Multivariate Bayesian Optimization of CoO Nanoparticles for CO2 Hydrogenation Catalysis.

The hydrogenation of CO2 holds promise for transforming the production of renewable fuels and chemicals. However, the challenge lies in developing robust and selective catalysts for this process. Transition metal oxide catalysts, particularly cobalt oxide, have shown potential for CO2 hydrogenation, with performance heavily reliant on crystal phase and morphology. Achieving precise control over these catalyst attributes through colloidal nanoparticle synthesis could pave the way for catalyst and process advancement. Yet, navigating the complexities of colloidal nanoparticle syntheses, governed by numerous input variables, poses a significant challenge in systematically controlling resultant catalyst features. We present a multivariate Bayesian optimization, coupled with a data-driven classifier, to map the synthetic design space for colloidal CoO nanoparticles and simultaneously optimize them for multiple catalytically relevant features within a target crystalline phase. The optimized experimental conditions yielded small, phase-pure rock salt CoO nanoparticles of uniform size and shape. These optimized nanoparticles were then supported on SiO2 and assessed for thermocatalytic CO2 hydrogenation against larger, polydisperse CoO nanoparticles on SiO2 and a conventionally prepared catalyst. The optimized CoO/SiO2 catalyst consistently exhibited higher activity and CH4 selectivity (ca. 98%) across various pretreatment reduction temperatures as compared to the other catalysts. This remarkable performance was attributed to particle stability and consistent H* surface coverage, even after undergoing the highest temperature reduction, achieving a more stable catalytic species that resists sintering and carbon occlusion.

High-Throughput Selection and Experimental Realization of Two New Ce-Based Nitride Perovskites: CeMoN3 and CeWN3.

Nitride perovskites have only been experimentally realized in very few cases despite the widespread existence and commercial importance of perovskite materials. From oxide perovskites used in ultrasonics to halide perovskites that have revolutionized the photovoltaics industry, the discovery of new perovskite materials has historically impacted a wide number of fields. Here, we add two new perovskites, CeWN3 and CeMoN3, to the list of experimentally realized perovskite nitrides using high-throughput computational screening and subsequent high-throughput thin film growth techniques. Candidate compositions are first down-selected using a tolerance factor and then thermochemical stability. A novel competing fluorite-family phase is identified for both material systems, which we hypothesize is a transient intermediate phase that crystallizes during the evolution from an amorphous material to a stable perovskite. Different processing routes to overcome the competing fluorite phase and obtain phase-pure nitride perovskites are demonstrated for the CeMoN3-x and CeWN3-x material systems, which provide a starting point for the development of future nitride perovskites. Additionally, we find that these new perovskite phases have interesting low-temperature magnetic behavior: CeMoN3-x orders antiferromagnetically below T N ≈ 8 K with indications of strong magnetic frustration, while CeWN3-x exhibits no long-range order down to T = 2 K but has strong antiferromagnetic correlations. This work demonstrates the importance and effectiveness of using high-throughput techniques, both computational and experimental: they are integral to optimize the process of realizing two entirely novel nitride perovskites.

Synthesis of LaWN3 nitride perovskite with polar symmetry.

Oxide materials with the perovskite structure have been used in sensors and actuators for half a century, and halide perovskites transformed photovoltaics research in the past decade. Nitride perovskites have been computationally predicted to be stable, but few have been synthesized, and their properties remain largely unknown. We synthesized and characterized a nitride perovskite lanthanum tungsten nitride (LaWN3) in the form of oxygen-free sputtered thin films, according to spectroscopy, scattering, and microscopy techniques. We report a large piezoelectric response measured with scanning probe microscopy that together with synchrotron diffraction confirm polar symmetry of the perovskite LaWN3. Our LaWN3 synthesis should inspire growth of other predicted nitride perovskites, and measurements of their properties could lead to functional integration with nitride semiconductors for microelectromechanical devices.

Back-Surface Passivation of CdTe Solar Cells Using Solution-Processed Oxidized Aluminum.

Although back-surface passivation plays an important role in high-efficiency photovoltaics, it has not yet been definitively demonstrated for CdTe. Here, we present a solution-based process, which achieves passivation and improved electrical performance when very small amounts of oxidized Al3+ species are deposited at the back surface of CdTe devices. The open circuit voltage (Voc) is increased and the fill factor (FF) and photoconversion efficiency (PCE) are optimized when the total amount added corresponds to ∼1 monolayer, suggesting that the passivation is surface specific. Addition of further Al3+ species, present in a sparse alumina-like layer, causes the FF and PCE to drop as the interface layer becomes blocking to current flow. The optimized deposit increases the average baseline PCE for both Cu-free devices and devices where Cu is present as a dopant. The greatest improvement is found when the Al3+ species are deposited prior to the CdCl2 activation step and Cu is employed. In this case, the best-cell efficiency was improved from 12.6 to 14.4%. Time-resolved photoluminescence measurements at the back surface and quantum efficiency measurements performed at the maximum power point indicate that the performance enhancement is due to a reduction in the interface recombination current at the back surface.

SnO2-Catalyzed Oxidation in High-Efficiency CdTe Solar Cells.

Interfaces at the front of superstrate CdTe-based solar cells are critical to carrier transport, recombination, and device performance, yet determination of the chemical structure of these nanoscale regions has remained elusive. This is partly due to changes that occur at the front interfaces during high temperature growth and substantive changes occurring during postdeposition processing. In addition, these buried interfaces are extremely difficult to access in a way that preserves chemical information. In this work, we use a recently developed thermomechanical cleaving technique paired with X-ray photoelectron spectroscopy to probe oxidation states at the SnO2 interface of CdTe solar cells. We show that the tin oxide front electrode promotes the formation of nanometer-scale oxides of tellurium and sulfur. Most oxidation occurs during CdCl2/O2 activation. Surprisingly, we show that relatively low-temperature anneals (180-260 °C) used to diffuse and activate copper acceptors in a doping/back contact process also cause significant changes in oxidation at the front of the cell, providing a heretofore missing aspect of how back contact processes can modify device transport, recombination, and performance. Device performance is shown to correlate with the extent of tellurium and sulfur oxidation within this nanometer-scale region. Mechanisms responsible for these beneficial effects are proposed.

Two-Dimensional Cadmium Chloride Nanosheets in Cadmium Telluride Solar Cells.

In this study we make use of a liquid nitrogen-based thermomechanical cleavage technique and a surface analysis cluster tool to probe in detail the tin oxide/emitter interface at the front of completed CdTe solar cells. We show that this thermomechanical cleavage occurs within a few angstroms of the SnO2/emitter interface. An unexpectedly high concentration of chlorine at this interface, ∼20%, was determined from a calculation that assumed a uniform chlorine distribution. Angle-resolved X-ray photoelectron spectroscopy was used to further probe the structure of the chlorine-containing layer, revealing that both sides of the cleave location are covered by one-third of a unit cell of pure CdCl2, a thickness corresponding to about one Cl-Cd-Cl molecular layer. We interpret this result in the context of CdCl2 being a true layered material similar to transition-metal dichalcogenides. Exposing cleaved surfaces to water shows that this Cl-Cd-Cl trilayer is soluble, raising questions pertinent to cell reliability. Our work provides new and unanticipated details about the structure and chemistry of front surface interfaces and should prove important to improving materials, processes, and reliability of next-generation CdTe-based solar cells.

Revisiting the Valence and Conduction Band Size Dependence of PbS Quantum Dot Thin Films.

We use a high signal-to-noise X-ray photoelectron spectrum of bulk PbS, GW calculations, and a model assuming parabolic bands to unravel the various X-ray and ultraviolet photoelectron spectral features of bulk PbS as well as determine how to best analyze the valence band region of PbS quantum dot (QD) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) are commonly used to probe the difference between the Fermi level and valence band maximum (VBM) for crystalline and thin-film semiconductors. However, we find that when the standard XPS/UPS analysis is used for PbS, the results are often unrealistic due to the low density of states at the VBM. Instead, a parabolic band model is used to determine the VBM for the PbS QD films, which is based on the bulk PbS experimental spectrum and bulk GW calculations. Our analysis highlights the breakdown of the Brillioun zone representation of the band diagram for large band gap, highly quantum confined PbS QDs. We have also determined that in 1,2-ethanedithiol-treated PbS QD films the Fermi level position is dependent on the QD size; specifically, the smallest band gap QD films have the Fermi level near the conduction band minimum and the Fermi level moves away from the conduction band for larger band gap PbS QD films. This change in the Fermi level within the QD band gap could be due to changes in the Pb:S ratio. In addition, we use inverse photoelectron spectroscopy to measure the conduction band region, which has similar challenges in the analysis of PbS QD films due to a low density of states near the conduction band minimum.

Co-solvent enhanced zinc oxysulfide buffer layers in Kesterite copper zinc tin selenide solar cells.

A co-solvent, dimethylsulfoxide (DMSO), is added to the aqueous chemical "bath" deposition (CBD) process used to grow ZnOS buffer layers for thin film Cu2ZnSnSe4 (CZTSe) solar cells. Device performance improves markedly as fill factors increase from 0.17 to 0.51 upon the co-solvent addition. X-ray photoelectron spectroscopy (XPS) analyses are presented for quasi-in situ CZTSe/CBD-ZnOS interfaces prepared under an inert atmosphere and yield valence band offsets equal to -1.0 eV for both ZnOS preparations. When combined with optical band gap data, conduction band offsets exceed 1 eV for the water and the water/DMSO solutions. XPS measurements show increased downward band bending in the CZTSe absorber layer when the ZnOS buffer layer is deposited from water only. Admittance spectroscopy data shows that the ZnOS deposited from water increases the built-in potential (Vbi) yet these solar cells perform poorly compared to those made with DMSO added. The band energy offsets imply an alternate form of transport through this junction. Possible mechanisms are discussed, which circumvent the otherwise large conduction band spike between CZTSe and ZnOS, and improve functionality with the low-band gap absorber, CZTSe (Eg = 0.96 eV).

Substrate-controlled band positions in CH3NH3PbI3 perovskite films.

Using X-ray and ultraviolet photoelectron spectroscopy, the surface band positions of solution-processed CH3NH3PbI3 perovskite thin films deposited on an insulating substrate (Al2O3), various n-type (TiO2, ZrO2, ZnO, and F:SnO2 (FTO)) substrates, and various p-type (PEDOT:PSS, NiO, and Cu2O) substrates are studied. Many-body GW calculations of the valence band density of states, with spin-orbit interactions included, show a clear correspondence with our experimental spectra and are used to confirm our assignment of the valence band maximum. These surface-sensitive photoelectron spectroscopy measurements result in shifting of the CH3NH3PbI3 valence band position relative to the Fermi energy as a function of substrate type, where the valence band to Fermi energy difference reflects the substrate type (insulating-, n-, or p-type). Specifically, the insulating- and n-type substrates increase the CH3NH3PbI3 valence band to Fermi energy difference to the extent of pinning the conduction band to the Fermi level; whereas, the p-type substrates decrease the valence band to Fermi energy difference. This observation implies that the substrate's properties enable control over the band alignment of CH3NH3PbI3 perovskite thin-film devices, potentially allowing for new device architectures as well as more efficient devices.

Role of dopants in long-range charge carrier transport for p-type and n-type graphene transparent conducting thin films.

Monolayer to few-layer graphene thin films have several attractive properties such as high transparency, exceptional electronic transport, mechanical durability, and environmental stability, which are required in transparent conducting electrodes (TCs). The successful incorporation of graphene TCs into demanding applications such as thin film photovoltaics requires a detailed understanding of the factors controlling long-range charge transport. In this study, we use spectroscopic and electrical transport measurements to provide a self-consistent understanding of the macroscopic (centimeter, many-grain scale) transport properties of chemically doped p-type and n-type graphene TCs. We demonstrate the first large-area n-type graphene TCs through the use of hydrazine or polyethyleneimine as dopants. The n-type graphene TCs utilizing PEI, either as the sole dopant or as an overcoat, have good stability in air compared to TCs only doped with hydrazine. We demonstrate a shift in Fermi energy of well over 1 V between the n- and p-type graphene TCs and a sheet resistance of ~50 Ω/sq at 89% visible transmittance. The carrier density is increased by 2 orders of magnitude in heavily doped graphene TCs, while the mobility is reduced by a factor of ~7 due to charged impurity scattering. Temperature-dependent measurements demonstrate that the molecular dopants also help to suppress processes associated with carrier localization that may limit the potential of intrinsic graphene TCs. These results suggest that properly doped graphene TCs may be well-suited as anodes or cathodes for a variety of opto-electronic applications.

PbSe quantum dot field-effect transistors with air-stable electron mobilities above 7 cm2 V(-1) s(-1).

PbSe quantum dot (QD) field effect transistors (FETs) with air-stable electron mobilities above 7 cm(2) V(-1) s(-1) are made by infilling sulfide-capped QD films with amorphous alumina using low-temperature atomic layer deposition (ALD). This high mobility is achieved by combining strong electronic coupling (from the ultrasmall sulfide ligands) with passivation of surface states by the ALD coating. A series of control experiments rule out alternative explanations. Partial infilling tunes the electrical characteristics of the FETs.

Iron pyrite thin films synthesized from an Fe(acac)3 ink.

Iron pyrite (cubic FeS2) is a promising candidate absorber material for earth-abundant thin-film solar cells. Here, we report on phase-pure, large-grain, and uniform polycrystalline pyrite films that are fabricated by solution-phase deposition of an iron(III) acetylacetonate molecular ink followed by sequential annealing in air, H2S, and sulfur gas at temperatures up to 550 °C. Phase and elemental compositions of the films are characterized by conventional and synchrotron X-ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, and X-ray photoelectron spectroscopy (XPS). These solution-deposited films have more oxygen and alkalis, less carbon and hydrogen, and smaller optical band gaps (E(g) = 0.87 ± 0.05 eV) than similar films made by chemical vapor deposition. XPS is used to assess the chemical composition of the film surface before and after exposure to air and immersion in water to remove surface contaminants. Optical measurements of films rich in marcasite (orthorhombic FeS2) show that marcasite has a band gap at least as large as pyrite and that the two polymorphs share similar absorptivity spectra, in excellent agreement with density functional theory models. Regardless of the marcasite and elemental impurity contents, all films show p-type, weakly activated transport with curved Arrhenius plots, a room-temperature resistivity of ~1 Ω cm, and a hole mobility that is too small to measure by Hall effect. This universal electrical behavior strongly suggests that a common defect or a hole-rich surface layer governs the electrical properties of most FeS2 thin films.

Robust, functional nanocrystal solids by infilling with atomic layer deposition.

Thin films of colloidal semiconductor nanocrystals (NCs) are inherently metatstable materials prone to oxidative and photothermal degradation driven by their large surface-to-volume ratios and high surface energies. (1) The fabrication of practical electronic devices based on NC solids hinges on preventing oxidation, surface diffusion, ripening, sintering, and other unwanted physicochemical changes that can plague these materials. Here we use low-temperature atomic layer deposition (ALD) to infill conductive PbSe NC solids with metal oxides to produce inorganic nanocomposites in which the NCs are locked in place and protected against oxidative and photothermal damage. Infilling NC field-effect transistors and solar cells with amorphous alumina yields devices that operate with enhanced and stable performance for at least months in air. Furthermore, ALD infilling with ZnO lowers the height of the inter-NC tunnel barrier for electron transport, yielding PbSe NC films with electron mobilities of 1 cm2 V(-1) s(-1). Our ALD technique is a versatile means to fabricate robust NC solids for optoelectronic devices.

n-Type transition metal oxide as a hole extraction layer in PbS quantum dot solar cells.

The n-type transition metal oxides (TMO) consisting of molybdenum oxide (MoO(x)) and vanadium oxide (V(2)O(x)) are used as an efficient hole extraction layer (HEL) in heterojunction ZnO/PbS quantum dot solar cells (QDSC). A 4.4% NREL-certified device based on the MoO(x) HEL is reported with Al as the back contact material, representing a more than 65% efficiency improvement compared with the case of Au contacting the PbS quantum dot (QD) layer directly. We find the acting mechanism of the hole extraction layer to be a dipole formed at the MoO(x) and PbS interface enhancing band bending to allow efficient hole extraction from the valence band of the PbS layer by MoO(x). The carrier transport to the metal anode is likely enhanced through shallow gap states in the MoO(x) layer.

Microstructure and pseudocapacitive properties of electrodes constructed of oriented NiO-TiO2 nanotube arrays.

We report on the synthesis and electrochemical properties of oriented NiO-TiO(2) nanotube (NT) arrays as electrodes for supercapacitors. The morphology of the films prepared by electrochemically anodizing Ni-Ti alloy foils was characterized by scanning and transmission electron microscopies, X-ray diffraction, and photoelectron spectroscopies. The morphology, crystal structure, and composition of the NT films were found to depend on the preparation conditions (anodization voltage and postgrowth annealing temperature). Annealing the as-grown NT arrays to a temperature of 600 °C transformed them from an amorphous phase to a mixture of crystalline rock salt NiO and rutile TiO(2). Changes in the morphology and crystal structure strongly influenced the electrochemical properties of the NT electrodes. Electrodes composed of NT films annealed at 600 °C displayed pseudocapacitor (redox-capacitor) behavior, including rapid charge/discharge kinetics and stable long-term cycling performance. At similar film thicknesses and surface areas, the NT-based electrodes showed a higher rate capability than the randomly packed nanoparticle-based electrodes. Even at the highest scan rate (500 mV/s), the capacitance of the NT electrodes was not much smaller (within 12%) than the capacitance measured at the slowest scan rate (5 mV/s). The faster charge/discharge kinetics of NT electrodes at high scan rates is attributed to the more ordered NT film architecture, which is expected to facilitate electron and ion transport during the charge-discharge reactions.

Structural, optical, and electrical properties of PbSe nanocrystal solids treated thermally or with simple amines.

We describe the structural, optical, and electrical properties of films of spin-cast, oleate-capped PbSe nanocrystals that are treated thermally or chemically in solutions of hydrazine, methylamine, or pyridine to produce electronically coupled nanocrystal solids. Postdeposition heat treatments trigger nanocrystal sintering at approximately 200 degrees C, before a substantial fraction of the oleate capping group evaporates or pyrolyzes. The sintered nanocrystal films have a large hole density and are highly conductive. Most of the amine treatments preserve the size of the nanocrystals and remove much of the oleate, decreasing the separation between nanocrystals and yielding conductive films. X-ray scattering, X-ray photoelectron and optical spectroscopy, electron microscopy, and field-effect transistor electrical measurements are used to compare the impact of these chemical treatments. We find that the concentration of amines adsorbed to the NC films is very low in all cases. Treatments in hydrazine in acetonitrile remove only 2-7% of the oleate yet result in high-mobility n-type transistors. In contrast, ethanol-based hydrazine treatments remove 85-90% of the original oleate load. Treatments in pure ethanol strip 20% of the oleate and create conductive p-type transistors. Methylamine- and pyridine-treated films are also p-type. These chemically treated films oxidize rapidly in air to yield, after short air exposures, highly conductive p-type nanocrystal solids. Our results aid in the rational development of solar cells based on colloidal nanocrystal films.

Structural, optical, and electrical properties of self-assembled films of PbSe nanocrystals treated with 1,2-ethanedithiol.

We describe the structural, optical, and electrical properties of high-quality films of PbSe nanocrystals fabricated by a layer-by-layer (LbL) dip-coating method that utilizes 1,2-ethanedithiol (EDT) as an insolubilizing agent. Comparative characterization of nanocrystal films made by spin-coating and by the LbL process shows that EDT quantitatively displaces oleic acid on the PbSe surface, causing a large volume loss that electronically couples the nanocrystals while severely degrading their positional and crystallographic order of the films. Field-effect transistors based on EDT-treated films are moderately conductive and ambipolar in the dark, becoming p-type and 30-60 times more conductive under 300 mW cm(-2) broadband illumination. The nanocrystal films oxidize rapidly in air to yield, after short air exposures, highly conductive p-type solids. The LbL process described here is a general strategy for producing uniform, conductive nanocrystal films for applications in optoelectronics and solar energy conversion.