Enhanced Long-term and Thermal Stability of Polymer Solar Cells in Air at High Humidity with the Formation of Unusual Quantum Dot Networks.

Due to the practical applications of polymer solar cells (PSCs), their stability recently has received increasing attention. Herein, a new strategy was developed to largely enhance the long-term and thermal stability of PSCs in air with a relatively high humidity of 50-60% without any encapsulation. In this strategy, semiconductor PbS/CdS core/shell quantum dots (QDs) were incorporated into the photoactive blend of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM). By replacing the initial ligands of oleic acid with halide ligands on the surface of PbS/CdS QDs via solution-phase ligand exchange, we were able to form unusual, continuous QD networks in the film of P3HT:PCBM, which effectively stabilized the photoactive layer. Air-processed PSCs based on the stabilized P3HT:PCBM film showed excellent long-term stability under high humidity, providing over 3% of power conversion efficiency (PCE) simultaneously. Around 91% of pristine PCE was retained after 30 days storage in high-humidity air without encapsulation. This constitutes a remarkable improvement compared to ∼53% retained PCE for the QD-free devices, which can be ascribed to the efficient suppression of both PCBM aggregation and oxidation of the thiophene ring in P3HT, thanks to the formation of robust QD networks. Furthermore, the presence of QD networks was able to enhance the stability of the P3HT:PCBM film against thermal stress/oxidation under high-humidity environment (50-60%) as well. The device kept 60% of pristine PCE after thermal treatment for 12 h at 85 °C in air, which is more than twice higher than that for the QD-free device. To the best of our knowledge, the work represents the first unambiguous demonstration of the formation of QD networks in the photoactive layer and of their important contribution to the stability of PSCs. This strategy is highly promising for other fullerene-based PSCs and opens a new avenue toward achieving PSCs with high PCE and excellent stability.

Covellite CuS nanocrystals: realizing rapid microwave-assisted synthesis in air and unravelling the disappearance of their plasmon resonance after coupling with carbon nanotubes.

Semiconductor nanocrystals that show plasmonic resonance represent an emerging class of highly promising plasmonic materials with potential applications in diverse fields, such as sensing and optical and optoelectronic devices. We report a new approach to synthesizing homogeneous covellite CuS nanoplatelets in air and the almost complete disappearance of their plasmonic resonance once coupled with multiwalled carbon nanotubes (MWCNTs). These nanoplatelets were rapidly synthesized by a simple microwave-assisted approach at a relatively low reaction temperature in air, instead of under N2 as reported previously. These less severe synthesis conditions were enabled by appropriately selecting a Cu precursor and preparing a precursor sulfur solution (instead of using solid sulfur) and by using microwave radiation as the heat source. The advantages of utilizing microwave irradiation, including uniform and rapid heating, became clear after comparing the results of the synthesis with those achieved using a conventional oil-bath method under N2. The CuS nanoplatelets prepared in this way showed very strong plasmon resonance at c. 1160 nm as a result of their free charge carriers at the calculated density of nh = 1.5 × 10(22) cm(-3) based on the Drude model. With the aim of exploring their potential for near-infrared responsive optoelectronic devices, they were hybridized with functionalized MWCNTs. Their strong plasmon resonance almost completely disappeared on hybridization. Detailed investigations excluded the effect of possible structural changes in the CuS nanoplatelets during the hybridization process and a possible effect on the plasmon resonance arising from the chemical bonding of surface ligands. Charge transfer was considered to be the main reason for the almost complete disappearance of the plasmon resonance, which was further confirmed by terahertz (THz) time-domain spectrometry and THz time-resolved spectrometry measurements performed on the CuS-MWCNT nanohybrids. By extracting the rising and relaxation constants through fitting a single-exponential rising function and a bi-exponential relaxation function, in combination with the results of THz differential transmission as a function of the NIR pump fluence, it was found that hole injection changed the electronic properties of the MWCNTs only subtly on a short picosecond time scale, whereas the nature of the band structure of the MWCNTs remained largely unchanged. These findings aid our understanding of recently emerging semiconductor plasmonics and will also help in developing practical applications.

Quantum-Dot-Based Solar Cells: Recent Advances, Strategies, and Challenges.

Among next-generation photovoltaic systems requiring low cost and high efficiency, quantum dot (QD)-based solar cells stand out as a very promising candidate because of the unique and versatile characteristics of QDs. The past decade has already seen rapid conceptual and technological advances on various aspects of QD solar cells, and diverse opportunities, which QDs can offer, predict that there is still ample room for further development and breakthroughs. In this Perspective, we first review the attractive advantages of QDs, such as size-tunable band gaps and multiple exciton generation (MEG), beneficial to solar cell applications. We then analyze major strategies, which have been extensively explored and have largely contributed to the most recent and significant achievements in QD solar cells. Finally, their high potential and challenges are discussed. In particular, QD solar cells are considered to hold immense potential to overcome the theoretical efficiency limit of 31% for single-junction cells.

Towards high efficiency air-processed near-infrared responsive photovoltaics: bulk heterojunction solar cells based on PbS/CdS core-shell quantum dots and TiO2 nanorod arrays.

Near infrared (NIR) PbS quantum dots (QDs) have attracted significant research interest in solar cell applications as they offer several advantages, such as tunable band gaps, capability of absorbing NIR photons, low cost solution processability and high potential for multiple exciton generation. Nonetheless, reports on solar cells based on NIR PbS/CdS core-shell QDs, which are in general more stable and better passivated than PbS QDs and thus more promising for solar cell applications, remain very rare. Herein we report high efficiency bulk heterojunction QD solar cells involving hydrothermally grown TiO2 nanorod arrays and PbS/CdS core-shell QDs processed in air (except for a device thermal annealing step) with a photoresponse extended to wavelengths >1200 nm and with a power conversion efficiency (PCE) as high as 4.43%. This efficiency was achieved by introducing a thin, sputter-deposited, uniform TiO2 seed layer to improve the interface between the TiO2 nanorod arrays and the front electrode, by optimizing TiO2 nanorod length and by conducting QD annealing treatment to enhance charge carrier transport. It was found that the effect of the seed layer became more obvious when the TiO2 nanorods were longer. Although photocurrent did not change much, both open circuit voltage and fill factor clearly changed with TiO2 nanorod length. This was mainly attributed to the variation of charge transport and recombination processes, as evidenced by series and shunt resistance studies. The optimal PCE was obtained at the nanorod length of ∼450 nm. Annealing is shown to further increase the PCE by ∼18%, because of the improvement of charge carrier transport in the devices as evidenced by considerably increased photocurrent. Our results clearly demonstrate the potential of the PbS/CdS core-shell QDs for the achievement of high PCE, solution processable and NIR responsive QD solar cells.

Semiconductor and metallic core-shell nanostructures: synthesis and applications in solar cells and catalysis.

Nano-heterostructures have attracted great attention due to their extraordinary properties beyond those of their single-component counterparts. This review focuses on a specific type of hybrid structures: core-shell structures. In particular, we present and discuss the recent wet-chemical synthesis approaches for semiconductor and metallic core-shell nanostructures, and their relevant properties and potential applications in photovoltaics and catalysis, respectively.

Hollow and concave nanoparticles via preferential oxidation of the core in colloidal core/shell nanocrystals.

Hollow and concave nanocrystals find applications in many fields, and their fabrication can follow different possible mechanisms. We report a new route to these nanostructures that exploits the oxidation of Cu(2-x)Se/Cu(2-x)S core/shell nanocrystals with various etchants. Even though the Cu(2-x)Se core is encased in a thick Cu(2-x)S shell, the initial effect of oxidation is the creation of a void in the core. This is rationalized in terms of diffusion of Cu(+) ions and electrons from the core to the shell (and from there to the solution). Differently from the classical Kirkendall effect, which entails an imbalance between in-diffusion and out-diffusion of two different species across an interface, the present mechanism can be considered as a limiting case of such effect and is triggered by the stronger tendency of Cu(2-x)Se over Cu(2-x)S toward oxidation and by fast Cu(+) diffusion in copper chalcogenides. As the oxidation progresses, expansion of the inner void erodes the entire Cu(2-x)Se core, accompanied by etching and partial collapse of the shell, yielding Cu(2-x)S(y)Se(1-y) concave particles.

Charge separation in Pt-decorated CdSe@CdS octapod nanocrystals.

We synthesize colloidal CdSe@CdS octapod nanocrystals decorated with Pt domains, resulting in a metal-semiconductor heterostructure. We devise a protocol to control the growth of Pt on the CdS surface, realizing both a selective tipping and a non-selective coverage. Ultrafast optical spectroscopy, particularly femtosecond transient absorption, is employed to correlate the dynamics of optical excitations with the nanocrystal morphology. We find two regimes for capture of photoexcited electrons by Pt domains: a slow capture after energy relaxation in the semiconductor, occurring in tipped nanocrystals and resulting in large spatial separation of charges, and an ultrafast capture of hot electrons occurring in nanocrystals covered in Pt, where charge separation happens faster than energy relaxation and Auger recombination. Besides the relevance for fundamental materials science and control at the nanoscale, our nanocrystals may be employed in solar photocatalysis.

Influence of chloride ions on the synthesis of colloidal branched CdSe/CdS nanocrystals by seeded growth.

We studied the influence of chloride ions (Cl(-)), introduced as CdCl(2), on the seeded growth synthesis of colloidal branched CdSe(core)/CdS(pods) nanocrystals. This is carried out by growing wurtzite CdS pods on top of preformed octahedral sphalerite CdSe seeds. When no CdCl(2) is added, the synthesis of multipods has a low reproducibility, and the side nucleation of CdS nanorods is often observed. At a suitable concentration of CdCl(2), octapods are formed and they are stable in solution during the synthesis. Our experiments indicate that Cl(-) ions introduced in the reaction reduce the availability of Cd(2+) ions in solution, most likely via formation of strong complexes with both Cd and the various surfactants. This prevents homogeneous nucleation of CdS nanocrystals, so that the heterogeneous nucleation of CdS pods on top of the CdSe seeds is the preferred process. Once such optimal concentration of CdCl(2) is set for a stable growth of octapods, the pod lengths can be tuned by varying the relative ratios of the various alkyl phosphonic acids used. Furthermore, at higher concentrations of CdCl(2) added, octapods are initially formed, but many of them evolve into tetrapods over time. This transformation points to an additional role of Cl species in regulating the growth rate and stability of various crystal facets of the CdS pods.

Cation exchange reactions in colloidal branched nanocrystals.

Octapod-shaped colloidal nanocrystals composed of a central "core" region of cubic sphalerite CdSe and pods of hexagonal wurtzite CdS are subject to a cation exchange reaction in which Cd(2+) ions are progressively exchanged by Cu(+) ions. The reaction starts from the tip regions of the CdS pods and proceeds toward the center of the nanocrystals. It preserves both the shape and the anionic lattices of the heterostructures. During the exchange, the hexagonal wurtzite CdS pods are converted gradually into pods of hexagonal Cu(2)S chalcocite. Therefore, the partial cation exchange reactions lead to the formation of a ternary nanostructure, consisting of an octapod in which the central core is still CdSe, while the pods have a segmented CdS/Cu(2)S composition. When the cation exchange reaches the core, the cubic sphalerite CdSe core is converted into a core of cubic Cu(2-x)Se berzelianite phase. Therefore fully exchanged octapods are composed of a core of Cu(2-x)Se and eight pods of Cu(2)S. All these structures are stable, and the epitaxial interfaces between the various domains are characterized by low lattice mismatch. The Cu(2-x)Se(core)/Cu(2)S(pods) octapod represents another example of a nanostructure in which branching is achieved by proper organization of cubic and hexagonal domains in a single nanocrystal.

Reversible tunability of the near-infrared valence band plasmon resonance in Cu(2-x)Se nanocrystals.

We demonstrate that colloidal Cu(2-x)Se nanocrystals exhibit a well-defined infrared absorption band due to the excitation of positive charge carrier oscillations (i.e., a valence band plasmon mode), which can be tuned reversibly in width and position by varying the copper stoichiometry. The value of x could be incrementally varied from 0 (no plasmon absorption, then a broad peak at 1700 nm) to 0.4 (narrow plasmon band at 1100 nm) by oxidizing Cu(2)Se nanocrystals (upon exposure either to oxygen or to a Ce(IV) complex), and it could be incrementally restored back to zero by the addition of a Cu(I) complex. The experimentally observed plasmonic behavior is in good agreement with calculations based on the electrostatic approximation.

Fabrication, spectroscopy, and dynamics of highly luminescent core-shell InP@ZnSe quantum dots.

InP quantum dots of 3 nm in diameter have been prepared using a dehalosilylation reaction and passivated with ZnSe to enhance photoluminescence by 6.8 times. Core-shell InP@ZnSe quantum dots dispersed in n-hexane have then been investigated using time-resolved spectroscopy to understand their photoluminescence dynamics. The observed decay times of 0.1, 7, and 1100 ns have been attributed to the relaxation times of electrons in the conduction band, trap sites, and surface states. The surface-state luminescence of core-shell InP@ZnSe quantum dots having the maximum at 760 nm has been distinguished spectrally and dynamically from their band-edge emission having the maximum at 620 nm or from their trap-site emission having the maximum at 660 nm.

Nanopattern transfer and wettability modification of regularly structured metallic and polymeric surfaces with replication.

The hexagonally arranged close-packed concave nanotexture of the master surface of nanoporous alumina has been imprinted several times on aluminum films and gold films by thermal evaporation and on polystyrene films by spin coating. The degradation of the nanotextures with replica pattern transfer has been monitored by measuring the topology and the wettability of duplicated films. The trough-to-crest height of the topography decreases while the wettability of the nanotexture increases significantly as replication goes on. Air fractions calculated with measured water contact angles decrease substantially with replication although they also depend strongly on the materials and the shapes of duplicating nanotextures.

Spectroscopy and dynamics of Mn(2+) in ZnS nanoparticles.

Both spectra of transient absorption (lambda(max) = 390 nm) and luminescence (lambda(max) = 590 nm) for the (4)T(1) state of Mn(2+) in ZnS nanoparticles shift to long wavelengths by 40 nm and broaden by 1.7 times as the state becomes banded. The (4)T(1) band of capping Mn(2+) in ZnS nanoparticles decays on the time scale of 0.35 mus, which is much shorter than either the decay time of the (4)T(1) state (2000 micros) for lattice-bound isolated Mn(2+) or that (180 micros) for surface-bound isolated Mn(2+) in ZnS nanoparticles.

One-step fabrication of well-defined hollow CdS nanoboxes.

Hollow CdS nanoboxes, having paper-thin walls of well-defined facets, were synthesized at 170 degrees C via a simple reaction using Na(2)SeO(3) for interior quasitemplates and ethylenediamine for exterior molecular templates.

Shape transformation and relaxation dynamics of photoexcited TiO2/Ag nanocomposites.

The laser-induced sintering of TiO2 nanoparticles into larger nanospheres is accelerated by adsorbed silver particles. For the same weight fraction of silver, silver nanoparticles of 5 nm in diameter modify TiO2 nanoparticles more effectively than those of 1.5 nm do, suggesting that the photocatalysis of TiO2 nanoparticles as well as their stability is highly dependent on the sizes, the shapes, and the distribution of adsorbed metal nanoparticles. The photoexcited electrons of TiO2 nanoparticles are quenched at trap sites and surface states by transfer to the conduction band of silver, implying that the presence of adsorbed silver nanoparticles enhances the photocatalytic effect of TiO2.

Preparation and characterization of titania/ZnS core-shell nanotubes.

Core-shell nanocomposites of titania nanotubes/ZnS quantum dots have been prepared by using a hydrothermal synthetic method and characterized by using various microscopic and spectroscopic methods. ZnS quantum dots surround the outsides of titania nanotubes having the inner and the outer diameters of 15 and 30 nm, respectively, with a thickness of 2 nm. The nanocomposites suspended in water show a broader absorption spectrum shifted to a longer wavelength by 20 nm and emit substantially stronger ZnS luminescence having significantly slower decay kinetics than bare ZnS nanoparticles in water. The support of TiO2 nanotubes is found to enhance the optical properties of ZnS considerably.