Harnessing the Synergetic Effects of Ag, Mn Dopants in Eco-Friendly Ultraviolet Selective Quantum Dots for Luminescent Solar Concentrators.

Quantum dots (QDs) are promising building blocks for luminescent solar concentrators (LSCs), yet most QD-based LSCs suffer from toxic metal composition and color tinting. UV-selective harvesting QDs can enable visible transparency, but their development is restricted by large reabsorption losses and low photoluminescence quantum yield (PLQY). The developed here Ag, Mn: ZnInS2/ZnS QDs show a high PLQY of 53% due to the passivating effect of ZnS shell. These QDs selectively absorb UV light and emit orange-red light with a large Stokes shift of 180 nm. A LSC of 5 × 5 × 0.2 cm3, fabricated using a poly(lauryl methacrylate) (PLMA) as a matrix, maintains 87% of integrated PL after 7 h of UV exposure. The QD-PLMA achieved 90.7% average visible transparency (AVT) and a color rendering index (CRI) of 95.8, which is close to plain PLMA (AVT = 90.8%; CRI = 99.5), yielding excellent visible light transparency. Incorporating Si-PVs at LSC edges, the Ag, Mn: ZIS/ZnS QD-LSC achieved an optical efficiency of 1.42%, ranking competitively among high-performing UV-harvesting LSCs.

Highly bright solid-state carbon dots for efficient anticounterfeiting.

Carbon dots (C-dots) as promising fluorescent materials have attracted much attention because of their low toxicity and excellent optoelectronic properties. However, the aggregation-caused quenching (ACQ) of the solid-state C-dots has limited their potential applications in anti-counterfeiting and optoelectronic devices. In this work, C-dot powder was prepared by directly dispersing the as-prepared C-dots in a polymer matrix or in situ formation of the C-dot/Ca-complex by vacuum heating in the presence of boric acid. The as-prepared C-dots have high quantum yields (QYs) in the range of 40-67% with temperature-dependent photoluminescent (PL) properties. As a proof of concept, the as-synthesized C-dots were used to produce a flexible anti-counterfeiting code and showed high-level security. This highlights the potential of C-dots in solid-state information, anti-information encryption and anti-counterfeiting.

Rational Control of Near-Infrared Colloidal Thick-Shell Eco-Friendly Quantum Dots for Solar Energy Conversion.

Thick-shell colloidal quantum dots (QDs) are promising building blocks for solar technologies due to their size/composition/shape-tunable properties. However, most well-performed thick-shell QDs suffer from frequent use of toxic metal elements including Pb and Cd, and inadequate light absorption in the visible and near-infrared (NIR) region due to the wide bandgap of the shell. In this work, eco-friendly AgInSe2 /AgInS2 core/shell QDs, which are optically active in the NIR region and are suitable candidates to fabricate devices for solar energy conversion, are developed. Direct synthesis suffers from simultaneously controlling the reactivity of multiple precursors, instead, a template-assisted cation exchange method is used. By modulating the monolayer growth of template QDs, gradient AgInSeS shell layers are incorporated into AgInSe2 /AgInS2 QDs. The resulting AgInSe2 /AgInSeS/AgInS2 exhibits better charge transfer than AgInSe2 /AgInS2 due to their favorable electronic band alignment, as predicted by first-principle calculations and confirmed by transient fluorescence spectroscopy. The photoelectrochemical cells fabricated with AgInSe2 /AgInSeS/AgInS2 QDs present ≈1.5-fold higher current density and better stability compared to AgInSe2 /AgInS2 . The findings define a promising approach toward multinary QDs and pave the way for engineering the QDs' electronic band structures for solar-energy conversion.

Surface engineering of two-dimensional hexagonal boron-nitride for optoelectronic devices.

Two-dimensional hexagonal boron nitride (2D h-BN) is being extensively studied in optoelectronic devices due to its electronic and photonic properties. However, the controlled optimization of h-BN's insulating properties is necessary to fully explore its potential in energy conversion and storage devices. In this work, we engineered the surface of h-BN nanoflakes via one-step in situ chemical functionalization using a liquid-phase exfoliation approach. The functionalized h-BN (F-h-BN) nanoflakes were subsequently dispersed on the surface of TiO2 to tune the TiO2/QDs interface of the optoelectronic device. The photoelectrochemical (PEC) devices based on TiO2/F-h-BN/QDs with optimized addition of carbon nanotubes (CNTs) and scattering layers showed 46% improvement compared to the control device (TiO2/QDs). This significant improvement is attributed to the reduced trap/carrier recombination and enhanced carrier injection rate of the TiO2-CNTs/F-h-BN/QDs photoanode. Furthermore, by employing an optimized TiO2-CNTs/F-h-BN/QDs photoanode, QDs-sensitized solar cells (QDSCs) yield an 18% improvement in photoconversion efficiency. This represents a potential and adaptability of our approach, and pathway to explore surface-engineered 2D materials to optimize the interface of solar energy conversion and other emerging optoelectronic devices.

Efficient Photoelectrochemical Hydrogen Generation Using Eco-Friendly "Giant" InP/ZnSe Core/Shell Quantum Dots.

InP quantum dots (QDs) are promising building blocks for use in solar technologies because of their low intrinsic toxicity, narrow bandgap, large absorption coefficient, and low-cost solution synthesis. However, the high surface trap density of InP QDs reduces their energy conversion efficiency and degrades their long-term stability. Encapsulating InP QDs into a wider bandgap shell is desirable to eliminate surface traps and improve optoelectronic properties. Here, we report the synthesis of "giant" InP/ZnSe core/shell QDs with tunable ZnSe shell thickness to investigate the effect of the shell thickness on the optoelectronic properties and the photoelectrochemical (PEC) performance for hydrogen generation. The optical results demonstrate that ZnSe shell growth (0.9-2.8 nm) facilitates the delocalization of electrons and holes into the shell region. The ZnSe shell simultaneously acts as a passivation layer to protect the surface of InP QDs and as a spatial tunneling barrier to extract photoexcited electrons and holes. Thus, engineering the ZnSe shell thickness is crucial for the photoexcited electrons and hole transfer dynamics to tune the optoelectronic properties of "giant" InP/ZnSe core/shell QDs. We obtained an outstanding photocurrent density of 6.2 mA cm-1 for an optimal ZnSe shell thickness of 1.6 nm, which is 288% higher than the values achieved from bare InP QD-based PEC cells. Understanding the effect of shell thickness on surface passivation and carrier dynamics offers fundamental insights into the suitable design and realization of eco-friendly InP-based "giant" core/shell QDs toward improving device performance.

Electrophoretic deposition of collagen/chitosan films with copper-doped phosphate glasses for orthopaedic implants.

Coatings with bioactive properties play a key role in the success of orthopaedic implants. Recent studies focused on composite coatings incorporating biocompatible elements that can increase the nucleation of hydroxyapatite (HA), the mineral component of bone, and have promising bioactive and biodegradable properties. Here we report a method of fabricating composite collagen, chitosan and copper-doped phosphate glass (PG) coatings for biomedical applications using electrophoretic deposition (EPD). The use of collagen and chitosan (CTS) allows for the co-deposition of PG particles at standard ambient temperature and pressure (1 kPa, 25 °C), and the addition of collagen led to the steric stabilization of PG in solution. The coating composition was varied by altering the collagen/CTS concentrations in the solutions, as well as depositing PG with 0, 5 and 10 mol% CuO dopant. A monolayer of collagen/CTS containing PG was obtained on stainless steel cathodes, showing that deposition of PG in conjunction with a polymer is feasible. The mass of the monolayer varied depending on the polymer (collagen, CTS and collagen/CTS) and combination of polymer + PG (collagen-PG, CTS-PG and collagen/CTS-PG), while the presence of copper led to agglomerates during deposition at higher concentrations. The deposition yield was studied at different time points and showed a profile typical of constant voltage deposition. Increasing the concentration of collagen in the PG solution allows for a higher deposition yield, while pure collagen solutions resulted in hydrogen gas evolution at the cathode. The ability to deposit polymer-PG coatings that can mimic native bone tissue allows for the potential to fabricate orthopaedic implants with tailored biological properties with lower risk of rejection from the host and exhibit increased bioactivity.

Stand-Alone CuFeSe2 (Eskebornite) Nanosheets for Photothermal Cancer Therapy.

Two-dimensional CuFeSe2 nanosheets have been successfully obtained via solution-phase synthesis using a sacrificial template method. The high purity was confirmed by X-ray diffraction and the two-dimensional morphology was validated by transmission electron microscopy. The intense absorption in the 400-1400 nm region has been the basis for the CuFeSe2 nanosheets' photothermal capabilities testing. The colloidal CuFeSe2 (CFS) nanosheets capped with S2- short ligands (CFS-S) exhibit excellent biocompatibility in cell culture studies and strong photothermal effects upon 808 nm laser irradiation. The nanosheets were further loaded with the cancer drug doxorubicin and exposed to laser irradiation, which accelerated the release of doxorubicin, achieving synergy in the therapeutic effect.

Synergistic Effect of Plasmonic Gold Nanoparticles Decorated Carbon Nanotubes in Quantum Dots/TiO2 for Optoelectronic Devices.

Here, a facile approach to enhance the performance of solar-driven photoelectrochemical (PEC) water splitting is described by means of the synergistic effects of a hybrid network of plasmonic Au nanoparticles (NPs) decorated on multiwalled carbon nanotubes (CNTs). The device based on TiO2-Au:CNTs hybrid network sensitized with colloidal CdSe/(CdSe x S1- x )5/(CdS)1 core/alloyed shell quantum dots (QDs) yields a saturated photocurrent density of 16.10 ± 0.10 mA cm-2 [at 1.0 V vs reversible hydrogen electrode (RHE)] under 1 sun illumination (AM 1.5G, 100 mW cm-2), which is ≈26% higher than the control device. The in-depth mechanism behind this significant improvement is revealed through a combined experimental and theoretical analysis for QDs/TiO2-Au:CNTs hybrid network and demonstrates the multifaceted impact of plasmonic Au NPs and CNTs: i) hot-electron injection from Au NPs into CNTs and TiO2; ii) near-field enhancement of the QDs absorption and carrier generation/separation processes by the plasmonic Au NPs; iii) enhanced photoinjected electron transport due to the highly directional pathways offered by CNTs. These results provide fundamental insights on the properties of QDs/TiO2-Au:CNTs hybrid network, and highlights the possibility to improve the performance of other solar technologies.

Synthesis and optoelectronic properties of Cu3VSe4 nanocrystals.

The ternary chalcogenide Cu3VSe4 (CVSe) with sulvanite structure has been theoretically predicted to be a promising candidate for photovoltaic applications due to its suitable bandgap for solar absorption and the relatively earth-abundant elements in its composition. To realize the absorber layer via an inexpensive route, printed thin-films could be fabricated from dispersions of nano-sized Cu3VSe4 precursors. Herein, cubic Cu3VSe4 nanocrystals were successfully synthesized via a hot-injection method. Similar with reported Cu3VS4 nanocrystals, Cu3VSe4 nanocrystals with cubic structure exhibit three absorption bands in the UV-Visible range indicative of a potential intermediate bandgap existence. A thin film fabricated by depositing the nanoparticles Cu3VSe4 on FTO coated glass substrate, exhibited a p-type behavior and a photocurrent of ~ 4 µA/cm2 when measured in an electrochemical cell setting. This first demonstration of photocurrent exhibited by a CVSe nanocrystals thin film signifies a promising potential in photovoltaic applications.

A colloidal heterostructured quantum dot sensitized carbon nanotube-TiO2 hybrid photoanode for high efficiency hydrogen generation.

Solar-driven photoelectrochemical (PEC) hydrogen (H2) generation is a promising approach to harvest solar energy for the production of a clean chemical fuel. However, the low photon-to-fuel conversion efficiency and long-term stability of PEC devices are major challenges to be addressed to enable large-scale commercialization. Here we report a simple, fast and cost-effective approach to fabricate high efficiency and stable PEC devices for H2 generation, by fabricating a hybrid photoanode obtained by incorporating small amounts of multiwall carbon nanotubes (MWCNTs) into a TiO2 mesoporous film and sensitizing with colloidal heterostructured CdSe/(CdSexS1-x)5/(CdS)2 quantum dots (QDs). The latter were specially designed to accelerate the exciton separation through a band engineering approach. The PEC devices based on the TiO2/QD-MWCNT (T/Q-M) hybrid photoanode with an optimized amount of MWCNTs (0.015 wt%) yield a saturated photocurrent density of 15.90 mA cm-2 (at 1.0 VRHE) under one sun illumination (AM 1.5G, 100 mW cm-2), which is 40% higher than that of the reference device based on TiO2/QD (T/Q) photoanodes. This is attributed to a synergistic effect of the promising optoelectronic properties of the colloidal heterostructured QDs and improved electron transport (reduced charge transfer resistance) within the TiO2-MWCNT hybrid anodes enabled by the directional path of MWCNTs for the photo-injected electrons towards FTO. Furthermore, the PEC device based on the T/Q-M hybrid photoanode is more stable (∼19% loss of its initial photocurrent density) when compared with the T/Q photoanode (∼35% loss) after two hours of continuous one sun illumination. Our results provide fundamental insights and a different approach to improve the efficiency and long-term stability of PEC devices and represent an essential step towards the commercialization of this emerging solar-to-fuel conversion technology.

Towards Long-Term Thermal Stability of Dye-Sensitized Solar Cells Using Multiwalled Carbon Nanotubes.

In this study, the effect of incorporating multiwalled carbon nanotubes (MWCNTs) on the thermal stability of dye-sensitized solar cells (DSSCs) was investigated. Under identical measurement conditions (aging at 80 °C for 240 h), DSSCs based on a bare TiO2 anode presented a significant loss in photoconversion efficiency (PCE), dropping to 59 % of their initial value, whereas the DSSCs based on a TiO2 -MWCNT nanocomposite anode attained a promising thermal stability with only 20 % loss of PCE. This degradation of cell performance is mainly associated with a dramatic reduction in the short-circuit current density (Jsc ). To understand the mechanisms that underpin these changes in device performance under thermal stress, both types of cells were investigated using various techniques. The incorporation of MWCNTs could eliminate the formation of cracks and improve electron charge transfer. The results of this study indicate a promising new method to enhance the thermal stability of DSSCs using a nanocomposite anode made of one-dimensional carbon materials.

Dye-sensitized solar cells based on a push-pull zinc phthalocyanine bearing diphenylamine donor groups: computational predictions face experimental reality.

Computational studies have suggested that the integration of secondary amine as donor groups in the structure of unsymmetrical zinc phthalocyanine (ZnPc) should have positive effects on photovoltaic performance, once the molecule is integrated as light harvester in dye sensitized solar cells (DSSCs). Aiming at obtaining experimental confirmation, we synthesized a peripherally substituted push-pull ZnPc bearing three electron donating diphenylamine substituents and a carboxylic acid anchoring group and integrated it as sensitizer in TiO2-based DSSCs. Detailed functional characterization of solar energy converting devices resulted in ruling out the original hypothesis. The causes of this discrepancy have been highlighted, leading to a better understanding of the conditions for an effective design of push-pull diarylamino substituted ZnPcs for DSSCs.

A Player Often Neglected: Electrochemical Comprehensive Analysis of Counter Electrodes for Quantum Dot Solar Cells.

The role played by the counter electrode (CE) in quantum dot sensitized solar cells (QDSSCs) is crucial: it is indeed responsible for catalyzing the regeneration of the redox electrolyte after its action to take back the oxidized light harvesters to the ground state, thus keeping the device active and stable. The activity of CE is moreover directly related to the fill factor and short circuit current through the resistance of the interface electrode-electrolyte that affects the series resistance of the cell. Despite that, too few efforts have been devoted to a comprehensive analysis of this important device component. In this work we combine an extensive electrochemical characterization of the most common materials exploited as CEs in QDSSCs (namely, Pt, Au, Cu2S obtained by brass treatment, and Cu2S deposited on conducting glass via spray) with a detailed characterization of their surface composition and morphology, aimed at systematically defining the relationship between their nature and electrocatalytic activity.

Metal-free organic dyes for TiO2 and ZnO dye-sensitized solar cells.

We report the synthesis and characterization of new metal-free organic dyes (namely B18, BTD-R, and CPTD-R) which designed with D-π-A concept to extending the light absorption region by strong conjugation group of π-linker part and applied as light harvester in dye sensitized solar cells (DSSCs). We compared the photovoltaic performance of these dyes in two different photoanodes: a standard TiO2 mesoporous photoanode and a ZnO photoanode composed of hierarchically assembled nanostructures. The results demonstrated that B18 dye has better photovoltaic properties compared to other two dyes (BTD-R and CPTD-R) and each dye has higher current density (Jsc) when applied to hierarchical ZnO nanocrystallites than the standard TiO2 mesoporous film. Transient photocurrent and photovoltage decay measurements (TCD/TVD) were applied to systematically study the charge transport and recombination kinetics in these devices, showing the electron life time (τR) of B18 dye in ZnO and TiO2 based DSSCs is higher than CPTD-R and BTD-R based DSSCs, which is consistent with the photovoltaic performances. The conversion efficiency in ZnO based DSSCs can be further boosted by 35%, when a compact ZnO blocking layer (BL) is applied to inhibit electron back reaction.

Effect of blocking layer to boost photoconversion efficiency in ZnO dye-sensitized solar cells.

The effect of a ZnO compact blocking layer (BL) in dye-sensitized solar cells (DSSCs) based on ZnO photoanodes is investigated. BL is generated through spray deposition onto fluorine-doped tin oxide (FTO) conducting glass before the deposition of a ZnO active layer. The functional properties of dye-sensitized solar cells (DSSCs) are then investigated as a function of the thickness of the BL for two different kinds of ZnO active layer, i.e., hierarchically self-assembled nanoparticles and microcubes composed of closely packed ZnO sheets. Presence of BL leads to the improvement of photoconversion efficiency (PCE), by physically insulating the electrolyte and the FTO. This effect increases at increasing BL thickness up to around 800 nm, while thicker BL results in reduced cell performance. Remarkable increase in Jsc is recorded, which doubles as compared to cells without blocking layer, leading to PCE as high as 5.6% in the best cell under one sun irradiation (AM 1.5 G, 100 mW cm(-2)). Electrochemical impedance spectroscopy (EIS) elucidates the mechanism boosting the functional features of the cells with BL, which relies with enhanced chemical capacitance together with an almost unchanged recombination resistance, which are reflected in an increased electron lifetime. The results foresee a straightforward way to significantly improve the performance of ZnO-based DSSCs.