Probing the Metal Oxide Local Environment for Thermochromic and Photovoltaic Applications

Energy demand is predicted to increase by 28% between 2015 and 2040, placing strain on the current reserves of petroleum, coal and natural gas. There are two different approaches to alleviating the demand on Earth’s natural resources: increase energy efficiency or utilize renewable resources. Vanadium dioxide (VO2) thermochromic windows passively modulate infrared (IR) transparency, aiding in reducing undesirable heat exchange from outside to indoors. This occurs through a semiconductor to metal transition upon heating which is coupled with an optical change from IR transparent to IR absorbing, respectively. The metallic phase exhibits a plasmon resonance and we can control the local environment by embedding the VO2 nanoparticles in a high refractive index material (i.e. a polymer) where the plasmon absorption intensity increases as does the overall device performance. Alternatively, to increase the production of renewable energy, p-type dye sensitized solar cells (DSSCs) are studied as a precursor to tandem devices for solar fuel production. A novel p-type semiconductor (photocathode), lead titanate was identified through a material informatics approach and utilized in fundamental studies of the semiconductor-electrolyte interaction. By tuning the electrolyte composition to increase the concentration of an efficient electron scavenger, I2, the photocurrent and fill factor approximately doubled resulting in a four-fold increase in power conversion efficiency. Simply changing the concentration of I2, and electron scavenger, in the electrolyte allows for more efficient charge separation at the semiconductor-chromophore-electrolyte interface, which improves two of the most problematic device performance metrics in p-type DSSCs, low photocurrent and low fill factor.Doctor of Philosoph

CsI‐Antisolvent Adduct Formation in All‐Inorganic Metal Halide Perovskites

The excellent optoelectronic properties demonstrated by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high‐performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead‐halide precursor salts. These adduct‐based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all‐inorganic perovskites such as CsPbI3. In this work, inorganic perovskite composition CsPbI3 is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A‐site cation salts. These CsI adducts control nucleation more so than the PbI2–dimethyl sulfoxide (DMSO) adduct and demonstrate how the A‐site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI–MeOAc adduct and results in solar cells with a power conversion efficiency of 14.4%.It is found that unique adducts form between CsI and dimethyl sulfoxide (DMSO) and certain antisolvents, such as methyl acetate, during film formation of the all‐inorganic perovskite CsPbI3. These adducts significantly influence crystallization and the power conversion efficiency of the resulting solar cells.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/154525/1/aenm201903365-sup-0001-SuppMat.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/154525/2/aenm201903365.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/154525/3/aenm201903365_am.pd

CsI‐Antisolvent Adduct Formation in All‐Inorganic Metal Halide Perovskites

The excellent optoelectronic properties demonstrated by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high‐performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead‐halide precursor salts. These adduct‐based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all‐inorganic perovskites such as CsPbI3. In this work, inorganic perovskite composition CsPbI3 is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A‐site cation salts. These CsI adducts control nucleation more so than the PbI2–dimethyl sulfoxide (DMSO) adduct and demonstrate how the A‐site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI–MeOAc adduct and results in solar cells with a power conversion efficiency of 14.4%.It is found that unique adducts form between CsI and dimethyl sulfoxide (DMSO) and certain antisolvents, such as methyl acetate, during film formation of the all‐inorganic perovskite CsPbI3. These adducts significantly influence crystallization and the power conversion efficiency of the resulting solar cells.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/154525/1/aenm201903365-sup-0001-SuppMat.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/154525/2/aenm201903365.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/154525/3/aenm201903365_am.pd

Machine learning for molecular and materials science

Here we summarize recent progress in machine learning for the chemical sciences. We outline machine-learning techniques that are suitable for addressing research questions in this domain, as well as future directions for the field. We envisage a future in which the design, synthesis, characterization and application of molecules and materials is accelerated by artificial intelligence.</p

Emergence and control of gorse seedlings after the 2017 Port Hills fire

An experiment on the Port Hills, Canterbury, after mature gorse was burnt in the fires of February 2017, showed an oversown Italian ryegrass mix out-competed the rapidly germinating gorse seedlings. The shaded gorse seedling population reached a peak of 680 plants/m² in June, declining to ~450 plants/m² in October compared with >600 plants/m² in the unshaded plots. As soil moisture dropped in summer, the gorse seedling population decreased to 10 plants/m² by March 2018, compared with 73 plants/m² in the unshaded plots. Gorse seedlings that had been shaded by Italian ryegrass had shorter roots and lower dry weights than those grown without competition. The oversown mix was more successful on the south than north-facing slope where more bare ground enabled patches of gorse to re-establish. The oversowing of Italian ryegrass was shown to be a viable option to control gorse particularly after an unplanned burn that removed the fences and water supply

Yield of subterranean clover after post-emergence herbicide application for broadleaf weed control

A field experiment was established in Lincoln, Canterbury in autumn 2018 to evaluate the effect of acetolactate synthase (ALS) inhibiting herbicides on subterranean (sub) clover. Two herbicides, imazethapyr and flumetsulam, were applied to seven sub clover cultivars at the 4–5 trifoliate leaf stage during July 2018. By December 2018, both herbicides had reduced the broadleaf weed yield by 1000 kg DM/ha. Sub clover herbage yield in spring (3 Oct 2018) increased only for ‘Antas’ and ‘Napier’ cultivars but all cultivars had an increase in total annual herbage yield when herbicides were applied. Plots were managed for seed set so re-establishment was examined. Imazethapyr had a longer residual than flumetsulam, with greater control of broad-leaved dock (Rumex obtusifolius) eight months after application. Herbicide application had no effect on subsequent sub clover emergence the following year. This experiment demonstrated the potential to establish a pure sward of sub clover with the use of ALS inhibiting herbicides, which could be used to create a high legume base pasture before overdrilling grass the following year

Quantitative Analysis of Simulated Illicit Street-Drug Samples Using Raman Spectroscopy and Partial Least Squares Regression

Modern drug laws require that a seized sample be characterized for both the illegal substances present and the quantity of each of those substances. The goal of this work was to develop a common approach to model development based on Raman spectroscopic analysis followed by partial least squares (PLS) regression that would allow us to obtain quantitative information from simulated street-drug samples. Each drug sample contained one drug surrogate—either isoxsuprine, norephedrine, benzocaine, or lidocaine—and up to 3 different cutting agents. All spectra were acquired on a homebuilt Raman instrument equipped with a rotating sample holder. The same steps were employed for developing separate models for each drug surrogate, including spectral preprocessing by Savitsky-Golay smoothing, differentiation, mean-centering, and autoscaling. PLS models were developed using 2 latent variables that yielded root mean square errors of calibration (RMSEC) values in the 3% range and root mean square error of prediction (RMSEP) values in the 4% range

Yield and botanical composition of four dryland pastures at Ashley Dene Research Farm over 8 years

Dry matter yield and botanical composition of four grazed dryland pasture types were compared over 8 years in summer-dry conditions at Ashley Dene, Canterbury, New Zealand. The experiment was sown in March 2013 to evaluate cocksfoot (CF)- or meadow fescue/ryegrass hybrid (RG)-based pastures established with either subterranean (Sub) or subterranean and balansa (S+B) clovers. Plantain was included in all pasture types. Perennial ryegrass established poorly on the low soil moisture holding capacity Lismore soil and in Year 2 was re-broadcast into the RG pastures. Despite this, plantain was the main sown species in RG pastures beyond Year 3. Total spring yield was greatest in Year 5 at 6720 kg DM/ha and varied with spring rainfall. Cocksfoot-based pastures had 60% of sown species present in the spring of Year 8, compared with 28% in RG-based pastures. Balansa clover was only present up to Year 5 after a managed seeding event in the first spring. White clover did not persist in the dryland environment past Year 2. Sub clover yield depended on the time and amount of autumn rainfall but contributed up to 45% of the spring yield. Cocksfoot-sub clover pastures appear to be most resilient in this summer-dry environment with variable spring rainfall

Cation Effects in p-Type Dye-Sensitized Solar Cells

The performance of dye-sensitized solar cells (DSSCs) depends on the properties and interactions of three fundamental components: the semiconductor, chromophore, and electrolyte. For the electrolyte, the dependence of DSSC performance on the identity and valence state of the spectator cation has not been well studied in p-type semiconductor systems, although the effects of these species in n-type TiO2 devices are significant, producing large shifts in semiconductor flat-band potential, charge-transfer kinetics, photocurrent, and open-circuit voltage (VOC). Here, we vary the spectator cation in p-type NiO DSSCs and demonstrate an increase in VOC by over 50% with two common redox couples. Using optimal cations, we achieved high VOC values without a significant reduction in photocurrent. Mott–Schottky analysis and electrochemical impedance spectroscopy reveal that the cation can shift the flat-band potential of NiO by nearly 1 V and substantially alter the lifetime of charge carriers and charge-transfer resistance at the semiconductor–electrolyte interface. Differences between the anionic and cationic redox couples employed suggest favorable and unfavorable interactions, respectively, with divalent cations at the NiO surface, causing increases and decreases in charge carrier recombination rate constants. Our results highlight the complex interaction between the semiconductor and electrolyte solution and indicate that varying the cation should yield immediate improvements in device metrics for most p-type DSSC systems

News in Nanocrystals seminar: Self-assembly of early career researchers toward globally accessible nanoscience

In 2020, many in-person scientific events were canceled due to the COVID-19 pandemic, creating a vacuum in networking and knowledge exchange between scientists. To fill this void in scientific communication, a group of early career nanocrystal enthusiasts launched the virtual seminar series, News in Nanocrystals, in the summer of 2020. By the end of the year, the series had attracted over 850 participants from 46 countries. In this Nano Focus, we describe the process of organizing the News in Nanocrystals seminar series; discuss its growth, emphasizing what the organizers have learned in terms of diversity and accessibility; and provide an outlook for the next steps and future opportunities. This summary and analysis of experiences and learned lessons are intended to inform the broader scientific community, especially those who are looking for avenues to continue fostering discussion and scientific engagement virtually, both during the pandemic and after