Leveraging hierarchical self-assembly pathways for realizing colloidal photonic crystals

Colloidal open crystals are attractive materials, especially for their photonic applications. Self-assembly appeals as a bottom-up route for structure fabrication, but self-assembly of colloidal open crystals has proven to be elusive for their mechanical instability due to being low-coordinated. For such a bottom-up route to yield a desired colloidal open crystal, the target structure is required to be thermodynamically favored for designer building blocks and also kinetically accessible via self- assembly pathways in preference to metastable structures. Additionally, the selection of a particular polymorph poses a challenge for certain much sought-after colloidal open crystals for their applications as photonic crystals. Here, we devise hierarchical self-assembly pathways, which, starting from designer triblock patchy particles, yield in a cascade of well-separated associations first tetrahedral clusters and then tetrastack crystals. The designed pathways avoid trapping into an amorphous phase. Our analysis reveals how such a two-stage self-assembly pathway via tetrahedral clusters promotes crystallization by suppressing five- and seven-membered rings that hinder the emergence of the ordered structure. We also find that slow annealing promotes a bias toward the cubic polymorph relative to the hexagonal counterpart. Finally, we calculate the photonic band structures, showing that the cubic polymorph exhibits a complete photonic band gap for the dielectric filling fraction directly realizable from the designer triblock patchy particles. Unexpectedly, we find that the hexagonal polymorph also supports a complete photonic band gap, albeit only for an increased filling fraction, which can be realized via postassembly processing

Impact of the scattering physics on the power factor of complex thermoelectric materials

We assess the impact of the scattering physics assumptions on the thermoelectric properties of five Co-based p-type half-Heusler alloys by considering full energy-dependent scattering times vs the commonly employed constant scattering time. For this, we employ density functional theory band structures and a full numerical scheme that uses Fermi's golden rule to extract the momentum relaxation times of each state at every energy, momentum, and band. We consider electron-phonon scattering (acoustic and optical), as well as ionized impurity scattering, and evaluate the qualitative and quantitative differences in the power factors of the materials compared to the case where the constant scattering time is employed. We show that the thermoelectric power factors extracted from the two different methods differ in terms of (i) their ranking between materials, (ii) the carrier density where the peak power factor appears, and (iii) their trends with temperature. We further show that the constant relaxation time approximation smoothens out the richness in the band structure features, thus limiting the possibilities of exploring this richness for material design and optimization. These details are more properly captured under full energy/momentum-dependent scattering time considerations. Finally, by mapping the conductivities extracted within the two schemes, we provide appropriate density-dependent constant relaxation times that could be employed as a fast first-order approximation for extracting charge transport properties in the half-Heuslers we consider

WUDAPT: Facilitating advanced urban canopy modeling for weather, climate and air quality applications

Environmental issues and impacts to society will be exacerbated with increased population, diminishing resources and the prospects for extreme weather events and climate changes. Current community-based models available for weather, climate and air quaity applications are powerful state-of-science modeling systems, which, with careful considerations, can be employed to address the impact of these issues fo urban areas. Given the complex and high degree of spatial inhomogeneity of the underlying surface area we will review mesh size, appropriate multi-scale science and morphological descriptions and their data requirements including unique city specific gridded morphology and material composition for their forecasting and climate applications. For this presentation, we discuss, describe and show examples from an ongoing but preliminary prototypic collaborative effort, whose design bases is to provide the experience and recommendations toward extending the scope of the National Urban Database and Access Portal Tools (NUDAPT) to worldwide coverage (WUDAPT). WUDAPT would thus provide requisite gridded data for urban applications of advanced forecast and climate models throughout the world. Strategically, the prototypic efforts will be designed to provide proven protocols for the facilitaton of the data gathering and processing based on available remote sensing and ground-based sampling. Tactically, we employ an iterative approach first obtaining coarse gridded Local Climate Zone (LCZ) classification derived from available Web-based products such as Google-Earth, and Landsat satellite magery. Further sub-class discretization of LCZs and the application of GeoWiki technology facilitates further refinements and ground truthing to yield the desired gridded building morphological distribution parameters and their material composition. Local experts would be encouraged to become involved to ensure factors unique to their area in the world would be incorporated. Finally, given that model applications may require data with different grid resolution we present an outline that employs the new and powerful Multiple Resolution Analyses scheme that can address this need within the scope of WUDAPT

Role of oxygen within end group substituents on film morphology and charge carrier transport in thiophene/phenylene small-molecule semiconductors

In this study, the end group polarity of (5,5′)-biphenyl-(2,2’)-bithiophenes (PTTPs) was systematically varied from alkyl (1) to alkoxy (2) with one oxygen atom to glycol (3) with two oxygen atoms while the overall length of the end groups is kept constant. Thin films of the three compounds were sublimated at different substrate temperatures and their morphology, crystallinity and charge carrier transport in field-effect transistors was investigated to draw structure-property relationships for the PTTP derivatives. For all three compounds, the effective charge carrier mobility is improved with higher substrate temperatures at which films with higher crystallinity and larger grains are formed. The effective mobility decreases with higher polarity of the end groups from alkyl to alkoxy and glycol. The reliability factor of the alkyl (1) and alkoxy (2) substituted PTTPs decreases with higher substrate temperature, but at the same time this value is enhanced for the glycol substituted molecules (3). The transistors of 3 prepared at higher substrate temperatures also show a reduced threshold voltage and smaller hysteresis in the transfer characteristics. These insights are important for the understanding of the impact of oxygen incorporation into side chain/end group substituents of organic semiconductors and their implementation in organic electrochemical transistors, thermoelectrics and photovoltaics

Modeling cross-national differences in automated vehicle acceptance

The technology that allows fully automated driving already exists and it may gradually enter the market over the forthcoming decades. Technology assimilation and automated vehicle acceptance in different countries is of high interest to many scholars, manufacturers, and policymakers worldwide. We model the mode choice between automated vehicles and conventional cars using a mixed multinomial logit heteroskedastic error component type model. Specifically, we capture preference heterogeneity assuming a continuous distribution across individuals. Different choice scenarios, based on respondents’ reported trip, were presented to respondents from six European countries: Cyprus, Hungary, Iceland, Montenegro, Slovenia, and the UK. We found that large reservations towards automated vehicles exist in all countries with 70% conventional private car choices, and 30% automated vehicles choices. We found that men, under the age of 60, with a high income who currently use private car, are more likely to be early adopters of automated vehicles. We found significant differences in automated vehicles acceptance in different countries. Individuals from Slovenia and Cyprus show higher automated vehicles acceptance while individuals from wealthier countries, UK, and Iceland, show more reservations towards them. Nontrading mode choice behaviors, value of travel time, and differences in model parameters among the different countries are discussed

Thermoelectric inks and power factor tunability in hybrid films through all solution process

Thermoelectric (TE) materials can have a strong benefit to harvest thermal energy if they can be applied to large areas without losing their performance over time. One way of achieving large-area films is through hybrid materials, where a blend of TE materials with polymers can be applied as coating. Here, we present the development of all solution-processed TE ink and hybrid films with varying contents of TE Sb2Te3 and Bi2Te3 nanomaterials, along with their characterization. Using (1-methoxy-2-propyl) acetate (MPA) as the solvent and poly (methyl methacrylate) as the durable polymer, large-area homogeneous hybrid TE films have been fabricated. The conductivity and TE power factor improve with nanoparticle volume fraction, peaking around 60–70% solid material fill factor. For larger fill factors, the conductivity drops, possibly because of an increase in the interface resistance through interface defects and reduced connectivity between the platelets in the medium. The use of dodecanethiol (DDT) as an additive in the ink formulation enabled an improvement in the electrical conductivity through modification of interfaces and the compactness of the resultant films, leading to a 4–5 times increase in the power factor for both p- and n-type hybrid TE films, respectively. The observed trends were captured by combining percolation theory with analytical resistive theory, with the above assumption of increasing interface resistance and connectivity with polymer volume reduction. The results obtained on these hybrid films open a new low-cost route to produce and implement TE coatings on a large scale, which can be ideal for driving flexible, large-area energy scavenging technologies such as personal medical devices and the IoT

WUDAPT: an urban weather, climate and environmental modeling infrastructure for the Anthropocene

WUDAPT is an international community-based initiative to acquire and disseminate climate relevant data on the physical geographies of cities for modeling and analyses purposes. The current lacuna of globally consistent information on cities is a major impediment to urban climate science towards informing and developing climate mitigation and adaptation strategies at urban scales. WUDAPT consists of a database and a portal system; its database is structured into a hierarchy representing different levels of detail and the data are acquired using innovative protocols that utilize crowdsourcing approaches, Geowiki tools, freely accessible data, and building typology archetypes. The base level of information (L0) consists of Local Climate Zones (LCZ) maps of cities; each LCZ category is associated with range of values for model relevant surface descriptors (e.g. roughness, impervious surface cover, roof area, building heights, etc.). Levels 1 (L1) and 2 (L2) will provide specific intraurban values for other relevant descriptors at greater precision, such as data morphological forms, material composition data and energy usage. This article describes the status of the WUDAPT project and demonstrates its potential value using observations and models. As a community-based project, other researchers are encouraged to participate to help create a global urban database of value to urban climate scientists

Monitoring of species' genetic diversity in Europe varies greatly and overlooks potential climate change impacts.

Genetic monitoring of populations currently attracts interest in the context of the Convention on Biological Diversity but needs long-term planning and investments. However, genetic diversity has been largely neglected in biodiversity monitoring, and when addressed, it is treated separately, detached from other conservation issues, such as habitat alteration due to climate change. We report an accounting of efforts to monitor population genetic diversity in Europe (genetic monitoring effort, GME), the evaluation of which can help guide future capacity building and collaboration towards areas most in need of expanded monitoring. Overlaying GME with areas where the ranges of selected species of conservation interest approach current and future climate niche limits helps identify whether GME coincides with anticipated climate change effects on biodiversity. Our analysis suggests that country area, financial resources and conservation policy influence GME, high values of which only partially match species' joint patterns of limits to suitable climatic conditions. Populations at trailing climatic niche margins probably hold genetic diversity that is important for adaptation to changing climate. Our results illuminate the need in Europe for expanded investment in genetic monitoring across climate gradients occupied by focal species, a need arguably greatest in southeastern European countries. This need could be met in part by expanding the European Union's Birds and Habitats Directives to fully address the conservation and monitoring of genetic diversity