Surface Modification of ZnO Nanotubes by Ag and Au Coatings of Variable Thickness: Systematic Analysis of the Factors Leading to UV Light Emission Enhancement.

Surface modification by plasmonic metals is one of the most promising ways to increase the band-to-band excitonic recombination in zinc oxide (ZnO) nanostructures. However, the metal-induced modulation of the UV light emission depends strongly on the production method, making it difficult to recognize the mechanism responsible for charge/energy transfer between the semiconductor and a metal. Therefore, in this study, the ZnO/Ag and Au hybrids were produced by the same, fully controlled experimental approach. ZnO nanotubes (NTs), fabricated by a template-assisted ALD synthesis, were coated by metals of variable mass thickness (1-6.5 nm thick) using the electron beam PVD technique. The deposited Ag and Au metals grew in the form of island films made of metallic nanoparticles (NPs). The size of the NPs and their size distribution decreased, while the spacing between the NPs increased as the mass of the deposited Ag and Au metals decreased. Systematic optical analysis allowed us to unravel a specific role of surface defects in ZnO NTs in the processes occurring at the ZnO/metal interface. The enhancement of the UV emission was observed only in the ZnO/Ag system. The phenomena were tentatively ascribed to the coupling between the defect-related (DL) excitonic recombination in ZnO and the localized surface plasmon resonance (LSPR) at the Ag NPs. However, the enhancement of UV light was observed only for a narrow range of Ag NP dimensions, indicating the great importance of the size and internanoparticle spacing in the plasmonic coupling. Moreover, the enhancement factors were much stronger in ZnO NTs characterized by robust DL-related emission before metal deposition. In contrast to Ag, Au coatings caused quenching of the UV emission from ZnO NTs, which was attributed to the uncoupling between the DL and LSP energies in this system and a possible formation of the ohmic contact between the Au metal and the ZnO.

α-Amino Acids as Reducing and Capping Agents in Gold Nanoparticles Synthesis Using the Turkevich Method.

Amino acid-capped gold nanoparticles (AuNPs) are a promising tool for various applications, including therapeutics and diagnostics. Most often, amino acids are used to cap AuNPs synthesized with other reducing agents. However, only a few studies have been dedicated to using α-amino acids as reducing and capping agents in AuNPs synthesis. Hence, there are still several gaps in understanding their role in reducing gold salts. Here, we used 20 proteinogenic α-amino acids and one non-proteinogenic α-amino acid in analogy to sodium citrate as reducing and capping agents in synthesizing AuNPs using the Turkevich method. Only four of the twenty-one investigated amino acids have not yielded gold nanoparticles. The shape, size distribution, stability, and optical properties of synthesized nanoparticles were characterized by scanning electron microscopy, differential centrifugal sedimentation, the phase analysis light scattering technique, and UV-vis spectroscopy. The physicochemical characteristics of synthesized AuNPs varied with the amino acid used for the reduction. We proposed that in the initial stage of gold salts reduction most of the used α-amino acids behave similarly to citrate in the Turkevich method. However, their different physicochemical properties resulting from differences in their chemical structures significantly influence the outcomes of reactions.

Editorial for the Special Issue on Corrosion and Etching at Micro/Nanoscale.

Micro- and nanoscale corrosion and etching at are important in several fields, from the fabrication of sensors and membranes to investigations of the properties of micro- and nanocomposites [...].

Designing porous photonic crystals for MIR spectral region-a deeper insight into the anodic alumina layer thickness versus charge density relation.

The mid-infrared region (MIR) is crucial for many applications in security and industry, in chemical and biomolecular sensing, since it contains strong characteristic vibrational transitions of many important molecules and gases (e.g. CO2, CH4, CO). Despite its great potential, the optical systems operating in this spectral domain are still under development. The situation is caused mainly by the lack of inexpensive and adequate optical materials which show no absorption in the MIR. In this work, we present an easy and affordable way to develop 1D photonic crystals (PCs) based on porous anodic alumina for MIR region. The porous PCs were produced by the pulse anodization of aluminum using charge-controlled mode. The first order photonic stopbands (λ1) were located within ca. 3.5-6.5µm. Annealing of the material at 1100 °C for an hour has allowed to recover the wavelength range from around 5.8 to 7.5µm owing to the decomposition of the absorption centers (oxalate anions) present in the anodic oxide framework while maintaining the PC structural stability. The spectral position and the shape of the resonances were regulated by the charge passing under high (UH) and low (UL) voltage pulses, porosity of the correspondingdHanddLsegments, and dura tion of the process (ttot). The thickness of thedHanddLlayers was proportional to the charge passing under respective pulses, with the proportionality coefficient increasing with the applied voltage. Despite the constant charge (2500 mC cm-2) applied during the anodization, the thickness of anodic alumina (d) increased with applied voltage (10-60 V) and anodizing temperature (5 °C-30 °C). This behavior was ascribed to the different kinetics of the anodic alumina formation prompted by the variable electrochemical conditions. The photonic material can be used in portable nondispersive gas sensors as an enhancement layer operating up to around 9µm.

Influence of Ethanol on Porous Anodic Alumina Growth in Etidronic Acid Solutions at Various Temperatures.

Etidronic acid, used in aluminum anodization, has a great potential for the fabrication of porous anodic alumina (PAA) with large cell sizes (>540 nm). PAAs are particularly suited to applications in optics and photonics where large-scale periodicity corresponding to visible or infrared light is needed. Additionally, such PAAs should be characterized by long-range pore ordering. However, to obtain regular pore arrangement in an etidronic electrolyte, the anodization should be performed at high electric fields using relatively high temperatures, which makes the process challenging in terms of its stability. To stabilize the process, the electrolyte can be modified with ethanol. In this work, the impact of ethanol on pore geometry and a level of pore ordering is systematically analyzed. It is shown that the additive tends to reduce pore ordering. Moreover, by changing the anodizing temperature and the amount of ethanol, it is possible to tune the porosity of the PAA template. At 20 °C, porosity drops from 14% in PAA grown in a pure water-based electrolyte to ca. 8% in PAA fabricated in the 1:3 v/v EtOH:H2O electrolyte. The larger PAA thickness obtained for the same charge density strongly suggests that PAA formation efficiency increases in the 1:3 v/v EtOH:H2O mixture.

Structural stability and optical properties of 1D photonic crystals based on porous anodic alumina after annealing at different temperatures.

Porous anodic alumina (PAA) photonic crystals with a photonic stop-band (PSB) placed in the mid-infrared (MIR) spectral region represent a promising approach for increasing of gas sensors sensitivity. An onion-like layered distribution of anionic impurities is a hallmark of PAA, and its presence is generally considered to demarcate the boundary between transparent and opaque ranges in the infrared spectral region. Here, we study the effect of annealing in the temperature range of 450 °C-1 100 °C on the structural stability and optical properties in photonic crystals based on PAA fabricated by pulse anodization in oxalic acid. Pulse sequences were selected in a way to obtain photonic crystals of different periodic structures with a PSB located in visible and MIR spectral regions. The first photonic crystal was composed of layers with gradually changing porosity, whereas the second photonic crystal consisted of a sequentially repeated double-layer unit with an abrupt change in porosity. We investigated the response of alumina with rationally designed porosities and different arrangements of porous layers for high-temperature treatment. The microstructure (scanning electron microscopy), phase composition (x-ray diffraction), and optical properties (optical spectroscopy) were analysed to track possible changes after annealing. Both photonic crystals demonstrated an excellent structural stability after 24 h annealing up to 950 °C. At the same time, the evaporation of the anionic impurities from PAA walls caused a shift of the PSB towards the shorter wavelengths. Furthermore, the annealing at 1 100 °C induced a high transparency (up to 90%) of alumina in MIR spectral region. It was shown thus that properly selected electrochemical and annealing conditions enable the fabrication of porous photonic crystals with the high transparency spanning the spectral range up to around 10µm.

Peculiarities of Aluminum Anodization in AHAs-Based Electrolytes: Case Study of the Anodization in Glycolic Acid Solution.

The anodization of aluminum (Al) in three alpha-hydroxy acids (AHAs): glycolic (GC), malic (MC), and citric (CC), was analyzed. Highly ordered pores in GC were obtained for the first time. However, the hexagonal cells were characterized by a non-uniform size distribution. Although common features of current density behavior are visible, the anodization in AHAs demonstrates some peculiarities. The electric conductivity (σ) of 0.5 M GC, MC, and CC electrolytes was in the following order: σ(CC) > σ(MC) > σ(GC), in accordance with the acid strength pKa(CC) < pKa(MC) < pKa(GC). However, the anodization voltage, under which a self-organized pore formation in anodic alumina (AAO) was observed (Umax), decreased with increasing pKa: Umax(CC) > Umax(MC) ≥ Umax(GC). This unusual behavior is most probably linked with the facility of acid ions to complex Al and the active participation of the Al complexes in the AAO formation. Depending on the AHA, its tendency and different modes to coordinate Al ions, the contribution of stable Al complexes to the AAO growth is different. It can be concluded that the structure of Al complexes, their molecular mass, and the ability to lose electrons play more important roles in the AAO formation than pKa values of AHAs.

Peculiar Porous Aluminum Oxide Films Produced via Electrochemical Anodizing in Malonic Acid Solution with Arsenazo-I Additive.

The influence of arsenazo-I additive on electrochemical anodizing of pure aluminum foil in malonic acid was studied. Aluminum dissolution increased with increasing arsenazo-I concentration. The addition of arsenazo-I also led to an increase in the volume expansion factor up to 2.3 due to the incorporation of organic compounds and an increased number of hydroxyl groups in the porous aluminum oxide film. At a current density of 15 mA·cm-2 and an arsenazo-I concentration 3.5 g·L-1, the carbon content in the anodic alumina of 49 at. % was achieved. An increase in the current density and concentration of arsenazo-I caused the formation of an arsenic-containing compound with the formula Na1,5Al2(OH)4,5(AsO4)3·7H2O in the porous aluminum oxide film phase. These film modifications cause a higher number of defects and, thus, increase the ionic conductivity, leading to a reduced electric field in galvanostatic anodizing tests. A self-adjusting growth mechanism, which leads to a higher degree of self-ordering in the arsenazo-free electrolyte, is not operative under the same conditions when arsenazo-I is added. Instead, a dielectric breakdown mechanism was observed, which caused the disordered porous aluminum oxide film structure.

Optical Properties of Porous Alumina Assisted Niobia Nanostructured Films-Designing 2-D Photonic Crystals Based on Hexagonally Arranged Nanocolumns.

Three types of niobia nanostructured films (so-called native, planarized, and column-like) were formed on glass substrates by porous alumina assisted anodizing in a 0.2 M aqueous solution of oxalic acid in a potentiostatic mode at a 53 V and then reanodizing in an electrolyte containing 0.5 M boric acid and 0.05 M sodium tetraborate in a potentiodynamic mode by raising the voltage to 230 V, and chemical post-processing. Anodic behaviors, morphology, and optical properties of the films have been investigated. The interference pattern of native film served as the basis for calculating the effective refractive index which varies within 1.75-1.54 in the wavelength range 190-1100 nm. Refractive index spectral characteristics made it possible to distinguish a number of absorbance bands of the native film. Based on the analysis of literature data, the identified oxide absorbance bands were assigned. The effective refractive index of native film was also calculated using the effective-medium models, and was in the range of 1.63-1.68. The reflectance spectra of all films show peaks in short- and long-wave regions. The presence of these peaks is due to the periodically varying refractive index in the layers of films in two dimensions. FDTD simulation was carried out and the morphology of a potential 2-D photonic crystal with 92% (wavelength 462 nm) reflectance, based on the third type of films, was proposed.

Fabrication of Porous Anodic Alumina (PAA) by High-Temperature Pulse-Anodization: Tuning the Optical Characteristics of PAA-Based DBR in the NIR-MIR Region.

In this work, the influence of various electrochemical parameters on the production of porous anodic alumina (PAA)-based DBRs (distributed Bragg reflector) during high-temperature-pulse-anodization was studied. It was observed that lowering the temperature from 30 to 27 °C brings about radical changes in the optical performance of the DBRs. The multilayered PAA fabricated at 27 °C did not show optical characteristics typical for DBR. The DBR performance was further tuned at 30 °C. The current recovery (iamax) after application of subsequent UH pulses started to stabilize upon decreasing high (UH) and low (UL) voltage pulses, which was reflected in a smaller difference between initial and final thickness of alternating dH and dL segments (formed under UH and UL, respectively) and a better DBR performance. Shortening UH pulse duration resulted in a progressive shift of photonic stopbands (PSBs) towards the blue part of the spectrum while keeping intensive and symmetric PSBs in the NIR-MIR range. Despite the obvious improvement of the DBR performance by modulation of electrochemical parameters, the problem with regarding full control over the homogeneous formation of dH+dL pairs remains. Solving this problem will certainly lead to the production of affordable and efficient PAA-based photonic crystals with tunable photonic properties in the NIR-MIR region.

Towards Self-Organized Anodization of Aluminum in Malic Acid Solutions-New Aspects of Anodization in the Organic Acid.

In this work, aluminum (Al) anodization in malic acid electrolytes of different concentrations (0.15 M, 0.25 M, and 0.5 M) was studied. The close-packed hexagonal pore structure was obtained for the first time in this organic acid in a 0.5 M solution, at 250 V and temperature of 5 °C. Moreover, the process was investigated as a function of the number of cycles carried out in the same electrolyte. A repetition of anodization under seemingly the same external electrochemical parameters (applied voltage, temperature, etc.) induced serious changes in the electrolyte. The changes were reflected in the current density vs. time curves and were most evident in the higher concentrated electrolytes. This phenomenon was tentatively explained by a massive incorporation of malate anions into anodic alumina (AAO) framework. The impoverishment of the electrolyte of the malate anions changed internal electrochemical conditions making easier the attraction of the anions to the Al anode and thus the AAO formation. The electrolyte modification was advantageous in terms of pore organization: In a 0.25 M solution, already after the second anodization, the pore arrangement transformed from irregular towards regular, hexagonal close-packed structure. To the best of our knowledge, this is the first observation of this kind.

Influence of Anodization Temperature on Geometrical and Optical Properties of Porous Anodic Alumina(PAA)-Based Photonic Structures.

In this work, the influence of a wide range anodizing temperature (5-30 °C) on the growth and optical properties of PAA-based distributed Bragg reflector (DBR) was studied. It was demonstrated that above 10 °C both structural and photonic properties of the DBRs strongly deteriorates: the photonic stop bands (PSBs) decay, broaden, and split, which is accompanied by the red shift of the PSBs. However, at 30 °C, new bands in transmission spectra appear including one strong and symmetric peak in the mid-infrared (MIR) spectral region. The PSB in the MIR region is further improved by a small modification of the pulse sequence which smoothen and sharpen the interfaces between consecutive low and high refractive index layers. This is a first report on PAA-based DBR with a good quality PSB in MIR. Moreover, it was shown that in designing good quality DBRs a steady current recovery after subsequent application of high potential (UH) pulses is more important than large contrast between low and high potential pulses (UH-UL contrast). Smaller UH-UL contrast helps to better control the current evolution during pulse anodization. Furthermore, the lower PSB intensity owing to the smaller UH-UL contrast can be partially compensated by the higher anodizing temperature.

Structural and Optical Characterization of ZnS Ultrathin Films Prepared by Low-Temperature ALD from Diethylzinc and 1.5-Pentanedithiol after Various Annealing Treatments.

The structural and optical evolution of the ZnS thin films prepared by atomic layer deposition (ALD) from the diethylzinc (DEZ) and 1,5-pentanedithiol (PDT) as zinc and sulfur precursors was studied. A deposited ZnS layer (of about 60 nm) is amorphous, with a significant S excess. After annealing, the stoichiometry improved for annealing temperatures ≥400 °C and annealing time ≥2 h, and 1:1 stoichiometry was obtained when annealed at 500 °C for 4 h. ZnS crystallized into small crystallites (1-7 nm) with cubic sphalerite structure, which remained stable under the applied annealing conditions. The size of the crystallites (D) tended to decrease with annealing temperature, in agreement with the EDS data (decreased content of both S and Zn with annealing temperature); the D for samples annealed at 600 °C (for the time ≤2 h) was always the smallest. Both reflectivity and ellipsometric spectra showed characteristics typical for quantum confinement (distinct dips/peaks in UV spectral region). It can thus be concluded that the amorphous ZnS layer obtained at a relatively low temperature (150 °C) from organic S precursor transformed into the layers built of small ZnS nanocrystals of cubic structure after annealing at a temperature range of 300-600 °C under Ar atmosphere.

Revisiting semicontinuous silver films as surface-enhanced Raman spectroscopy substrates.

Surface-enhanced Raman spectroscopy (SERS) is a very promising analytical technique for the detection and identification of trace amounts of analytes. Among the many substrates used in SERS of great interest are nanostructures fabricated using physical methods, such as semicontinuous metal films obtained via electron beam physical vapor deposition. In these studies, we investigate the influence of morphology of semicontinuous silver films on their SERS properties. The morphologies studied ranged from isolated particles through percolated films to almost continuous films. We found that films below the percolation threshold (transition from dielectric-like to metal-like) made of isolated silver structures provided the largest SERS enhancement of 4-aminothiophenol (4-ATP) analyte signals. The substrate closest to the percolation threshold has the SERS signal about four times lower than the highest signal sample.

Heterogeneous carbon gels: N-doped carbon xerogels from resorcinol and N-containing heterocyclic aldehydes.

Direct, acid (HCl) initiated sol-gel polycondensation of resorcinol with pyrrole-2-carboxaldehyde or its derivative N-methyl-2-pyrrolecarboxaldehyde yields thermosetting phenolic organic gels with N-content of up to 8.4 wt %. After carbonization, sturdy monoliths of N-doped carbon xerogels with N-content of up to 8 wt % are produced. The morphology and porosity of the doped carbons can be tuned by the solvent composition and the amount of polymerization catalyst used. An increase in carbonization temperature from 600 to 1000 °C strongly affects the carbon gels' microporosity, resulting in a decrease in N2 adsorption capacity, but a significant increase in H2 adsorption capacity (at -196 °C). The growing H2 sorption capacity with the decreasing specific surface area (measured by N2) is related to the gradual shrinkage of the carbon xerogel matrix and narrowing of the small micropores. In addition, it is demonstrated that pyridine-based heterocyclic aldehydes, that is, 2- or 4-pyridinecarboxaldehyde, condensate with resorcinol in basic conditions (KOH, NH4OH). However, in this case, monoliths cannot be produced and powders/rigid solid precipitates are obtained instead. If NH4OH is used as a sol-gel polycondensation catalyst, N-doped foams are obtained as a final carbonaceous product.

NMR transversal relaxivity of aqueous suspensions of particles of Ln(3+)-based zeolite type materials.

A series of zeolite-type silicates containing stoichiometric amounts of Ln(3+) ions in the framework (Ln-AV-9 materials), with composition (Na(4)K(2))(Ln(2)Si(16)O(38)).10H(2)O (Ln = Nd, Sm, Eu, Tb, Gd, Dy) has recently been synthesized and characterized. They form paramagnetic microparticles, which as aqueous suspensions have negligible water (1)H longitudinal relaxivities (r(1)) for all Ln(3+) ions studied and quite large transverse relaxivities (r(2)). In this work we further analysed the size distribution of the Ln-AV-9 particles and their r(2)* and r(2) relaxivities. The r(2)* relaxivity effects are explained by the static dephasing regime (SDR) theory. The r(2) relaxivities appear to be strongly dependent on the interval between two consecutive refocusing pulses (tau(CP)) in the train of 180 degrees pulses applied. For long tau(CP) values, the r(2) of the systems saturates at a value, which is always an order of magnitude smaller than r(2)*. These features are explained by a crude model, which takes into account the residual diffusion effect in the static dephasing regime. The large microparticles, although not efficient in T(1) relaxation, are quite effective in enhancing T(2) relaxation, particularly at high magnetic fields. The r(2)* values and the saturation values for r(2) were found to increase linearly with B(0) and mu(0)(2). The largest transversal relaxation rate enhancements were observed for Dy-AV-9 with a saturation value of r(2) of 60 s(-1) mM(-1) and a r(2)* value of 566 s(-1) mM(-1) at 9.4 T and 298 K.

Tuning of the size of Dy2O3 nanoparticles for optimal performance as an MRI contrast agent.

The transverse 1H relaxivities of aqueous colloidal solutions of dextran coated Dy2O3 nanoparticles of different sizes were investigated at magnetic field strengths (B) between 7 and 17.6 T. The particle size with the maximum relaxivity (r2) appears to vary between 70 nm at 7 T (r2 approximately = 190 s(-1) mM(-1)) and 60 nm at 17.6 T (r2 approximately = 675 s(-1) mM(-1)). A small difference between r2 and r2* was observed, which was ascribed to the effect of the dextran coating. The value of r2 is proportional to B2 up to 12 T after which it saturates. Independent magnetization measurements on these particles at room temperature at magnetic field strengths up to 30 T, however, show a typical paramagnetic behavior with a magnetization of the particle that is proportional to the field strength. The saturation in the curve of r2 as a function of B2 was tentatively explained by the presence of an extremely fast relaxing component of the signal at high field strengths, which is not observable on the NMR time scale. The results of this study can be exploited for the rational design of MRI contrast agents, based on lanthanide oxide particles, with high efficiencies at magnetic field strengths of more than 1.5 T.

(1)H relaxivity of water in aqueous suspensions of Gd(3+)-loaded NaY nanozeolites and AlTUD-1 mesoporous material: the influence of Si/Al ratio and pore size.

The results of a (1)H nuclear magnetic relaxation dispersion (NMRD) and EPR study on aqueous suspensions of Gd(3+)-loaded NaY nanozeolites and AlTUD-1 mesoporous material are described. Upon increase of the Si/Al ratio from 1.7 to 4.0 in the Gd(3+)-loaded zeolites, the relaxation rate per mM Gd(3+) (r1) at 40 MHz and 25 degrees C increases from 14 to 27 s(-)1 mM(-1). The NMRD and EPR data were fitted with a previously developed two-step model that considers the system as a concentrated aqueous solution of Gd(3+) in the interior of the zeolite that is in exchange with the bulk water outside the zeolite. The results show that the observed increase in relaxivity can mainly be attributed to the residence lifetime of the water protons in the interior of the material, which decreased from 0.3 to 0.2 micros, upon the increase of the Si/Al ratio. This can be explained by the decreased interaction of water with the zeolite walls as a result of the increased hydrophobicity. The importance of the exchange rate of water between the inside and the outside of the material was further demonstrated by the relatively high relaxivity (33 s(-1) mM(-1) at 40 MHz, 25 degrees C) observed for a suspension of the Gd(3+)-loaded mesoporous material AlTUD-1. Unfortunately, Gd(3+) leaches rather easily from that material, but not from the Gd(3+)-loaded NaY zeolites, which may have potential as contrast agents for magnetic resonance imaging.