Tunable Localized Surface Plasmon-Enabled Broadband Light-Harvesting Enhancement for High-Efficiency Panchromatic Dye-Sensitized Solar Cells

In photovoltaic devices, light harvesting (LH) and carrier collection have opposite relations with the thickness of the photoactive layer, which imposes a fundamental compromise for the power conversion efficiency (PCE). Unbalanced LH at different wavelengths further reduces the achievable PCE. Here, we report a novel approach to broadband balanced LH and panchromatic solar energy conversion using multiple-core–shell structured oxide-metal-oxide plasmonic nanoparticles. These nanoparticles feature tunable localized surface plasmon resonance frequencies and the required thermal stability during device fabrication. By simply blending the plasmonic nanoparticles with available photoactive materials, the broadband LH of practical photovoltaic devices can be significantly enhanced. We demonstrate a panchromatic dye-sensitized solar cell with an increased PCE from 8.3% to 10.8%, mainly through plasmon-enhanced photoabsorption in the otherwise less harvested region of solar spectrum. This general and simple strategy also highlights easy fabrication, and may benefit solar cells using other photoabsorbers or other types of solar-harvesting devices.Eni-MIT Energy Initiative Founding Member ProgramNational Science Foundation (U.S.) (ECCS Award 1028568)United States. Air Force Office of Scientific Research (AFOSR MURI Award FA9550-12-1-0488

Microsecond Carrier Lifetimes, Controlled p-Doping, and Enhanced Air Stability in Low-Bandgap Metal Halide Perovskites.

Mixed lead-tin halide perovskites have sufficiently low bandgaps (∼1.2 eV) to be promising absorbers for perovskite-perovskite tandem solar cells. Previous reports on lead-tin perovskites have typically shown poor optoelectronic properties compared to neat lead counterparts: short photoluminescence lifetimes (<100 ns) and low photoluminescence quantum efficiencies (<1%). Here, we obtain films with carrier lifetimes exceeding 1 μs and, through addition of small quantities of zinc iodide to the precursor solutions, photoluminescence quantum efficiencies under solar illumination intensities of 2.5%. The zinc additives also substantially enhance the film stability in air, and we use cross-sectional chemical mapping to show that this enhanced stability is because of a reduction in tin-rich clusters. By fabricating field-effect transistors, we observe that the introduction of zinc results in controlled p-doping. Finally, we show that zinc additives also enhance power conversion efficiencies and the stability of solar cells. Our results demonstrate substantially improved low-bandgap perovskites for solar cells and versatile electronic applications.EPSRC (EP/M005143/1 and DTP funding) Royal Society ER

Charting the Irreversible Degradation Modes of Low Bandgap Pb‐Sn Perovskite Compositions for De‐Risking Practical Industrial Development

The commercialization of a solar technology necessitates the fulfillment of specific requirements both regarding efficiency and stability to enter and gain space in the photovoltaic market. These aims are heavily dependent on the selection of suitable materials, which is critical for suppressing any reliability risks arising from inherent instabilities. Focusing on the absorber material, herein the most suitable low bandgap lead‐tin composition candidate for all‐perovskite tandem applications is investigated by studying their degradation mechanisms with both widely available and advanced characterization techniques. Three irreversible degradation processes are identified in narrow bandgap Pb‐Sn perovskite absorbers: 1) Tin (Sn) oxidation upon air exposure, 2) methylammonium (MA) loss upon heat exposure, and 3) formamidinium (FA) and cesium (Cs) segregation leading to impurity phase formation. From an industrial perspective, it is proposed to refocus attention on FASn0.5Pb0.5I3 which minimizes all three effects while maintaining a suitable bandgap for a bottom cell and good performance. Moreover, a practical and highly sensitive characterization method is proposed to monitor the oxidation, which can be deployed both in laboratory and industrial environments and provide useful information for the technological development process, including, the effectiveness of encapsulation methods, and the acceptable time windows for air exposure

HLA-DM Mediates Epitope Selection by a “Compare-Exchange” Mechanism when a Potential Peptide Pool Is Available

BACKGROUND: HLA-DM (DM) mediates exchange of peptides bound to MHC class II (MHCII) during the epitope selection process. Although DM has been shown to have two activities, peptide release and MHC class II refolding, a clear characterization of the mechanism by which DM facilitates peptide exchange has remained elusive. METHODOLOGY/PRINCIPAL FINDINGS: We have previously demonstrated that peptide binding to and dissociation from MHCII in the absence of DM are cooperative processes, likely related to conformational changes in the peptide-MHCII complex. Here we show that DM promotes peptide release by a non-cooperative process, whereas it enhances cooperative folding of the exchange peptide. Through electron paramagnetic resonance (EPR) and fluorescence polarization (FP) we show that DM releases prebound peptide very poorly in the absence of a candidate peptide for the exchange process. The affinity and concentration of the candidate peptide are also important for the release of the prebound peptide. Increased fluorescence energy transfer between the prebound and exchange peptides in the presence of DM is evidence for a tetramolecular complex which resolves in favor of the peptide that has superior folding properties. CONCLUSION/SIGNIFICANCE: This study shows that both the peptide releasing activity on loaded MHCII and the facilitating of MHCII binding by a candidate exchange peptide are integral to DM mediated epitope selection. The exchange process is initiated only in the presence of candidate peptides, avoiding possible release of a prebound peptide and loss of a potential epitope. In a tetramolecular transitional complex, the candidate peptides are checked for their ability to replace the pre-bound peptide with a geometry that allows the rebinding of the original peptide. Thus, DM promotes a "compare-exchange" sorting algorithm on an available peptide pool. Such a "third party"-mediated mechanism may be generally applicable for diverse ligand recognition in other biological systems

Acculturation and individualism as predictors of work-family conflict in a diverse workforce

Ethnic and cultural diversity is an increasing reality in the US workplace. The current study highlights the importance of acknowledging the culturally heterogeneous nature of ethnic groups, and the need to focus on social identity characteristics such as cultural values when assessing group differences. We demonstrate that cultural values (i.e., individualism) contribute to employees' experiences of work-family conflict beyond the effects of ethnicity. Specifically, we introduce a model informed by social identity theory that explains why acculturation is related to work-family conflict. The model was tested with a sample of 309 employed Caucasian and Hispanic Americans. An empirical test of our model provides evidence that individualism mediates the relationship between language- and social-based acculturation and work-family conflict, even when controlling for ethnicity. Additionally, alternative models further reveal that the effects of acculturation and individualism contribute t

M13 Virus-Enabled Synthesis of Titanium Dioxide Nanowires for Tunable Mesoporous Semiconducting Networks

Mesoporous semiconducting networks exhibit advantageous photoelectrochemical properties. The M13 virus is a versatile biological scaffold that has been genetically engineered to organize various materials into nanowire (NW)-based mesoporous structures. In this study, high-aspect ratio titanium dioxide NWs are synthesized by utilizing M13 viruses as templates, and the NWs are assembled into semiconducting mesoporous networks with tunable structural properties. To understand the effects of different morphologies on the photovoltaic performance, the as-fabricated networks are employed as photoanodes in liquid-state dye-sensitized solar cells (DSCs). Compared with traditional nanoparticle-based photoanodes, the NW-based DSC photoanodes demonstrate much higher electron diffusion lengths while maintaining a comparable light harvesting capacity, thus leading to improved power conversion efficiencies. In addition, the NW-based semiconducting mesoporous thin films are able to load sufficient organolead iodide perovskite materials into the interconnected pores, and the perovskite-coated films are utilized as efficient photoanodes for solid-state organolead iodide perovskite hybrid solar cells and achieve power conversion efficiencies superior to those of liquid-state DSCs.Eni S.p.A. (Firm) (Eni-MIT Energy Fellowship)Natural Sciences and Engineering Research Council of Canada (Postgraduate Scholarship

Versatile Three-Dimensional Virus-Based Template for Dye-Sensitized Solar Cells with Improved Electron Transport and Light Harvesting

By genetically encoding affinity for inorganic materials into the capsid proteins of the M13 bacteriophage, the virus can act as a template for the synthesis of nanomaterial composites for use in various device applications. Herein, the M13 bacteriophage is employed to build a multifunctional and three-dimensional scaffold capable of improving both electron collection and light harvesting in dye-sensitized solar cells (DSSCs). This has been accomplished by binding gold nanoparticles (AuNPs) to the virus proteins and encapsulating the AuNP–virus complexes in TiO₂ to produce a plasmon-enhanced and nanowire (NW)-based photoanode. The NW morphology exhibits an improved electron diffusion length compared to traditional nanoparticle-based DSSCs, and the AuNPs increase the light absorption of the dye-molecules through the phenomenon of localized surface plasmon resonance. Consequently, we report a virus-templated and plasmon-enhanced DSSC with an efficiency of 8.46%, which is achieved through optimizing both the NW morphology and the concentration of AuNPs loaded into the solar cells. In addition, we propose a theoretical model that predicts the experimentally observed trends of plasmon enhancement