Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “crystal engineering”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Programmable Matter: The Nanoparticle Atom and DNA Bond

Colloidal crystal engineering with DNA has led to significant advances in bottom-up materials synthesis and a new way of thinking about fundamental concepts in chemistry. Here, programmable atom equivalents (PAEs), comprised of nanoparticles (the “atoms”) functionalized with DNA (the “bonding elements”), are assembled through DNA hybridization into crystalline lattices. Unlike atomic systems, the “atom” (e.g., the nanoparticle shape, size, and composition) and the “bond” (e.g., the DNA length and sequence) can be tuned independently, yielding designer materials with unique catalytic, optical, and biological properties. Here in this review, nearly three decades of work that have contributed to the evolution of this class of programmable matter is chronicled, starting from the earliest examples based on gold-core PAEs, and then delineating how advances in synthetic capabilities, DNA design, and fundamental understanding of PAE-PAE interactions have led to new classes of functional materials that, in several cases, have no natural equivalent.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Observation of large Rashba spin–orbit coupling at room temperature in compositionally engineered perovskite single crystals and application in high performance photodetectors

Indirect absorption extended below the direct transition edge and increase in carrier lifetime derived from Rashba spin–orbit coupling may advance the optoelectronic applications of metal halide perovskites. Spin-orbit coupling in halide perovskites is due to the presence of heavy elements in their structure. However, when these materials lack an inversion symmetry, for example by the application of strain, spin–orbit coupling becomes odd in the electron’s momentum giving rise to a splitting in the electronic energy bands. Here we report on the observation of a large Rashba splitting of 117 meV at room temperature, as predicted by relativistic first-principles calculations, in halide perovskite single crystals through a facile compositional engineering approach. Partial substitution of organic cations by rubidium in single crystals induces significant indirect absorption and dual peak photoluminescence as a result of a large Rashba splitting. We measured circularly polarized photoluminescence and magneto-photoluminescence in perovskite films printed by single crystals as well as magneto-electroluminescence and magneto-photocurrent in spin-LEDs based on perovskite single crystals. They indicated significant spin-momentum locking due to the large Rashba effect. A hybrid perovskite single crystal photodetector achieved record figures of merit, including detectivity of more than 1.3 × 10 18 Jones which represents a three orders of magnitude improvement compared to the to date record. Furthermore, these findings show that facile compositional engineering of perovskite single crystals holds great promise for further advancing the optoelectronic properties of existing materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Local Thermal Conductivity Patterning in Rotating Lattice Crystals of Anisotropic Sb 2 S 3

The ability to control material heat transport properties over space and time can drive advanced functionalities in thermal management for electronics and system-on-chip, and enable thermal circuits. Despite the technological relevance, there are limited demonstrations of local thermal property control. Rotating lattice single (RLS) crystals—formed via laser-induced crystallization of an amorphous substrate—offer a novel avenue for local crystal engineering, unlocking opportunities for microscale property patterning. Here, thermal conductivity (𝜅) imaging is applied to RLS crystals of Sb2S3 to resolve microscale 𝜅 variations across patterned regions. Amorphous areas exhibit 𝜅 as low as 0.6 Wm −1 K −1 , while crystalline regions display periodic 𝜅 variations from 0.7 to over 2.5 Wm −1 K −1 . These variations correspond to changes in crystal orientation, revealing marked 𝜅 anisotropy. The crystal out-of-plane direction (c axis)—featuring van der Waals bonds—shows amorphous-like transport, whereas in-plane directions (a, b axes) exhibit 3.5x and 1.7x larger 𝜅, respectively. First-principles calculations, in excellent agreement with experiments, suggest that the in-plane anisotropy originates from expressed Sb lone pairs, which impart a corrugation along the b axis affecting bond stiffness and 𝜅. These findings demonstrate microscale control of thermal properties via laser-processed metastructures, with significant implications for next-generation thermal management.

14 SOLAR ENERGY↗
DOE OSTI2024

Direct observation of twisted stacking domains in the van der Waals magnet CrI 3

Van der Waals (vdW) stacking is a powerful technique to achieve desired properties in condensed matter systems through layer-by-layer crystal engineering. A remarkable example is the control over the twist angle between artificially-stacked vdW crystals, enabling the realization of unconventional phenomena in moiré structures ranging from superconductivity to strongly correlated magnetism. Here, we report the appearance of unusual 120° twisted faults in vdW magnet CrI 3 crystals. In exfoliated samples, we observe vertical twisted domains with a thickness below 10 nm. The size and distribution of twisted domains strongly depend on the sample preparation methods, with as-synthesized unexfoliated samples showing tenfold thicker domains than exfoliated samples. Cooling induces changes in the relative populations among different twisting domains, rather than the previously assumed structural phase transition to the rhombohedral stacking. The stacking disorder induced by sample fabrication processes may explain the unresolved thickness-dependent magnetic coupling observed in CrI 3 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Emerged Metallicity in Molecular Ferromagnetic Wires

Supramolecular engineering bridges molecular assembly with macromolecular charge-transfer salts, promising the design to construct supramolecular architectures that integrate cooperative properties difficult or impossible to find in conventional lattices. Here, we report the crystal engineering design and kinetic growth of one-dimensional supramolecular wires composed of bis(ethylenedithio)tetrathiafulvalene (ET + ) cation and polymeric Cu[N(CN) 2 ] 2 – anion. A bulk ferromagnetic order is discovered for filling up the gap where strong ferromagnetism is missing in such ET molecule-based charge-transfer salts. Metallicity is induced by electric current from the semiconducting wire, which is attributed to strain effect by tuning its close molecular contact. This structural feature is evidenced through the combination of various mechanistic spectroscopic studies. Further, electric dipole is established from the close molecular contacts and is suggestive to stabilize ferromagnetic spin interaction through anions bridging spin sites. The breakthrough shown here provides a pathway to explore low-dimensional supramolecular materials exhibiting strong electron correlation, metallicity, and ferromagnetism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

From Nonclassical to Classical: Crystallization Seeds Reshape Nucleation Mechanisms

Crystalline seeds are widely employed in crystallization to accelerate nucleation and control product polymorphs; yet, their impact on nucleation mechanisms remains poorly understood. While homogeneous nucleation of crystals from solution often proceeds through nonclassical pathways involving amorphous intermediates, it is unclear how seeds that promote heterogeneous nucleation reshape these mechanisms and govern polymorph selection. Here, in this study, we provide the first direct evidence that crystalline seeds can bypass the need for amorphous intermediates as nucleation sites, converting nonclassical nucleation mechanisms into classical, monomer-by-monomer crystallization pathways. Using molecular dynamics simulations of zeolite synthesis, we uncover a complex reaction network of competing nucleation processes mediated by intermediate interfacial polymorphs. The interplay between thermodynamic stability and kinetic favorability of these interfacial polymorphs dictates nucleation outcomes, creating a dynamic balance between the interfacial polymorph stability and crystallization rates. Furthermore, we show that the synthesis environment-whether monomers or aggregates serve as reactants-profoundly impacts these pathways. At moderate supersaturation, seeds eliminate amorphous intermediates and promote classical nucleation, whereas high supersaturation or aggregate-based reactants favor nonclassical pathways, even in the presence of seeds. These findings establish a general framework for understanding how seeds govern crystallization mechanisms, with broad implications for controlling nucleation kinetics, polymorph selection, and material properties. While focused on zeolites, this work reveals insights that may be applicable to biominerals, pharmaceuticals, functional materials, and catalysts, providing a basis for engineering crystallization pathways in diverse applications.

Chu-Jon, Carlos [Univ. of Utah, Salt Lake City, UT↗
DOE OSTI2020

Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials

Hydrogen-bonded organic frameworks (HOFs) are a class of porous molecular materials that rely on the assembly of organic building blocks by means of hydrogen-bonding interactions to form two-dimensional (2D) and three-dimensional (3D) crystalline networks. The reversible nature of the hydrogen-bond formation endows HOFs with the attributes of solution processability and simple regeneration. High-quality single crystals of HOFs can be grown easily for unambiguous superstructure determination by single-crystal X-ray diffraction, which is crucial for the elucidation of superstructure–property relationships. During the past decade, considerable progress has been achieved in realizing stable HOFs with permanent porosities by focusing on the design of molecular building blocks in order to introduce rigidity, auxiliary [π···π] interactions, and interpenetration of their frameworks to sustain the extended networks. The applications of HOFs are far-reaching, spanning catalysis, energy, and biomedical products as well as the storage and separation of fine chemicals. In this paper, we, first of all, provide an overview of the chronological development of HOFs, starting from the seminal work by Marsh and Duchamp in 1969 on the crystal superstructure of the hydrogen-bonded networks of trimesic acid. We identify the development of novel hydrogen-bonding motifs such as diaminotriazine (DTA), the introduction of the concept of molecular tectonics, and the establishment of permanent porosity in HOFs as being some of the milestones, which incentivized the current burgeoning research endeavors on developing HOFs as multifunctional materials. This Account is focused primarily on surveying the strategies for constructing porous 3D HOFs based on organic building blocks with peripheral carboxyl groups. These strategies are presented in the following categories: (1) the polycatenation of 2D networks by trigonal building blocks to form global 3D frameworks, (2) the utilization of building blocks with 3D geometries—tetrahedral and trigonal prismatic—that are predisposed to form 3D networks, and (3) the docking by shape-fitting of geometrically labile building blocks. We emphasize how the molecular geometry of the building blocks plays an important role in modulating the superstructures of extended frameworks so as to address specific applications. Recognizing that the in silico design of HOFs is the ultimate goal of researchers in this field, we also discuss the recent advances in superstructure prediction that lead to the formation of porous supramolecular crystals and assess the complications in implementing computational methods for HOFs with complex superstructures. We hope this Account will inspire the development of new supramolecular designs and creative approaches to crystal engineering that aid and abet the assembly of multifunctional HOFs with customizable properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Structural characterization of a new samarium–sodium heterometallic coordination polymer

Lanthanide-containing materials are of interest in the field of crystal engineering because of their unique properties and distinct structure types. In this context, a new samarium–sodium heterometallic coordination polymer, poly[tetrakis(μ 2 -2-formyl-6-methoxyphenolato)samarium(III)sodium(I)], {[SmNa(C 8 H 7 O 3 ) 4 ]·solvent} n ( Sm-1 ), was synthesized and crystallized via slow evaporation from a mixture of ethanol and acetonitrile. The compound features alternating Sm III and Na I ions, which are linked by ortho -vanillin ( o -vanillin) ligands to form a mono-periodic chain-like coordination polymer. The chains propagate along the [001] direction. Residual electron density of disordered solvent molecules in the void space could not be reasonably modeled, thus the SQUEEZE function was applied. The structural, vibrational, and optical properties are reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Structure-Dependent Lithium Metal Reactivity of Lithium Lanthanum Titanium Oxide Solid Electrolytes

Ongoing efforts to design stable, ionically conductive solid-state electrolytes (SSEs) for next-generation solid-state batteries make it clear that both long and short-range structural order strongly influence materials performance. However, clear structure-property relationships are generally lacking, making it difficult to develop design rules for improving the (electro) chemical stability of SSEs. Here, in this work, we synthesize epitaxial, single-crystal lithium lanthanum titanium oxide (LLTO) films and demonstrate that the kinetics of Ti 4+ reduction and lithium intercalation depend sensitively on the crystal orientation, with electrochemical stability increasing as LLTO (001) < (110) similar to (112) < (100). However, thermodynamic stability is ultimately unaffected-all orientations fully reduce after extended contact with Li metal. In contrast, amorphous LLTO films exhibit minimal, self-limiting reactivity that results in an interface that is stable to extended contact with Li metal. The results demonstrate the potential to engineer crystal lattice strain and long-range order to differentially tune the stability of the solid electrolyte toward reactive lithium metal and cathode materials, suggesting strategies for enabling the wider deployment of LLTO and other ionically conductive ceramic films in advanced energy storage technologies

Ketter, Benjamin [Argonne National Laboratory (ANL↗
DOE OSTI2020

Automated Identification of Molecular Crystals’ Packing Motifs

Packing motifs—patterns in how molecules orient relative to one another in a crystal structure—are an important concept in many subdisciplines of materials science because of correlations observed between specific packing motifs and properties of interest. That said, packing motif data sets have remained small and noisy due to intensive manual labeling processes and insufficient labeling schemes. The most prominent labeling algorithms calculate relative interplanar angles of nearest neighbor molecules to determine the packing motif of a molecular crystal, but this simple approach can fail when neighbors are naively sampled isotropically around the crystal structure. To remedy this issue, here we propose an optimization algorithm, which rotates the molecular crystal structure to find representative molecules that inform the packing motif. We package this algorithm into an automated framework—Autopack—which both optimally rotates the crystal structure and labels the packing motif based on the appropriate neighboring molecules. In this work, we detail the Autopack framework and its performance, which shows improvements compared to previous state-of-the-art labeling methods, providing the first quantitative point of comparison for packing motif labeling algorithms. Furthermore, using Autopack (available at https://ipo.llnl.gov/technologies/software/autopack), we perform the first large-scale study of potential relationships between chemicals’ compositions and packing motifs, which shows that these relationships are more complex than previously hypothesized from studies that used only tens of polycyclic aromatic hydrocarbon molecules. Autopack’s capabilities help pose next steps for crystal engineering research focusing not only on a molecule’s adoption of a specific packing motif but also on new structure–property relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Mie-Resonant Three-Dimensional Metacrystals

Optical metamaterials, engineered to exhibit electromagnetic properties not found in natural materials, may enable new light-based applications including cloaking and optical computing. While there have been significant advances in the fabrication of two-dimensional metasurfaces, planar structures create nontrivial angular and polarization sensitivities, making omnidirectional operation impossible. Although three-dimensional (3D) metamaterials have been proposed, their fabrication remains challenging. In this work, we use colloidal crystal engineering with DNA to prepare isotropic 3D metacrystals from Au nanocubes. We show that such structures can exhibit refractive indices as large as ~8 in the mid-infrared, far greater than that of common high-index dielectrics. Additionally, we report the first observation of multipolar Mie resonances in metacrystals with well-formed habits, occurring in the mid-infrared for sub-micron metacrystals, which we measured using synchrotron infrared microspectroscopy. Finally, we predict that arrays of metacrystals could exhibit negative refraction. The results present a promising platform for engineering devices with unnatural optical properties.

3D metamaterials↗
DOE OSTI2022

The emergence of valency in colloidal crystals through electron equivalents

Colloidal crystal engineering of complex, low-symmetry architectures is challenging when isotropic building blocks are assembled. In this study we describe an approach to generating such structures based upon programmable atom equivalents (nanoparticles functionalized with many DNA strands) and mobile electron equivalents (small particles functionalized with a low number of DNA strands complementary to the programmable atom equivalents). Under appropriate conditions, the spatial distribution of the electron equivalents breaks the symmetry of isotropic programmable atom equivalents, akin to the anisotropic distribution of valence electrons or coordination sites around a metal atom, leading to a set of well-defined coordination geometries and access to three new low-symmetry crystalline phases. All three phases represent the first examples of colloidal crystals, with two of them having elemental analogues (body-centred tetragonal and high-pressure gallium), while the third (triple double-gyroid structure) has no known natural equivalent. This approach enables the creation of complex, low-symmetry colloidal crystals that might find use in various technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Salt-Induced Polymorphs Observed in Colloidal Single Crystals

Polymorphs are solid materials with the same chemical composition but different crystallographic structures. A unique aspect of polymorphs is that they exhibit different physical properties, such as solubility, melting point, density, color, hardness, and bioavailability. Here, we synthesized polymorphs of colloidal crystals engineered with DNA by slow-cooling gold nanoparticle-core programmable atom equivalents (PAEs, particles with DNA sequences that control their bonding characteristics) under salt concentrations ranging from 0.5 to 4 M NaCl. This approach yielded a diverse set of single-crystalline phases with cubic, tetragonal, and hexagonal lattice symmetries. The structural transitions observed here arise solely from the modulation of interparticle repulsion via ionic strength and thermal processing. Notably, in certain cases, we observed diffusionless phase transformations, wherein the superlattices evolve from cubic to lower-symmetry tetragonal lattices. By tuning the thermal stability and salt concentration, we captured intermediate, metastable body-centered tetragonal structures during the slow-cool process, indicating that subtle changes in free energy can direct crystallization to low-symmetry phases. In conclusion, this study demonstrates that thermal and ionic parameters can be tuned to access and stabilize colloidal crystal polymorphs with emergent structures and interesting functional properties.

Colloidal crystallization↗
DOE OSTI2021

Amino‐Functionalised Hybrid Ultramicroporous Materials that Enable Single‐Step Ethylene Purification from a Ternary Mixture

Abstract Pyrazine‐linked hybrid ultramicroporous (pore size <7 Å) materials (HUMs) offer benchmark performance for trace carbon capture thanks to strong selectivity for CO 2 over small gas molecules, including light hydrocarbons. That the prototypal pyrazine‐linked HUMs are amenable to crystal engineering has enabled second generation HUMs to supersede the performance of the parent HUM, SIFSIX‐3‐Zn , mainly through substitution of the metal and/or the inorganic pillar. Herein, we report that two isostructural aminopyrazine‐linked HUMs, MFSIX‐17‐Ni (17=aminopyrazine; M=Si, Ti), which we had anticipated would offer even stronger affinity for CO 2 than their pyrazine analogs, unexpectedly exhibit reduced CO 2 affinity but enhanced C 2 H 2 affinity. MFSIX‐17‐Ni are consequently the first physisorbents that enable single‐step production of polymer‐grade ethylene (>99.95 % for SIFSIX‐17‐Ni ) from a ternary equimolar mixture of ethylene, acetylene and CO 2 thanks to coadsorption of the latter two gases. We attribute this performance to the very different binding sites in MFSIX‐17‐Ni versus SIFSIX‐3‐Zn .

Mukherjee, Soumya↗
DOE OSTI2023

Deinterpenetration of IRMOF‐9.

One of the iconic characteristics of metal-organic frameworks (MOFs) is the possesssion of guest-accessible pores. Increasing pore size has a direct and often beneficial impact on a MOF's adsorption and separation properties. However, as pore size increases, the resulting void spaces are often filled by interpenetrated frameworks, where one or more networks crystallize within the pore system of another identical network, reducing the MOF's free volume and pore size. Furthermore, due to the thermodynamic favorability of interpenetration during solvothermal synthesis, techniques to synthetically differentiate interpenetrated from non-interpenetrated MOFs are paramount. This study reports the synthesis of deinterpenetrated IRMOF-9 via halide mediated deinterpenetrative conversion of Zn 4 O-derived IRMOF-9. IRMOF-9, when treated with ethylammonium bromide, is quasi-selectively etched, revealing the non-interpenetrated analogue, IRMOF-10 (deinterpenetrated IRMOF-9), which can be isolated prior to complete dissolution by the bromide solution. Dye adsorption, surface area and pore size distribution analysis, and powder X-ray diffraction are consistent with successful deinterpenetration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Near Quantitative Removal of Selenate and Sulfate Anions from Wastewaters by Cocrystallization with Chelating Hydrogen-Bonding Guanidinium Ligands

Selenium (Se) has become an environmental contaminant of aquatic ecosystems as a result of human activities, particularly mining, fossil fuel combustion, and agricultural activities. By leveraging the high sulfate concentrations relative to Se oxyanions (i.e., SeO n 2– , n = 3, 4) present in some wastewaters, we have developed an efficient approach to Se-oxyanion removal by cocrystallization with bisiminoguanidinium (BIG) ligands that form crystalline sulfate/selenate solid solutions. The crystallization of the sulfate, selenate and selenite, oxyanions and of sulfate/selenate mixtures with five candidate BIG ligands are reported along with the thermodynamics of crystallization and aqueous solubilities. Oxyanion removal experiments with the top two performing candidate ligands show a near quantitative removal (>99%) of sulfate or selenate from solution. When both sulfate and selenate are present, there is near quantitative removal (>99%) of selenate, down to sub-ppb Se levels, with no discrimination between the two oxyanions during cocrystallization. Reducing the selenate concentrations by 3 orders of magnitude or more relative to sulfate, as found in many wastewaters, led to no measurable loss in Se removal efficiencies. This work offers a simple and effective alternative to selective separation of trace amounts of highly toxic selenate oxyanions from wastewaters, to meet stringent regulatory discharge limits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗