Self-Organized SERS Substrates with Efficient Analyte Enrichment in the Hot Spots.

One of the requirements of an efficient surface-enhanced Raman spectroscopy (SERS) substrate is a developed surface morphology with a high density of "hot spots", nm-scale spacings between plasmonic nanoparticles. Of particular interest are plasmonic architectures that could enable self-localization (enrichment) of the analyte in the hot spots. We report a straightforward method of fabrication of efficient SERS substrates that comply with these requirements. The basis of the substrate is a large-area film of tightly packed SiO2 spheres formed by their quick self-assembling upon drop casting from the solution. Thermally evaporated thin Ag layer is converted by quick thermal annealing into nanoparticles (NPs) self-assembled in the trenches between the silica spheres, i.e., in the places where the analyte molecules get localized upon deposition from solution and drying. Therefore, the obtained substrate morphology enables an efficient enrichment of the analyte in the hot spots formed by the densely arranged plasmonic NPs. The high efficiency of the developed SERS substrates is demonstrated by the detection of Rhodamine 6G down to 10-13 mol/L with an enhancement factor of ∼108, as well as the detection of low concentrations of various nonresonant analytes, both small dye molecules and large biomolecules. The developed approach to SERS substrates is very straightforward for implementation and can be further extended to using gold or other plasmonic NPs.

Correction: Luminescence and photoelectrochemical properties of size-selected aqueous copper-doped Ag-In-S quantum dots.

[This corrects the article DOI: 10.1039/C8RA00257F.].

SERS-substrates based on ZnO nanoflowers prepared by green synthesis.

ZnO nanoparticles (NPs) with a flower-like morphology, synthesized by an affordable colloidal route using an aqueous fungi extract of Ganoderma lucidum as a reducing agent and stabilizer, are investigated as SERS-substrate. Each "flower" has large effective surface that is preserved at packing particles into a dense film and thus exhibits an advantageous property for SERS and similar sensing applications. The mycoextract used in our low-cost and green synthesis as surface stabilizer allows subsequent deposition of metal NPs or layers. One type of SERS substrates studied here was ZnO NPs decorated in situ in the solution by Ag NPs, another type was prepared by thermally evaporating Ag layer on the ZnO NP film on a substrate. A huge difference in the enhancement of the same analyte in the solution and in the dried form is found and discussed. Detection down to 10-7 M of standard dye analytes such as rhodamine 6G and methylene blue was achieved without additional optimization of the SERS substrates. The observed SERS-activity demonstrate the potential of both the free-standing flower-like ZnO NPs and thereof made dense films also for other applications where large surface area accessible for the external agent is crucial, such as catalysis or sensing.

Enhanced photoconductivity of hybrid 2D-QD MoS2-AgInS2 structures.

This study describes the fabrication of hybrid two-dimensional (2D)-quantum dot (QD) MoS2-AgInS2 photoconductive devices through the mechanical pressing of a MoS2 flake onto an AgInS2 QD film. The devices exhibit an enhanced photoresponse at both continuous and modulated optical excitations, compared with the bare MoS2 or AgInS2 layer, due to the formation of a built-in electric field near the MoS2/AgInS2 interface. The continuous wave photoresponse is significantly higher due to the effective photoconductive gain when electrons flow freely through the MoS2 flake, whereas holes are effectively trapped in AgInS2 QDs. The study highlights the potential of hybrid 2D-QD MoS2-AgInS2 devices for photovoltaic and optoelectronic applications.

Influence of Thermal and Flash-Lamp Annealing on the Thermoelectrical Properties of Cu2ZnSnS4 Nanocrystals Obtained by "Green" Colloidal Synthesis.

The problem with waste heat in solar panels has stimulated research on materials suitable for hybrid solar cells, which combine photovoltaic and thermoelectric properties. One such potential material is Cu2ZnSnS4 (CZTS). Here, we investigated thin films formed from CZTS nanocrystals obtained by "green" colloidal synthesis. The films were subjected to thermal annealing at temperatures up to 350 °C or flash-lamp annealing (FLA) at light-pulse power densities up to 12 J/cm2. The range of 250-300 °C was found to be optimal for obtaining conductive nanocrystalline films, for which the thermoelectric parameters could also be determined reliably. From phonon Raman spectra, we conclude that in this temperature range, a structural transition occurs in CZTS, accompanied by the formation of the minor CuxS phase. The latter is assumed to be a determinant for both the electrical and thermoelectrical properties of CZTS films obtained in this way. For the FLA-treated samples, the film conductivity achieved was too low to measure the thermoelectric parameters reliably, although the partial improvement of the CZTS crystallinity is observed in the Raman spectra. However, the absence of the CuxS phase supports the assumption of its importance with respect to the thermoelectric properties of such CZTS thin films.

Bactericidal activity of Ag nanoparticles biosynthesized from Capsicum annuum pericarps against phytopathogenic Clavibacter michiganensis.

Metallic nanoparticles of different compositions have already found numerous applications in various branches of industry, agriculture, and medicine. Given the well-known antibacterial activity of Ag, silver nanoparticles (AgNPs) are constantly being investigated for their promising ability to fight antibiotic-resistant pathogens. A promising candidate for AgNPs biosynthesis is chili pepper Capsicum annuum, cultivated worldwide and known for accumulating significant amounts of active substances. Phytochemical screening of aqueous extract of C. annuum pericarps demonstrated accumulation of 4.38 mg/g DW of total capsaicinoids, 14.56 mg GAE/g DW of total phenolic compounds, 1.67 mg QE/g DW of total flavonoids, and 1.03 mg CAE/g DW of total phenolic acids. All determined aromatic compounds carry various active functional groups, which effectively participate in the biosynthesis of AgNPs and are characterized by high antioxidant potential. Therefore, the present research focused on the facile, quick, and effective procedure for the biosynthesis of AgNPs, which were analyzed for their morphology such as shape and size through UV-visible, Fourier-transform infrared spectroscopy (FTIR) assays, and scanning electron microscopy. We found that the AgNPs biosynthesis resulted in changes in FTIR spectra, depicting the rearrangement of numerous functional groups, while the nanoparticles themselves were shown to be stable, spherical, 10-17 nm in size. Also we investigated the antibacterial properties of biosynthesized AgNPs, obtained with C. annuum fruit extracts, against a common phytopathogen Clavibacter michiganensis subsp. michiganensis. As was shown by zone inhibition assay, AgNPs showed dose-dependent 5.13-6.44 cm antibacterial activity, greatly exceeding the 4.98 cm inhibition area, produced by the precursor salt, AgNO3.

Core and Shell Contributions to the Phonon Spectra of CdTe/CdS Quantum Dots.

The parameters of the shell and interface in semiconductor core/shell nanocrystals (NCs) are determinant for their optical properties and charge transfer but are challenging to be studied. Raman spectroscopy was shown earlier to be a suitable informative probe of the core/shell structure. Here, we report the results of a spectroscopic study of CdTe NCs synthesized by a facile route in water, using thioglycolic acid (TGA) as a stabilizer. Both core-level X-ray photoelectron (XPS) and vibrational (Raman and infrared) spectra show that using thiol during the synthesis results in the formation of a CdS shell around the CdTe core NCs. Even though the spectral positions of the optical absorption and photoluminescence bands of such NCs are determined by the CdTe core, the far-infrared absorption and resonant Raman scattering spectra are dominated by the vibrations related with the shell. The physical mechanism of the observed effect is discussed and opposed to the results reported before for thiol-free CdTe Ns as well as CdSe/CdS and CdSe/ZnS core/shell NC systems, where the core phonons were clearly detected under similar experimental conditions.

Phonon Raman spectroscopy of nanocrystalline multinary chalcogenides as a probe of complex lattice structures.

Ternary (I-III-VI) and quaternary (I-II-IV-VI) metal-chalcogenides like CuInS2or Cu2ZnSn(S,Se)4are among the materials currently most intensively investigated for various applications in the area of alternative energy conversion and light-emitting devices. They promise more sustainable and affordable solutions to numerous applications, compared to more developed and well understood II-VI and III-V semiconductors. Potentially superior properties are based on an unprecedented tolerance of these compounds to non-stoichiometric compositions and polymorphism. However, if not properly controlled, these merits lead to undesirable coexistence of different compounds in a single polycrystalline lattice and huge concentrations of point defects, becoming an immense hurdle on the way toward real-life applications. Raman spectroscopy of phonons has become one of the most powerful tools of structural diagnostics and probing physical properties of bulk and microcrystalline I-III-VI and I-II-IV-VI compounds. The recent explosive growth of the number of reports on fabrication and characterization of nanostructures of these compounds must be pointed out as well as the steady use of Raman spectroscopy for their characterization. Interpretation of the vibrational spectra of these compound nanocrystals (NCs) and conclusions about their structure can be complicated compared to bulk counterparts because of size and surface effects as well as emergence of new structural polymorphs that are not realizable in the bulk. This review attempts to summarize the present knowledge in the field of I-III-VI and I-II-IV-VI NCs regarding their phonon spectra and capabilities of Raman and IR spectroscopies in the structural characterizations of these promising families of compounds.

Plasmonic colloidal Au nanoparticles in DMSO: a facile synthesis and characterisation.

We report a new pathway for the synthesis of plasmonic gold nanoparticles (Au NPs) in a bio-compatible medium. A modified room temperature approach based on the standard Turkevich synthesis, using sodium citrate as a reducing and stabilizing agent, results in a highly stable colloidal suspension of Au NPs in dimethyl sulfoxide (DMSO). The mean NP size of about 15 nm with a fairly low size distribution is revealed by scanning electron microscopy. The stability test through UV-vis absorption spectroscopy indicates no sign of aggregation for months. The Au NPs are also characterized by X-ray photoelectron, Raman scattering, and FTIR spectroscopies. The stabilisation mechanism of the Au NPs in DMSO is concluded to be similar to that of NPs synthesized in water. The Au NPs obtained in this work are applicable as SERS substrates, as proved by common analytes. In terms of bio-applications, they do not possess such side-effects as pronounced antibacterial activity, based on the tests performed on non-pathogenic Gram-positive or Gram-negative bacteria.

Self-assembly of colloidal single-layer carbon nitride.

We introduce a new concept of a "bottom-to-top" design of intercalate carbon nitride compounds based on the effects of self-assembly of colloidal single-layer carbon nitride (SLCN) sheets stabilized by tetraethylammonium hydroxide NEt4OH upon ambient drying of the water solvent. These effects include (i) formation of stage-1 intercalates of NEt4OH during the ambient drying of SLCN colloids on glass substrates and (ii) the spontaneous formation of layered hexagonally-shaped networks of SLCN sheets on freshly-cleaved mica surfaces. The dynamics of the intercalate formation was followed by in situ X-ray diffraction allowing different stages to be identified, including the deposition of a primary "wet" intercalate of hydrated NEt4OH and the gradual elimination of excessive water during its ambient drying. The intercalated NEt4+ cations show a specific "flattened" conformation allowing the dynamics of formation and structure of the intercalate to be probed by vibrational spectroscopies. The two-dimensional self-assembly on mica is assumed to be driven both by the internal hexagonal symmetry of heptazine units and by a templating effect of the mica surface.

Raman Spectroscopy and Thermoelectric Characterization of Composite Thin Films of Cu2ZnSnS4 Nanocrystals Embedded in a Conductive Polymer PEDOT:PSS.

Cu2ZnSnS4 (CZTS) is an intensively studied potential solar cell absorber and a promising thermoelectric (TE) material. In the form of colloidal nanocrystals (NCs), it is very convenient to form thin films on various substrates. Here, we investigate composites of CZTS NCs with PEDOT:PSS, a widely used photovoltaics polymer. We focus on the investigation of the structural stability of both NCs and polymers in composite thin films with different NC-to-polymer ratios. We studied both pristine films and those subjected to flash lamp annealing (FLA) or laser irradiation with various power densities. Raman spectroscopy was used as the main characterization technique because the vibrational modes of CZTS NCs and the polymer can be acquired in one spectrum and thus allow the properties of both parts of the composite to be monitored simultaneously. We found that CZTS NCs and PEDOT:PSS mutually influence each other in the composite. The thermoelectric properties of PEDOT:PSS/CZTS composite films were found to be higher compared to the films consisting of bare materials, and they can be further improved by adding DMSO. However, the presence of NCs in the polymer deteriorates its structural stability when subjected to FLA or laser treatment.

ZnO and Ag NP-decorated ZnO nanoflowers: green synthesis using Ganoderma lucidum aqueous extract and characterization.

Fungi produce and excrete various proteins, enzymes, polysaccharides, and secondary metabolites, which may be used as media for the "green" synthesis of metal and semiconductor nanoparticles (NPs). ZnO NPs with a flower-like morphology were synthesized by an affordable colloidal route, using an aqueous extract of Ganoderma lucidum as a reducing agent and stabilizer. Each individual "flower" has a large effective surface, which is preserved when the particles are close packed into a dense film, which is advantageous for numerous applications. The phonon Raman spectrum and X-ray diffraction (XRD) pattern prove the high crystallinity of the NPs, with the distinct pattern of a hexagonal (wurtzite) lattice, negligible residual stress, and a crystallite size of 12-14 nm determined from the XRD. The photoluminescence (PL) spectrum of the as-synthesized ZnO NPs contains a structured defect-related feature in the violet-blue range, while the green PL, common for nanostructures synthesized by "green" routes, is very weak. By applying dimethylsulfoxide as an additional passivating agent, the excitonic (UV) PL band was activated without enhancement of the defect-related features. Ag NP-decorated ZnO flowers were synthesized by subsequent silver reduction by pepper extract. The ZnO/Ag NPs exhibited efficient surface-enhanced Raman scattering (SERS) of a standard dye analyte, rhodamine 6G, ensuring the feasibility of other applications that require close contact of ZnO/Ag to other nanostructures or molecules to realize the energy of the charge transfer.

Colloidal Cu-Zn-Sn-Te Nanocrystals: Aqueous Synthesis and Raman Spectroscopy Study.

Cu-Zn-Sn-Te (CZTTe) is an inexpensive quaternary semiconductor that has not been investigated so far, unlike its intensively studied CZTS and CZTSe counterparts, although it may potentially have desirable properties for solar energy conversion, thermoelectric, and other applications. Here, we report on the synthesis of CZTTe nanocrystals (NCs) via an original low-cost, low-temperature colloidal synthesis in water, using a small-molecule stabilizer, thioglycolic acid. The absorption edge at about 0.8-0.9 eV agrees well with the value expected for Cu2ZnSnTe4, thus suggesting CZTTe to be an affordable alternative for IR photodetectors and solar cells. As the main method of structural characterization multi-wavelength resonant Raman spectroscopy was used complemented by TEM, XRD, XPS as well as UV-vis and IR absorption spectroscopy. The experimental study is supported by first principles density functional calculations of the electronic structure and phonon spectra. Even though the composition of NCs exhibits a noticeable deviation from the Cu2ZnSnTe4 stoichiometry, a common feature of multinary NCs synthesized in water, the Raman spectra reveal very small widths of the main phonon peak and also multi-phonon scattering processes up to the fourth order. These factors imply a very good crystallinity of the NCs, which is further confirmed by high-resolution TEM.

Raman and X-ray Photoelectron Spectroscopic Study of Aqueous Thiol-Capped Ag-Zn-Sn-S Nanocrystals.

The synthesis of (Cu,Ag)-Zn-Sn-S (CAZTS) and Ag-Zn-Sn-S (AZTS) nanocrystals (NCs) by means of "green" chemistry in aqueous solution and their detailed characterization by Raman spectroscopy and several complementary techniques are reported. Through a systematic variation of the nominal composition and quantification of the constituent elements in CAZTS and AZTS NCs by X-ray photoemission spectroscopy (XPS), we identified the vibrational Raman and IR fingerprints of both the main AZTS phase and secondary phases of Ag-Zn-S and Ag-Sn-S compounds. The formation of the secondary phases of Ag-S and Ag-Zn-S cannot be avoided entirely for this type of synthesis. The Ag-Zn-S phase, having its bandgap in near infrared range, is the reason for the non-monotonous dependence of the absorption edge of CAZTS NCs on the Ag content, with a trend to redshift even below the bandgaps of bulk AZTS and CZTS. The work function, electron affinity, and ionization potential of the AZTS NCs are derived using photoelectron spectroscopy measurements.

Multifunctional Magneto-Plasmonic Fe3O4/Au Nanocomposites: Approaching Magnetophoretically-Enhanced Photothermal Therapy.

Magneto-plasmonic nanocomposites can possess properties inherent to both individual components (iron oxide and gold nanoparticles) and are reported to demonstrate high potential in targeted drug delivery and therapy. Herein, we report on Fe3O4/Au magneto-plasmonic nanocomposites (MPNC) synthesized with the use of amino acid tryptophan via chemical and photochemical reduction of Au ions in the presence of nanosized magnetite. The magnetic field (MF) induced aggregation was accompanied by an increase in the absorption in the near-infrared (NIR) spectral region, which was demonstrated to provide an enhanced photothermal (PT) effect under NIR laser irradiation (at 808 nm). A possibility for therapeutic application of the MPNC was illustrated using cancer cells in vitro. Cultured HeLa cells were treated by MPNC in the presence of MF and without it, following laser irradiation and imaging using confocal laser scanning microscopy. After scanning laser irradiation of the MPNC/MF treated cells, a formation and rise of photothermally-induced microbubbles on the cell surfaces was observed, leading to a damage of the cell membrane and cell destruction. We conclude that the synthesized magneto-plasmonic Fe3O4/Au nanosystems exhibit magnetic field-induced reversible aggregation accompanied by an increase in NIR absorption, allowing for an opportunity to magnetophoretically control and locally enhance a NIR light-induced thermal effect, which holds high promise for the application in photothermal therapy.

Photoinduced Enhancement of Photoluminescence of Colloidal II-VI Nanocrystals in Polymer Matrices.

The environment strongly affects both the fundamental physical properties of semiconductor nanocrystals (NCs) and their functionality. Embedding NCs in polymer matrices is an efficient way to create a desirable NC environment needed for tailoring the NC properties and protecting NCs from adverse environmental factors. Luminescent NCs in optically transparent polymers have been investigated due to their perspective applications in photonics and bio-imaging. Here, we report on the manifestations of photo-induced enhancement of photoluminescence (PL) of aqueous colloidal NCs embedded in water-soluble polymers. Based on the comparison of results obtained on bare and core/shell NCs, NCs of different compounds (CdSe, CdTe, ZnO) as well as different embedding polymers, we conclude on the most probable mechanism of the photoenhancement for these sorts of systems. Contrary to photoenhancement observed earlier as a result of surface photocorrosion, we do not observe any change in peak position and width of the excitonic PL. Therefore, we suggest that the saturation of trap states by accumulated photo-excited charges plays a key role in the observed enhancement of the radiative recombination. This suggestion is supported by the unique temperature dependence of the trap PL band as well as by power-dependent PL measurement.

Ultra-small aqueous glutathione-capped Ag-In-Se quantum dots: luminescence and vibrational properties.

We introduce a direct aqueous synthesis of luminescent 2-3 nm Ag-In-Se (AISe) quantum dots (QDs) capped by glutathione (GSH) complexes, where sodium selenosulfate Na2SeSO3 is used as a stable Se2- precursor. A series of size-selected AISe QDs with distinctly different positions of absorption and PL bands can be separated from the original QD ensembles by using anti-solvent-induced size-selective precipitation. The AISe-GSH QDs emit broadband PL with the band maximum varying from 1.65 eV (750 nm) to 1.90 eV (650 nm) depending on the average QD size and composition. The PL quantum yield varies strongly with basic synthesis parameters (ratios of constituents, Zn addition, duration of thermal treatment, etc.) reaching 4% for "core" AISe and 12% for "core/shell" AISe/ZnS QDs. The shape and position of PL bands is interpreted in terms of the model of radiative recombination of a self-trapped exciton. The AISe-GSH QDs reveal phonon Raman spectra characteristic for small and Ag-deficient tetragonal Ag-In-Se QDs. The ability of ultra-small AISe QDs to support such "bulk-like" vibrations can be used for future deeper insights into structural and optical properties of this relatively new sort of QDs.

Mercury-indium-sulfide nanocrystals: A new member of the family of ternary in based chalcogenides.

A general synthesis approach of aqueous glutathione-capped ternary Ag-In-S, Cu-In-S, and Hg-In-S nanocrystals (NCs) is introduced, allowing the NC composition to be varied in a broad range. Ternary Hg-In-S (HIS) NCs are reported for the first time and found to have the same tetragonal chalcopyrite motif as Cu-In-S and Ag-In-S NCs, corroborated by phonon spectra, while X-ray photoelectron spectroscopic data indicate mercury to be present as Hg+ in the Hg-In-S NCs. Colloidal HIS and Hg-In-S/ZnS NCs showed little or no variations of the spectral width of the photoluminescence band upon NC size selection, temperature variation in a broad range of 10-350 K, deposition of a ZnS shell, or postsynthesis annealing. All these observations are similar to those reported earlier for Ag-In-S and Ag-In-S/ZnS NCs and allowed us to assume a general photoluminescence mechanism for all three ternary compounds, based on the model of radiative self-trapped exciton recombination.

Flexible plasmonic graphene oxide/heterostructures for dual-channel detection.

Graphene oxide (GO) films are deposited on flexible Kapton substrates and selectively modified to conductive reduced graphene oxide (rGO) electrodes using laser patterning. Based on this, we design, fabricate, and test a flexible sensor integrating laser-reduced GO with silver plasmonic nanostructures. The fabricated device results in dual transduction channels: for electrochemical and plasmonic nanostructure-based surface-enhanced Raman spectroscopy (SERS) detection. The spectroscopic analysis verifying the formation of rGO and the modification by silver nanostructures is performed by Raman, energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The morphological investigation is followed by optical and scanning electron microscopy imaging. In addition to pristine silver nanostructures, the Raman spectroscopy results show the formation of species such as Ag2O, Ag2CO3, and Ag2SOx. A dual-channel sensor device based on electrochemical and plasmonic detection is fabricated as a demonstration of our Ag-rGO flexible concept architecture. The dual-channel device performance is successfully demonstrated in the electrochemical and SERS detection of 4-nitrobenzenethiol (4-NBT) using the same device. Our results show that without Ag nanostructures the sensitivity in the electrochemical and optical channels is not sufficient to detect 4-NBT. The performance and stability of the silver modified device are also verified. This work demonstrates an inexpensive, highly efficient, and greener way that is compatible with solution-processing technology for the production of flexible GO-based electrochemical and SERS detection devices integrated with plasmonic nanostructures.