Rescaling of metal oxide nanocrystals for energy storage having high capacitance and energy density with robust cycle life.

Nanocrystals are promising structures, but they are too large for achieving maximum energy storage performance. We show that rescaling 3-nm particles through lithiation followed by delithiation leads to high-performance energy storage by realizing high capacitance close to the theoretical capacitance available via ion-to-atom redox reactions. Reactive force-field (ReaxFF) molecular dynamics simulations support the conclusion that Li atoms react with nickel oxide nanocrystals (NiO-n) to form lithiated core-shell structures (Ni:Li2O), whereas subsequent delithiation causes Ni:Li2O to form atomic clusters of NiO-a. This is consistent with in situ X-ray photoelectron and optical spectroscopy results showing that Ni(2+) of the nanocrystal changes during lithiation-delithiation through Ni(0) and back to Ni(2+). These processes are also demonstrated to provide a generic route to rescale another metal oxide. Furthermore, assembling NiO-a into the positive electrode of an asymmetric device enables extraction of full capacitance for a counter negative electrode, giving high energy density in addition to robust capacitance retention over 100,000 cycles.

Enhancing the efficiency of solution-processed polymer:colloidal nanocrystal hybrid photovoltaic cells using ethanedithiol treatment.

Advances in colloidal inorganic nanocrystal synthesis and processing have led to the demonstration of organic-inorganic hybrid photovoltaic (PV) cells using low-cost solution processes from blends of conjugated polymer and colloidal nanocrystals. However, the performance of such hybrid PV cells has been limited due to the lack of control at the complex interfaces between the organic and inorganic hybrid active materials. Here we show that the efficiency of hybrid PV devices can be significantly enhanced by engineering the polymer-nanocrystal interface with proper chemical treatment. Using two different conjugated polymers, poly(3-hexylthiophene) (P3HT) and poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), we show that treating the polymer:nanocrystal hybrid film in an ethanedithiol-containing acetonitrile solution can increase the efficiency of the hybrid PV devices by 30-90%, and a maximum power conversion efficiency of 5.2 ± 0.3% was obtained in the PCPDTBT:CdSe devices at 0.2 sun (AM 1.5G), which was slightly reduced to 4.7 ± 0.3% at 1 sun. The ethanedithiol treatment did not result in significant changes in the morphology and UV-vis optical absorption of the hybrid thin films; however, infrared absorption, NMR, and X-ray photoelectron spectroscopies revealed the effective removal of organic ligands, especially the charged phosphonic acid ligands, from the CdSe nanorod surface after the treatment, accompanied by the possible monolayer passivation of nanorod surfaces with Cd-thiolates. We attribute the hybrid PV cell efficiency increase upon the ethanedithiol treatment to the reduction in charge and exciton recombination sites on the nanocrystal surface and the simultaneous increase in electron transport through the hybrid film.

Solution-processed, nanostructured hybrid solar cells with broad spectral sensitivity and stability.

Hybrid organic-inorganic solar cells, as an alternative to all-organic solar cells, have received significant attention for their potential advantages in combining the solution-processability and versatility of organic materials with high charge mobility and environmental stability of inorganic semiconductors. Here we report efficient and air-stable hybrid organic-inorganic solar cells with broad spectral sensitivity based on a low-gap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and spherical CdSe nanoparticles. The solvents used for depositing the hybrid PCPDTBT:CdSe active layer were shown to strongly influence the film morphology, and subsequently the photovoltaic performance of the resulted solar cells. Appropriate post-deposition annealing of the hybrid film was also shown to improve the solar cell efficiency. The inclusion of a thin ZnO nanoparticle layer between the active layer and the metal cathode leads to a significant increase in device efficiency especially at long wavelengths, due to a combination of optical and electronic effects including more optimal light absorption in the active layer and elimination of unwanted hole leakage into the cathode. Overall, maximum power conversion efficiencies up to 3.7 ± 0.2% and spectral sensitivity extending above 800 nm were achieved in such PCPDTBT:CdSe nanosphere hybrid solar cells. Furthermore, the devices with a ZnO nanoparticle layer retained ∼70% of the original efficiency after storage under ambient laboratory conditions for over 60 days without any encapsulation.

Hybrid polymer-nanocrystal materials for photovoltaic applications.

Hybrid polymer-nanocrystal photovoltaic (PV) cells have received much attention during the past decade as promising low-cost solar energy harvesting devices, and showed significant progress with power conversion efficiency reaching 5% recently. This review starts from the introduction of hybrid materials to their application in electronic devices, with particular focus on bulk-heterojunction hybrid polymer-nanocrystal PV devices. The synthesis, surface chemistry, and electronic properties of colloidal inorganic nanocrystals are described. The recent development of hybrid PV devices will be discussed from the perspective of tailoring both inorganic nanocrystals and conjugated polymers, controlling polymer-nanocrystal hybrid morphology, engineering polymer-nanocrystal interface, and optimizing device architecture. Finally, future directions for further advancing hybrid PV technology to potential commercialization are also discussed.

Blending of HAuCl4 and histidine in aqueous solution: a simple approach to the Au10 cluster.

Water-soluble, monodispersed, and bluish green-emitting Au(10) nanoclusters were synthesized through a simple reaction, in which histidine served as both a reducing agent and a protecting ligand. UV-visible absorption, photoluminescence, electrospray ionization (ESI) mass spectrometry, and X-ray photoelectron spectroscopy (XPS) were carried out to demonstrate the chemical composition and optical properties of the Au(10) clusters. The mechanism of this proposed reaction was explored and the reducing ability of histidine was proved from its imidazole group. Finally, the fluorescence of Au NCs at different reaction times, pH value, and temperature was measured in situ. Then a synthetic strategy was proposed for gold nanoclusters with a defined chemical composition, and the resulting Au(10) clusters stabilized by histidine are biocompatible with bioorganisms, showing a great potential for applications such as biological labeling and biosensors.

Solvent-dependent fluorescence property of multi-walled carbon nanotubes noncovalently functionalized by pyrene-derivatized polymer.

Multi-walled carbon nanotubes (MWCNTs) were supramolecularly functionalized by pyrene-derivatized hydrolyzed poly(styrene-co-maleic anhydride) (pyrene-HSMA) in aqueous solution. The MWCNTs/pyrene-HSMA conjugates were found to exhibit a solvent-dependent fluorescence property by photoluminescence measurements. The fluorescence intensity of the MWCNTs/pyrene-HSMA conjugate was used as a probe to estimate the interaction between polymer and MWCNTs in solvents. The polymer conformation around the MWCNTs was demonstrated by atomic force microscopy. We suggested that pyrene-HSMA functionalized MWCNTs in a non-wrapping mode, and that the conformation change of the polymer around the MWCNTs resulted in the solvent-dependent fluorescence property. The dispersion state of the MWCNTs/pyrene-HSMA conjugate in various solvents was also investigated by transmission electron microscopy. The fluorescence responses of the MWCNTs/pyrene-HSMA conjugate to pH value and temperature were studied as well.

Atomically monodispersed and fluorescent sub-nanometer gold clusters created by biomolecule-assisted etching of nanometer-sized gold particles and rods.

Atomically monodispersed gold clusters were synthesized by etching gold nanocrystals (particles and rods) with the assistance of biomolecules (amino acids, peptides, proteins, and DNA) under sonication in water. The resulting gold clusters were exclusively composed of eight atoms, as demonstrated by photoluminescence, optical absorption, electrospray ionization mass spectrometry, and transmission electron microscopy measurements. The gold clusters exhibited solvent-dependent photoluminescence properties when exposed to organic solvents, such as chloroform, tetrahydrofuran, or N,N-dimethylformamide, which was attributed to the rich surface properties of the clusters. This strategy, based on top-down etching, offers an approach to create metal clusters from nanomaterials, which show great potential applications in biological labeling/imaging and sensors that utilize photoluminescence properties as the response.

The preparation of highly water-soluble multi-walled carbon nanotubes by irreversible noncovalent functionalization with a pyrene-carrying polymer.

Multi-walled carbon nanotubes (MWNTs) have been solubilized in water via a noncovalent method of exfoliation and centrifugation cycles with the assistance of hydrolyzed poly(styrene-co-maleic anhydride) carrying pyrene (HPSMAP). After the obtained solution was micro-filtered and dried, a water-soluble complex of HPSMAP-MWNTs was obtained. The solubility of HPSMAP-MWNTs was measured to be 46.2 mg ml(-1) with a net MWNT concentration of 7.4 mg ml(-1) in water. Thermal gravimetric analyses showed that there was a large amount of polymer remaining on the surface of MWNTs irreversibly after thoroughly removing the free polymer. Other characterizations using transmission electron microscopy, Fourier transform infrared (FTIR) spectroscopy, fluorescence spectra, and fluorescence decay were conducted.

Well-defined nanoarrays from an n-type organic perylene-diimide derivative for photoconductive devices.

Well-defined one-dimensional (1D) perylene-diimide derivative (PDD) nanowire arrays were prepared via a simple electrophoretic deposition method by using anodic aluminum oxide (AAO) templates. The morphology of the as-deposited films was characterized by field emission scanning electron microscope and transmission electron microscopy. The highly ordered nanoarrays were free-standing after removing the AAO supports. Further studies revealed that the growth process of the nanowires in the AAO pores followed a 'bottom-up' growth model. A photoreceptor with PDD nanowire arrays as the charge generation layer was fabricated. It exhibited a better photoconductivity under light illumination when compared to that of its bulk counterpart. Our results suggested that electron-accepting PDD nanowire arrays can be used as a potential candidate for photoconduction devices, which would facilitate further exploration of new technological applications of the photoimaging process.

A green route to water soluble carbon nanotubes and in situ loading of silver nanoparticles.

A green approach has been developed to synthesize water soluble multi-walled carbon nanotubes (MWNTs). Ag nanoparticles have been loaded on the as-synthesized MWNTs via the in situ solution method. The strategy is based on the introduction of hydroxyl and carboxyl groups through a mild modification of MWNTs via polycondensation of citric acid and D-sorbitol, improving the water solubility of MWNTs, giving rise to preferred sites of Ag nucleation, and providing mild in situ reducing agents. The modification of MWNTs and loading of Ag nanoparticles on MWNTs were demonstrated by Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, and scanning electron microscopy.