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At least 19 records

X-Ray Diffraction and Electron Microscopy Studies of the Size Effects on Pressure-Induced Phase Transitions in CdS Nanocrystals

In recent years, investigations of the phase transition behavior of semiconducting nanoparticles under high pressure has attracted increasing attention due to their potential applications in sensors, electronics, and optics. However, current understanding of how the size of nanoparticles influences this pressure-dependent property is somewhat lacking. In particular, phase behaviors of semiconducting CdS nanoparticles under high pressure have not been extensively reported. Therefore, in this work, CdS nanoparticles of different sizes are used as a model system to investigate particle size effects on high-pressure-induced phase transition behaviors. In particular, 7.5, 10.6, and 39.7 nm spherical CdS nanoparticles are synthesized and subjected to controlled high pressures up to 15 GPa in a diamond anvil cell. Analysis of all three nanoparticles using in-situ synchrotron wide-angle X-ray scattering (WAXS) data shows that phase transitions from wurtzite to rocksalt occur at higher pressures than for bulk material. Bulk modulus calculations not only show that the wurtzite CdS nanomaterial is more compressible than rocksalt, but also that the compressibility of CdS nanoparticles depends on their particle size. Furthermore, sintering of spherical nanoparticles into nanorods was observed for the 7.5 nm CdS nanoparticles. Our results provide new insights into the fundamental properties of nanoparticles under high pressure that will inform designs of new nanomaterial structures for emerging applications.

Meng, Lingyao↗

Shape Dependence of Pressure-Induced Phase Transition in CdS Semiconductor Nanocrystals

Understanding structural stability and phase transformation of nanoparticles under high pressure is of great scientific interest, as it is one of the crucial factors for design, synthesis, and application of materials. Even though high-pressure research on nanomaterials has been widely conducted, their shape-dependent phase transition behavior still remains unclear. Examples of phase transitions of CdS nanoparticles are very limited, despite the fact that it is one of the most studied wide band gap semiconductors. Here we have employed in-situ synchrotron wide-angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) to investigate the high-pressure behaviors of CdS nanoparticles as a function of particle shapes. We observed that CdS nanoparticles transform from wurtzite to rocksalt phase at elevated pressure in comparison to their bulk counterpart. Phase transitions also vary with particle shape—rod-shaped particles show a partially reversible phase transition and the onset of the structural phase transition pressure decreases with decreasing surface-to-volume ratios, while spherical particles undergo irreversible phase transition with relatively low phase transition pressure. Additionally, TEM images of spherical particles exhibited sintering-induced morphology change after high-pressure compression. Calculations of the bulk modulus reveals that spheres are more compressible than rods in the wurtzite phase. These results indicate that the shape of the particle plays an important role in determining their high-pressure properties. Our study provides important insights into understanding of the phase-structure-property relationship, guiding future design and synthesis of nanoparticles for promising applications.

36 MATERIALS SCIENCE↗

Toward Computation-Guided Design of Tunable Organic-Inorganic CdS Quantum Dot Binary Superlattices

Combining the advantages of structural programmability in sequence-defined biomimetic molecules and the controllable packing geometry in nanoparticle superlattices, we demonstrate a self-assembled organic-inorganic superlattice whose structure can be altered with the slightest change in the sequence of the organic counterpart. Here, oleate-coated CdS quantum dots (QDs) form a square-packed superlattice with a 1:1 molar equivalence of a di-block amphiphilic peptoid (Nbrpe6Dig) in chloroform. In contrast, no apparent structure is observed in the organic solvent alone. Based on theoretical evidence, we show that the assembly is a binary superlattice where both the CdS QDs and the peptoids serve as building blocks and further predict a correlation between the superlattice structure and the peptoid sequence. The computationally guided prediction is validated by experiments where superlattice transformation is observed with modified peptoids. The mechanism identified in our work inspires new ways to control and tune organic-inorganic hybrid nanomaterial self-assembly.

Qi, Xin↗

Pathways of CdS Quantum Dot Degradation during Photocatalysis: Implications for Enhancing Stability and Efficiency for Organic Synthesis

CdS quantum dots (QDs) are widely employed as photocatalysts for reactions such as hydrogen evolution, and their degradation under aerobic aqueous conditions is well understood. However, despite evidence of aggregation and precipitation of CdS QD photocatalysts under anaerobic conditions, catalyst speciation and degradation under such conditions are underexplored. In this work, we demonstrate that during a reductive dehalogenation reaction, CdS QDs undergo surface ligand etching, which leads to a loss of colloidal stability and the formation of microcrystalline cadmium metal deposits. We hypothesize that this results from the accumulation of electrons on the QD surface. In addition, we demonstrate mild surface sulfur oxidation and the formation of an ammonium salt byproduct of a commonly used hole quencher. Furthermore, this work adds to our atomic-level understanding of the reactions occurring at the QD surface during photocatalysis, so that we can design more stable and efficient photocatalysts for organic synthesis.

cadmium sulfide↗

Electrical and optical characterization of CdTe solar cells with CdS and CdSe buffers—A comparative study

A study is reported comparing the electrical and optical properties of CdTe solar cells, prepared using CdS and CdSe buffer layers, to investigate defects in the bulk and interface, carrier transport, and recombination. Temperature dependent capacitance-voltage measurement and admittance spectroscopy were used to extract carrier concentration, resistivity, charge carrier mobility, and their temperature dependence. We identify the presence of two defect signatures corresponding to carrier freeze-out and the formation of a Schottky back-contact barrier. The back-contact barrier height (≈ 300 meV) extracted from the temperature dependent current density-voltage (JVT) experiment was confirmed by conventional admittance spectroscopy. The activation energies of mobility (resistivity) are 101.2 ± 2.5 meV (92.6 ± 2.3 meV) and 84.7 ± 2.7 meV (77.6 ± 4.5 meV) for CdS and CdSe buffer layers, respectively. Intensity dependent photoluminescence analysis demonstrates that the CdSe/CdTe device exhibits lower radiative efficiency than the CdS/CdTe device. This confirms the presence of higher defects in CdSe/CdTe device corroborated by temperature-dependent V OC analysis. Here, the comparative electrical and optical analysis provides insight to improving the performance of CdTe solar cell device by selenization.

14 SOLAR ENERGY↗

Photovoltaic performance of Ag-doped CdS quantum dots for solar cell application

Graphical abstract: Photovoltaic performance of un-doped and Ag-doped CdS quantum dots were studied. The enhancement in photovoltaic performance might be due to the increase in carrier concentration and additional energy level creation due to Ag doping in FTO/TiO{sub 2}/Ag-doped CdS QDs solar cell. - Highlights: • Un-doped and Ag-doped CdS QDs were successfully deposited on TiO{sub 2}/FTO. • Optical response was found to be high for 3% Ag-doped CdS QDs. • The absorption edge for the 3% Ag-doped CdS was found to be 550 nm. • The highest power conversion efficiency was 1.25% for 3% Ag-doped CdS QDs. - Abstract: Un-doped and Ag-doped CdS quantum dots (QDs) were deposited on spin coated TiO{sub 2} photoanode material by Successive Ionic Layer Adsorption and Reaction (SILAR) method. Systematic investigations were carried out in the deposited un-doped and Ag-doped CdS QDs using powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FESEM) and UV–vis-NIR spectrum. Finally, the FTO/TiO{sub 2}/un-doped CdS and FTO/TiO{sub 2}/Ag-doped CdS QDs were successfully assembled to study the photovoltaic performance under standard one sun illumination of AM 1.5, 100 mW/cm{sup 2}. Photovoltaic parameters, such as short-circuit photocurrent density, open circuit voltage, fill factor and conversion efficiency were found to be 1.37 mA/cm{sup 2}, 0.72 V, 61.5% and 0.61% respectively, for un-doped CdS. Ag-doped CdS QDs shows enhanced photovoltaic parameters such as short-circuit photocurrent density, open circuit voltage, fill factor and conversion efficiency which were 2.35 mA cm{sup 2}, 0.74 V, 71.8% and 1.25% respectively.

36 MATERIALS SCIENCE↗

Synthesis of cuboid BiOCl nanosheets coupled with CdS quantum dots by region-selective deposition process with enhanced photocatalytic activity

Highlights: • Region-selective deposition process was adopted to prepare high-dispersed CdS QDs/BiOCl nanocomposites consisting of cuboid BiOCl nanosheets exposing (001) facet and CdS QDs with size of 5–10 nm. • The TGA was used as bridge linked the CdS QDs and BiOCl, which enables CdS QDs spread homogeneously on the (001) facet of BiOCl. • The optical absorption properties and charge transfer efficiency of CdS QDs/BiOCl nanocomposites are much improved owing to the widespread heterojunction between CdS QDs and BiOCl. • The photocatalytic degradation activities of CdS QDs/BiOCl composites are excellent for MO dyes and phenol contaminants under simulated solar and UV light, respectively. - Abstract: A facile region-selective deposition process was adopted to prepare high-dispersed CdS QDs on BiOCl nanosheets with the surface modification of thioglycollic acid (TGA). The samples were systematically characterized by XRD, SEM, TEM, HRTEM, EDS, XPS, UV–vis DRS, EIS and PL. The results indicate that CdS QDs with size of 5–10 nm dispersed uniformly on the surface of cuboid BiOCl nanosheets. The photocatalytic performance tests reveal that the CdS QDs-3%/BiOCl composite exhibits an excellent photocatalytic activity, which is over 4.0 and 4.8 times as high as pure BiOCl for methyl orange (MO) and phenol photodegradation rate under simulated solar light and UV light illumination, respectively. The enhanced photocatalytic performance of the CdS QDs/BiOCl composites should be attributed to the improved visible light absorption and the high migration efficiency of the photogenerated electron-holes due to the matched band gap and the widespread heterostructure between CdS QDs and BiOCl.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Amorphous MoS{sub x} on CdS nanorods for highly efficient photocatalytic hydrogen evolution

Loading cocatalyst on semiconductors was crucially necessary for improving the photocatalytic hydrogen evolution. Amorphous MoS{sub x} as a novel and noble metal-free cocatalyst was loaded on CdS nanorods by a simple photodeposition method. Efficient hydrogen evolution with amount of 15 mmol h{sup −1} g{sup −1} was observed over the MoS{sub x} modified CdS nanorods, which was about 6 times higher than that by using Pt as cocatalyst. Meanwhile, with MoS{sub x} cocatalyst, the efficiency of CdS nanorods was superior to that of CdS nanoparticles and bulk CdS. No deactivation could be observed in the efficiency of MoS{sub x} modified CdS nanorods under irradiation for successive 10 h. Further experimental results indicated that the efficient electrons transfer, low overpotential of hydrogen evolution and active S atoms over the MoS{sub x} modified CdS nanorods were responsible for the higher efficiency. Our results provided guidance for synthesizing noble metal-free materials as cocatalyst for photocatalytic hydrogen evolution. - Graphical abstract: Photodeposition of amorphous MoS{sub x} on CdS nanorods for highly efficient photocatalytic hydrogen evolution. - Highlights: • Amorphous MoSx cocatalyst was loaded on CdS NRs by a simple photodeposition. • MoS{sub x}/CdS NRs exhibited 6 times higher hydrogen evolution efficiency than Pt/CdS NRs. • The hydrogen evolution of MoS{sub x}/CdS NRs linearly increased with prolonging time. • Lower overpotential and efficient electron transfer were observed over MoS{sub x}/CdS NRs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular self-assembled designing and characterization of TiO2 NPs-CdS QDs-dye composite for photoanode materials

Highlights: • Initially TiO{sub 2} NPs were synthesized by sol-gel method and CdS QDs by one pot synthesis method. • The connectivity between TiO{sub 2} NPs and CdS QDs was well revealed by zeta potential and FTIR techniques. • This binary system was sensitized with N719 dye molecule for better photoanode material. • Ternary TiO{sub 2} NPs-CdS QDs-N719 dye photoanode showed higher conversion efficiency than its binary photoanode devices. - Abstract: Ternary based photoanodes have been prepared by using titanium dioxide (TiO{sub 2}) nanoparticles (NPs), cadmium sulfide (CdS) quantum dots (QDs) and N719 dye. Initially, CdS QDs and TiO{sub 2} NPs were synthesized by one pot synthesis and sol-gel method, respectively. CdS QDs were connected electrostatically to the surfaces of TiO{sub 2} NPs, and after that, this binary hybrid further self-assembled with N719 dye to form the composites. The NPs, QDs and the resultant composites are characterized by using different techniques. The connectivity of these anatase TiO{sub 2} NPs with cubic CdS QDs are confirmed by FTIR; while the broad coverage of these materials is studied through UV–Visible diffuse reflectance spectroscopy (DRS). The surface topology and the cross-sectional morphology of thin films are studied by high resolution transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM) techniques; while the structural properties of NPs and QDs are studied by X-ray diffractometer (XRD). The synergetic co-sensitization of CdS and N719 dye significantly enhancing the overall power conversion efficiency (η) of TiO{sub 2} up to 2.37% (J{sub sc} = 10.31 mA/cm{sup 2} and V{sub oc} of 550 mV) (100 mW/cm{sup 2}). The J{sub sc}, V{sub oc}, and η values along with Incident photon to current conversion efficiency (IPCE) value of ternary photoelectrode-based solar devices, is almost double to that of either binary TiO{sub 2} NPs-CdS QDs or binary TiO{sub 2} NPs-N719 binary systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Growth, microstructure, structural and optical properties of PVP-capped CdS nanoflowers for efficient photocatalytic activity of Rhodamine B

Highlights: • Synthesis of un-capped and PVP-capped CdS microstructures by Hydrothermal. • Growth of both the flower and dendrite microstructures controlled by the growth time. • Phase transition of CdS from cubic zinc blend to hexagonal by the growth time. • CdS flowers enhanced the photocatalytic performance of RhB under visible light. • PVP-capped CdS showed the highest degradation of 95% of RhB within 120 min. - Abstract: Size and structure tunability of polyvinyl pyrolidone (PVP) capped cadmium sulfide (PVP-capped CdS) flowers were synthesized by controlling the reaction time. XRD pattern indicated a phase transition from the cubic zinc blend to the hexagonal phase of CdS powder as the reaction time increased. As per the microstructure analysis with respect to the reaction time, the spherical nanoparticles were transformed in to the flower like morphology consisting of sword like nanorods and confirmed by the bright field images of TEM, while, HR-TEM images showed the uniform lattice spacing. UV-spectra exhibited a red shift due to the excitations of CdS nanoparticles. The near band edge (NBE) peak of PVP-capped CdS was completely diminished which indicated to sulphur vacancies on the surface of flowers. The photocatalytic activity of PVP-capped CdS flowers was detected the fast degradation of Rhodamine B (RhB) dye (95% for 120 min) by irradiation of visible light.

36 MATERIALS SCIENCE↗

Wet chemical synthesis of ZnO-CdS composites and their photocatalytic activity

Highlights: • ZnO-CdS composites were synthesized by wet chemical method. • TEM, correlated SAED pattern, XRD, and SEM confirmed the structure of composites. • CdS amount added during composites synthesis influences their morphologies. • RhB degradation efficiency is higher for composites than that of pristine ZnO, depending on the catalyst morphology. - Abstract: The present study is focused on the wet chemical synthesis and the characterization of ZnO-CdS composites. The X-ray diffraction shows that the composites contain ZnO in hexagonal wurtzite structure and CdS in cubic phase. The scanning/transmission electron microscopy images reveal flower-like structures with different sizes depending on the CdS content. The optical investigations on composites reveal that the reflectance spectra disclose two thresholds of ∼370 nm and ∼460 nm associated with the ZnO and CdS, respectively. The photocatalytic activity measurements evidenced that the degradation efficiency of RhB in the presence of composites is higher comparatively with pristine ZnO, depending on the catalyst morphology, which varies with CdS content and the pH value of RhB solution. The electron paramagnetic resonance revealed the presence of the paramagnetic point defects in the samples. Thus, the wet chemical approaches are suitable for a large scale production of such ZnO-CdS composites having enhanced photocatalytic activity.

36 MATERIALS SCIENCE↗

Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures

We report solar-to-fuel conversion reaction often requires multiple proton-coupled electron transfer (PCET) processes powered by the energetic electrons and/or holes generated by the absorption of multiple photons. The effective coupling of multiple electron transfer from the light absorber with the multiple PCET reactions at the catalytic center is one of the key challenges in efficient and selective conversion of solar energy to chemical fuels. In this paper, we examine the dynamics of multiple electron transfer in quantum confined CdS nanorods with a Pt tip, in which the CdS rod functions as the light absorber and the Pt tip the catalytic center. By excitation-fluence-dependent transient absorption spectroscopic measurements, we show that the multiexciton Auger recombination rate in CdS rods follows a carrier-collision model, k n A = n 2 (n – 1)/4k 2 A , with a biexciton lifetime (1/k 2 A ) of 2.0 ± 0.2 ns. In CdS–Pt nanorods, electron transfer kinetics from the CdS conduction band edge to the Pt show negligible dependence on the excitation fluence, occurring with a half-life time of 5.6 ± 0.6 ps. The efficiency of multiple exciton dissociation by multiple electron transfer to Pt decreases from 100% in biexciton states to ~41% at 22 exciton state due to the competition with Auger recombination. The half-lifetime of the n-charge separated state recombination (with n electrons in the Pt and n holes in the CdS) decreases from 10 μs in the single charge separated state to 42 ns in nine charge separated states. Our findings suggest the possibility of driving multielectron photocatalytic reactions under intense illumination and controlling product selectivity through multielectron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of oxygen doping on elemental intermixing at the PVD-CdS/Cu (InGa)Se 2 heterojunction

Elemental intermixing at the CdS/CuIn 1-x Ga x Se 2 (CIGS) heterojunction in thin-film photovoltaic devices plays a crucial role in carrier separation and thus device efficiency. Here, using scanning transmission electron microcopy in combination with energy dispersive X-ray mapping, we find that by controlling the oxygen in the sputtering gas during physical vapor deposition (PVD) of the CdS, we can tailor the degree of elemental intermixing. More oxygen suppresses Cu migration from the CIGS into the CdS, while facilitating Zn doping in the CdS from the ZnO transparent contact. Very high oxygen levels induce nanocrystallinity in the CdS, while moderate or no oxygen content can promote complete CdS epitaxy on the CIGS grains. Regions of cubic Cu 2 S phase were observed in the Cu-rich CdCuS when no oxygen is included in the CdS deposition process. In the process-of-record sample (moderate O 2 ) that exhibits the highest solar conversion efficiency, we observe a ~26-nm-thick Cu-deficient CIGS surface counter-doped with the highest Cd concentration among all of the samples. Cd movement into the CIGS was found to be less than 10 nm deep for samples with either high or zero O 2 . Lastly, the results are consistent with the expectation that Cd doping of the CIGS surface and lack of Zn diffusion into the buffer both enhance device performance.

14 SOLAR ENERGY↗

Nanomolar Sensitivity Chirality Transfer from Designed Helical Repeat Proteins to Achiral CdS Nanorods

Bridging chirality across length scales with inorganic− organic hybrid materials is a rapidly expanding area of research. Here, we establish asymmetry at CdS nanorod (NR) interfaces using a designed helical repeat protein bearing four cysteine residues (DHR- 4Cys). Hydrophobic NRs are transferred into water with glycine, and then glycine is displaced by DHR-4Cys, leveraging the thiophilicity of cadmium. Circular dichroism (CD) in the visible, coincident with CdS electronic transitions, reveals a chiral DHR-4Cys:CdS interface. Here, the dissymmetry factor [g-factor = 4.5 × 10 −4 (short NRs) and 5.0 × 10 −4 (long NRs)] is weakly dependent on the NR length, and CD persists at nanomolar protein loadings. Additionally, control experiments demonstrate that DHR-4Cys:CdS NR chirality is dictated by the local coordination of Cys with no significant contribution from the chiral secondary structure of the protein (g-factors of short and long Cys:CdS NRs are 4.8 × 10 −4 and 4.0 × 10 −4 , respectively). Together with far-UV CD and transmission electron microscopy, which provide evidence of preserved protein structure, these results provide the first demonstration that a structurally defined protein can induce chirality in CdS nanocrystals while maintaining protein structure at biologically relevant concentrations.

Cadmium sulfide↗