Mesoflowers: A new class of highly efficient surface-enhanced Raman active and infrared-absorbing materials

A method for the synthesis of a new class of anisotropic mesostructured gold material, which we call “mesoflowers”, is demonstrated. The mesoflowers, unsymmetrical at the single particle level, resemble several natural objects and are made up of a large number of stems with unusual pentagonal symmetry. The mesostructured material has a high degree of structural purity with star-shaped, nano-structured stems. The mesoflowers were obtained in high yield, without any contaminating structures and their size could be tuned from nano- to meso-dimensions. The dependence of various properties of the mesoflowers on their conditions of formation was studied. The near-infrared-infrared (NIR-IR) absorption exhibited by the mesoflowers has been used for the development of infrared filters. Using a prototypical device, we demonstrated the utility of the gold mesoflowers in reducing the temperature rise in an enclosure exposed to daylight in peak summer. These structures showed a high degree of surface-enhanced Raman scattering (SERS) activity compared to spherical analogues. SERS-based imaging of a single mesoflower is demonstrated. The high SERS activity and NIR-IR absorption property open up a number of exciting applications in diverse areas. Electronic Supplementary Material  Supplementary material is available in the online version of this article at http://dx.doi.org/ and is accessible free of charge.     

Au/Si-NPA复合纳米体系的SERS增强能力研究

利用具有准周期结构的硅纳米孔柱阵列(silicon nanoprous pillar array,Si-NPA)为衬底使用浸渍法制备优化Au/Si-NPA活性基底。并利用最优化制备的Au/Si-NPA活性基底对罗丹明6G(Rhoda-mine 6G,R6G)进行探测,研究其表面增强拉曼散射(surface enhanced Raman scattering,SERS)光谱并对其增强原理进行解释。     

Thickness-dependent morphologies of Ag on <Emphasis Type="Italic">n</Emphasis>-layer MoS<Subscript>2</Subscript> and its surface-enhanced Raman scattering

The size and density of Ag nanoparticles on n-layer MoS₂ exhibit thicknessdependent behavior. The size and density of these particles increased and decreased, respectively, with increasing layer number (n) of n-layer MoS₂. Furthermore, the surface-enhanced Raman scattering (SERS) of Ag on this substrate was observed. The enhancement factor of this scattering varied with the thickness of MoS₂. The mechanisms governing the aforementioned thickness dependences are proposed and discussed.

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3D nano-arrays of silver nanoparticles and graphene quantum dots with excellent surface-enhanced Raman scattering

Active surface-enhanced Raman scattering (SERS) substrates, 3D nano-arrays of Ag nanoparticles (NPs) and graphene quantum dots (GQDs), were prepared using a photochemical approach and an electrophoresis deposition technique with the formation mechanism addressed. The GQDs (ca. 6?nm average) fit into the inter-particle gaps between Ag NPs, as verified by their scanning electron microscopy and high-resolution transmission electron microscopy. This deliberately designed 3D assembly of Ag NPs and GQDs could promote the synergistic effects of both components to further enhance the SERS performances according to both electromagnetic mechanism and chemical mechanism. Preliminary experiments show that the 3D substrates exhibited strong SERS signals comparing with bare Si substrates. This work provides a promising way for 3D SERS substrates.     

Preparation of Ag2S–Graphene nanocomposite from a single source precursor and its surface-enhanced Raman scattering and photoluminescent activity

Ag₂S–Graphene nanocomposite was prepared via a relatively facile hydrothermal method, using a single-source molecular (silver diethyldithiocarbamate [Ag(DDTC)]) as precursor and graphene sheets as a support material. The composite was characterized by X-ray power diffraction, X-ray photoelectron spectroscopy, Field-emission scanning electron microscope, transmission electron microscopy, Fourier transform infrared, Raman spectra and fluorescence spectroscopy. The experimental results show that the Ag₂S–Graphene nanocomposite displays surface-enhanced Raman scattering (SERS) activity for graphene oxide and reveals relatively better fluorescence property compared with pure Ag₂S.     

Raman scattering analysis of Cu-poor Cu(In,Ga)Se2 cells fabricated on polyimide substrates: Effect of Na content on microstructure and phase structure

This work reports the Raman scattering surface and in-depth resolved analysis of Cu-poor Cu(In,Ga)Se₂ (CIGS) grown on polyimide substrates. In order to study the effect of Na on the formation and microstructure of the CIGS and the corresponding Cu-poor ordered vacancy compound (OVC) phases, a NaF precursor layer with different thicknesses was deposited on the Mo-coated substrates before growing of the samples. The Raman spectroscopy data are correlated with the analysis of the samples by Auger electron spectroscopy and scanning electron microscopy. These data corroborate the significant role of Na on the inhibition of Ga-In interdiffusion and on the formation of the MoSe₂ interfacial phase at the back region of the layers. Presence of Na also leads to an enhancement in the formation of the chalcopyrite CIGS phase and a decrease in the occurrence of the dominant OVC phase at the surface region. This study confirms the strong dependence of the microstructure and phase distribution in CIGS absorber layers on the Na available during their growth.     

Electrodeposition based synthesis of S-rich CuIn(S,Se)2 layers for photovoltaic applications: Raman scattering analysis of electrodeposited CuInSe2 precursors

Single step electrodeposition (ED) of Se-rich CuInSe₂ precursors, followed by RTP annealing under sulphurising conditions leading to S-rich CuIn(S,Se)₂ films, constitutes a promising technology for low cost high efficiency solar cells. In this work, a Raman scattering (RS) analysis of Se rich precursors grown under ED conditions leading to different chemical compositions is reported. RS has allowed identification of the main secondary phases in these layers with elemental Se, Cu-Se binary and ordered vacancy compound (OVC) phases. The experimental data show a strong dependence of the spectral contributions related to Se and Cu-Se with the layer molecularity, and the formation of these phases is mainly determined by the content of excess Se in the layers. The correlation of these data with the characteristics of the solar cells fabricated with these precursors, shows the strong impact of the presence of the Cu-Se phase on the performance of the final devices. These results point out the key role played by this binary phase on the formation of secondary phases after the sulphurising step.     

Quasi-phase-matched second harmonic generation device in Mg-doped LiNbO3 and its application to high-density optical disk system

The resistance to photorefractive damage is investigated for several nonlinear crystals. A quasi-phase-matched (QPM) second harmonic generation (SHG) waveguide device is fabricated in 5 mol% Mg-doped LiNbO₃ which has high resistance to optical damage. The SHG blue laser of the QPM-SHG waveguide device and a tunable distributed Bragg reflector (DBR) laser diode is demonstrated, wherein output stability of continuous blue light is measured. The SHG blue laser, using the QPM-SHG waveguide device with broadened flat matching response, shows good modulation characteristics. The pulsed peak power of 23 mW with rectangular modulated waveform is generated. The SHG blue laser is installed to an optical head, and good recording and readout characteristics are demonstrated. Moreover, butt-coupled SHG blue laser is examined to gain a miniature module with volume of 0·8 cc.     

In vitro biomechanical properties,fluorescence imaging,surface-enhanced Raman spectroscopy,and photothermal therapy evaluation of luminescent functionalized CaMoO4:Eu@Au hybrid nanorods on human lung adenocarcinoma epithelial cells

Highly dispersible Eu³⁺-doped CaMoO₄@Au-nanorod hybrid nanoparticles (HNPs) exhibit optical properties, such as plasmon resonances in the near-infrared region at 790 nm and luminescence at 615 nm, offering multimodal capabilities: fluorescence imaging, surface-enhanced Raman spectroscopy (SERS) detection and photothermal therapy (PTT). HNPs were conjugated with a Raman reporter (4-mercaptobenzoic acid), showing a desired SERS signal (enhancement factor 5.0 × 10⁵). The HNPs have a heat conversion efficiency of 25.6%, and a hyperthermia temperature of 42°C could be achieved by adjusting either concentration of HNPs, or laser power, or irradiation time. HNPs were modified with antibody specific to cancer biomarker epidermal growth factor receptor, then applied to human lung cancer (A549) and mouse hepatocyte cells (AML12), and in vitro PTT effect was studied. In addition, the biomechanical properties of A549 cells were quantified using atomic force microscopy. This study shows the potential applications of these HNPs in fluorescence imaging, SERS detection, and PTT with good photostability and biocompatibility.     

Growth and Raman scattering characterization of Cu2ZnSnS4 thin films

In the present work we report the results of the growth, morphological and structural characterization of Cu₂ZnSnS₄ (CZTS) thin films prepared by sulfurization of DC magnetron sputtered Cu/Zn/Sn precursor layers. The adjustment of the thicknesses and the properties of the precursors were used to control the final composition of the films. Its properties were studied by SEM/EDS, XRD and Raman scattering. The influence of the sulfurization temperature on the morphology, composition and structure of the films has been studied. With the presented method we have been able to prepare CZTS thin films with the kesterite structure.     

Raman spectroscopic and X-ray diffraction investigations of epitaxial BiCrO3 thin films

Epitaxial BiCrO₃ thin films were grown onto NdGaO₃ (110)- and (LaAlO₃)_0.3-(Sr₂AlTaO₆)_0.7 (100)-oriented substrates by pulsed laser deposition. High resolution X-ray diffraction and pole figure measurements were performed in order to obtain information about the crystal structure of the films, about their quality and about the mutual crystallographic orientation between the films and the substrates. The monoclinic (111) plane of BiCrO₃ was found out to be parallel to the substrate surface. The epitaxial relation between films and substrates was verified by using polarisation dependent Raman spectroscopic experiments and theoretical calculations based on symmetry.     

Rib waveguides based on Zn-substituted LiNbO3 films grown by liquid phase epitaxy

The fabrication of epitaxially grown Zn-substituted LiNbO₃ (Zn:LiNbO₃) waveguide films and rib waveguides is reported and detailed investigations about microstructure, morphology and optical waveguide properties are provided. Zn:LiNbO₃ films were grown on congruent X-cut LiNbO₃ substrates by a modified liquid phase epitaxy in solid–liquid coexisting solutions. The homogeneously Zn-substituted films exhibit high crystalline perfection and extremely flat surfaces with averaged surface roughness of rms = 0.2–0.3 nm. At the film/substrate interface a Zn-containing transient layer has been observed, which allows the growth of elastically strained Zn:LiNbO₃ film lattices. X-ray diffraction reciprocal-space measurements prove the pseudomorphic film growth. The refractive index difference between substrate and film depends on the zinc substitution content, which increase with rising growth temperatures. For films with 5.3 mol% Zn (Δn_o ≈ +5 × 10⁻³) only ordinary ray propagation was observed, while for films with 7.5 mol% Zn (Δn_o ≈ +8 × 10⁻³, Δn_e ≈ +5 × 10⁻³) both modes, TM and TE propagate. Stress-induced refractive index changes are in the order of Δn ≈ 10⁻⁴. In rib waveguide microstructures singlemode propagation with nearly symmetrical field distribution has been observed. To demonstrate the potential of the proton exchange-assisted dry-etching technique interferometer microstructures were fabricated.     

Raman spectroscopic study of structure of WO3La2O3B2O3 glasses with no color and crystallization of LaBWO6

Glasses with the nominal compositions of xWO₃25La₂O₃(75 − x)B₂O₃ (mol%) with x = 15, 25, and 50 were prepared using a conventional melt quenching method, and their structure and crystallization behavior were examined from Raman scattering spectra and X-ray diffraction analyses. The glasses are colorless in the visible light region and give the optical band gap energy of 3.49-3.61 eV. The glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing WO₃ content. The strong Raman bands at 840 and 940-960 cm⁻¹ suggest that the main coordination state of W⁶⁺ ions in the glasses is isolated (WO₄)²⁻ tetrahedral units. The formation of WO₆ octahedral units is also suggested in the glasses with high WO₃ contents. The main crystallization mechanism in the glasses is the surface crystallization, and the glass of 50WO₃25La₂O₃25B₂O₃ shows the crystallization of LaBWO₆ single phase. The present study proposes that WO₃La₂O₃B₂O₃ glasses and crystallized glasses are very interesting as optical functional materials.     

UV Raman spectroscopic study on the surface phase of ZrO2 modified with Nd2O3

The Nd₂O₃ modified ZrO₂ was synthesized using two methods of co-precipitation (Nd-ZrO₂) and wet impregnation (Nd/ZrO₂). The surface and bulk crystalline phases of Nd₂O₃ modified ZrO₂ were investigated by using UV Raman spectroscopy, visible Raman spectroscopy, and X-ray diffraction (XRD). It is observed that the tetragonal phase in the surface region of Nd-ZrO₂ was not effectively stabilized by Nd₂O₃, as Nd₂O₃ is mainly present in the bulk of Nd-ZrO₂. However, in Nd/ZrO₂, it is found that with the impregnation of 0.5 mol% Nd₂O₃ on ZrO₂, the surface tetragonal phase of Nd/ZrO₂ can be stabilized even after calcination at 700 °C. The UV Raman results indicate that a disordered structure, or intermediate structure, which is involved in the transition from the tetragonal to the cubic phase, is formed at the surface region of Nd/ZrO₂. The formation of the aforementioned intermediate structure inhibits the phase transition from tetragonal to monoclinic in the surface region of Nd/ZrO₂. Furthermore, it is observed that the mixed tetragonal and monoclinic phases in the surface region of ZrO₂ which has been impregnated with Nd₂O₃ can also be stabilized after calcination at 700 °C. This work provides a simple method for controlling the surface phase of ZrO₂ at high temperatures.     

Organic/inorganic nanocomposite films based on poly(3-methoxythiophene) and WO3

Organic/inorganic nanocomposite films based on poly(3-methoxythiophene) (PMOT) and WO₃ were prepared by a consecutive two-step electrochemical method. The products were characterized in detail by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDS) and Fourier-transform infrared spectroscopies (FTIR). The results show that the PMOT/WO₃ nanocomposite films consist of two layers, the substrate WO₃ with 30 nm grains and superstratum PMOT, which average grain size is 60 nm. The obtained PMOT/WO₃ nanocomposite films were also characterized by cyclic voltammetry to investigate their electrochemistry properties which display significant enhancement of electrochemical activity than that of pure PMOT and WO₃ films.     

Facile fabrication of La(OH)3 nanorod arrays and their application in wastewater treatment

Hexagonal and vertically aligned La(OH)₃ nanorod arrays have been fabricated in a large scale via a simple electrochemical method without any hard templates and surfactants. By the aid of potential-time curve, a possible formation process of the La(OH)₃ nanorod arrays is proposed, and the gas bubbles functioning as a dynamic template might be responsible for the growth of ordered La(OH)₃ nanorods. The total absorption capacities of the as-prepared products for Congo red is about 73.5 mg g^− 1, which shows an environmental engineering application in removing organic dye from water. In short, this synthetic method shows prominent advantages such as its low-cost, easy preparation, good adherence and suitability for preparing other nanoarrays.     

Comparative study of In2S3-ITO bilayers deposited on glass and different plastic substrates

In this work ITO thin films have been grown onto glass, polyethylene terephthalate (PET) and Arylite polymer substrates by sputtering at room temperature.The In₂S₃ films were chemically deposited on ITO during different times, forming bilayers for subsequent photovoltaic applications. Optical properties of the films were investigated from the transmittance and the structural properties by XRD. Transmittance of the films varies with deposition time and the different substrates used, the same as the adherence and the homogeneity of the films.     

Effects of Ho2O3 addition on defects of BaTiO3

Effects of Ho₂O₃ addition on defects of BaTiO₃ ceramic have been studied in terms of electrical conductivity at 1200 °C as a function of oxygen partial pressure (P_O2°) and oxygen vacancy concentration. The substitution of Ho³⁺ for the Ti site in Ba(Ti_1−xHo_x)O_3−0.5x resulted in a significant shift of conductivity minimum toward lower oxygen pressures and showed an acceptor-doped behavior. The solubility limit of Ho on Ti sites was confirmed less than 3.0 mol% by measuring the electrical conductivity and the lattice constant. Oxygen vacancy concentrations were calculated from the positions of P_O2° in the conductivity minima and were in good agreement with theoretically estimated values within the solubility limit. The Curie point moved to lower temperatures with increasing the oxygen vacancy concentration and Ho contents.     

Structural and electrical properties of HfO2/Dy2O3 gate stacks on Ge substrates

In the present work we report on the structural and electrical properties of metal-oxide-semiconductor (MOS) devices with HfO₂/Dy₂O₃ gate stack dielectrics, deposited by molecular beam deposition on p-type germanium (Ge) substrates. Structural characterization by means of high-resolution Transmission Electron Microscopy (TEM) and X-ray diffraction measurements demonstrate the nanocrystalline nature of the films. Moreover, the interpretation of the X-ray reflectivity measurements reveals the spontaneous growth of an ultrathin germanium oxide interfacial layer which was also confirmed by TEM. Subsequent electrical characterization measurements on Pt/HfO₂/Dy₂O₃/p-Ge MOS diodes show that a combination of a thin Dy₂O₃ buffer layer with a thicker HfO₂ on top can give very good results, such as equivalent oxide thickness values as low as 1.9 nm, low density of interfacial defects (2-5 × 10¹² eV^− 1 cm^− 2) and leakage currents with typical current density values around 15 nA/cm² at V_g = V_FB − 1V.