Nanoscale Matter Research Articles

Bringing atom probe tomography to transmission electron microscopes

For the purpose of enhancing the structural insights within the three-dimensional composition fields revealed by atom probe tomography, correlative microscopy approaches, combining (scanning) transmission electron microscopy with atom probe tomography, have emerged and demonstrated their relevance. To push the boundaries further and facilitate a more comprehensive analysis of nanoscale matter by coupling numerous two- or three-dimensional datasets, there is an increasing interest in combining transmission electron microscopy and atom probe tomography into a unified instrument. This study presents the tangible outcome of an instrumental endeavour aimed at integrating atom probe tomography into a commercial transmission electron microscope. The resulting instrument demonstrates the feasibility of combining in situ 3D reconstructions of composition fields with the detailed structural analysis afforded by transmission electron microscopy. This study shows a promising approach for converging these two important nanoscale microscopy techniques.

Continuous Space-Time Crystal State Driven by Nonreciprocal Optical Forces.

We show that the continuous time crystal state can arise in an ensemble of linear oscillators from nonconservative coupling via optical radiation pressure forces. This new mechanism comprehensively explains observations of the time crystal state in an array of nanowires illuminated with light [T. Liu et al., Nat. Phys. 19, 986 (2023).NPAHAX1745-247310.1038/s41567-023-02023-5]. Being fundamentally different from regimes of nonlinear synchronization, it has relevance to a wide range of interacting many-body systems, including in the realms of chemistry, biology, weather, and nanoscale matter.

Engineering Anisotropy into Organized Nanoscale Matter.

Programming the organization of discrete building blocks into periodic and quasi-periodic arrays is challenging. Methods for organizing materials are particularly important at the nanoscale, where the time required for organization processes is practically manageable in experiments, and the resulting structures are of interest for applications spanning catalysis, optics, and plasmonics. While the assembly of isotropic nanoscale objects has been extensively studied and described by empirical design rules, recent synthetic advances have allowed anisotropy to be programmed into macroscopic assemblies made from nanoscale building blocks, opening new opportunities to engineer periodic materials and even quasicrystals with unnatural properties. In this review, we define guidelines for leveraging anisotropy of individual building blocks to direct the organization of nanoscale matter. First, the nature and spatial distribution of local interactions are considered and three design rules that guide particle organization are derived. Subsequently, recent examples from the literature are examined in the context of these design rules. Within the discussion of each rule, we delineate the examples according to the dimensionality (0D-3D) of the building blocks. Finally, we use geometric considerations to propose a general inverse design-based construction strategy that will enable the engineering of colloidal crystals with unprecedented structural control.

Imaging 3D chemistry at 1 nm resolution with fused multi-modal electron tomography

Measuring the three-dimensional (3D) distribution of chemistry in nanoscale matter is a longstanding challenge for metrological science. The inelastic scattering events required for 3D chemical imaging are too rare, requiring high beam exposure that destroys the specimen before an experiment is completed. Even larger doses are required to achieve high resolution. Thus, chemical mapping in 3D has been unachievable except at lower resolution with the most radiation-hard materials. Here, high-resolution 3D chemical imaging is achieved near or below one-nanometer resolution in an Au-Fe3O4 metamaterial within an organic ligand matrix, Co3O4-Mn3O4 core-shell nanocrystals, and ZnS-Cu0.64S0.36 nanomaterial using fused multi-modal electron tomography. Multi-modal data fusion enables high-resolution chemical tomography often with 99% less dose by linking information encoded within both elastic (HAADF) and inelastic (EDX/EELS) signals. We thus demonstrate that sub-nanometer 3D resolution of chemistry is measurable for a broad class of geometrically and compositionally complex materials.

Petrographic Insights into the Evolution of Nano-Scale Organic Matter Pores with Organic Matter Conversion

To investigate the influence of organic matter conversion on the evolution of organic matter pores, fractional conversion (TRHI) and loss of TOC (TOCL) from the organic matter conversion of Middle Jurassic Dameigou Formation shale samples were calculated using petrographic analysis. The TRHI of organic matter varies from 0.30 to 0.88 and TOCL content ranges from 0.62% and 4.09%. Relative to samples of Type III organic matter in shales, type II samples exhibit higher TRHI and TOCL values. Petrographic calculations of TRHI reveal that the fractional conversion of different kerogens differs for the same thermal maturity level. The specific surface area (SBET) ranges between 1.25 and 6.63 m2/g and micropore surface area (Smic) ranges between 4.16 and 21.27 m2/g. Correlations between pore structure parameters and TOCL content are higher than those between pore structure parameters and TOC content. The original TOC content decreases with increasing maturity level owing to hydrocarbon generation from organic matter conversion. The development of organic matter pores depends mainly on organic matter conversion, which is influenced by the richness, organic maceral compositions, and thermal maturity of the organic matter. The contents of kaolinite, illite, and mixed-layer illite/smectite (I/S) in the studied shales are 17.83%–37.05%, 5.36%–11.31%, and 5.27%–14.36%, respectively. Pore structure parameters (SBET and Smic) exhibit moderate positive correlations with illite content and I/S content, and moderate negative correlations with kaolinite content, indicating that different clay minerals have differential effects on pore structure.

Nanomaterials: An overview of synthesis, classification, characterization, and applications

AbstractSignificant research employing nanomaterials has been conducted in the field of nanotechnology over the past few years. Due to the significant advancements made in a number of industries, including electronics, energy, medical, cosmetics, food engineering, telecommunications, and agriculture, nanotechnology is advancing quickly. As a result, nanomaterials are the foundation of nanotechnology. Due to their small size, nanomaterials have special optical, magnetic, electrical, and physical, reactivity, strength, surface area, sensitivity, and stability features. Surprisingly, the phase change occurs when bulk materials are converted into nanomaterials, which means that materials that were previously non‐magnetic become magnetic at the nanoscale. Because of its unique features, nanoscale matter is a separate form of matter from the solid, liquid, gaseous, and plasma states. Nanomaterials' characteristics are mostly determined by their shapes and sizes. In this paper a critical overview of nanomaterials, their varieties, characteristics, synthesis techniques, and applications in various fields is offered.

Energy transfer and charge transfer between semiconducting nanocrystals and transition metal dichalcogenide monolayers.

Nowadays, as a result of the emergence of low-dimensional hybrid structures, the scientific community is interested in their interfacial carrier dynamics, including charge transfer and energy transfer. By combining the potential of transition metal dichalcogenides (TMDs) and nanocrystals (NCs) with low-dimensional extension, hybrid structures of semiconducting nanoscale matter can lead to fascinating new technological scenarios. Their characteristics make them intriguing candidates for electronic and optoelectronic devices, like transistors or photodetectors, bringing with them challenges but also opportunities. Here, we will review recent research on the combined TMD/NC hybrid system with an emphasis on two major interaction mechanisms: energy transfer and charge transfer. With a focus on the quantum well nature in these hybrid semiconductors, we will briefly highlight state-of-the-art protocols for their structure formation and discuss the interaction mechanisms of energy versus charge transfer, before concluding with a perspective section that highlights novel types of interactions between NCs and TMDs.

Complementary Surface‐Enhanced Raman Scattering (SERS) and IR Absorption Spectroscopy (SEIRAS) with Nanorods‐on‐a‐Mirror

AbstractThe surface‐enhanced counterparts of Raman scattering (SERS) and infrared (IR) absorption (SEIRAS) are commonly used to probe and identify nanoscale matter and small populations of molecules. The contrasting selection rules offer complementary vibrational information of bulk solids or solutions. In this study, a complementary surface‐enhanced vibrational spectroscopy approach is presented to probe the vibrational signature of metal‐bound molecular monolayers. Nanocavities are designed and produced with sharp and tunable visible (VIS) and mid‐IR gap resonances by placing nanorods on a mirror that is coated with a thin dielectric spacer. Their VIS resonances are tuned to match a 1.61 eV (770 nm) resonant excitation for SERS, while their mid‐IR resonances span the 1500–2800 cm−1 range (6.5–3.5 µm) in high resolution for SEIRAS, targeting CN bond vibrations at 2220 cm−1. Both the VIS and mid‐IR gap modes support spatially overlapping and highly enhanced near‐fields ensuring strong SERS and SEIRAS signals from the same monolayer molecular population. The differences in the vibrational information obtained with the two surface‐enhanced spectroscopies when probing coupled molecular vibrations are highlighted and the advantages of using such a platform for investigating cavity‐modified chemical reactions are discussed.

Sorting Nanoparticles by Valency with DNA Barcoding.

Self-assembly of DNA-labeled nanoparticles is an effective strategy to fabricate new nanocomposite materials and nanoscale devices from the bottom-up. To tailor the properties of the resulting material or device, one requires access to a wide range of nanoparticle sizes and shapes, as well as control over the number (valency) of DNA molecules on the nanoparticle surface. Currently, nanoparticles with a defined DNA valency can only be obtained in a narrow range of sizes, and in small quantities, limiting the properties of the resulting composite structures and their applications. Here, we leverage the digital information encoded in the number and sequence of short DNA barcodes to generate preparatory amounts of nanoparticles bearing a specific number of DNA molecules, irrespective of the identity of the nanocomponent. We show that this DNA valency sorting chromatography, which is driven by the selective affinity of Watson-Crick base pairs, is applicable to arbitrary DNA sequences and a broad range of nanoparticle sizes, shapes, and material compositions. To further demonstrate this fact, we use valency-sorted large gold nanospheres directly in self-assembly schemes to create, in one synthesis step, large amounts of several previously inaccessible molecule-like dimer and trimer nanostructures with unique optical properties. We anticipate that the expanded scope of DNA valency-defined nanoparticle reagents, and the increased scale at which they can be produced, will open new avenues for the molecularly precise manipulation of nanoscale matter.

Analytical separation techniques: toward achieving atomic precision in nanomaterials science.

The size- and shape-dependence of the properties are the most characteristic features of nanoscale matter. In many types of nanomaterials, there is a size regime wherein every atom counts. In order to fully realize the idea of 'maneuvering things atom by atom' envisioned by Richard Feynman, synthesis and separation of nanoscale matter with atomic precision are essential. It is therefore not surprising that analytical separation techniques have contributed tremendously toward understanding the size- as well as shape-dependent properties of nanomaterials. Fascinating properties of nanomaterials would not have been explored without the use of these techniques. Here we discuss the pivotal role of analytical separation techniques in the progress of nanomaterials science. We begin with a brief overview of some of the key analytical separation techniques that are of tremendous importance in nanomaterials research. Then we describe how each of these techniques has contributed to the advancements in nanomaterials science taking some of the nanosystems as examples. We discuss the limitations and challenges of these techniques and future perspectives.

Modeling Non-adiabatic Dynamics in Nanoscale and Condensed Matter Systems.

Rapid, far-from-equilibrium processes involving excitation of electronic, vibrational, spin, photon, topological, and other degrees of freedom form the basis of modern technologies, including electronics and optoelectronics, solar energy harvesting and conversion to electrical and chemical energy, quantum information processing, spin- and valleytronics, chemical detection, and medical therapies. Such processes are studied experimentally with various time-resolved spectroscopies that allow scientists to track system's evolution on ultrafast time scales and at close to atomistic level of detail. The availability of various forms of lasing has made such measurements easily accessible to many experimental groups worldwide, to study atoms and small molecules, nanoscale and condensed matter systems, proteins, cells, and mesoscopic materials. The experimental work necessitates parallel theoretical efforts needed to interpret the experiments and to provide insights that cannot be gained through measurements due to experimental limitations.Non-adiabatic (NA) molecular dynamics (MD) allows one to study processes at the atomistic level and in the time domain most directly mimicking the time-resolved experiments. Atomistic modeling takes full advantage of chemical intuition and principles that guide design and fabrication of molecules and materials. It provides atomistic origins of quasi-particles, such as holes, excitons, trions, plasmons, phonons, polarons, polaritons, spin-waves, momentum-resolved and topological states, electrically and magnetically polarized structures, and other abstract concepts. An atomistic description enables one to study realistic aspects of materials, which necessarily contain defects, dopants, surfaces, interfaces, passivating ligands, and solvent layers. Often, such realistic features govern material properties and are hard to account for phenomenologically. NA-MD requires few approximations and assumptions. It does not need to assume that atomic motions are harmonic, that electrons are Drude oscillators, that coupling between different degrees of freedom is weak, that dynamics is Markovian or has short memory, or that evolution occurs by exponential kinetics of transitions between few states. The classical or semiclassical treatment of atomic motions constitutes the main approximation of NA-MD and is used because atoms are 3-5 orders of magnitude heavier than electrons. NA-MD is limited by system size, typically hundreds or thousands of atoms, and time scale, picoseconds to nanoseconds. The quality of NA-MD simulations depends on the electronic structure method used to obtain excited state energies and NA couplings.NA-MD has been largely popularized and advanced in the chemistry community that focuses on molecules. Modeling far-from-equilibrium dynamics in nanoscale and condensed matter systems often has to account for other types of physics. At the same time, condensed phase NA-MD allows for approximations that may not work in molecules. Focusing on the recent NA-MD developments aimed at studying excited state processes in nanoscale and condensed phases, this Account considers how the phenomena important on the nanoscale can be incorporated into NA-MD and what approximations can be made to increase its efficiency with complex systems and processes.

Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase

Programming living and soft complex matter via primary structure and self-organization represents the key methodology employed to design functions in biological and synthetic nanoscience. Memory effects have been used to create commercial technologies including liquid crystal displays and biomedical applications based on shape memory polymers. Supramolecular orientational memory (SOM), induced by an epitaxial nucleation mediated by the close contact spheres of cubic phases, emerged as a pathway to engineer complex nanoscale soft matter of helical columnar hexagonal arrays. SOM preserves the crystallographic directions of close contact supramolecular spheres from the 3D phase upon cooling to the columnar hexagonal periodic array. Despite the diversity of 3D periodic and quasiperiodic nanoarrays of supramolecular dendrimers, including Frank-Kasper and quasicrystal, all examples of SOM to date were mediated by Im3¯m (body-centered cubic, BCC) and Pm3¯n (Frank-Kasper A15) cubic phases. Expanding the scope of SOM to non-cubic arrays is expected to generate additional morphologies that were not yet available by any other methods. Here we demonstrate the SOM of a dendronized triphenylene that self-organizes into helical columnar hexagonal and tetragonal P42/mnm (Frank-Kasper σ) phases. Structural analysis of oriented fibers by X-ray diffraction reveals that helical columnar hexagonal domains self-organize an unusual rectangular bipyramidal morphology upon cooling from the σ phase. The discovery of SOM in a non-cubic Frank-Kasper phase indicates that this methodology may be expanded to other periodic and quasiperiodic nanoarrays organized from self-assembling dendrimers and, most probably, to other soft and living complex matter.

Experimental Study on the Development Characteristics and Controlling Factors of Microscopic Organic Matter Pore and Fracture System in Shale

Research on microscopic pore and fracture system of shale is a hot spot in the field of unconventional petroleum geology. Micro- and nano-scale organic matter pores in shale play a vital role in the accumulation of hydrocarbons. Research on the types, evolution rules and controlling factors of organic matter pore-fracture system in shale reservoirs can provide scientific guidance for the prediction of shale “sweet spots”. In this paper, taking the shales from the Napo Formation, Oriente Basin, the Shahejie Formation, Zhanhua Sag, Bohai Bay Basin, and the Longmaxi and Wufeng Formations, Sichuan Basin as an example, the developmental characteristics of organic matter pore-fracture system were systematically studied using thin section, argon ion profiling scanning electron microscopy, X-ray diffraction, N2 adsorption and desorption, geochemistry experiments, and image processing technology. The types of shale organic matter pores were divided into kerogen-hosted pores, organic matter microfractures (intra-organic matter and organic matter edge microfractures), and asphalt pores (or intra-asphalt pores). The circumferences of organic pore were generally within 100 nm, and the areas of most pores were smaller than 1,000 nm2. Face rates of the organic pores were generally less than 1.5%, and the proportion of shale samples with a shape factor of 1 reached more than 50%. In addition, the deviation angles of organic matter pores at (0°, 45°) reached 90%, which showed that most of the organic matter pores tended to be oriented pores. The increase in the degree of thermal evolution provided driving force for the formation of circular pores in the organic matter. Internal factors (abundance of organic matter, kerogen types, and maturity) and external factors (diagenesis and mineral composition) controled the development of shale organic matter pores. Maturity, TOC content and inorganic minerals such as clay and pyrite content were positively correlated with the development of organic matter pores. However, brittle minerals caused a decrease in the face ratio of organic matter pores. Diagenetic compaction caused the organic matter pores being deformed or eventually disappeared. This research can provide scientific guidance for the high-efficiency exploration of hydrocarbons in shale.

Essential semiconductor films in micro-/nano-biosensors: Current scenarios

BackgroundEngineering nanoscale matter in a controlled functional system has expanded the area of science in the state-of-art of nanotechnology. The urgency in introducing real-time health monitoring sensors and rapid diagnostic tools in medical health is indeed high and crucial to date. The efforts are accompanied by nanotechnology to improve the sensors performances. In this line, semiconductor materials (Silicon/Silica) have been in well-focus to develop micro-/nano-sensors. MethodsFurther, additional layering such as metal oxide and graphene material have elevated the current scenario in biosensor developments. Among these, two-dimensional graphene nanomaterial owns its remarkable mechanical, electronic, electrochemical, and optical properties, has excited the medical field to develop graphene-based biosensors for human health diagnosis and monitoring. The oxygen rich graphene materials enhance the bio-functionalization of recognition bio-elements for excellent graphene-based biosensor development. SignificanceThis review encloses the excellence of semiconductor materials in conjunction with biosensors for monitoring health and diagnosis. The advances and challenges encountered with developing semiconductors for nanobiosensors from laboratory set-up to the novel hand-held device for rapid and accurate human health care are outlined.

Characterisation of nano-assemblies inside mesopores using neutron scattering*

Adsorption of molecular and nanoscale matter in mesoporous materials is important in filtration and chromatography as well as membrane processes. However, the morphology and distribution of self-assembled structures of adsorbate formed within nanoconfined environments is largely unknown. Small Angle Neutron Scattering (SANS) with porous matrix matching the neutron scattering length density of the solvent has the potential to provide detailed information on the self-assemblies formed in pore spaces. However, analysis of such SANS profiles remains a challenge. In this study, we extend the SANS analysis method previously developed by Findenegg and co-workers to include interparticle correlations, providing a qualitative characterisation of the adsorption state of surfactants and nanoparticles in the cylindrical pores of silica nanomaterials. We find that the pore filling fraction and the self-assembled state of the adsorbate governs the scattering profile. We apply the model to two materials namely, triethyleneglycol monohexyl ether (C6E3) surfactant and gold nanoparticles adsorbed in SBA-15 mesoporous silica. In contrast to the C6E3 system, Bragg scattering dominates the diffuse scattering in gold nanoparticle system, which we attribute to the immobile internal structure of the nanoparticles. This new SANS analysis method has potential to elucidate structures of soft matter nanoassemblies inside mesopores.

A NIST facility for resonant soft x-ray scattering measuring nano-scale soft matter structure at NSLS-II

We present the design and performance of a polarized resonant soft x-ray scattering (RSoXS) station for soft matter characterization built by the national institute of standards and technology at the national synchrotron light source-II (NSLS-II). The RSoXS station is located within the spectroscopy soft and tender beamline suite at NSLS-II located in Brookhaven national laboratory, New York. Numerous elements of the RSoXS station were designed for optimal performance for measurements on soft matter systems, where it is of critical importance to minimize beam damage and maximize collection efficiency of polarized x-rays. These elements include a novel optical design, sample manipulator and sample environments, as well as detector setups. Finally, we will report the performance of the measurement station, including energy resolution, higher harmonic content and suppression methods, the extent and mitigation of the carbon absorption dip on optics, and the range of polarizations available from the elliptically polarized undulator source.

Self-assembled, Programmable DNA Nanodevices for Biological and Biomedical Applications.

The broad field of structural DNA nanotechnology has diverged into various areas of applications ranging from computing, photonics, synthetic biology, and biosensing to in-vivo bioimaging and therapeutic delivery, to name but a few. Though the field began to exploit DNA to build various nanoscale architectures, it has now taken a new path to diverge from structural DNA nanotechnology to functional or applied DNA nanotechnology. More recently a third sub-branch has emerged-biologically oriented DNA nanotechnology, which seeks to explore the functionalities of combinatorial DNA devices in various biological systems. In this review, we summarize the key developments in DNA nanotechnology revealing a current trend that merges the functionality of DNA devices with the specificity of biomolecules to access a range of functions in biological systems. This review seeks to provide a perspective on the evolution and biological applications of DNA nanotechnology, where the integration of DNA structures with biomolecules can now uncover phenomena of interest to biologists and biomedical scientists. Finally, we conclude with the challenges, limitations, and perspectives of DNA nanodevices in fundamental and applied research.

Magnetic anisotropy and core-shell structure origin of the biogenic ferrihydrite nanoparticles

Ferrihydrite is a low-crystalline nanoscale matter. The uncompensated magnetic moment of the ferrihydrite caused by the antiferromagnetic ordering of the magnetic moments of iron atoms and leads to the magnetic properties very similar to those of ferro- and ferrimagnetic nanoparticles. In this study, we investigated the biogenic ferrihydrite nanoparticles with the narrow size distribution and an average diameter of ≈2 nm obtained by the bacteria life cycle. The features caused by the surface effects and the inhomogeneous structure of ferrihydrite have been examined in the temperature range of 4–300 K using Mössbauer spectroscopy and magnetometry. Based on the Mössbauer data, we identified the superparamagnetic blocking temperature at the temperature of 30 K for the largest ferryhidrite particles. We established that the exceptional magnetic anisotropy of ferrihydrite (KV=1.2⋅105 erg/cm3 and KS=0.1 erg/cm2) is reached because of the highly developed ferrihydrite nanoparticles’ surface. According to the Mössbauer data, we propose a core-shell structural model of the biogenic ferrihydrite particles. We found that the size of the dense core depends on the particle size. The well-crystallized core is formed only for nanoparticles larger than ≈2 nm, whereas smaller particles consist entirely of a matter with a lower density of iron atoms.

Nanodielectrics

Polymers and insulating fluids as dielectrics and electrical insulation are the cornerstones of electrical as well as electronics engineering. The former because of their excellent electrical properties, ease of processing and low cost, and the latter due to their superior heat transfer capabilities. With the increasing requirements for transfer power, hence increasing voltage level of power systems, the properties of dielectrics, in particular high-field electrical properties, need to be significantly improved to fulfill the requirements for operational safety and reliability of power systems in the long term. However, the techniques used for large scale production of dielectrics meet a bottleneck, when further improvement of electrical properties are necessary, while maintaining key thermo-mechanical properties. Fortunately, nanotechnology may provide solutions to this problem. Some nanoparticles have been identified to exhibit great potential for improving the electrical properties of dielectrics. In this case the nanoparticles-containing dielectric polymers they have been termed as Nanodielectrics, while liquid insulation systems with nanoscale matter are referred to as Nanofluids.

Controlled Preparation of Nanoparticle Gradient Materials by Diffusion.

Nanoparticle gradient materials combine a concentration gradient of nanoparticles with a macroscopic matrix. This way, specific properties of nanoscale matter can be transferred to bulk materials. These materials have great potential for applications in optics, electronics, and sensors. However, it is challenging to monitor the formation of such gradient materials and prepare them in a controlled manner. In this study, we present a novel universal approach for the preparation of this material class using diffusion in an analytical ultracentrifuge. The nanoparticles diffuse into a molten thermoreversible polymer gel and the process is observed in real-time by measuring the particle concentrations along the length of the material to establish a systematic understanding of the gradient generation process. We extract the apparent diffusion coefficients using Fick’s second law of diffusion and simulate the diffusion behavior of the particles. When the desired concentration gradient is achieved the polymer solution is cooled down to fix the concentration gradient in the formed gel phase and obtain a nanoparticle gradient material with the desired property gradient. Gradients of semiconductor nanoparticles with different sizes, fluorescent silica particles, and spherical superparamagnetic iron oxide nanoparticles are presented. This method can be used to produce tailored nanoparticle gradient materials with a broad range of physical properties in a simple and predictable way.