Cation exchange synthesis of AgBiS2 quantum dots for highly efficient solar cells

Silver bismuth sulfide (AgBiS2) nanocrystals have emerged as a promising eco-friendly, low-cost solar cell absorber material. Their direct synthesis often relies on the hot-injection method, requiring the application of high temperatures and vacuum for prolonged times. Here, we demonstrate an alternative synthetic approach via a cation exchange reaction. In the first-step, bis(stearoyl)sulfide is used as an air-stable sulfur precursor for the synthesis of small, monodisperse Ag2S nanocrystals at room-temperature. In a second step, bismuth cations are incorporated into the nanocrystal lattice to form ternary AgBiS2 nanocrystals, without altering their size and shape. When implemented into photovoltaic devices, AgBiS2 nanocrystals obtained by cation exchange reach power conversion efficiencies of up to 7.35%, demonstrating the efficacy of the new synthetic approach for the formation of high-quality, ternary semiconducting nanocrystals

Sonication-assisted liquid phase exfoliation of two-dimensional CrTe3 under inert conditions

Liquid phase exfoliation (LPE) has been used for the successful fabrication of nanosheets from a large number of van der Waals materials. While this allows to study fundamental changes of material properties’ associated with reduced dimensions, it also changes the chemistry of many materials due to a significant increase of the effective surface area, often accompanied with enhanced reactivity and accelerated oxidation. To prevent material decomposition, LPE and processing in inert atmosphere have been developed, which enables the preparation of pristine nanomaterials, and to systematically study compositional changes over time for different storage conditions. Here, we demonstrate the inert exfoliation of the oxidation-sensitive van der Waals crystal, CrTe3. The pristine nanomaterial was purified and size-selected by centrifugation, nanosheet dimensions in the fractions quantified by atomic force microscopy and studied by Raman, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX) and photo spectroscopic measurements. We find a dependence of the relative intensities of the CrTe3 Raman modes on the propagation direction of the incident light, which prevents a correlation of the Raman spectral profile to the nanosheet dimensions. XPS and EDX reveal that the contribution of surface oxides to the spectra is reduced after exfoliation compared to the bulk material. Further, the decomposition mechanism of the nanosheets was studied by time-dependent extinction measurements after water titration experiments to initially dry solvents, which suggest that water plays a significant role in the material decomposition

Effects of Counter Anions on AC and DC Electrical Conductivity in Poly(Dimethylsiloxane) Crosslinked by Metal-Ligand Coordination

There is an urgent need for the development of elastic dielectric materials for flexible organic field effect transistors (OFETs). In this work, detailed analysis of the AC and DC electrical conductivity of a series of flexible poly(dimethylsiloxane) (PDMS) polymers crosslinked by metal-ligand coordination in comparison to neat PDMS was performed for the first time by means of broadband dielectric spectroscopy. The ligand was 2,2-bipyridine-4,4-dicarboxylic amide, and Ni2+, Mn2+, and Zn2+ were introduced for Cl−, Br−, and I− salts. Introduction of metal salt and creation of coordination bonds resulted in higher permittivity values increasing in an order: neat PDMS < Ni2+ < Mn2+ < Zn2+; accompanied by conductivity values of the materials increasing in an order: neat PDMS < Cl− < I− < Br−. Conductivity relaxation time plot as a function of temperature, showed Vogel-Fulcher–Tammann dependance for the Br− salts and Arrhenius type for the Cl− and I− salts. Performed study revealed that double-edged challenge can be obtained, i.e., dielectric materials with elevated value of dielectric permittivity without deterioration too much the non-conductive nature of the polymer. This opens up new perspectives for the production of flexible dielectrics suitable for gate insulators in OFETs. Among the synthesized organometallic materials, those with chlorides salts are the most promising for such applications

Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl2-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl− counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl− counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems

Anodic Electrodeposition of Chitosan-AgNP Composites Using In Situ Coordination with Copper Ions

Chitosan is an attractive material for biomedical applications. A novel approach for the anodic electrodeposition of chitosan–AgNP composites using in situ coordination with copper ions is proposed in this work. The surface and cross-section morphology of the obtained coating with varying concentrations of AgNPs were evaluated by SEM, and surface functional groups were analyzed with FT-IR spectroscopy. The mechanism of the formation of the coating based on the chelation of Cu(II) ions with chitosan was discussed. The antibacterial activity of the coatings towards Staphylococcus epidermidis ATCC 35984/RP62A bacteria was analyzed using the live–dead approach. The presented results indicate that the obtained chitosan–AgNP-based films possess some limited anti-biofilm-forming properties and exhibit moderate antibacterial efficiency at high AgNP loads

Ultrasonic-assisted electrodeposition of Cu-Sn-TiO2 nanocomposite coatings with enhanced antibacterial activity

Copper-based coatings are known for their high antibacterial activity. In this study, nanocomposite Cu–Sn–TiO2 coatings were obtained by electrodeposition from an oxalic acid bath additionally containing 4 g/dm3 TiO2 with mechanical and ultrasonic agitation. Ultrasound treatment was performed at 26 kHz frequency and 32 W/dm3 power. The influence of agitation mode and the current load on the inclusion and distribution of the TiO2 phase in the Cu–Sn metallic matrix were evaluated. Results indicated that ultrasonic agitation decreases agglomeration of TiO2 particles and allows for the deposition of dense Cu–Sn–TiO2 nanocomposites. It is shown that nanocomposite Cu–Sn–TiO2 coatings formed by ultrasonic-assisted electrodeposition exhibit excellent antimicrobial properties against E. coli bacteria

Zero waste, single step methods of fabrication of reduced graphene oxide decorated with gold nanoparticles

This paper reports a novel approach to the use of carbon, in the form of reduced graphene oxide, as a reducing agent for Au(III) chloride complex ions. This approach allows fabrication of a composite material Au@GOr in a single-step process. The reduction of Au(III) complex ions was performed using high pressure, 50 bar, and high temperature, 250°C, reactor. The average diameter of obtained gold nanoparticles was below 3 nm. The advantage of the reduced graphene oxide as the reducing agent is its high surface area. This accelerates the reaction rate significantly. The greenness and sustainability of the process are assessed by green chemistry metrics and circularity indicators recently applied for the first time to a nanomaterial synthesis. As a key green metrics, atom economy (AE) measures the degree of the incorporation of reactant atoms into the final product and in the case of the research presented scoring 99%

Zero waste, single step methods of fabrication of reduced graphene oxide decorated with gold nanoparticles

This paper reports a novel approach to the use of carbon, in the form of reduced graphene oxide, as a reducing agent for Au(III) chloride complex ions. This approach allows fabrication of a composite material Au@GOr in a single-step process. The reduction of Au(III) complex ions was performed using high pressure, 50 bar, and high temperature, 250°C, reactor. The average diameter of obtained gold nanoparticles was below 3 nm. The advantage of the reduced graphene oxide as the reducing agent is its high surface area. This accelerates the reaction rate significantly. The greenness and sustainability of the process are assessed by green chemistry metrics and circularity indicators recently applied for the first time to a nanomaterial synthesis. As a key green metrics, atom economy (AE) measures the degree of the incorporation of reactant atoms into the final product and in the case of the research presented scoring 99%

Narrow optical gap ferroelectric Bi2ZnTiO6 thin films deposited by RF sputtering

This work reports the deposition of single phase Bi2ZnTiO6 thin films onto Pt/Si-based substrates using the RF-sputtering method and the respective structural, morphological, optical and local ferroelectric characterization. The thin film grows in the polycrystalline form with tetragonal P4mm symmetry identified by X-ray diffraction. The lack of a spatial inversion centre was confirmed by the second harmonic generation. A narrow indirect optical gap of 1.48 eV was measured using optical diffuse reflectance. The ferroelectric domain reversal was further demonstrated through piezo-response force microscopy. This work demonstrates a practical method to fabricate the BZT perovskite phase, without resorting to high pressure and temperature conditions necessary to synthetize the bulk form, with outstanding optical and ferroelectric properties.This work was supported by national funds through the Portuguese Foundation for Science and Technology (FCT/MEC) and COMPETE 2020. when appropriate, co-financed by FEDER under the PT2020 Partnership Agreement: Grants SFRH/BPD/80663/2011 and SFRH/BPD/92896/2013; Projects IFIMUP-IN:Norte-070124-FEDER-000070; CICECO-AIM: POCI-01-0145- FEDER-007679, PTDC/FIS-NAN/0533/2012, UID/CTM/50011/2013, UID/FIS/04650/2013, CERN/FIS/NUC/0004/2015 and NECL: NORTE-01-0145-FEDER-022096 and UID/NAN/50024/2019. Foundation CAPES through the project PNPD-UFAM/Física/1671526 is also acknowledged