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Abstract Magnetic monolayers show great promise for future applications in nanoelectronics, data storage, and sensing. The research in magnetic two‐dimensional (2D) materials focuses on synthetic iodides and tellurides, which suffer from a lack of ambient stability. So far, naturally occurring layered magnetic materials have been overlooked. These minerals offer a unique opportunity to explore complex air‐stable layered systems with high concentration of magnetic ions. Magnetic ordering in iron‐rich phyllosilicates is demonstrated, focusing on minnesotaite, annite, and biotite. These naturally occurring layered materials integrate local moment baring ions of iron via magnesium/aluminum substitution in their octahedral sites. Self‐inherent capping by silicate/aluminate tetrahedral groups enables air stability of ultra‐thin layers. Their structure and iron oxidation states are determined via Raman and X‐ray spectroscopies. Superconducting quantum interference device magnetometry measurements are performed to examine the magnetic ordering. Paramagnetic or superparamagnetic characteristics at room temperature are observed. Below 40 K ferrimagnetic or antiferromagnetic ordering occurs. In‐field magnetic force microscopy on exfoliated flakes confirms that the paramagnetic response at room temperature persists down to monolayers. Further, a correlation between the mixture of the oxidation states of iron and the critical ordering temperature is established, indicating a path to design materials with higher critical temperatures via oxidation state engineering.

Abstract Abstract This article presents a cost-effective ultraviolet-ozone cleaner (UV/O3 Cleaner) for surface pre-treatment of substrates in the field of semiconductor technology. The cleaner consists of two chambers, the upper one contains the electronics, including the time counter. The lower chamber contains the two UV sterilisation lamps and a UV reflector of anodized aluminium, which confines the area of high Ozone concentration in the area of interest. The device is successfully used for surface cleaning and modification of different materials. To this end, the two important wavelengths 253.7 nm (excitation of organic residues) and 184.9 nm (production of ozone from the atmospheric environment as a strong oxidant) were first detected. The effectiveness of UV/O3 cleaning is demonstrated by improving the properties of indium tin oxide (ITO) for OLED fabrication. The contact angle of water to ITO could be reduced from 90° to 3° and for diiodomethane, it was reduced from 55° to 31° within the 10 min of irradiation. This greatly improved wettability for polar and non-polar liquids can increase the flexibility in further process control. In addition, an improvement in wettability is characterized by measuring the contact angles for titanium dioxide (TiO2) and polydimethylsiloxane (PDMS). The contact angle of water to TiO2 decreased from 70° to 10°, and that of diiodomethane to TiO2 from 54° to 31°. The wettability of PDMS was also greatly increased. Here, the contact angle of water was reduced from 109° to 24° and the contact angle to diiodomethane from 89° to 49°. Article Highlights We report a cost-effective dry-cleaning device for surface cleaning and modification based on ultraviolet-ozone irradiation. Contact angle measurements show an increase of wettability for different materials due to surface modification. The UVO3 pre-treatment improves layer formation and optoelectrical properties of OLEDs.

Long operational stability is essential to commercialisation of organic solar cells. Here, the authors investigate the thermal degradation of inverted photovoltaic devices based on PM6:Y6 non-fullerene system to reveal that trap-induced transport resistance is primarily responsible for the drop in fill factor.

Thin films of colloidal CZTS nanocrystals (NCs) synthesized using a “green” approach in water with a variation of the copper-to-tin ratio are investigated by Raman scattering, mid-infrared (molecular vibrations) and near-infrared (free carrier) absorption, X-ray photoemission spectroscopy (XPS), electrical conductivity, and conductive atomic force microscopy (cAFM). We determined the effect of the actual Cu content on the phonon spectra, electrical conductivity, and spectral parameters of the plasmon band. An increase in the electrical conductivity of the NC films upon annealing at 220 °C is explained by three factors: formation of a CuxS nanophase at the CZTS NC surface, partial removal of ligands, and improved structural perfection. The presence of the CuxS phase is concluded to be the determinant factor for the CZTS NC film conductivity. CuxS can be reliably detected based on the analysis of the modified Auger parameter of copper, derived from XPS data and corroborated by Raman spectroscopy data. Partial removal of the ligand is concluded from the agreement of the core-level XPS and vibrational IR spectra. The degree of lattice perfection can be conveniently assessed from the Raman data as well. Further important information derived from a combination of photoelectron and optical data is the work function, ionization potential, and electron affinity of the NC films.

Abstract The opto‐electronic properties of semiconducting 2D materials can be flexibly manipulated by engineering the atomic‐scale environment. This can be done by including 2D materials in tailored van der Waals (vdW) stacks, whose optical response is a function of the number and the type of adjacent 2D layers. This work reports a systematic investigation of the dielectric function of 2D semiconducting WS2 in various stacking configurations: monolayer, 3R/2H homobilayer, and WS2/MoS2 heterobilayer. Reliable, Kramers–Kronig‐consistent dielectric functions are obtained for WS2 in each configuration by means of spectroscopic ellipsometry (SE) and related parametric optical modeling in a wide spectral range (1.55–3.10 eV). The results of SE are combined with photoluminescence and absorbance spectra to identify the spectral position of the main excitonic features in WS2, which manifest sizable redshifts depending on the stacking configuration. These results represent a consistent reference set for the dielectric function of WS2 in vdW stacking configurations of particular interest for the scientific and technological field, and can be fruitfully exploited for reliable predictions of the optical response of WS2‐containing systems.

Abstract Intrinsically magnetic layered materials – especially monolayers – suffer from the lack of ambient stability and mostly exhibit magnetic ordering only at cryogenic temperatures. These restrains impose a great challenge for the integration of two-dimensional magnetic materials into future technologies. We propose to overcome this by exploiting phyllosilicates, such as iron-rich talc. Via combined magnetic force microscopy in applied external magnetic fields, superconducting quantum interference device magnetometry, first-principle calculations, and structural analysis, we demonstrate that incorporated iron ions in talc are in a very robust high spin state, resulting in a weak ferromagnetic behavior at room temperature. Iron-rich talc can be thinned down to a monolayer, remaining fully stable under ambient conditions, and retaining magnetic properties even in monolayers. Finally, we propose iron-rich end members of the phyllosilicates as very promising platforms for air-stable magnetic monolayers.

Abstract Local crystallization of ferromagnetic layers is crucial in the successful realization of miniaturized tunneling magnetoresistance (TMR) devices. In the case of Co–Fe–B TMR devices, used most successfully so far in applications and devices, Co–Fe–B layers are initially deposited in an amorphous state and annealed post-deposition to induce crystallization in Co–Fe, thereby increasing the device performance. In this work, first direct proof of locally triggered crystallization of 10 nm thick Co–Fe–B films by laser irradiation is provided by means of X-ray diffraction (XRD) using synchrotron radiation. A comparison with furnace annealing is performed for benchmarking purposes, covering different annealing parameters, including temperature and duration in the case of furnace annealing, as well as laser intensity and scanning speed for the laser annealing. Films of Co–Fe–B with different stoichiometry sandwiched between a Ru and a Ta or MgO layer were systematically assessed by XRD and SQUID magnetometry in order to elucidate the crystallization mechanisms. The transformation of Co–Fe–B films from amorphous to crystalline is revealed by the presence of pronounced CoFe(110) and/or CoFe(200) reflexes in the XRD θ-2θ scans, depending on the capping layer. For a certain window of parameters, comparable crystallization yields are obtained with furnace and laser annealing. Samples with an MgO capping layer required a slightly lower laser intensity to achieve equivalent Co–Fe crystallization yields, highlighting the potential of laser annealing to locally enhance the TMR ratio.

Electron-phonon coupling plays a central role in a variety of low dimensional structures. The authors unveiled the subtle interaction between optical phonons and charge carriers by applying Raman spectroscopy to plasmonic nanostructures fabricated on atomically thin InSe. These findings provide insights to develop future high-performance nanoelectronic devices.

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.

In this work, the deposition of β-Ga2O3 microstructures and thin films was performed with Ga(NO3)3 solutions by ultrasonic nebulization and spray coating as low-cost techniques. By changing the deposition parameters, the shape of β-Ga2O3 microstructures was controlled. Micro-spheres were obtained by ultrasonic nebulization. Micro-flakes and vortices were fabricated by spray coating aqueous concentrated and diluted precursor solutions, respectively. Roundish flakes were achieved from water–ethanol mixtures, which were rolled up into tubes by increasing the number of deposition cycles. Increasing the ethanol-to-water ratio allows continuous thin films at an optimal Ga(NO3)3 concentration of 0.15 M and a substrate temperature of 190 °C to be formed. The monoclinic β-Ga2O3 phase was achieved by thermal annealing at 1000 °C in an ambient atmosphere. Scanning electronic microscopy (SEM), X-ray diffraction (XRD), and UV-Raman spectroscopy were employed to characterize these microstructures. In the XRD study, in addition to the phase information, the residual stress values were determined using the sin2(ψ) method. Raman spectroscopy confirms that the β-Ga2O3 phase and relative shifts of the Raman modes of the different microstructures can partially be assigned to residual stress. The high-frequency Raman modes proved to be more sensitive to shifting and broadening than the low-frequency Raman modes.

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.

AgGaGeS4 is an emerging material with promising nonlinear properties in the near- and mid-infrared spectral ranges. Here, the experimental phonon spectra of AgGaGeS4 single crystals synthesized by a modified Bridgman method are presented. The infrared absorption spectra are reported. They are obtained from the fitting of reflectivity to a model dielectric function comprising a series of harmonic phonon oscillators. In the Raman spectra, several modes are registered, which were not detected in previous works. The analysis of the experimental vibrational bands is performed on the basis of a comparison with reported data on structurally related binary, ternary, and quaternary metal chalcogenides. The temperature dependence of the Raman spectra between room temperature and 15 K is also investigated.

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.

Vertical stacking of two-dimensional (2D) homo- and heterostructures are intriguing research objects, as they are essential for fundamental studies and a key towards 2D device applications. It is paramount to understand the interlayer coupling in 2D materials and to find a fast yet precise characteristic signature. In this work, we report on a Raman fingerprint of interlayer coupling in 2D transition metal dichalcogenides (TMDCs). We observed that the out-of-plane B2g vibrational mode is absent when two monolayers form a vertical stack yet remain uncoupled but emerges after strong coupling. Using systematic Raman, photoluminescence (PL), and atomic force microscopy (AFM) studies of WSe2/WSe2 homo-bilayers and MoSe2/WSe2 hetero-bilayers, we conclude that the B2g vibrational mode is a distinct Raman fingerprint of interlayer coupling in 2D TMDCs. Our results propose an easy, fast, precise, and reliable measure to evaluate the interlayer coupling in 2D TMDCs.

The effect of flash-lamp annealing (FLA) on the re-crystallization of thin films made of colloidal Cu2ZnSnS4 nanocrystals (NCs) is investigated by Raman spectroscopy. Unlike similar previous studies of NCs synthesized at high temperatures in organic solvents, NCs in this work, which have diameters as small as 2–6 nm, were synthesized under environmentally friendly conditions in aqueous solution using small molecules as stabilizers. We establish the range of FLA conditions providing an efficient re-crystallization in the thin film of NCs, while preserving their kesterite structure and improving their crystallinity remarkably. The formation of secondary phases at higher FLA power densities, as well as the dependence of the formation on the film thickness are also investigated. Importantly, no inert atmosphere for the FLA treatment of the NCs is required, which makes this technology even more suitable for mass production, in particular for printed thin films on flexible substrates.

This work presents an overview of the latest results and new data on the optical response from spherical CdSe nanocrystals (NCs) obtained using surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS). SERS is based on the enhancement of the phonon response from nanoobjects such as molecules or inorganic nanostructures placed on metal nanostructured substrates with a localized surface plasmon resonance (LSPR). A drastic SERS enhancement for optical phonons in semiconductor nanostructures can be achieved by a proper choice of the plasmonic substrate, for which the LSPR energy coincides with the laser excitation energy. The resonant enhancement of the optical response makes it possible to detect mono- and submonolayer coatings of CdSe NCs. The combination of Raman scattering with atomic force microscopy (AFM) using a metallized probe represents the basis of TERS from semiconductor nanostructures and makes it possible to investigate their phonon properties with nanoscale spatial resolution. Gap-mode TERS provides further enhancement of Raman scattering by optical phonon modes of CdSe NCs with nanometer spatial resolution due to the highly localized electric field in the gap between the metal AFM tip and a plasmonic substrate and opens new pathways for the optical characterization of single semiconductor nanostructures and for revealing details of their phonon spectrum at the nanometer scale.

Bismuth compounds are of growing interest with regard to potential applications in catalysis, medicine, and electronics, for which their environmentally benign nature is one of the key factors. One thing that currently hampers the further development of bismuth oxido-based materials, however, is the often low solubility of the precursors, which makes targeted immobilisation on substrates challenging. We present an approach towards the solubilisation of bismuth oxido clusters by introducing an amino carboxylate as a functional group. For this purpose, the bismuth oxido cluster [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (dmso = dimethyl sulfoxide) was reacted with the sodium salt of tert-butyloxycabonyl (Boc)-protected phenylalanine (L-Phe) to obtain the soluble and chiral nanocluster [Bi38O45(Boc–Phe–O)24(dmso)9]. The exchange of the nitrates by the amino carboxylates was proven by nuclear magnetic resonance, Fourier-transform infrared spectroscopy, as well as elemental analysis and X-ray photoemission spectroscopy. The solubility of the bismuth oxido cluster in a protic as well as an aprotic polar organic solvent and the growth mode of the clusters upon spin, dip, and drop coating on gold surfaces were studied by a variety of microscopy, as well as spectroscopic techniques. In all cases, the bismuth oxido clusters form crystalline agglomerations with size, height, and distribution on the substrate that can be controlled by the choice of the solvent and of the deposition method.

The affordable and scalable synthesis of noble metal nanoparticles that are biocompatible without additional functionalization steps has been a growing field of research, stimulated by numerous prospective applications of these NPs. In the case of phytosynthesized or biogenic noble metal NPs, the mechanism of NP stabilization by biomolecules contained in each particular plant extract or living organism determines the possible applications of these NPs. In this work, we investigated Ag NPs synthesized in water with plant extracts of common toothwort (Lathraea squamaria) and two species of pepper (Capsicum annuum and Capsicum chinense). From FTIR and XPS, we drew conclusions about the composition of the functional groups and molecules that stabilize NPs in each extract, such as polysaccharide compounds (pectins, cellulose, glycosides and phenolic acids). Distinct characteristic IR features of amide I and amide II proteins were observed, which are common in plant extracts, while features of amide III were not distinctly observed in our extracts. A Raman spectroscopy study revealed weak own-SERS activity of the biomolecules of the extract and high efficiency of the NPs in the enhancement of “external” analytes, such as dyes and antibodies. This is the first report of the efficient SERS application of phytosynthesized Ag NPs.

The combination of metallic nanostructures with two-dimensional transition metal dichalcogenides is an efficient way to make the optical properties of the latter more appealing for opto-electronic applications. In this work, we investigate the optical properties of monolayer WS2 flakes grown by chemical vapour deposition and transferred onto a densely-packed array of plasmonic Au nanoparticles (NPs). The optical response was measured as a function of the thickness of a dielectric spacer intercalated between the two materials and of the system temperature, in the 75–350 K range. We show that a weak interaction is established between WS2 and Au NPs, leading to temperature- and spacer-thickness-dependent coupling between the localized surface plasmon resonance of Au NPs and the WS2 exciton. We suggest that the closely-packed morphology of the plasmonic array promotes a high confinement of the electromagnetic field in regions inaccessible by the WS2 deposited on top. This allows the achievement of direct contact between WS2 and Au while preserving a strong connotation of the properties of the two materials also in the hybrid system.

We report a study of the infrared response by localized surface plasmon resonance (LSPR) modes in gold micro- and nanoantenna arrays with various morphologies and surface-enhanced infrared absorption (SEIRA) by optical phonons of semiconductor nanocrystals (NCs) deposited on the arrays. The arrays of nano- and microantennas fabricated with nano- and photolithography reveal infrared-active LSPR modes of energy ranging from the mid to far-infrared that allow the IR response from very low concentrations of organic and inorganic materials deposited onto the arrays to be analyzed. The Langmuir–Blodgett technology was used for homogeneous deposition of CdSe, CdS, and PbS NC monolayers on the antenna arrays. The structural parameters of the arrays were confirmed by scanning electron microscopy. 3D full-wave electromagnetic simulations of the electromagnetic field distribution around the micro- and nanoantennas were employed to realize the maximal SEIRA enhancement for structural parameters of the arrays whereby the LSPR and the NC optical phonon energies coincide. The SEIRA experiments quantitatively confirmed the computational results. The maximum SEIRA enhancement was observed for linear nanoantennas with optimized structural parameters determined from the electromagnetic simulations. The frequency position of the feature’s absorption seen in the SEIRA response evidences that the NC surface and transverse optical phonons are activated in the infrared spectra.

Abstract Structure, composition, and optical properties of colloidal mercaptoacetate-stabilized Cu2ZnSnS4 (CZTS) nanocrystal inks produced by a “green” method directly in aqueous solutions were characterized. A size-selective precipitation procedure using 2-propanol as a non-solvent allows separating a series of fractions of CZTS nanocrystals with an average size (bandgap) varying from 3 nm (1.72 eV) to 2 nm (2.04 eV). The size-selected CZTS nanocrystals revealed also phonon confinement, with the main phonon mode frequency varying by about 4 cm−1 between 2 nm and 3 nm NCs.

While photoelectrochemical devices combine light-absorption with fuel and electricity generation, their implementation is hampered by high costs and low output. Here, the authors synthesized acetylene-rich carbon fibers by copper-mediated polymerization for high-activity, metal-free photocathodes.

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.

The bottom-up approach to replace existing devices by molecular-based systems is a subject that attracts permanently increasing interest. Molecular-based devices offer not only to miniaturize the device further, but also to benefit from advanced functionalities of deposited molecules. Furthermore, the molecules itself can be tailored to allow via their self-assembly the potential fabrication of devices with an application potential, which is still unforeseeable at this time. Herein, we review efforts to use discrete (metallo)porphyrins for the formation of (sub)monolayers by surface-confined polymerization, of monolayers formed by supramolecular recognition and of thin films formed by sublimation techniques. Selected physical properties of these systems are reported as well. The application potential of those ensembles of (metallo)porphyrins in materials science is discussed.

Manganese phthalocyanine (MnPc) is a member of the family of transition-metal phthalocyanines, which combines interesting electronic behavior in the fields of organic and molecular electronics with local magnetic moments. MnPc is characterized by hybrid states between the Mn 3d orbitals and the π orbitals of the ligand very close to the Fermi level. This causes particular physical properties, different from those of the other phthalocyanines, such as a rather small ionization potential, a small band gap and a large electron affinity. These can be exploited to prepare particular compounds and interfaces with appropriate partners, which are characterized by a charge transfer from or to MnPc. We summarize recent spectroscopic and theoretical results that have been achieved in this regard.

The chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII2L(L’)](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L’ is a ω-mercapto-carboxylato ligand (L’ = HS(CH2)5CO2− (6), HS(CH2)10CO2− (7), or HS(C6H4)2CO2− (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV–vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm−1) and 8 (J = +20.8 cm−1; H = −2JS1S2). The reactivity of complexes 6–8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.

The investigation of the vibrational properties of epitaxial silicene and two-dimensional (2D) Si structures on the silver(111) surface aims for a better understanding of the structural differences and of the simplification of the seemingly complex phase diagrams reported over the last years. The spectral signatures of the main silicene phases epitaxially grown on Ag(111) were obtained using in situ Raman spectroscopy. Due to the obvious 2D nature of various epitaxial silicene structures, their fingerprints consist of similar sets of Raman modes. The reduced phase diagram also includes other Si phases, such as amorphous and crystalline silicon, which emerge on the Ag surface at low and high preparation temperatures, respectively. The Raman signatures obtained along with their interpretations provide the referential basis for further studies and for potential applications of epitaxial silicene.

We report light-induced negative organic magnetoresistance (OMAR) measured in ambient atmosphere in solution-processed 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) planar hybrid devices with two different device architectures. Hybrid electronic devices with trench-isolated electrodes (HED-TIE) having a channel length of ca. 100 nm fabricated in this work and, for comparison, commercially available pre-structured organic field-effect transistor (OFET) substrates with a channel length of 20 µm were used. The magnitude of the photocurrent as well as the magnetoresistance was found to be higher for the HED-TIE devices because of the much smaller channel length of these devices compared to the OFETs. We attribute the observed light-induced negative magnetoresistance in TIPS-pentacene to the presence of electron–hole pairs under illumination as the magnetoresistive effect scales with the photocurrent. The magnetoresistance effect was found to diminish over time under ambient conditions compared to a freshly prepared sample. We propose that the much faster degradation of the magnetoresistance effect as compared to the photocurrent was due to the incorporation of water molecules in the TIPS-pentacene film.

Nanoantenna-assisted plasmonic enhancement of IR absorption and Raman scattering was employed for studying the vibrational modes in organic molecules. Ultrathin cobalt phthalocyanine films (3 nm) were deposited on Au nanoantenna arrays with specified structural parameters. The deposited organic films reveal the enhancement of both Raman scattering and IR absorption vibrational modes. To extend the possibility of implementing surface-enhanced infrared absorption (SEIRA) for biological applications, the detection and analysis of the steroid hormone cortisol was demonstrated.

A microfluidic setup which enables on-line monitoring of residues of malachite green (MG) using surface-enhanced Raman scattering (SERS) is reported. The SERS active substrate was prepared via laser induced synthesis of silver or gold nanoparticles spot on the bottom of a 200 μm inner dimension glass capillary, by focusing the laser beam during a continuous flow of a mixture of silver nitrate or gold chloride and sodium citrate. The described microfluidic setup enables within a few minutes the monitoring of several processes: the synthesis of the SERS active spot, MG adsorption to the metal surface, detection of the analyte when saturation of the SERS signal is reached, and finally, the desorption of MG from the spot. Moreover, after MG complete desorption, the regeneration of the SERS active spot was achieved. The detection of MG was possible down to 10−7 M concentration with a good reproducibility when using silver or gold spots as SERS substrate.

The study of infrared absorption by linear gold nanoantennas fabricated on a Si surface with underlying SiO2 layers of various thicknesses allowed the penetration depth of localized surface plasmons into SiO2 to be determined. The value of the penetration depth derived experimentally (20 ± 10 nm) corresponds to that obtained from electromagnetic simulations (12.9–30.0 nm). Coupling between plasmonic excitations of gold nanoantennas and optical phonons in SiO2 leads to the appearance of new plasmon–phonon modes observed in the infrared transmission spectra the frequencies of which are well predicted by the simulations.

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.

We present the results of an investigation of surface-enhanced Raman scattering (SERS) by optical phonons in colloidal CdSe nanocrystals (NCs) homogeneously deposited on both arrays of Au nanoclusters and Au dimers using the Langmuir–Blodgett technique. The coverage of the deposited NCs was less than one monolayer, as determined by transmission and scanning electron microscopy. SERS by optical phonons in CdSe nanocrystals showed a significant enhancement that depends resonantly on the Au nanocluster and dimer size, and thus on the localized surface plasmon resonance (LSPR) energy. The deposition of CdSe nanocrystals on the Au dimer nanocluster arrays enabled us to study the polarization dependence of SERS. The maximal SERS signal was observed for light polarization parallel to the dimer axis. The polarization ratio of the SERS signal parallel and perpendicular to the dimer axis was 20. The SERS signal intensity was also investigated as a function of the distance between nanoclusters in a dimer. Here the maximal SERS enhancement was observed for the minimal distance studied (about 10 nm), confirming the formation of SERS “hot spots”.

We present the results of a Raman study of optical phonons in CuS nanocrystals (NCs) with a low areal density fabricated through the Langmuir–Blodgett technology on nanopatterned Au nanocluster arrays using a combination of surface- and interference-enhanced Raman scattering (SERS and IERS, respectively). Micro-Raman spectra of one monolayer of CuS NCs deposited on a bare Si substrate reveal only features corresponding to crystalline Si. However, a new relatively strong peak occurs in the Raman spectrum of CuS NCs on Au nanocluster arrays at 474 cm−1. This feature is related to the optical phonon mode in CuS NCs and manifests the SERS effect. For CuS NCs deposited on a SiO2 layer this phonon mode is also observed due to the IERS effect. Its intensity changes periodically with increasing SiO2 layer thickness for different laser excitation lines and is enhanced by a factor of about 30. CuS NCs formed on Au nanocluster arrays fabricated on IERS substrates combine the advantages of SERS and IERS and demonstrate stronger SERS enhancement allowing for the observation of Raman signals from CuS NCs with an ultra-low areal density.

The optical and electrical properties of terbium(III) bis(phthalocyanine) (TbPc2) films on cobalt substrates were studied using variable angle spectroscopic ellipsometry (VASE) and current sensing atomic force microscopy (cs-AFM). Thin films of TbPc2 with a thickness between 18 nm and 87 nm were prepared by organic molecular beam deposition onto a cobalt layer grown by electron beam evaporation. The molecular orientation of the molecules on the metallic film was estimated from the analysis of the spectroscopic ellipsometry data. A detailed analysis of the AFM topography shows that the TbPc2 films consist of islands which increase in size with the thickness of the organic film. Furthermore, the cs-AFM technique allows local variations of the organic film topography to be correlated with electrical transport properties. Local current mapping as well as local I–V spectroscopy shows that despite the granular structure of the films, the electrical transport is uniform through the organic films on the microscale. The AFM-based electrical measurements allow the local charge carrier mobility of the TbPc2 thin films to be quantified with nanoscale resolution.

We have investigated single-walled carbon nanotube (SWCNT) networks wrapped with the cationic surfactant sodium dodecyl-benzenesulfonate (SBDS) as promising candidates for water detection. This is the first time that the humidity behavior of endohedral Li-doped (Li@) and undoped SWCNTs/SDBS has been shown. We identified a strong and almost monotonic decrease in resistance as humidity increased from 11 to 97%. Sensitivities varied between −3 and 65% in the entire humidity range. Electrical characterization, Raman spectroscopy, and high-resolution transmission electron microscopy (HRTEM) analysis revealed that a combination of the electron donor behavior of the water molecules with Poole-Frenkel conduction accounted for the resistive humidity response in the Li@SWCNT/SDBS and undoped SWCNT/SDBS networks. We found that Li@SWCNTs boosted the semiconducting character in mixtures of metallic/semiconducting SWCNT beams. Moreover, electrical characterization of the sensor suggested that endohedral Li doping produced SWCNT beams with high concentration of semiconducting tubes. We also investigated how frequency influenced film humidity sensing behavior and how this behavior of SWCNT/SDBS films depended on temperature from 20 to 80 ° C. The present results will certainly aid design and optimization of SWCNT films with different dopants for humidity or gas sensing in general.

The application of porous carbon is versatile. It is used for high-performance catalyst support, electrode material in batteries, and gas storage. In each of these application fields nanostructuring improves the material properties. Supercapacitors store a high energy density. Exactly adapted carbon structures increase the life of lithium batteries and protect catalysts with increasing reaction rate and selectivity. Most of porous carbon materials have a spherical shape. To the best of our knowledge, there is no procedure to synthesize nanostructured cylindrical porous carbon systematically. Here, template glass fibres and SiO2-tubes were modified with nanostructured SiO2/phenolic resin and SiO2/poly(furfuryl alcohol) layers by surface twin polymerization (TP) of 2,2′-spirobi[4H-1,3,2-benzodioxasiline] and tetrafurfuryloxysilane. Afterwards the SiO2/polymer layer on the template is thermally transformed into a defect-free nanostructured SiO2/carbon layer. After completely removing the SiO2 components microporous carbon tubes or rods are finally achieved. The diameters of the carbon rods and the inner as well as the outer diameter of the carbon tubes are adjustable according to the shape and size of the template. Thus, a huge variety of microporous carbon materials can be easily produced by template-assisted TP.