Bulk Heterojunction versus Diffused Bilayer: The Role of Device Geometry in Solution p-Doped Polymer-Based Solar Cells

We exploit the effect of molecular p-type doping of P3HT in diffused bilayer (DB) polymer solar cells. In this alternative device geometry, the p-doping is accomplished in solution by blending the F₄-TCNQ with P3HT. The p-doping both increases the film conductivity and reduces the potential barrier at the interface with the electrode. This results in an excellent power conversion efficiency of 4.02%, which is an improvement of ∼48% over the p-doped standard bulk heterojunction (BHJ) device. Combined <i>V</i>_OC–light intensity dependence measurements and Kelvin probe force microscopy reveal that the DB device configuration is particularly advantageous, if compared to the conventional BHJ, because it enables optimization of the donor and acceptor layers independently to minimize the effect of trapping and to fully exploit the improved transport properties

Charge Carrier Generation and Extraction in Hybrid Polymer/Quantum Dot Solar Cells

Here we investigate charge carrier generation and extraction processes in hybrid polymer/nanocrystal solar cells by means of time-resolved optical and photoelectrical techniques. We addressed the role of both poly­(3-hexylthiophene) and colloidal arenethiolate-capped PbS quantum dots, which constitute the hybrid composite nanomaterial, in the photoinduced processes most relevant to device operation by changing the compositional ratio and applying chemical and thermal postdeposition treatments. The carrier generation processes were found to be wavelength-dependent: excitons generated in the polymer domains led to long-lived weakly bound charge pairs upon electron transfer to PbS nanocrystals; whereas charge carrier generation in the nanocrystal domains is highly efficient, although effective separation required the application of external electric field. Overall, charge carrier generation was found efficient and almost independent of the strength of applied electric field; therefore, competition between separation of electron–hole pairs into free carriers and geminate recombination is the major factor limiting the fill factor of nanocomposite-based solar cells. Device efficiency improvements thus require faster interfacial charge transfer processes, which are deeply related to the refinement of nanocrystal surface chemistry

Multilayered Magnetic Nanobeads for the Delivery of Peptides Molecules Triggered by Intracellular Proteases

In this work, the versatility of layer-by-layer technology was combined with the magnetic response of iron oxide nanobeads to prepare magnetic mesostructures with a degradable multilayer shell into which a dye quenched ovalbumin conjugate (DQ-OVA) was loaded. The system was specifically designed to prove the protease sensitivity of the hybrid mesoscale system and the easy detection of the ovalbumin released. The uptake of the nanostructures in the breast cancer cells was followed by the effective release of DQ-OVA upon activation via the intracellular proteases degradation of the polymer shells. Monitoring the fluorescence rising due to DQ-OVA digestion and the cellular dye distribution, together with the electron microscopy studying, enabled us to track the shell degradation and the endosomal uptake pathway that resulted in the release of the digested fragments of DQ ovalbumin in the cytosol

[1]Benzothieno[3,2‑<i>b</i>]benzothiophene-Based Organic Dyes for Dye‑Sensitized Solar Cells

Three new metal-free organic dyes with the [1]­benzothieno­[3,2-<i>b</i>]­benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π<i>-</i>A) and labeled as <b>19</b>, <b>20</b> and <b>21</b>, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the <b>19</b> dye, which shows a molar extinction coefficient ε of over 14,000 M^–1 cm^–1 and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M^–1 cm^–1), until reaching the higher value (ε > 69,000 M^–1 cm^–1) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices

Shape and Morphology Effects on the Electronic Structure of TiO₂ Nanostructures: From Nanocrystals to Nanorods

We carry out an accurate computational analysis on the nature and distribution of electronic trap states in shape-tailored anatase TiO₂ structures, investigating the effect of the morphology on the electronic structure. Linear nanocrystal models up to 6 nm in length with various morphologies, reproducing both flattened and elongated rod-shaped TiO₂ nanocrystals, have been investigated by DFT calculations, to clarify the effect of the crystal facet percentage on the nanocrystal electronic structure, with particular reference to the energetics and distribution of trap states. The calculated densities of states below the conduction band edge have been very well fitted assuming an exponential distribution of energies and have been correlated with experimental capacitance data. In good agreement with the experimental phenomenology our calculations show that elongated rod-shaped nanocrystals with higher values of the ratio between (100) and (101) facets exhibit a relatively deeper distribution of trap states. Our results point at the crucial role of the nanocrystal morphology on the trap state density, highlighting the importance of a balance between the low-energy (101) and high-energy (100)/(001) surface facets in individual TiO₂ nanocrystals

Stark Effect in Perovskite/TiO₂ Solar Cells: Evidence of Local Interfacial Order

To unveil the mechanisms controlling photovoltaic conversion in high-performing perovskite-based mesostructured solar cells, we focus on the key role played by the mesoporous oxide/perovskite interface. We employ several spectroscopic techniques to design a complete scenario and corroborate our results with first principle density functional theory calculations. In particular Stark spectroscopy, a powerful tool allowing interface-sensitive analysis is employed to prove the existence of oriented permanent dipoles, consistent with the hypothesis of an ordered perovskite layer, close to the oxide surface. The existence of a structural order, promoted by specific local interactions, could be one of the decisive reasons for highly efficient carriers transport within perovskite films

Role of Polymer in Hybrid Polymer/PbS Quantum Dot Solar Cells

Hybrid nanocomposites (HCs) obtained by blend solutions of conjugated polymers and colloidal semiconductor nanocrystals are among the most promising materials to be exploited in solution-processed photovoltaic applications. The comprehension of the operating principles of solar cells based on HCs thus represents a crucial step toward the rational engineering of high performing photovoltaic devices. Here we investigate the effect of conjugated polymers on hybrid solar cell performances by taking advantage from an optimized morphology of the HCs comprising lead sulfide quantum dots (PbS QDs). Uncommonly, we find that larger photocurrent densities are achieved by HCs incorporating wide-bandgap polymers. A combination of spectroscopic and electro-optical measurements suggests that wide-bandgap polymers promote efficient charge/exciton transfer processes and hinder the population of midgap states on PbS QDs. Our findings underline the key role of the polymer in HC-based solar cells in the activation/deactivation of charge transfer/loss pathways

Sustainability of Organic Dye-Sensitized Solar Cells: The Role of Chemical Synthesis

The synthesis of a novel and efficient π-extended D-A-π-A organic sensitizer (<b>G3</b>, η = 8.64%) for dye-sensitized solar cells has been accomplished by applying the green chemistry pillars, aiming at overriding traditional routes involving organometallic intermediates with innovative synthetic strategies for reducing the waste burden and dye production costs. It has been demonstrated that the obtainment of a complex target sensitizer can be exclusively pursued via direct arylation reactions. Green metrics comparison with those of a traditional synthetic pathway clearly indicates that the new approach has a lower environmental impact in terms of chemical procedures and generated wastes, stressing the importance of the synergy between the molecular design and the synthetic plan in the framework of environmentally friendly routes to back up sustainable development of third-generation photovoltaics. Additionally, the stability of the <b>G3</b>-based photovoltaic devices was also investigated in aging tests on large area devices, evidencing the excellent potentialities of the proposed structure for all practical applications involving inorganic semiconductor/organic dye interfaces

Electrochemical Assessment of the Band-Edge Positioning in Shape-Tailored TiO₂‑Nanorod-Based Photoelectrodes for Dye Solar Cells

Three families of linear shaped TiO₂ anatase nanocrystals with variable aspect ratio (4, 8, 16) and two sets of branched TiO₂ anatase nanocrystals (in the form of open-framework sheaf-like nanorods and compact braid-like nanorod bundles, respectively) were employed to fabricate high-quality mesoporous photoelectrodes and then implemented into dye-sensitized solar cells to elucidate the intrinsic correlation holding between the photovoltaic performances and the structure of the nanocrystal building blocks. To this aim, the chemical capacitance and the charge-transfer resistance of the photoelectrodes were extrapolated from electrochemical impedance spectroscopy measurements and used to draw a quantitative energy diagram of the dye-sensitized solar cells realized, on the basis of which their photovoltaic performances have been discussed. It has thus been revealed that photoanodes made from braid-like branched-nanorod bundles exhibited the most favorable conditions to minimize recombination at the interface with the electrolyte due to their deep distribution of trap states, whereas linear-shaped nanorods with higher aspect-ratios result in more remarkable downshift of the conduction band edge

Mid-Infrared Plasmonic Excitation in Indium Tin Oxide Microhole Arrays

Transparent conducting oxides (TCOs) are emerging as possible alternative constituent materials to replace noble metals such as silver and gold for low-loss plasmonic applications in the near-infrared (NIR) and mid-infrared (MIR) regimes. In particular, TCO-based nanostructures are extensively investigated for biospectroscopy exploiting their surface-enhanced infrared absorption (SEIRA). The latter enhances the absorption from vibrational and rotational modes of nearby biomolecules, making TCO nanostructures a promising candidate for IR sensing applications. Nevertheless, in order to produce inexpensive devices for lab-on-a-chip diagnostics, it would be favorable to achieve surface-enhanced infrared absorption with very simple microstructures not requiring nanosize control. In this work, we attempt to demonstrate a SEIRA effect with the least challenging fabrication, μm-scale instead of nm-scale, by tailoring both device design and charge density of the indium tin oxide (ITO) film. We show that microperiodic hole arrays in a ITO film are able to produce SEIRA via grating coupling. Such a study opens the way for innovative and disrupting biosensing devices