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At least 145 records · Page 8

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DOE OSTI2021

Deciphering exopolysaccharide functional specificity via visualization of chemical motifs that mediate microbial-microenvironment interactions in soil micromodels

Exopolysaccharides (EPS) are carbohydrate-based matrices of microbial biofilms that microbes use to adapt to their surroundings. Microbial EPS also promotes soil aggregate stability and contributes toward soil health by reducing erosion caused by continued land use. The chemical structure of EPS, even within single species biofilms, can vary greatly: from repeating units and branching patterns to the non-carbohydrate decorations. Despite the wealth of knowledge on EPS chemistry, many unresolved questions regarding the biological implications of EPS chemical variations remain. Here, we develop a mass spectrometry imaging toolbox that reveal how EPS chemistry enables microbial adaptation to different microenvironments such as specific moisture, soil-biofilm interfaces, and food source proximity. First, we developed emulated soil micromodels (ESMs), microfluidic channels that simulate the physical properties of soil, for biofilm formation in different microenvironments. Then, in order to map chemical features of EPS in these micromodels, we develop strategies for in-situ releasing of oligosaccharides using specific enzymes. Lastly, we optimized matrix-assisted laser desorption ionization (MALDI) mass spectrometry imaging (MSI) to spatially analyze the released compounds in ESMs.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Sectoral and growth rate control on elemental uptake by individual calcite crystals

Heterogeneous distribution of trace elements (impurities) within individual calcite crystals is a phenomenon commonly observed in natural and laboratory systems. Changes in thermodynamic intensive parameters (mostly chemical potential and temperature) cannot always explain the inhomogeneous impurity patterns in calcite crystals and it has been suggested that growth rate and crystallographic orientation may exert strong effects on elemental incorporation into calcite. In addition, there are a number of experimental studies on micro-scale element (E) distribution between non-equivalent pairs of calcite vicinal faces (known as sectoral zoning); however, the variability of partition coefficients (e.g., K E = (E/Ca) calcite /(E/Ca) fluid ) within individual crystals remains undetermined. In this study, we have extended the work on elemental distribution between crystal sectors to evaluation of partition coefficients of trace and minor elements (Li, B, Mg, and Sr) in calcite crystal faces (10–14) and (01-12), whose growth rates were assessed. Growth entrapment model (GEM) and lattice strain theory were applied to explain K E heterogeneity by varying near-surface diffusivity of Mg and Sr and by varying surface enrichment factor for Li, B, Mg, and Sr. Decoupling of sectoral and growth rate effects reveals that sectoral zoning plays a key role in elemental distribution. More specifically, K Li and K B vary by more than one order of magnitude and K Mg varies by a factor of two within individual crystal faces. Strontium sectoral distribution is different from those of Li, B, and Mg and K Sr varies by up to a factor of two. Finally, these behaviors likely reflect different mechanisms of incorporation of Li, B, Mg, and Sr into calcite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Nanoscale friction of CVD single-layer MoS 2 with controlled defect formation

Two-dimensional (2D) layered nanomaterials such as graphene, molybdenum disulfide (MoS 2 ), or tungsten disulfide offer a promising solution in areas of solid-state lubrication, due to their excellent mechanical properties as well as low friction. However, defects can influence their friction and reduce their superior tribological properties. Thus, it is crucial to understand the effects of defects on sliding behavior in 2D nanomaterials, to foster a functional strategy for utilizing 2D nanomaterials as solid-state tribological films. In this study, frictional effects of defects, grain boundaries, and atomic-scale structural defects were explored on chemical vapor deposition (CVD) grown single layer MoS 2 . Selective patterning of defects into MoS 2 was accomplished via controlled irradiation of helium ions with varying ion doses. The friction of MoS 2 was characterized by friction force microscopy (FFM) and was found that friction depends on the defect formation controlled by helium ion irradiation. This approach offers a correlation between surface topography, defects and friction. Understanding the relative friction of MoS 2 in the presence of different levels of defects is foundational to studying tribological properties of a single layer MoS 2 at both nanoscales and macroscales.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Infrared nanospectroscopy characterization of metal oxide photoresists

Implementation of extreme ultraviolet (EUV) lithography in high-volume semiconductor manufacturing requires a reliable and scalable EUV resist platform. A mechanistic understanding of the pros and cons of different EUV resist materials is critically important. However, most material characterization methods with nanometer resolution use an x-ray photon or electron beam as the probe, which often cause damage to the photoresist film during measurement. Here, we illustrated the use of non-destructive infrared nanospectroscopy [or nano-Fourier-Transform infrared spectroscopy (nano-FTIR)] to obtain spatially resolved composition information in patterned photoresist films. Further, clear evidence of exposure-induced chemical modification was observed at a spatial resolution down to 40 nm, well below the diffraction limit of infrared light. With improvements, such a nano-FTIR technique with nanoscale spatial resolution, chemical sensitivity, and minimal radiation damage can be a promising candidate for the fundamental study of material properties relevant to EUV lithography.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Multilevel peel-off patterning of a prototype semitransparent organic photovoltaic module

Semitransparent organic photovoltaics (ST-OPVs) with applications to power generating windows have shown substantial increases in power conversion efficiency (PCE) and average photopic transmission (APT) at the laboratory scale. Here, the demonstration of similarly efficient, large-scale ST-OPV modules with geometric fill factors (GFF) approaching 100%, however, remains a challenge. Here, we employ a multilevel peel-off patterning method that can achieve micron-scale resolution without exposing chemically sensitive organic materials to solvents. Eight, 4 cm × 0.4 cm cells are connected in series to realize a prototype ST-OPV module with GFF = 95.8%, with PCE = 7.3 ± 0.2% under simulated AM 1.5G illumination at 1 sun intensity, APT = 41.8 ± 1.4%, and a light utilization efficiency of LUE = 3.1 ± 0.1%. A neutral color STOPV module is also demonstrated with 1.7 ± 0.1% and International Commission on Illumination (CIE) LAB coordinates of (L*, a*, b*) = (53.7, -1.9, -3.9).

14 SOLAR ENERGY↗

DOE OSTI2020

Continental-scale patterns of extracellular enzyme activity in the subsoil: an overlooked reservoir of microbial activity

Abstract Chemical stabilization of microbial-derived products such as extracellular enzymes (EE) onto mineral surfaces has gained attention as a possibly important mechanism leading to the persistence of soil organic carbon (SOC). While the controls on EE activities and their stabilization in the surface soil are reasonably well-understood, how these activities change with soil depth and possibly diverge from those at the soil surface due to distinct physical, chemical, and biotic conditions remains unclear. We assessed EE activity to a depth of 1 m (10 cm increments) in 19 soil profiles across the Critical Zone Observatory Network, which represents a wide range of climates, soil orders, and vegetation types. For all EEs, activities per mass of soil correlated positively with microbial biomass (MB) and SOC, and all three of these variables decreased logarithmically with depth ( p < 0.05). Across all sites, over half of the potential EE activities per mass soil consistently occurred below 20 cm for all measured EEs. Activities per unit MB or SOC were substantially higher at depth (soils below 20 cm accounted for 80% of whole-profile EE activity), suggesting an accumulation of stabilized (i.e. mineral sorbed) EEs in subsoil horizons. The pronounced enzyme stabilization in subsurface horizons was corroborated by mixed-effects models that showed a significant, positive relationship between clay concentration and MB-normalized EE activities in the subsoil. Furthermore, the negative relationships between soil C, N, and P and C-, N-, and P-acquiring EEs found in the surface soil decoupled below 20 cm, which could have also been caused by EE stabilization. This finding suggests that EEs may not reflect soil nutrient availabilities deeper in the soil profile. Taken together, our results suggest that deeper soil horizons hold a significant reservoir of EEs, and that the controls of subsoil EEs differ from their surface soil counterparts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Physiochemical Machine Learning Models Predict Operational Lifetimes of CH3NH3PbI3 Perovskite Solar Cells

Halide perovskites are promising photovoltaic (PV) materials with the potential to lower the cost of electricity and greatly expand the penetration of PV if they can demonstrate long-term stability under illumination in the presence of moisture and oxygen. The solar cell service lifetime as quantified by the T80 (the time required for the power conversion efficiency to drop to 80% of its starting value) is a useful metric to assess stability. The T80 for utility, commercial, or residential PV systems needs to be several decades in order to yield low-cost electricity, and thus it is not practical to directly measure the T80. It would be useful if T80 could be predicted from the initial dynamics of a solar cell’s performance, but until now no models have been developed to forecast T80. In this work, we report the development of machine learning models to predict T80 of ITO/NiOx/CH3NH3PbI3/C60/BCP/Ag solar cells operating at maximum power point under 1-sun equivalent photon flux in air at varying temperatures and relative humidities. Efficiency losses are driven by short-circuit current and fill factor, indicating that chemical decomposition of the perovskite is a major contributor to degradation. Spatial patterns evident from in situ dark field optical microscopy suggest that the electric field gradient at device edges plays a significant role in perovskite decomposition, along with photochemical reactions with O2 and H2O. Models are trained using a menu of features from three distinct categories: (i) features based on measurements of the initial rates of change of device parameters, (ii) features based on the ambient conditions during operation (temperature, & partial pressure of H2O), and (iii) features based on underlying physics and chemistry. We show that a theory-based physiochemical feature derived from a model of the chemical reaction kinetics of the rate of degradation of the CH3NH3PbI3 is particularly valuable for prediction. This physiochemical feature was selected as the first or second most dominant feature in the best performing models. With a dataset consisting of 45 accelerated degradation experiments with T80 that range over a factor of 30, the model predicts T80 with an accuracy of about 40% (|predicted T80 - observed T80| / observed T80) on samples not used in training. This hybrid ML approach should be effective when applied to other compositions, device architectures, and advanced packaging schemes.

14 SOLAR ENERGY↗

DOE OSTI2022

Physiochemical Machine Learning Models Predict Operational Lifetimes of CH3NH3PbI3 Perovskite Solar Cells

14 SOLAR ENERGY↗

DOE OSTI2022

Splitting the Ring: Impact of Ortho and Meta Pi Conjugation Pathways through Disjointed [8]Cycloparaphenylene Electronic Materials

In this report, we describe the synthesis and electronic properties of small-molecule and polymeric [8]cycloparaphenylenes ([8]CPPs) with disjointed pi conjugated substituents. Arylene-ethynylene linkers were installed on opposite sides of the [8]CPP nanohoop as separated by three phenyl units on either side such that the monomer systems have syn (C2 symmetry) and anti (C1 symmetry) conformers with a small energy gap (0.1-0.6 kcal/mol). This disjoined substitution pattern necessarily forces delocalization through and around the CPP radial structure. We demonstrate new electronic states from this radial/linear mixing in both the small molecules and the pi extended polymers. Quantum chemical calculations reveal these electronic processes to arise from multiple operative radial/linear conjugation pathways, as the disjoint pattern results in both ortho and meta connections to the CPP ring. Furthermore, these results affirm the unique nature of hybrid radial and linear pi electron delocalization operative in these new conjugation pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Mechanism of Vapor-Phase Infiltration of Organometallic Hf in Poly(Methyl Methacrylate) for Hybrid Resist Applications

Inorganic–organic hybrid thin films synthesized by vapor-phase infiltration (VPI) of metal oxides into organic photoresists, such as poly(methyl methacrylate) (PMMA), have recently demonstrated their utility in extreme ultraviolet lithography, critical for angstrom-era semiconductor device miniaturization. Hafnium oxide infiltration has been reported recently for this purpose, but its detailed VPI mechanism has remained largely unexplored. In this study, we investigated the VPI characteristics and mechanisms of tetrakis(dimethylamido)hafnium (TDMAHf)─the hafnium precursor predominantly used for VPI in the field─into PMMA and examined its impact on electron-beam lithography (EBL) exposure behavior. VPI was performed at temperatures ranging from 85 to 150 °C, with chemical interactions characterized using infrared reflection-absorption spectroscopy, and resist patterning performance was evaluated through EBL dose-sensitivity assessments. The results indicate that TDMAHf forms a reversible adduct with PMMA at temperatures up to 120 °C, whereas at 150 °C, covalent bond formation occurs, most likely via dealkylation that leads to acetate formation. EBL studies reveal that resist sensitivity is influenced by both infiltration temperature and developer selection, with aqueous isopropyl alcohol development demonstrating enhanced sensitivity compared to organic solvent-based development. The optimized infiltration protocol at 120 °C ensures a uniform inorganic distribution without compromising resist dissolution. These findings not only help refine hybrid resist patterning performance but also offer insights potentially applicable to the VPI of other homoleptic metal-amide organometallic VPI precursors that include TDMA ligands.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Mixed-Flux Techniques for Rational Synthesis and Structural Control in Silver Chalcogenides

The functionality of materials is intrinsically linked to their structures, an axiom encapsulated in the principle of structure-property relationships. The pinnacle of materials design is the tailoring of its structure for a specific function, which requires the ability of rational synthesis and the development of synthesis science. This idea, however, remains elusive for the synthesis of complex extended solids. A major obstacle is the difficulty in using established chemical principles selectively to control reaction paths and favor certain structural patterns over numerous other possible results. In this context, we are developing a synthesis science approach that facilitates the control of the structure and bonding to create new structures. This is achieved by employing a two-component flux consisting of mixed hydroxides and halides as the reaction medium. This enables reaction conditions that allow better control of the structure dimensionality and composition by manipulating the temperature and solvent basicity (via the flux component ratio). Here, we demonstrate the efficacy of this method in controlling their structural motifs to arrive at 23 unreported compositions and 6 unique structure types. These materials are expected to exhibit a broad range of properties, from metallic to semiconducting, with calculations suggesting the potential for emergent phenomena such as Dirac semimetals. The reaction paths afforded by these mixed fluxes establish a direct correlation between the synthetic variables and properties, providing significant insight into a broadly applicable approach for new materials.

Zhou, Xiuquan [Argonne National Laboratory (ANL), ↗

DOE OSTI2020

Single crystal structure and photocatalytic behavior of grafted uranyl on the Zr-node of a pyrene-based metal–organic framework

Accurately characterizing actinide oxides bound to metal–organic frameworks (MOFs) is important for designing MOFs as radioactive waste sorbents and catalytic supports. Here, the zirconium MOF NU-1000 was post-synthetically modified through solvothermal deposition to include the uranyl (UO 2 2+ ) ion and characterized via single-crystal X-ray diffraction. Additonally, bond lengths derived from the diffraction pattern and Raman spectroscopy indicate that UO 2 2+ maintains its chemical properties upon deposition, while alcohol oxidation photocatalysis reveals photo-interactions between the pyrene linkers and the UO 2 2+ ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

SPRUCE S1 Bog Production of Newly-Grown Fine Roots Assessed Using Root Ingrowth Cores in 2013

This dataset contains data from root ingrowth cores from the Spruce and Peatland Responses Under Changing Environments (SPRUCE) experimental site within the Marcell Experimental Forest in northern Minnesota, USA. Root ingrowth cores were used to capture newly-grown fine roots during the 2013 growing season (June - October) at 20 locations at the southern end of the S1-Bog. Rates of fine root production were measured with root ingrowth cores and fine root traits were measured on roots that grew into ingrowth cores. Traits are reported by plant species and root orders and include nitrogen (N) content, root tissue density, specific root length, average diameter. Ingrowth cores were used to compare species-specific depth distribution patterns with minirhizotron analyses and to obtain newly produced roots for chemical analysis and measurement of morphological traits prior to the construction of the SPRUCE experimental plots. This dataset contains two data files in comma-separate values (*.csv) format. Additional metadata are provided: two data dictionaries and a file-level metadata file in comma-separate values (.csv) format and a user guide in PDF (*.pdf) format.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Characterization of latent image of electron beam resist via critical-dimension resonant soft X-ray scattering

Metrology plays a crucial role in semiconductor manufacturing by providing accurate and precise measurement and characterization of critical parameters. With the development of high-resolution extreme ultraviolet lithography (EUVL) processes, critical dimensions are shrinking to sub-10 nm. Resist materials encounter the challenge of providing heightened sensitivity and a handle on exacerbating stochastic variations. A comprehensive understanding of the chemical profile of the latent image is pivotal for mitigating stochastic effects and optimizing pattern quality. However, the subtle differences in chemistry between the exposed and unexposed regions of the resists make it extremely challenging to characterize the latent images with sub-nanometer precision. Here, we develop the metrology with critical-dimension resonant soft X-ray scattering (CD-RSoXS) to probe the chemical profiles of latent images stored in resist after exposure. The combination of absorption spectroscopy and enhanced scattering contrast makes it possible to characterize the subtle structural and chemical variations in the latent image. Moreover, the results of the measurements are compared with the simulations with a finite element method–based Maxwell solver to extract a detailed profile of the latent and developed images. We demonstrate that the CD-RSoXS technique can provide valuable insights into the high spatial resolution and local chemical sensitivity simultaneously, which is crucial to understanding the resolution limits and stochastic effects in EUVL processes.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Enhancement of chemical oscillations by self-generated convective flows

Chemical feedback loops in fluids can produce not only chemical oscillations, but also density variations that generate solutal buoyancy forces, which in turn initiate fluid flow. Using analytical and computational models, we herein examine how the reaction-induced flows alter the chemical oscillations in a fluid-filled chamber whose top and bottom walls are coated with different enzymes. Due to this chemo-fluidic coupling, the systems form oscillating flow patterns, which combine the characteristic size of the buoyancy-driven convection rolls with the frequency of the chemical oscillations. With changes in the distance between the enzyme-coated walls, the convective flows not only enhance or suppress the chemical oscillations, but also substantially increase the amplitude and frequency of the oscillations and extend the regime of the oscillatory behavior. These design principles can facilitate the development of artificial biochemical networks that act as chemical clocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Rapid Patterning and Advanced Device Structures for Low Cost Manufacturable Crystalline Si IBC Cells

Recent record efficiency Si cells have had an interdigitated back contact (IBC) design where both positive and negative contacts are fabricated on the back side of the Si wafer. Many industry groups have investigated IBC cells but used photolithography to pattern the rear contacts although it is considered impractical for low cost, high volume manufacturing. Alternative patterning methods using lasers and mechanical masking have been utilized in fabrication of patterned regions in IBC Si solar cells to replace photolithography. Another exciting advance in Si solar cell technology has been replacing the high temperature diffusion of doped regions inside the crystalline Si wafer with low temperature deposition of very thin layers of doped amorphous hydrogenated Si (a-Si:H) on the Si wafer. This is called a Si heterojunction (HJ) device. The a-Si:H provides excellent passivation of surface defects and has produced the highest open circuit voltages (VOC) of any Si solar cell device structure. The Institute of Energy Conversion (IEC) demonstrated the first IBC-HJ solar cell combining these two strategies in 2007 and has fabricated IBC-HJ cells with 20% efficiency using three photolithography steps. Despite the demonstrated efficiency potential of this device by industry groups (>26%) there is no commercial production because of the challenges of patterning and processing the structure in an industrial environment. Our work sought to address that challenge. The objective of this 3 year project was to develop the processing for the IBC-HJ Si solar cell using lasers for patterning and contact formation instead of photolithography. Laser patterning enables rapid, contactless manufacturing of patterned regions. We intensively studied laser fired contacts, laser patterning of the a-Si multi-layer stacks and metal layers and the use of plasma shadow masks. After an exhaustive focus in the first year on the laser fired emitter (LFE) and contact (LFC), we were unable to achieve VOC greater than 660 mV, compared to the 720 mV required to meet our milestones. We discovered that an additional issue with our original IBC structure was the presence of an inversion layer at the back surface connecting the p and n regions which reduced the VOC and fill factor (FF). We developed innovative methods for characterizing the inversion layer. These two limitations in the original design lead to development of a new IBC-HJ process sequence and device structure which we called Plasma Masked Laser Processed (PMLP). It retained the original high efficiency features including manufacturability. The LFC was replaced with a standard n-type a-Si HJ contact. The inversion layer was eliminated by replacing the previous p-type stack in the gap with an n-type or SiN stack. The PMLP used laser ablation of a multi-layer a-Si stack followed by chemical etching to open the n-contact. It required deposition of a patterned stack through a mask in the plasma deposition chamber. This turned out to be a source of significant problems due to inevitable unwanted deposition ‘leakage’ under the mask. This formed a blocking contact on the emitter which significantly reduced Voc and FF. Several iterations in PMLP device structure and chemical etching steps resulted in a large improvements, e.g. the efficiency increasing from 3 to 15% and Voc from 450 to 660 mV but they were unable to completely eliminate it. The best IBC-HJ device we fabricated had only 15% efficiency. For perspective, our standard FHJ devices had 20% efficiency.

14 SOLAR ENERGY↗

DOE OSTI2020

One Structure, Two Elements—LuGe 2 Superconductor vs Ordinary Metallic Conductor LuSn 2 . A Case Study on How Site-Selective Germanium for Tin Atom Substitution Leads to Modulating of the Charge Distribution

The substitution of chemically similar elements in a given crystal structure is an effective way to enhance physical properties, but the understanding on such improvements is usually impeded because the substitutions are random, and the roles of the different atoms cannot be distinguished by crystallographic symmetry. Herein, we provide a detailed crystallographic analysis and property measurements for the continuous solid solutions LuGe x Sn 2–x (0 < x < 2). The results show that there is no apparent change of the global symmetry, with the end-members LuGe 2 and LuSn 2 , as well as the intermediate LuGe x Sn 2–x compositions adopting the ZrSi 2 type structure (space group Cmcm, Pearson index oC12). Yet, the refinements of the crystal structures from single-crystal X-ray diffraction data show that Ge–Sn atom substitutions are not random, but occur preferentially at the zig-zag chain. The patterned distribution of two group 14 elements leads to a significant variation in chemical bonding and charge ordering within the other structural fragment, the 2D square nets, thereby resulting in tuned electron transport. The enhancement is greater than the typical Bloch-Gruneisen model, and more akin to the parallel-resistor model. Magnetization measurements on single crystals show bulk superconductivity in all LuGe x Sn 2–x samples with shielding fractions as high as 90%. Specific heat data confirm the effect to originate from residual metallic tin in the material, indicating that Sn atom substitutions in the 2D square nets cause disruptions of the hypervalent bonding and local anisotropy, which ultimately leads to vanishing of the superconducting state in the end-member LuGe 2 . This work sheds light on how the complexity in chemical interactions by two different carbon congeners leads to changes in the physical properties and how they can be correlated with the induced charge distribution. Furthermore, these studies also provide a general approach to modulation of charge density, and thus, of emerging physical properties in other classes of intermetallic systems based on the main-group elements of groups 13 to 15.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Artificial Intelligence Guided Studies of van der Waals Magnets

A materials informatics framework to explore a large number of candidate van der Waals (vdW) materials is developed. In particular, in this study a large space of monolayer transition metal halides is investigated by combining high-throughput density functional theory calculations and artificial intelligence (AI) to accelerate the discovery of stable materials and the prediction of their magnetic properties. Here, the formation energy is used as a proxy for chemical stability. Semi-supervised learning is harnessed to mitigate the challenges of sparsely labeled materials data in order to improve the performance of AI models. This approach creates avenues for the rapid discovery of chemically stable vdW magnets by leveraging the ability of AI to recognize patterns in data, to learn mathematical representations of materials from data and to predict materials properties. Using this approach, previously unexplored vdW magnetic materials with potential applications in data storage and spintronics are identified.

36 MATERIALS SCIENCE↗