Versatile Patterning of Liquid Metal via Multiphase 3D Printing.

This paper presents a scalable and straightforward technique for the immediate patterning of liquid metal/polymer composites via multiphase 3D printing. Capitalizing on the polymer's capacity to confine liquid metal (LM) into diverse patterns. The interplay between distinctive fluidic properties of liquid metal and its self-passivating oxide layer within an oxidative environment ensures a resilient interface with the polymer matrix. This study introduces an inventive approach for achieving versatile patterns in eutectic gallium indium (EGaIn), a gallium alloy. The efficacy of pattern formation hinges on nozzle's design and internal geometry, which govern multiphase interaction. The interplay between EGaIn and polymer within the nozzle channels, regulated by variables such as traverse speed and material flow pressure, leads to periodic patterns. These patterns, when encapsulated within a dielectric polymer polyvinyl alcohol (PVA), exhibit an augmented inherent capacitance in capacitor assemblies. This discovery not only unveils the potential for cost-effective and highly sensitive capacitive pressure sensors but also underscores prospective applications of these novel patterns in precise motion detection, including heart rate monitoring, and comprehensive analysis of gait profiles. The amalgamation of advanced materials and intricate patterning techniques presents a transformative prospect in the domains of wearable sensing and comprehensive human motion analysis.

Nanoparticle Assembly: From Self-Organization to Controlled Micropatterning for Enhanced Functionalities.

Nanoparticles form long-range micropatterns via self-assembly or directed self-assembly with superior mechanical, electrical, optical, magnetic, chemical, and other functional properties for broad applications, such as structural supports, thermal exchangers, optoelectronics, microelectronics, and robotics. The precisely defined particle assembly at the nanoscale with simultaneously scalable patterning at the microscale is indispensable for enabling functionality and improving the performance of devices. This article provides a comprehensive review of nanoparticle assembly formed primarily via the balance of forces at the nanoscale (e.g., van der Waals, colloidal, capillary, convection, and chemical forces) and nanoparticle-template interactions (e.g., physical confinement, chemical functionalization, additive layer-upon-layer). The review commences with a general overview of nanoparticle self-assembly, with the state-of-the-art literature review and motivation. It subsequently reviews the recent progress in nanoparticle assembly without the presence of surface templates. Manufacturing techniques for surface template fabrication and their influence on nanoparticle assembly efficiency and effectiveness are then explored. The primary focus is the spatial organization and orientational preference of nanoparticles on non-templated and pre-templated surfaces in a controlled manner. Moreover, the article discusses broad applications of micropatterned surfaces, encompassing various fields. Finally, the review concludes with a summary of manufacturing methods, their limitations, and future trends in nanoparticle assembly.

'Beneficial impurities' in colloidal synthesis of surfactant coated inorganic nanoparticles.

Colloidal synthesis of nanoparticles (NP) has advanced tremendously over the past 25 years, with an increasing number of research papers introducing nanomaterials with a variety of compositions, shapes, sizes, and phases. Although much progress has been achieved, commonly used synthetic procedures often fail to reproduce results, and the fine details of the syntheses are often disregarded. Reproducibility issues in synthesis can be ascribed to the effects of impurities, trace amounts of chemical moieties which significantly affect the reaction products. Impurities in NP synthesis are rarely reported or regularly studied, despite their impact, deleterious, or beneficial. This topical review discusses several case studies of colloidal NP synthesis where the sources and the chemistry of impurities are highlighted, and their role is examined.

The role of CdS doping in improving SWIR photovoltaic and photoconductive responses in solution grown CdS/PbS heterojunctions.

Low cost short wavelength infrared (SWIR) photovoltaic (PV) detectors and solar cells are of very great interest, yet the main production technology today is based on costly epitaxial growth of InGaAs layers. In this study, layers of p-type, quantum confined (QC) PbS nano-domains (NDs) structure that were engineered to absorb SWIR light at 1550 nm (Eg = 0.8 eV) were fabricated from solution using the chemical bath deposition (CBD) technique. The layers were grown on top of two different n-type CdS intermediate layers (Eg = 2.4 eV) using two different CBD protocols on fluoride tin oxide (FTO) substrates. Two types of CdS/PbS heterojunction were obtained to serve as SWIR PV detectors. The two resulting devices showed similar photoluminescence behavior, but a profoundly different electrical response to SWIR illumination. One type of CdS/PbS heterojunction exhibited a PV response to SWIR light, while the other demonstrated a photo-response to SWIR light only under an applied bias. To clarify this intriguing phenomenon, and since the only difference between the two heterojunctions could be the doping level of the CdS layer, we measured the doping level of this layer by means of the surface photo voltage (SPV). This yielded different polarizations for the two devices, indicating different doping levels of the CdS for the two different fabrication protocols, which was also confirmed by Hall Effect measurements. We performed current voltage measurements under super bandgap illumination, with respect to CdS, and got an electrical response indicating a barrier free for holes transfer from the CdS to the PbS. The results indicate that the different response does, indeed, originate from variations in the band structures at the interface of the CdS/PbS heterojunction due to the different doping levels of the CdS. We found that, unlike solar cells or visible light detectors having similar structure, in SWIR photodetectors, a type I heterojunction is formed having a barrier at the interface that limits the injection of the photo-exited electrons from the QC-PbS to the CdS side. Higher n-doped CdS generates a narrow depletion region on the CdS side, with a spike like barrier that is narrow enough to enable tunneling current, leading to a PV current. Our results show that an external quantum efficiency (EQE) of ∼2% and an internal quantum efficiency (IQE) of ∼20% can be obtained, at zero bias, for CBD grown SWIR sensitive CdS/PbS-NDs heterojunctions.

Beneficial Impurities and Phase Control in Colloidal Synthesis of Tin Monoselenide.

The effect of impurities in colloidal synthesis of SnSe in oleylamine surfactant was investigated. Specifically, it was found that impurities such as water, hydrochloric acid, and carbon dioxide stabilize the recently discovered cubic phase of tin monoselenide, π-SnSe. We describe the reaction that releases HCl to the reaction medium through reaction of SnCl2 with moisture and its subsequent reaction with oleylamine, transforming it from neutral to charged surfactant. A similar path occurs in the case of CO2, which reacts with oleylamine to give charged oleylammonium-oleylcarbamate molecular pairs. By exposing the reaction to controlled concentrations of "beneficial contaminants", hitherto a major source of irreproducibility in this synthesis, we demonstrate phase and shape control from π-SnSe cubes to α-SnSe rods.

Electric Response of CuS Nanoparticle Lubricant Additives: The Effect of Crystalline and Amorphous Octadecylamine Surfactant Capping Layers.

Octadecylamine-coated CuS nanoparticles were designed and confirmed to play an important role in their electric response and boundary lubrication in the ester lubricant. For the case of CuS nanoparticles coated with crystalline surfactant, the surface potential is 18.47 ± 0.99 mV higher than with amorphous surfactant, owing to the random chain conformations of the octadecylamine molecules. When used as a lubricant additive, CuS nanoparticles (in the form of nanoplates or nanoarrays) with a crystalline surfactant were positively charged due to the presence of the amino headgroup in octadecylamine. The observed friction coefficient decreased from 0.18 to 0.09 and 0.05, respectively, when negative potential (for the copper lower pair) was applied across untreated CuS nanoparticles. However, thermally treated CuS nanoparticles showed good lubricating effect, but almost no effect of potential control since the amino groups were obscured by the disordered carbon chains, hindering electron transfer and weakening the response to externally applied electric field.

Mapping Charge Distribution in Single PbS Core - CdS Arm Nano-Multipod Heterostructures by Off-Axis Electron Holography.

We synthesized PbS core-CdS arm nanomultipod heterostructures (NMHs) that exhibit PbS{111}/CdS{0002} epitaxial relations. The PbS-CdS interface is chemically sharp as determined by aberration corrected transmission electron microscopy (TEM) and compared to density functional theory (DFT) calculations. Ensemble fluorescence measurements show quenching of the optical signal from the CdS arms indicating charge separation due to the heterojunction with PbS. A finite-element three-dimensional (3D) calculation of the Poisson equation shows a type-I heterojunction, which would prevent recombination in the CdS arm after optical excitation. To examine charge redistribution, we used off-axis electron holography (OAEH) in the TEM to map the electrostatic potential across an individual heterojunction. Indeed, a built-in potential of 500 mV is estimated across the junction, though as opposed to the thermal equilibrium calculations significant accumulation of positive charge at the CdS side of the interface is detected. We conclude that the NMH multipod geometry prevents efficient removal of generated charge carriers by the high energy electrons of the TEM. Simulations of generated electron-hole pairs in the insulated CdS arm of the NMH indeed show charge accumulation in agreement with the experimental measurements. Thus, we show that OAEH can be used as a complementary methodology to ensemble measurements by mapping the charge distribution in single NMHs with complex geometries.

New nanocrystalline materials: a previously unknown simple cubic phase in the SnS binary system.

We report a new phase in the binary SnS system, obtained as highly symmetric nanotetrahedra. Due to the nanoscale size and minute amounts of these particles in the synthesis yield, the structure was exclusively solved using electron diffraction methods. The atomic model of the new phase (a = 11.7 Å, P2(1)3) was deduced and found to be associated with the rocksalt-type structure. Kramers-Kronig analysis predicted different optical and electronic properties for the new phase, as compared to α-SnS.

A bottom-up approach toward fabrication of ultrathin PbS sheets.

Two-dimensional (2D) sheets are currently in the spotlight of nanotechnology owing to high-performance device fabrication possibilities. Building a free-standing quantum sheet with controlled morphology is challenging when large planar geometry and ultranarrow thickness are simultaneously concerned. Coalescence of nanowires into large single-crystalline sheet is a promising approach leading to large, molecularly thick 2D sheets with controlled planar morphology. Here we report on a bottom-up approach to fabricate high-quality ultrathin 2D single crystalline sheets with well-defined rectangular morphology via collective coalescence of PbS nanowires. The ultrathin sheets are strictly rectangular with 1.8 nm thickness, 200-250 nm width, and 3-20 µm length. The sheets show high electrical conductivity at room and cryogenic temperatures upon device fabrication. Density functional theory (DFT) calculations reveal that a single row of delocalized orbitals of a nanowire is gradually converted into several parallel conduction channels upon sheet formation, which enable superior in-plane carrier conduction.

Real-time monitoring of phase transitions in π-SnS nanoparticles.

While the new cubic phase of tin monosulfide, π-SnS, shows potential for various applications, not much work was focused on the phase transitions, thermal stability, and thermal properties of π-SnS. In this work, we addressed these issues using temperature-resolved in situ X-ray diffraction combined with thermo-gravimetric differential scanning calorimetry and thermo-gravimetric infrared spectroscopy. The cubic π-SnS phase nanoparticles capped with polyvinylpyrrolidone were proven stable for 12 hours at 400 °C, pointing out the possible utilization of this new cubic phase at elevated temperatures. At the same time, heating above this temperature resulted in a phase transition to the high-temperature orthorhombic ß-SnS phase. Subsequent cooling to room temperature led to an additional phase transition to the stable orthorhombic α-SnS phase. Interestingly, heating-induced phase transformation of π-SnS nanoparticles always resulted in ß-SnS, even at temperatures below the α- to ß-SnS equilibrium transition temperature. It was shown that surfactant decomposition and evaporation triggers the phase transition. Several thermal parameters were calculated, including the phase transition activation energy and the thermal expansion of the unit cell parameter of π-SnS.

Electrical and Optical Properties of γ-SnSe: A New Ultra-narrow Band Gap Material.

We describe the unusual properties of γ-SnSe, a new orthorhombic binary phase in the tin monoselenide system. This phase exhibits an ultranarrow band gap under standard pressure and temperature conditions, leading to high conductivity under ambient conditions. Density functional calculations identified the similarity and difference between the new γ-SnSe phase and the conventional α-SnSe based on the electron localization function. Very good agreement was obtained for the band gap width between the band structure calculations and the experiment, and insight provided for the mechanism of reduction in the band gap. The unique properties of this material may render it useful for applications such as thermal imaging devices and solar cells.

Directed coassembly of oriented PbS nanoparticles and monocrystalline sheets of alkylamine surfactant.

We demonstrate control over the orientation of PbS nanoparticles by way of directed assembly, which in turn affects the crystal structure of alkylamine surfactants such as octadecylamine (ODA, C(18)H(37)NH(2)) and hexadecylamine (HDA, C(16)H(33)NH(2)). This directed assembly method results in the arrangement of PbS nanoparticles with a well-defined epitaxial orientation on lamellar alkylamine sheets, which undertake a new crystal structure to accommodate these relations. Understanding these surfactant-nanoparticle inter-relations is very instrumental in understanding surfactant-assisted nanoparticle synthesis and assembly.

Effect of metal cations on polydiacetylene Langmuir films.

Polydiacetylene (PDA) Langmuir films (LFs) are a unique class of materials that couple a highly aligned conjugated backbone with tailorable pendant side groups and terminal functionalities. The films exhibit chromatic transitions from monomer to blue polymer and finally to a red phase that can be activated optically, thermally, chemically, and mechanically. The properties of PDA LFs are strongly affected by the presence of metal cations in the aqueous subphase of the film due to their interaction with the carboxylic head groups of the polymer. In the present study the influence of divalent cadmium, barium, copper, and lead cations on the structural, morphological, and optical properties of PDA LFs was investigated by means of surface pressure-molecular area (π-A) isotherms, atomic force microscopy, optical absorbance, and Raman spectroscopy. The threshold concentrations for the influence of metal cations on the film structure, stability, and phase transformation were determined by π-A analyses. It was found that each of the investigated cations has a unique influence on the properties of PDA LFs. Cadmium cations induce moderate phase transition kinetics with reduced domain size and fragmented morphology. Barium cations contribute to stabilization of the PDA blue phase and enhanced linear strand morphology. On the other hand, copper cations enhance rapid formation of the PDA red phase and cause fragmented morphology of the film, while the presence of lead cations results in severe perturbation of the film with only a small area of the film able to be effectively polymerized. The influence of the metal cations is correlated with the solubility product (K(sp)), association strength, and ionic-covalent bond nature between the metal cations and the PDA carboxylic head groups.

Origin of the contact angle hysteresis of water on chemisorbed and physisorbed self-assembled monolayers.

Self-assembled monolayers (SAMs) are known to form on a variety of substrates either via chemisorption (i.e., through chemical interactions such as a covalent bond) or physisorption (i.e., through physical interactions such as van der Waals forces or "ionic" bonds). We have studied the behavior and effects of water on the structures and surface energies of both chemisorbed octadecanethiol and physisorbed octadecylamine SAMs on GaAs using a number of complementary techniques including "dynamic" contact angle measurements (with important time and rate-dependent effects), AFM, and electron microscopy. We conclude that both molecular overturning and submolecular structural changes occur over different time scales when such SAMs are exposed to water. These results provide new insights into the time-dependent interactions between surfaces and colloids functionalized with SAMs when synthesized in or exposed to high humidity or bulk water or wetted by water. The study has implications for a wide array of phenomena and applications such as adhesion, friction/lubrication and wear (tribology), surfactant-solid surface interactions, the organization of surfactant-coated nanoparticles, etc.

Hierarchical superstructure of alkylamine-coated ZnS nanoparticle assemblies.

We describe methodology for producing highly uniform, ordered and reproducible superstructures of surfactant-coated ZnS nanorod and nanowire assemblies, and propose a predictive multiscale "packing model" for superstructure formation based on electron microscopy and powder X-ray diffraction data on the superstructure, as well as on individual components of the nanostructured system. The studied nanoparticles showed a hierarchical structure starting from the individual faceted ZnS inorganic cores, onto which the crystalline surfactant molecules are adsorbed, to the superstructure of the nanoparticle arrays. Our results point out the critical role of the surfactant headgroup and polarity in nanoparticle assembly, and demonstrate the relationship between the molecular structure of the surfactant and the resulting superstructure of the nanoparticle assemblies.

Sample preparation induced phase transitions in solution deposited copper selenide thin films.

Thin films of CuSe were deposited onto GaAs substrate. XRD showed that the as-deposited films were of the Klockmannite (CuSe - P63/mmc 194) phase with lattice parameters a 0 = b 0 = 0.3939 nm, c 0 = 1.7250 nm; however, electron diffraction in the TEM surprisingly indicated the ß-Cu2-x Se phase (Cu1.95Se - R3̄m 166) with lattice parameters a 0 = b 0 = 0.412 nm, c 0 = 2.045 nm. The discrepancy originated from the specimen preparation method, where the energy of the focused ion beam resulted in loss of selenium which drives a phase transition to ß-Cu2-x Se in this system. The same phase transition was observed also upon thermal treatment in vacuum, as well as when the 200 keV electron beam was focused on a powder sample in the TEM. The initial phase can be controlled to some extent by changing the composition of the reactants in solution, resulting in thin films of the cubic α-Cu2-x Se (Cu1.95Se - Fm3̄m) phase co-existing together with the ß-Cu2-x Se phase.

Chemically programmed ultrahigh density two-dimensional semiconductor superlattice array.

Designing an ultrahigh density linear superlattice array consisting of periodic blocks of different semiconductors in the strong confinement regime via a direct synthetic route remains an unachieved challenge in nanotechnology. We report a general synthesis route for the formulation of a large-area ultrahigh density superlattice array that involves adjoining multiple units of ZnS rods by prolate CdS particles at the tips. A single one-dimensional wire is 300-500 nm long and consists of periodic quantum wells with a barrier width of 5 nm provided by ZnS and a well width of 1-2 nm provided by CdS, defining a superlattice structure. The synthesis route allows for tailoring of ultranarrow laserlike emissions (fwhm approximately 125 meV) originating from strong interwell energy dispersion along with control of the width, pitch, and registry of the superlattice assembly. Such an exceptional high-density superlattice array could form the basis of ultrahigh density memories in addition to offering opportunities for technological advancement in conventional heterojunction-based device applications.

Phase transition kinetics in Langmuir and spin-coated polydiacetylene films.

Thin films of 10,12-pentacosadiynoic acid were prepared using Langmuir and spin-coating techniques and polymerized using a controlled dosage of UV radiation. The radiation-induced phase transitions: from the colorless monomer, via the metastable blue phase, to the red polydiacetylene phase, and finally to degradation of the material, were monitored by optical absorbance spectroscopy. Deconvolution analysis of the absorbance curves allowed us to monitor quantitatively the dynamical changes in the chromatic properties of the films as a function of applied UV radiation dose. Several reaction kinetics models were applied in order to describe the phase transitions in the films. The results present the phase evolution in PDA and compare the kinetics for Langmuir films vs. spin-coated films. Polymerization directly at the air-water interface was found to be two-to-three orders of magnitude faster compared to solid-supported films of the same material. Moreover, we show that the data of the solid supported films is considerably better fitted when a reversible intermediate phase between the blue and the red phases is considered. Furthermore, a shift of the Raman active triple bond supports the presence of the intermediate phase.

Reaction of alkylamine surfactants with carbon dioxide: relevance to nanocrystal synthesis.

Exposure of tetradecylamine, hexadecylamine, and octadecylamine to CO(2) results in their transformation to alkylammonium alkylcarbamate (AAAC) pairs, which we find is a major source of irreproducibility in nanoparticle synthesis. Controlled exposure to CO(2) allows for highly uniform, ultranarrow ZnS nanorods coated with tetradecylamine to be reproducibly obtained in a single step. The crystal structures of the alkylamines and their AAAC analogs were investigated by powder X-ray diffraction and their isostructural three-dimensional unit cells are reported.

The temperature-dependent structure of alkylamines and their corresponding alkylammonium-alkylcarbamates.

In spite of the wide use of alkylamine (AA) surfactants, little attention has been paid to their spontaneous reactivity in air. Exposure of AA surfactants to CO(2) results in the formation of alkylammonium-alkylcarbamate (AAAC) molecular pairs. The effect of hydrocarbon chain length on the reactivity of AAs was followed by monitoring mass gain vs time under atmospheric conditions as well as in a saturated CO(2) environment. The rates of conversion to AAAC decreased with hydrocarbon chain length. Indexed powder X-ray diffractograms and the corresponding unit cells are presented for all phases of AAs and AAACs with chain lengths of 14, 16, and 18 carbons. Temperature-resolved powder X-ray diffraction of AAACs indicated anisotropic thermal expansion occurring exclusively along the a direction of the unit cell.