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At least 37 records · Page 2

Many routes to ferroelectric HfO 2 : A review of current deposition methods

Although 10 years have passed since the initial report of ferroelectricity in hafnia (HfO 2 ), researchers are still intensely fascinated by this material system and the promise it holds for future applications. A wide variety of deposition methods have been deployed to create ferroelectric HfO 2 thin films such as atomic layer deposition, chemical solution deposition, and physical vapor deposition methods such as sputtering and pulsed laser deposition. Process and design parameters such as deposition temperature, precursor choice, target source, vacuum level, reactive gases, substrate strain, and many others are often integral in stabilizing the polar orthorhombic phase and ferroelectricity. We examine processing parameters across four main different deposition methods and their effect on film microstructure, phase evolution, defect concentration, and resultant electrical properties. The goal of this review is to integrate the process knowledge collected over the past 10 years in the field of ferroelectric HfO 2 into a single comprehensive guide for the design of future HfO 2 -based ferroelectric materials and devices.

36 MATERIALS SCIENCE↗

Preshaping clear glass at low temperatures

Advances in available glass chemistries and glass processing methods have accompanied and enabled some of the biggest technology revolutions, from the development and mass production of light bulbs to low-loss fiber optics and durable smartphone touchscreens. An emerging generation of low-temperature processing technologies aims to continue this important trend and make a broader array of glass components mass producible. In the issue, Mader et al. (1) describe one such innovation in glass processing—the use of low-temperature injection molding to preshape silica particle–filled composites that can later be transformed into transparent fused silica glass objects. Traditionally, transparent glass objects are manufactured in high volume from molten or softened glass, which is floated, drawn, blown, cast, or blow-molded to a desired shape (see the figure, top). The glass composition and processing technique dictate the working temperature, which is usually quite high (near 1000°C) and often restricts the choice of compatible equipment or limits the choice of glass composition. Because geometry-specific capital investment is required for production, drastic or frequent component design changes or small batches may be cost prohibitive. Alternatively, transparent glass components can also be shaped at ambient temperature from solid glass by a series of subtractive processes, including cutting or multiple stages of grinding, followed by slower processing steps, such as polishing or etching. This approach is somewhat less amenable to mass production, and certain geometries containing tool-inaccessible regions cannot be fabricated in this way. Several emerging glass-shaping technologies aim to reduce the required manufacturing temperatures and still provide access to a broader range of glass compositions and component geometries (see the figure). These approaches use a three-step process. First, a desired shape is preformed at low temperature from a glass-forming, organic-inorganic composite. Next, the preform is dried, and organic materials used to bind particles are removed. Finally, the preform is heated (sintered) well below the glass-melting temperature to densify to transparent glass. Although the second and third steps do occur at increased temperatures, only standard, geometry-agnostic driers and furnaces are required. This strategy builds on the well-studied sol-gel approach to forming monolithic glass, where silica network–forming chemical solutions are poured into molds, slowly dried, and condensed into dense glass without melting (2). In a departure from the sol-gel process, these new technologies use solvents, cross-linkers, and polymers to formulate organic-inorganic composites tuned for compatibility with a particular shaping process, with formats ranging from photocurable liquids to shear-thickening pastes to solids. The composite inorganic loadings are also typically higher than those in the pure sol-gel approach, which drastically reduces shrinkage in comparison.

36 MATERIALS SCIENCE↗

Deposition and dielectric characterization of highly oriented V 2 O 5 thin films

The possibility of ferroelectricity in orthorhombic V 2 O 5 thin flms was investigated. Films were deposited via either a chemical solution deposition (CSD) route or by RF magnetron sputtering. Highly (001) oriented V 2 O 5 flms were achieved with both deposition routes at temperatures as low as 300°C. No evidence for ferroelectricity was observed, even in flms which had been doped to provide local nuclei for polarization reversal. Loss originated from mid-gap trap states stemming from oxygen vacancies that were observed with photoluminescence, supplemented by piezoresponse force microscopy measurements. Furthermore, these trap states may have helped mimic ferroelectricity in previous reports on V 2 O 5 .

36 MATERIALS SCIENCE↗

Thermodynamically Stable, Plasmonic Transition Metal Oxide Nanoparticle Solar Selective Absorbers towards 95% Optical-to-Thermal Conversion Efficiency at 750 °C

Generation 3 (Gen) concentrating solar power (CSP) systems requires a high operation temperature ≥750°C to increase the power-cycle efficiency towards ≥50%. However, such a high operation temperature poses a notable challenge to high temperature materials. On the receiver side, a critical challenge is the lack of solar selective absorbers that demonstrate both high optical-to-thermal energy conversion efficiency η therm approaching 95% and long-term thermal stability at >750°C in air. Existing solar absorbers either have limited η therm ≤89% or deteriorate significantly within 500 h at 750°C; some of these also require costly vacuum deposition for stringent thickness control. Therefore, it is highly desirable to simultaneously achieve η therm ~95% AND high thermal stability at 750°C for future generations of CSP receivers. This project has investigated and developed low-cost, highly scalable spray-coated transition metal oxide nanoparticle (NP) pigmented solar selective coatings on various types of Inconel alloy tube sections that are thermodynamically stable at 750-800°C in air, maintaining η therm >94.3%(93.2%) under a solar concentration ratio of C=1000 after 60 simulated day-night cycles at 750ºC (800ºC) (1 cycle=12 h at 750 or 800°C and 12h ramping down to 25°C). We have also coated up to 48 inches long receiver tubes for preliminary solar testing under Norwich Technology’s parabolic trough systems, demonstrating notably improved performance in solar heating compared to benchmark Pyromark 2500 coatings. Two key innovations have been developed in this project: (1) We achieved an unprecedented high thermal efficiency >94% by optimizing the d-band optical absorption spectra of transition metal ions, engineering their valences and stoichiometry; (2) We were able to maintain or even slightly increase the efficiency when operating at 750°C in air by engineering the interdiffusion of transition metal ions between the coating and the Inconel substrate to our advantage. Featuring high-temperature solar spectral selectivity and thermodynamic stability in air, as well as low-cost, highly scalable solution-chemical synthesis and spray coating techniques, this innovation in solar selective absorber technology alone accounts for nearly 40% of the targeted reduction in the levelized cost of electricity (LCOE) from the receiver, thermal energy storage, and operation & maintenance combined by 2030, as proposed by the U.S. Department of Energy. For a 110 MWe CSP power plant, this LCOE reduction from the solar selective coating alone transfers to ~$\$ $1.9 M increase in annual profit based on a sales price of 10¢/kWh (or an annual sale of $50 M/year). The high solar absorptance (~98%) NP pigment materials developed in this project are equally applicable to volumetric receivers either as a coating or as bigger ceramic microspheres after sintering, potentially benefiting Gen3 falling particle CSP technologies. All these contributions facilitate the larger scale deployment of CSP systems with energy storage capability to address the intermittency issue of solar energy towards dispatchable solar electricity, bridging the temporal gap between peak solar electricity production and peak electricity consumption. The collaboration with Norwich Technologies and Brayton Energy in this project will also facilitate the future commercialization of this new solar selective coating technology developed in this SIPS project.

14 SOLAR ENERGY↗

Improving Self-Driving Labs: Quantifying System-Level Experiment Repeatability and Broadening Instrument-Level Compatibility

Modular Autonomous Research System (MARS) is a self-driving laboratory (SDL) which performs wet-lab science with peptide-lanthanide combinations in an automated and, ultimately, an autonomous manner to aid in soil analysis for domestic lithium mining. Autonomous experimentation involves automated experimentation, experiment planning, and active learning. MARS consists of a 6-axis robotic arm (UR5e) on a linear rail, pipette robots (Opentrons 2), and microplate readers. These components transport, operate on, and collect data with chemical solutions in standard labware. For effective autonomy, MARS must perform system-level labware operations repeatably, plan experiments autonomously, and be portable between research-domains. Repeatability is evaluated by labware placement precision, such that future operations can properly locate labware, as well as the elapsed time, so that low variance mean estimates of experiment duration can inform high-level researcher decision making. Autonomous experiment planning is the next step to decouple experimentation from human management; however, there is a conflict between the ideal system-level experiment goals and the constraints imposed by instruments’ limitations. Sub-domain portability is a long-term goal to extend MARS’ research beyond the chemistry of peptide-lanthanide binding to other sub-domains without having to invest significant overhead to system retrofitting. To address these goals, we manually trained the robotic arm labware placement and modelled statistical failurerate and uncertainty Additionally, we benchmarked the duration and variance of each experiment sub-operation as a heuristic for research decision making. Next, we use a parameterized geometric program (PGP) approach to design experiments that optimize system-level objectives and satisfy instrument-level constraints. Lastly, we proposed a Python framework to maximize MARS’ extensibility to other scientific sub-domains through a JSON-based experiment specification.

36 MATERIALS SCIENCE↗

A Model of Large Scale Electrochemical Direct Ocean Capture Under Variable Power

Since limiting warming to 1.5 degrees C by 2100 will not only require an energy transition but also billions of tons of carbon dioxide (CO2) removal per year, it is essential to expand these efforts. This can be done offshore via electrochemical direct ocean capture (eChem DOC) which extracts CO2 from seawater that can later be stored underground or converted to products. Deployments of eChem DOC will be powered by renewable energy and therefore need to function with variable power inputs. This project aims to support future large-scale deployments by developing a model of eChem DOC operation, informed by industry and literature, and assessing its performance under variable power and varying designs. Initial analysis suggests that discretizing the eChem system has a higher impact on increasing overall capture than storing the chemical solutions to continue capture during periods of lower power availability, but this is likely situation dependent. Future work will use more realistic power profiles.

direct ocean capture↗

Transferable predictions of energetic and structural properties for refractory solid solution alloys across chemical compositions

We present a data-efficient approach to train graph neural networks (GNNs) on density functional theory (DFT) data for accurate and transferable predictions of energetic and structural properties of refractory solid solution alloys in the niobium-tantalum-vanadium (Nb-Ta-V) chemical space. We start by training the GNN model only on DFT data that describes refractory binary alloys niobium-tantalum (Nb-Ta), niobium-vanadium (Nb-V), and tantalum-vanadium (Ta-V) to predict formation enthalpy and root mean squared displacement. Once trained, the GNN predictions are tested on DFT data describing refractory ternary alloys Nb-Ta-V. While, unsurprisingly, direct transferability from binary to ternary is not sufficiently accurate, augmenting the training with only 1% of the available ternary data (uniformly distributed across the entire range of chemical compositions) improves significantly the quality of the GNN predictions. For comparison, we assess the transferability in the opposite direction by training GNN models on ternary Nb-Ta-V data and making predictions on binaries Nb-Ta, Nb-V, and Ta-V, which exhibits notably higher predictive errors. The proposed methodology, which favors transferability from lower-component to higher-component alloys, offers an efficient path towards avoiding the curse of dimensionality incurred when collecting DFT data for discovery and design of multi-component disordered alloys.

Density functional theory calculations↗

Chemical state of nickel nanoparticles during the oxygen evolution reaction in a carbonate-bicarbonate buffer solution

The chemical state of nickel anodes during the oxygen evolution reaction can impact their electrocatalytic performance. Here, X-ray photoelectron and absorption spectroscopies reveal the chemical state of nickel nanoparticles under oxygen evolution reaction conditions in amildly alkaline carbonate-bicarbonate buffer solution. Ni 2+ and Ni 3+ species are observed at the reaction onset potential with a 7:4 ratio, with no remaining metallic nickel. These species include NiO, which increasingly converts to other Ni 2+ and Ni 3+ species once the potential is increased above the onset potential. Conversely, when a 20-nm-thick nickel film is used instead of nickel nanoparticles, a significant amount of metallic nickel remains in the inner layers. Nickel nanoparticles also undergo significant morphological and structural changes during the reaction, as evidenced by ex situ transmission electron microscopy. Amorphization of the nanoparticles is attributed to significant H 2 O incorporation, with the oxygen intensity increasing both in operando and ex situ measurements.

36 MATERIALS SCIENCE↗

Hydrated Anions: From Clusters to Bulk Solution with Quasi-Chemical Theory

The interactions of hydrated ions with molecular and macromolecular solution and interface partners are strong on a chemical energy scale. Here we recount the foremost ab initio theory for the evaluation of the hydration free energies of ions, namely, quasi-chemical theory (QCT). We focus on anions, particularly halides but also the hydroxide anion, because they have been outstanding challenges for all theories. For example, this work supports understanding the high selectivity for F – over Cl – in fluoride-selective ion channels despite the identical charge and the size similarity of these ions. QCT is built by the identification of inner-shell clusters, separate treatment of those clusters, and then the integration of those results into the broader-scale solution environment. Recent work has focused on a close comparison with mass-spectrometric measurements of ion-hydration equilibria. We delineate how ab initio molecular dynamics (AIMD) calculations on ion-hydration clusters, elementary statistical thermodynamics, and electronic structure calculations on cluster structures sampled from the AIMD calculations obtain just the free energies extracted from the cluster experiments. That theory–experiment comparison has not been attempted before the work discussed here, but the agreement is excellent with moderate computational effort. This agreement reinforces both theory and experiment and provides a numerically accurate inner-shell contribution to QCT. The inner-shell complexes involving heavier halides display strikingly asymmetric hydration clusters. Asymmetric hydration structures can be problematic for the evaluation of the QCT outer-shell contribution with the polarizable continuum model (PCM). Nevertheless, QCT provides a favorable setting for the exploitation of PCM when the inner-shell material shields the ion from the outer solution environment. For the more asymmetrically hydrated, and thus less effectively shielded, heavier halide ions clustered with waters, the PCM is less satisfactory. We therefore investigate an inverse procedure in which the inner-shell structures are sampled from readily available AIMD calculations on the bulk solutions. This inverse procedure is a remarkable improvement; our final results are in close agreement with a standard tabulation of hydration free energies, and the final composite results are independent of the coordination number on the chemical energy scale of relevance, as they should be. Finally, a comparison of anion hydration structure in clusters and bulk solutions from AIMD simulations emphasize some differences: the asymmetries of bulk solution inner-shell structures are moderated compared with clusters but are still present, and inner hydration shells fill to slightly higher average coordination numbers in bulk solution than in clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study

The chemical expansion of Pr 0.1 Ce 0.9 O 2-δ (PCO) and CeO 2-δ thin films is investigated in the temperature range between 600 °C and 800 °C by laser Doppler vibrometry (LDV). It enables non-contact determination of nanometer scale changes in film thickness at high temperatures. The present study is the first systematic and detailed investigation of chemical expansion of doped and undoped ceria thin films at temperatures above 650 °C. The thin films were deposited on yttria stabilized zirconia substrates (YSZ), operated as an electrochemical oxygen pump, to periodically adjust the oxygen activity in the films, leading to reversible expansion and contraction of the film. This further leads to stresses in the underlying YSZ substrates, accompanied by bending of the overall devices. Film thickness changes and sample bending are found to reach up to 10 and several hundred nanometers, respectively, at excitation frequencies from 0.1 to 10 Hz and applied voltages from 0–0.75 V for PCO and 0–1 V for ceria. At low frequencies, equilibrium conditions are approached. As a consequence maximum thin-film expansion of PCO is expected due to full reduction of the Pr ions. The lower detection limit for displacements is found to be in the subnanometer range. At 800 °C and an excitation frequency of 1 Hz, the LDV shows a remarkable resolution of 0.3 nm which allows, for example, the characterization of materials with small levels of expansion, such as undoped ceria at high oxygen partial pressure. As the correlation between film expansion and sample bending is obtained through this study, a dimensional change of a free body consisting of the same material can be calculated using the high resolution characteristics of this system. A minimum detectable dimensional change of 5 pm is estimated even under challenging high-temperature conditions at 800 °C opening up opportunities to investigate electro-chemo-mechanical phenomena heretofore impossible to investigate. The expansion data are correlated with previous results on the oxygen nonstoichiometry of PCO thin films, and a defect model for bulk ceria solid solutions is adopted to calculate the cation and anion radii changes in the constrained films during chemical expansion. The constrained films exhibit anisotropic volume expansion with displacements perpendicular to the substrate plane nearly double that of bulk samples. The PCO films used here generate high total displacements of several 100 nm’s with high reproducibility. Consequently, PCO films are identified to be a potential core component of high-temperature actuators. They benefit not only from high displacements at temperatures where most piezoelectric materials no longer operate while exhibiting, low voltage operation and low energy consumption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical complexity suppresses interstitial solute segregation to screw dislocation cores in the bcc NbTaTiHfZr high-entropy alloy

Recent reports suggest that interstitial solute additions to body-centered cubic (bcc) high-entropy alloys (HEAs) may enhance their mechanical properties. However, details of interactions between interstitial atoms and dislocations in these HEAs remain incompletely understood. Using first-principles calculations, we examine the energetics of C, N, and O interstitial solutes in elemental bcc metals and NbTaTiHfZr, focusing on their segregation in screw dislocation cores. We examine two types of core sites and show that the low-energy configuration and associated segregation energy depend on the transition metal group. In NbTaTiHfZr, we find that chemical complexity substantially suppresses interstitial segregation in dislocation cores, as fluctuations in bulk solute energies induce energetically favorable sites that disfavor segregation to core sites. Local chemical order further enhances this effect by promoting solute clustering away from dislocation cores. These findings reveal fundamental differences between the behavior of interstitial atoms in elemental metals and HEAs, with implications for high-temperature plasticity and dynamic strain aging.

Body-centered cubic transition metals↗

Potentials of mean force fail to describe chemical bond-breaking in solution

Many liquid phase studies assume that the potential energy surfaces of reacting molecules are the same as in the gas phase, neglecting complex solvent dynamics that can completely alter the nature of chemical reactivity. Even studies that include solvent effects typically only consider them in an average, equilibrium way as part of a potential of mean force (PMF). In this work, we use mixed quantum/classical simulations to compare how equilibrium and non-equilibrium solvent motions affect the photodissociation of a simple diatomic molecule, NaK + , in liquid tetrahydrofuran. A PMF analysis shows that as the excited-state molecule dissociates with the solvent at equilibrium, the bonding electron remains associated with K + at short bond distances but eventually localizes on Na + at the end of dissociation. When we examine non-equilibrium dynamical photodissociation trajectories, however, we find that they fall into three distinct categories: about a quarter of them have the bonding electron mainly associated with Na + , another quarter stay mainly associated with K + , and about half have the bonding electron shared roughly equally between the two ions. The results show that equilibrium PMFs cannot accurately describe the dynamics of bond-breaking chemical reactions in solution because there is insufficient time for the solvent to reach equilibrium on the time scale over which bond dissociation occurs. Furthermore, our analysis shows that the solvent coupling between the electronic energy surfaces is similar at and away from equilibrium, suggesting that other factors, such as solute velocity-driven solvent memory effects, play a more important role in explaining the failure of the equilibrium PMF to predict the non-equilibrium dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Hydrogen Evolution Electrode

Green hydrogen produced through anion exchange membrane water electrolysis is a promising, low-cost chemical storage solution for intermittent renewable energy sources. Low-temperature electrolysis using anion exchange membranes (AEM) combines the benefits of established water electrolysis technologies based on alkaline electrolysis and proton exchange membrane electrolysis. The anion conductive ionomers (ACI) used in the AEM electrolyzer (AEMEL) electrodes has been investigated. The ACI serves two primary purposes: (i) facilitate hydroxide conduction between the catalyst and bulk electrolyte and (ii) bind the catalyst to the porous transport layer and membrane. High ion exchange capacity (IEC) ACIs are desired, however, high IEC can cause excessive water uptake (WU) and detrimental ACI swelling. Proper water management is a key factor in obtaining maximum performance in AEM-based devices. In this study, a series of poly(norbornene)-based ACIs were synthesized and deployed in hydrogen evolving AEMEL cathode electrodes. A balance between ionic conductivity, WU and ionomer swelling was achieved in the ACI by varying the IEC and degree of polymer cross-linking. It was found that higher IEC ACIs with light crosslinking are preferred in the HER electrode. Furthermore, such a configuration fine-tuned the WU and ionomer swelling to achieve optimum cell performance and reduce cell operating voltages.

08 HYDROGEN↗

Over 11% Efficient Eco-Friendly Kesterite Solar Cell: Effects of S-Enriched Surface of Cu2ZnSn(S,Se)4 Absorber and Band Gap Controlled (Zn,Sn)O Buffer

For high efficiency kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cell, CdS thin film was usually used as a buffer layer. However, due to the toxicity of Cd and pollution problems involved from the solution-based chemical bath deposition, eco-friendly high efficiency CZTSSe solar cell with Cd-free buffer is necessary. As an Cd-free buffer layer, we investigated (Zn,Sn)O (ZTO) film deposited by sputtering method. In order to achieve high power conversion efficiency, we controlled energy band gaps of CZTSSe absorber as well as ZTO buffer, which was required to optimize conduction band offset (CBO) between the absorber and the buffer and to increase open circuit voltage (Voc) and fill factor (FF). The CBO was optimized by controlling the band gap of ZTO. By varying the Sn/(Zn + Sn) ratio and its deposition temperature, band gap of ZTO was successfully adjusted. Experimental and computational calculation results showed that solar cell performance was strongly affected by the CBO between absorber and buffer. Besides CBO matching, larger band gap of ZTO improved short circuit current density (Jsc) with enhanced external quantum efficiency value in blue photon spectrum range. As an additional way to improve power conversion efficiency of solar cell, band graded CZTSSe absorber was developed by using spray-based two-step process. The sprayed CZTSSe film was engineered to have S-enriched surface, which makes surface band gap widened and surface passivated, and resultantly increases Voc, Jsc and fill factor (FF). By controlling band gaps of both CZTSSe absorber and ZTO buffer, we obtained 11.22% environment-friendly CZTSSe solar cell without MgF2 anti-reflection coating.

(Zn↗

Infrared compatible rapid mixer to probe millisecond chemical kinetics

Fast microfluidic mixers are a valuable tool for studying solution-phase chemical reaction kinetics and molecular processes with spectroscopy. However, microfluidic mixers that are compatible with infrared vibrational spectroscopy have seen only limited development due to the poor infrared transparency of the current microfabrication material. We describe the design, fabrication, and characterization of CaF2-based continuous flow turbulent mixers, which are capable of measuring kinetics in the millisecond time window with infrared spectroscopy, when integrated into an infrared microscope. Kinetics measurements demonstrate the ability to resolve relaxation processes with 1 millisecond time resolution, and straightforward improvements are described that should result in sub-100 µs time-resolution.

Instruments & Instrumentation↗

Deciphering the Solvent Effect for the Solvation Structure of Ca 2+ in Polar Molecular Liquids

Although the crystal structures for many inorganic compounds are readily available, researchers are still working hard to understand the relations between the structures and chemical properties of solutions because most of the chemical reactions take place in solutions. A huge amount of effort has been put toward modeling the ion solvation structure from the perspectives of both experiments and theories. In this study, the solvation structures of Ca 2+ ions in aqueous and alcoholic solutions at different concentrations were carefully evaluated by Ca K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. Further, density functional theory (DFT) calculations were also performed to correlate the results with the experimental data and then further extended to other similar systems. It was found that the number of coordinating solvent molecules decreases with increasing Ca 2+ concentration and increasing solvent molecule sizes. From the EXAFS data, it was observed that the first solvation shell of Ca 2+ splits into two Ca-O distances in a methanol solution and the counter ion Cl - might also be within the first shell at high concentrations. For the first time, the effects of solvents with different polarities and sizes on the ion solvation environment were systematically evaluated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optically tunable mesoscale CdSe morphologies via inorganic phototropic growth

Inorganic phototropic growth using only spatially conformal illumination generated Se–Cd films that exhibited precise light-defined mesoscale morphologies including highly ordered, anisotropic, and periodic ridge and trench nanotextures over entire macroscopic substrates. Growth was accomplished via a light-induced electrochemical method using an optically and chemically isotropic solution, an unpatterned substrate, and unstructured, incoherent, low-intensity illumination in the absence of chemical directing agents or physical templates and masks. The morphologies were defined by the illumination inputs: the nanotexture long axes aligned parallel to the optical E-field vector, and the feature sizes and periods scaled with the wavelength. Optically based modeling of the growth closely reproduced the experimental results, confirming the film morphologies were fully determined by the light–matter interactions during growth. Solution processing of the Se–Cd films resulted in stoichiometric, crystalline CdSe films that also exhibited ordered nanotextures, demonstrating that inorganic phototropic growth can effect tunable, template-free generation of ordered CdSe nanostructures over macroscopic length scales.

36 MATERIALS SCIENCE↗