with an extended ß-sheet structure adsorbed to a negatively charged lipid monolayer (DOPG). The adsorption of small, initially formed aggregates strongly destabilized both monolayers, but only the DOPC monolayer was completely disrupted. We showed that the intensity of the amide-II' band in achiral (SSP) and chiral (SPP) polarization combinations increased in time when Aß(1-42) aggregates accumulated at the DOPG monolayer. Nevertheless, almost no adsorption of preformed mature fibrils to DOPG monolayers was detected. By performing spectral VSFG calculations, we revealed a clear correlation between the amide-II' signal and the degree of amyloid aggregates (e.g., oligomers or (proto)fibrils) of various Aß(1-42) structures. The calculations showed that only structures with a significant amyloid ß-sheet content have a strong amide-II' intensity, in line with previous Raman studies. The combination of the presented results substantiates the amide-II(') band as a legitimate amyloid marker.

Photovoltaic effect-driven IR response of heterojunctions obtained by direct CVD synthesis of MoS2 nanolayers on crystalline silicon.

The development of technologies of hybrid structures with combined three-dimensional (3D) and two-dimensional (2D) materials is being recognised as a highly attractive opportunity to create new optoelectronic devices with unique properties originating from the atomic thin structures. In the present study, a novel approach in the direct synthesis of MoS2 2D-layers on p-Si was proved to be acceptable for fabricating a photovoltaic effect-driven photodetector based on a hybrid 2D/3D heterojunction that included an atomically thin n-MoS2 film and crystalline p-Si substrate. It was demonstrated experimentally that the heterojunction with the top and bottom contacts was highly sensitive to illumination between 650 and 1200 nm. The experimental study proved that the response to light was originated by the photovoltaic effect in the sample devices without an external power supply. The maximum sensitivity of the 2D/3D heterostructures to the optical power of the illumination was up to 210 V W-1 and was practically independent of the wavelength. The analysis of experimental I-V, C-V characteristics, Raman spectra and AFM surface images allowed us to construct a flat band model of the hybrid 2D/3D n-p-heterojunction that explained the electrical properties of the n-MoS2/p-Si photodetectors. The photovoltaic effect-driven light detectors offer highly promising possibilities in the development of autonomous photonic systems.

Influence of the graphene layer on the strong coupling in the hybrid Tamm-plasmon polariton mode.

The total internal refection ellipsometry (TIRE) method was used for the generation and study of the hybrid TPP-SPP mode on a photonic crystal structure with a thin layer of silver and graphene/PMMA. Raman spectroscopy showed a consistent monolayer graphene present on the Ag layer. Recent studies have also shown that TPP and SPP components in the hybrid plasmonic mode is sensitive to the variation of coupling strength due to presence of the graphene monolayer. The decrease of the TPP and SPP dip components in the TPP-SPP hybrid mode can be explained by the changes of the conductivity of the silver layer due to the presence of this additional graphene/PMMA structure, which results in the non-optimal resonance conditions for the hybrid plasmonic mode. The modified positions of the TPP and SPP components in the wavelength spectra when compared to their original, separate excitations, indicates a strong coupling regime. The design of these hybrid plasmonic/graphene-based nanostructures has attractive capabilities for the development of advanced optical sensors and integrated optical circuit technologies.

Structure Determination of Hen Egg-White Lysozyme Aggregates Adsorbed to Lipid/Water and Air/Water Interfaces.

We use vibrational sum-frequency generation (VSFG) spectroscopy to study the structure of hen egg-white lysozyme (HEWL) aggregates adsorbed to DOPG/D2O and air/D2O interfaces. We find that aggregates with a parallel and antiparallel ß-sheet structure together with smaller unordered aggregates and a denaturated protein are adsorbed to both interfaces. We demonstrate that to retrieve this information, fitting of the VSFG spectra is essential. The number of bands contributing to the VSFG spectrum might be misinterpreted, due to interference between peaks with opposite orientation and a nonresonant background. Our study identified hydrophobicity as the main driving force for adsorption to the air/D2O interface. Adsorption to the DOPG/D2O interface is also influenced by hydrophobic interaction; however, electrostatic interaction between the charged protein's groups and the lipid's headgroups has the most significant effect on the adsorption. We find that the intensity of the VSFG spectrum at the DOPG/D2O interface is strongly enhanced by varying the pH of the solution. We show that this change is not due to a change of lysozyme's and its aggregates' charge but due to dipole reorientation at the DOPG/D2O interface. This finding suggests that extra care must be taken when interpreting the VSFG spectrum of proteins adsorbed at the lipid/water interface.

Electrical activity of cellobiose dehydrogenase adsorbed on thiols: Influence of charge and hydrophobicity.

The interface between protein and material surface is of great research interest in applications varying from implants, tissue engineering to bioelectronics. Maintaining functionality of bioelements depends greatly on the immobilization process. In the present study direct electron transfer of cellobiose dehydrogenase from Humicola insolens (HiCDH), adsorbed on four different self-assembled monolayers (SAMs) formed by 5-6 chain length carbon thiols varying in terminal group structure was investigated. By using a combination of quartz crystal microbalance with dissipation, ellipsometry and electrochemistry the formation and function of the HiCDH film was studied. It was found that the presence of charged pyridinium groups was needed to successfully establish direct electron contact between the enzyme and electrode. SAMs formed from hydrophilic charged thiols achieved nearly two times higher current densities compared to hydrophobic charged thiols. Additionally, the results also indicated proportionality between HiCDH catalytic constant and water content of the enzyme film. Enzyme films on charged pyridine thiols had smaller variations in water content and viscoelastic properties than films adsorbed on the more hydrophobic thiols. This work highlights several perspectives on the underlying factors affecting performance of immobilized HiCDH.

Soft cutting of single-wall carbon nanotubes by low temperature ultrasonication in a mixture of sulfuric and nitric acids.

To decrease single-wall carbon nanotube (SWCNT) lengths to a value of 100-200 nm, aggressive cutting methods, accompanied by a high loss of starting material, are frequently used. We propose a cutting approach based on low temperature intensive ultrasonication in a mixture of sulfuric and nitric acids. The method is nondestructive with a yield close to 100%. It was applied to cut nanotubes produced in three different ways: gas-phase catalysis, chemical vapor deposition, and electric-arc-discharge methods. Raman and Fourier transform infrared spectroscopy were used to demonstrate that the cut carbon nanotubes have a low extent of sidewall degradation and their electronic properties are close to those of the untreated tubes. It was proposed to use the spectral position of the far-infrared absorption peak as a simple criterion for the estimation of SWCNT length distribution in the samples.

Raman spectroelectrochemical study of electrochemical decomposition of poly(neutral red) at a gold electrode.

A gold electrode, modified with poly(neutral red), has been studied with surface-enhanced resonance Raman spectroscopy at 676.4 nm excitation. It has been shown that both qualitative and quantitative changes in Raman spectra occur during prolonged holding of the modified electrode in pH 7.0 solution at a controlled electrode potential ranging from -0.6 to -0.2V vs. Ag/AgCl, indicating that a decomposition of the poly(neutral red) layer proceeds. The decomposition proceeds slower at a more negative electrode potential. From kinetic data obtained, first-order decomposition rate constants have been calculated, ranging from 9.17x10(-4) to 1.09x10(-2) min(-1) for electrode potential ranging from -0.6 to -0.2 V.

Anion effect on mediated electron transfer through ferrocene-terminated self-assembled monolayers.

Inorganic anions strongly influence the electron transfer rate from the ascorbate to the ferrocene-terminated self-assembled monolayer (SAM) composed of 9-mercaptononyl-5'-ferrocenylpentanoate (Fc(CH2)4COO(CH2)9SH, MNFcP). At the 1 M concentration level of the supporting anion (sodium salt electrolyte), a more than 10-fold increase in the electrocatalytic oxidation rate constant of the ascorbate is observed in the following sequence: PF6-, ClO4-, BF4-, NO3-, Cl-, SO4(2-), NH2SO3- (sulfamate), and F-. The sequence corresponds to the direction of increasing hydration energy of the corresponding anion, suggesting that highly hydrated ions promote electrocatalytic electron transfer to the ferrocene-terminated SAMs, while poorly hydrated ions inhibit it. Fourier transform surface-enhanced Raman spectroscopy (FT-SERS), in combination with cyclic voltammetry, indicates the formation of surface ion pairs between the ferricinium cation (Fc+) and low hydration energy anions, while, on the contrary, no ion pairs were observed in the electrolytes dominated by the high hydration energy anions. Though it is evident that the ion-pairing ability of hydrophobic anions is directly responsible for the electrocatalytic electron transfer inhibition, an estimate of the free, ion-unpaired Fc+ surface concentration shows that it cannot be directly related to the electron transfer rate. This suggests that the principal reason of the anion-induced electron transfer rate modulation might be related to the molecular level changes of the physical and chemical properties as well as the structure of the self-assembled monolayer.

Interactions of cyclic AMP and its dibutyryl analogue with model membrane: X-ray diffraction and Raman spectroscopic study using cubic liquid-crystalline phases of monoolein.

Interactions of adenosine 3':5'-cyclic monophosphate (cAMP) and its dibutyryl analogue, N6,2'-O-dibutyryladenosine 3':5'-cyclic monophosphate (dbcAMP), with a lipid bilayer were studied by small-angle X-ray diffraction (SAXD) and Raman spectroscopy. The cubic Pn3m phase of monoolein (MO) served as a bilayer-based model system. SAXD measurements have indicated that incorporation of approximately 3 wt.% cAMP leaves the phase parameters practically unaltered, whereas the same content of dbcAMP induces the intercubic Pn3m-->Ia3d transition. By applying the concepts of lipid shape parameter and infinite periodic minimal surface to these MO phases, we have suggested that, as opposed to cAMP, dbcAMP associates with the MO bilayer. This conclusion has been supported by the different effects of phase matrix on the Raman shifts of the adenine and phosphate vibrational modes of these two nucleotides. Moreover, Raman spectra have indicated that dbcAMP inserts into the bilayer through the butyryladenine group, positioning dbcAMP preferentially at the polar/apolar interface.

Electropolymerization of Preadsorbed Layers of Some Azine Redox Dyes on Graphite.

The redox-active azine dyes Nile blue A (NB) and Toluidine blue O (TB) were electropolymerized after preadsorption onto the surface of graphite electrodes by potential cycling, using an anodic scan limit of 0.9 or 1.0 V vs SCE, where irreversible electrooxidation of the dye proceeds, yielding polymerizable species. Electropolymerization of both dyes is followed by the progressive disappearance of the characteristic current peaks in the cyclic voltammograms, and formation of new ones, shifted by ca. 0.21 V to the positive direction. Also, a decrease and gradual disappearance of the characteristic luminescence at a maximum of 671 nm was observed during the electropolymerization of NB. The resulting electrodes, modified by electropolymerized derivatives of NB and TB, were shown to be able to catalyze the electrooxidation of the coenzyme NADH. Thus, the modified electrodes prepared can be used for amperometric detection of the reduced form of the coenzyme. Copyright 2000 Academic Press.

Stark Spectroscopy of Tryptamine Immobilized on a Gold Electrode.

Electroreflectance (ER), ellipsometry, and surface-enhanced Raman spectroscopy (SERS) measurements were performed for immobilized tryptamine on polycrystalline gold electrodes. SERS study indicates that the indole ring does not interact directly with the gold surface. Ellipsometric measurements yielded a thickness of the tryptamine layer of (1.98 +/- 0.05) nm and an inferred surface concentration of 3.3 x 10(-6) mol/m2. ER measurements were performed in the wavelength region 200-300 nm using the NIST synchrotron ultraviolet radiation facility (SURF). The ER response was interpreted as a Stark shift in the tryptamine absorption line at 218 nm. Assuming that the tryptamine layer consists of two stacked tryptamine molecules associated at the indole rings, a unified analysis of ER and ellipsometric data gave the difference between the static dipole moments of the solvated ground and excited states of 0.65 x 10(-30) C m in low ionic strength buffer (0.01 M PBS) and 0.25 x 10(-30) C m in high ionic strength buffer (0.01 M PBS + 1.0 M NaClO4). The results point to the importance of the composition of the solvation shell. Semiempirical quantum chemistry calculations of tryptamine molecules gave a qualitative explanation of the ER response in the low ionic buffer. The large ER response suggests that the method could be applied to the study of the tryptophan environment in adsorbed proteins. Copyright 1998 Academic Press.

Measurement of Electron Transfer Rates between Adsorbed Azurin and a Gold Electrode Modified with a Hexanethiol Layer

In this work we report the application of electroreflectance (ER) spectroscopy for the study of the redox reaction of the nonheme protein azurin. Azurin was irreversibly adsorbed on a polycrystalline gold surface modified with a hexanethiol layer. Surface-enhanced resonant Raman spectroscopy (SERRS) demonstrated that the immobilized azurin's copper site remained intact upon adsorption and that it underwent reversible reduction-oxidation. Cyclic voltammetry (CV) data showed that the peak current of the oxidation (or reduction) wave depended linearly on the sweep rate as appropriate for an immobilized species. The formal potential of the adsorbed azurin was 95 ± 8 mV vs Ag/AgCl electrode, nearly identical to the earlier observed value of the native azurin in solution. All measurements were analyzed in the context of Marcus theory of electron transfer. The separation of the reduction-oxidation peaks in the CV data gave an estimate of the electron transfer (ET) rate in the range from 4 to 12 s-1. ER, with light of wavelength of 640 nm, yielded a strong signal at the same potential as the midpotential determined in CV. The frequency dependence of the ER response was consistent with an ET rate of 150 to 200 s-1. Electrochemical impedance measurements indicated an ET rate of the order of 300 s-1. The disparity between the ET rates measured with CV and ER suggests that ET may not be a single-step process. The results also point to the importance of hydrophobic interactions in adsorption and redox transformations of azurin. Copyright 1997Academic Press