Direct printing of functional 3D objects using polymerization-induced phase separation.

3D printing has enabled materials, geometries and functional properties to be combined in unique ways otherwise unattainable via traditional manufacturing techniques, yet its adoption as a mainstream manufacturing platform for functional objects is hindered by the physical challenges in printing multiple materials. Vat polymerization offers a polymer chemistry-based approach to generating smart objects, in which phase separation is used to control the spatial positioning of materials and thus at once, achieve desirable morphological and functional properties of final 3D printed objects. This study demonstrates how the spatial distribution of different material phases can be modulated by controlling the kinetics of gelation, cross-linking density and material diffusivity through the judicious selection of photoresin components. A continuum of morphologies, ranging from functional coatings, gradients and composites are generated, enabling the fabrication of 3D piezoresistive sensors, 5G antennas and antimicrobial objects and thus illustrating a promising way forward in the integration of dissimilar materials in 3D printing of smart or functional parts.

Full Spectrum Raman Excitation Mapping Spectroscopy.

A generalization of the Raman scattering (RS) spectrum, the Raman excitation map (REM) is a hyperspectral two-dimensional (2D) data set encoding vibrational spectra, electronic spectra and their coupling. Despite the great potential of REM for optical sensing and characterization with remarkable sensitivity and selectivity, the difficulty of obtaining maps and the length of time required to acquire them has been practically limiting. Here we show, with a simple setup using current optical equipment, that maps can be obtained much more rapidly than before (~ms to ~100 s now vs. ~1000 s to hours before) over a broad excitation range (here ~100 nm is demonstrated, with larger ranges straightforward to obtain), thus taking better advantage of scattering resonance. We obtain maps from different forms of carbon: graphite, graphene, purified single walled carbon nanotubes (SWCNTs) and chirality enriched SWCNTs. The relative speed and simplicity of the technique make REM a practical and sensitive tool for chemical analysis and materials characterization.

Enrichment of Semiconducting Single-Walled Carbon Nanotubes with Indigo-Fluorene-Based Copolymers and Their Use in Printed Thin-Film Transistors and Carbon Dioxide Gas Sensors.

High-purity semiconducting single-walled carbon nanotubes (sc-SWCNTs) are promising for portable and high-sensitivity gas sensors because of their excellent physical and electrical properties. Here, we describe the synthesis of a novel indigo-fluorene-based copolymer (PFIDBoc) that has been designed to selectively enrich sc-SWCNTs with excellent purity (>99.9%) yet contain a latent function in the form of a tert-butoxy (t-BOC)-protected amine that can be later revealed and exploited for carbon dioxide (CO2) gas sensing. SWCNTs wrapped with the PFIDBoc polymer can be easily converted via an on-chip thermal process to reveal a vinylogous amide moiety with a secondary amine nitrogen within the indigo building block of the copolymer which is perfectly suited for CO2 recognition. Thin-film transistors and sensors were inkjet-printed onto rigid and flexible substrates, demonstrating the versatility of enriched PFIDBoc-derived sc-SWCNT dispersions. The printed transistors exhibited a mobility up to 9 cm2 V-1 s-1 and on/off current ratios >105. We further demonstrate herein a CO2 sensor for indoor air quality monitoring even in low humidity environments, possessing a linear response with up to ∼5.4% sensitivity and a dynamic range between 400 and 2000 ppm in air with a relative humidity of ∼ 40%.

Polymer Encapsulants for Threshold Voltage Control in Carbon Nanotube Transistors.

Although carbon nanotube transistors present outstanding performances based on key metrics, large-scale uniformity and repeatability required in printable electronics depend greatly on proper control of the electrostatic environment. Through a survey of polymer dielectric encapsulants compatible with printing processes, a simple correlation is found between the measured interfacial charge density and the onset of conduction in a transistor, providing a rational route to control the electrical characteristics of carbon nanotube transistors. Smooth and continuous balancing of the properties between unipolar p-type and n-type transport is achieved using a molar fraction series of poly(styrene-co-2-vinylpyridine) statistical copolymers combined with an electron-donating molecule. We further demonstrate the easy fabrication of a p-n diode which shows a modest rectification of 8:1.

Sorting of Semiconducting Single-Walled Carbon Nanotubes in Polar Solvents with an Amphiphilic Conjugated Polymer Provides General Guidelines for Enrichment.

Conjugated polymer extraction (CPE) has been shown to be a highly effective method to isolate high-purity semiconducting single-walled carbon nanotubes (sc-SWCNTs). In both literature reports and industrial manufacturing, this method has enabled enrichment of sc-SWCNTs with high purity (≥99.9%). High selectivity is typically obtained in nonpolar aromatic solvents, yet polar solvents may provide process improvements in terms of yield, purity and efficiency. Using an amphiphilic fluorene-alt-pyridine conjugated copolymer with hydrophilic side chains, we have investigated the enrichment of sc-SWCNTs in polar solvents. Various conditions such as polymer/SWCNT ratio, solvent polarity, solvent dielectric constant as well as polymer solubility and SWCNT dispersibility were explored in order to optimize the purity and yield of the enriched product. Herein, we provide insights on CPE by demonstrating that a conjugated polymer having a hydrophobic backbone and hydrophilic oligo(ethylene oxide) side chains provides near full recovery (95%) of sc-SWCNTs using a multiextraction protocol. High purity is also obtained, and differences in chiral selectivity compared to analogous hydrophobic systems were confirmed by optical absorption and Raman spectroscopy as well as photoluminescence excitation mapping. Taking into consideration the solvent dielectric constant, polarity index as well as polymer solubility and SWCNT dispersibility provides a better understanding of structure-property effects on sc-SWCNT enrichment. The resulting hydrophilic SWCNT dispersions demonstrate long-term colloidal stability, making them suitable for ink formulation and high-performance thin-film transistors fabrication.

Dopant-Modulated Conjugated Polymer Enrichment of Semiconducting SWCNTs.

Conjugated polymer extraction (CPE) is a low-cost, scalable process that can enrich single-walled carbon nanotube (SWCNT) materials in organic media. For other separation methods in aqueous phases, redox chemistry and/or pH control dramatically affect the sorting process of the SWCNTs. We have previously determined that the CPE process can be fine-tuned by adjusting the pH on the tube surface. Here, we systematically studied the effect of redox chemistry on the CPE process by adding organic p-/n-dopants. At a very strong p-/n-doping level, static repulsions dominated the interactions between the tubes and the CPE lost selectivity. When the doping level changed from a medium p-doping to a neutral state, the yield of CPE increased and the selectivity was compromised. We also observed chiral selectivity when a weak p-dopant was used. A photoluminescence excitation mapping under different titration conditions provided more insight into the doping level of the tubes relative to their diameters, chiralities, and redox potentials. We proposed a mechanism for the CPE process. The semiconducting and metallic tubes are separated because of their different solubilities, which are determined by the bundling energy between the tubes and are related to their doping level in polymer solutions.

High-Purity Semiconducting Single-Walled Carbon Nanotubes: A Key Enabling Material in Emerging Electronics.

Semiconducting single-walled carbon nanotubes (sc-SWCNTs) are emerging as a promising material for high-performance, high-density devices as well as low-cost, large-area macroelectronics produced via additive manufacturing methods such as roll-to-roll printing. Proof-of-concept demonstrations have indicated the potential of sc-SWCNTs for digital electronics, radiofrequency circuits, radiation hard memory, improved sensors, and flexible, stretchable, conformable electronics. Advances toward commercial applications bring numerous opportunities in SWCNT materials development and characterization as well as fabrication processes and printing technologies. Commercialization in electronics will require large quantities of sc-SWCNTs, and the challenge for materials science is the development of scalable synthesis, purification, and enrichment methods. While a few synthesis routes have shown promising results in making near-monochiral SWCNTs, gram quantities are available only for small-diameter sc-SWCNTs, which underperform in transistors. Most synthesis routes yield mixtures of SWCNTs, typically 30% metallic and 70% semiconducting, necessitating the extraction of sc-SWCNTs from their metallic counterparts in high purity using scalable postsynthetic methods. Numerous routes to obtain high-purity sc-SWCNTs from raw soot have been developed, including density-gradient ultracentrifugation, chromatography, aqueous two-phase extraction, and selective DNA or polymer wrapping. By these methods (termed sorting or enrichment), >99% sc-SWCNT content can be achieved. Currently, all of these approaches have drawbacks and limitations with respect to electronics applications, such as excessive dilution, expensive consumables, and high ionic impurity content. Excess amount of dispersant is a common challenge that hinders direct inclusion of sc-SWCNTs into electronic devices. At present, conjugated polymer extraction may represent the most practical route to sc-SWCNTs. By the use of polymers with a π-conjugated backbone, sc-SWCNTs with >99.9% purity can be dispersed in organic solvents via a simple sonication and centrifugation process. With 1000 times less excipient and the flexibility to accommodate a broad range of solvents via diverse polymer constructs, inks are readily deployable in solution-based fabrication processes such as aerosol spray, inkjet, and gravure. Further gains in sc-SWCNT purity, among other attributes, are possible with a better understanding of the structure-property relationships that govern conjugated polymer extraction. This Account covers three interlinked topics in SWCNT electronics: metrology, enrichment, and SWCNT transistors fabricated via solution processes. First, we describe how spectroscopic techniques such as optical absorption, fluorescence, and Raman spectroscopy are applied for sc-SWCNT purity assessment. Stringent requirements for sc-SWCNTs in electronics are pushing the techniques to new levels while serving as an important driver toward the development of quantitative metrology. Next, we highlight recent progress in understanding the sc-SWCNT enrichment process using conjugated polymers, with special consideration given to the effect of doping on the mechanism. Finally, developments in sc-SWCNT-based electronics are described, with emphasis on the performance of transistors utilizing random networks of sc-SWCNTs as the semiconducting channel material. Challenges and advances associated with using polymer-based dielectrics in the unique context of sc-SWCNT transistors are presented. Such transistor packages have enabled the realization of fully printed transistors as well as transparent and even stretchable transistors as a result of the unique and excellent electrical and mechanical properties of sc-SWCNTs.

Real Time Hyperspectroscopy for Dynamical Study of Carbon Nanotubes.

Photoluminescence excitation mapping used routinely to characterize semiconducting single-walled carbon nanotubes (sc-SWCNTs) is extended to provide time-dependent data. A hyperspectral method based on a supercontinuum light source and an imaging detector is demonstrated with excitation and emission wavelengths spanning 600-1000 and 1050-1650 nm, respectively, at time scales <100 ms. An example of a titration experiment is given to highlight the potential offered by the technique. Specifically, the dependence of luminescence yield on acceptor concentration is tracked for 18 different chirality assigned sc-SWCNT species. Dopant-induced quenching presents a simple dependence on nanotube diameter, with larger diameter being most affected, while chirality does not appear to be a dominant factor. In a second example, the successive addition of acceptor and donor molecules leads to a modulation of luminescence intensity upon hole doping and dedoping.

A hybrid enrichment process combining conjugated polymer extraction and silica gel adsorption for high purity semiconducting single-walled carbon nanotubes (SWCNT).

A novel purification process for the enrichment of sc-SWCNTs that combines selective conjugated polymer extraction (CPE) with selective adsorption using silica gel, termed hybrid-CPE (h-CPE), has been developed, providing a high purity sc-SWCNT material with a significant improvement in process efficiency and yield. Using the h-CPE protocol, a greater than 5 fold improvement in yield can be obtained compared to traditional CPE while obtaining sc-SWCNT with a purity >99.9% as assessed by absorption spectroscopy and Raman mapping. Thin film transistor devices using the h-CPE derived sc-SWCNTs as the semiconductor possess mobility values ranging from 10-30 cm(2) V(-1) s(-1) and current ON/OFF ratio of 10(4)-10(5) for channel lengths between 2.5 and 20 µm.

Enrichment of large-diameter semiconducting SWCNTs by polyfluorene extraction for high network density thin film transistors.

A systematic study on the use of 9,9-dialkylfluorene homopolymers (PFs) for large-diameter semiconducting (sc-) single-walled carbon nanotube (SWCNT) enrichment is the focus of this report. The enrichment is based on a simple three-step extraction process: (1) dispersion of as-produced SWCNTs in a PF solution; (2) centrifugation at a low speed to separate the enriched sc-tubes; (3) filtration to collect the enriched sc-SWCNTs and remove excess polymer. The effect of the extraction conditions on the purity and yield including molecular weight and alkyl side-chain length of the polymers, SWCNT concentration, and polymer/SWCNT ratio have been examined. It was observed that PFs with alkyl chain lengths of C10, C12, C14, and C18, all have an excellent capability to enrich laser-ablation sc-SWCNTs when their molecular weight is larger than ∼10 000 Da. More detailed studies were therefore carried out with the C12 polymer, poly(9,9-di-n-dodecylfluorene), PFDD. It was found that a high polymer/SWCNT ratio leads to an enhanced yield but a reduced sc-purity. A ratio of 0.5-1.0 gives an excellent sc-purity and a yield of 5-10% in a single extraction as assessed by UV-vis-NIR absorption spectra. The yield can also be promoted by multiple extractions while maintaining high sc-purity. Mechanistic experiments involving time-lapse dispersion studies reveal that m-SWCNTs have a lower propensity to be dispersed, yielding a sc-SWCNT enriched material in the supernatant. Dispersion stability studies with partially enriched sc-SWCNT material further reveal that m-SWCNTs : PFDD complexes will re-aggregate faster than sc-SWCNTs : PFDD complexes, providing further sc-SWCNT enrichment. This result confirms that the enrichment was due to the much tighter bundles in raw materials and the more rapid bundling in dispersion of the m-SWCNTs. The sc-purity is also confirmed by Raman spectroscopy and photoluminescence excitation (PLE) mapping. The latter shows that the enriched sc-SWCNT sample has a narrow chirality and diameter distribution dominated by the (10,9) species with d = 1.29 nm. The enriched sc-SWCNTs allow a simple drop-casting method to form a dense nanotube network on SiO2/Si substrates, leading to thin film transistors (TFTs) with an average mobility of 27 cm(2) V(-1) s(-1) and an average on/off current ratio of 1.8 × 10(6) when considering all 25 devices having 25 µm channel length prepared on a single chip. The results presented herein demonstrate how an easily scalable technique provides large-diameter sc-SWCNTs with high purity, further enabling the best TFT performance reported to date for conjugated polymer enriched sc-SWCNTs.

Type- and species-selective air etching of single-walled carbon nanotubes tracked with in situ Raman spectroscopy.

The thermal oxidation of carbon nanotubes in air is investigated by in situ Raman spectroscopy. Etching rates are directly seen to be diameter, chirality, and type dependent. We directly track the evolution of bundled nanotube networks that undergo air etching from 300 to 600 °C. Some species are more robust than others. Changes to radial breathing mode (RBM) and G- peak structures suggest that metallic species etch away more rapidly, with smaller diameter semiconducting species etching more slowly and large diameter nanotubes, including semiconductors, etching last. The decay in integrated G and D band intensities is tracked and fit reasonably well with biexponential decay. The RBM evolution is better represented by a single exponential. All bands are fit to activation plots with RBMs showing significantly different rates.

Photoinduced band gap shift and deep levels in luminescent carbon nanotubes.

Individual air-suspended single-walled carbon nanotubes are imaged both spatially and spectrally in photoluminescence. At low excitation power, photoluminescence is bright and stable with high quantum efficiency; however, higher power initially causes a gradual red shift and then more severe changes. Blinking, the loss of quantum efficiency, and the appearance of new deep levels are all seen and can be explained by the introduction of defects. We propose that optical excitation induces molecular deposition onto the nanotube by optically induced van der Waals interactions, leading to physisorption and ultimately chemisorption which severely degrades the luminescence.

Excited excitonic states in single-walled carbon nanotubes.

Polarized photoluminescence excitation spectroscopy on individual SWNTs reveals not only the longitudinal and transverse E 11, E 22, and E 12 ground-state excitons but also excited excitonic states including the continuum. When heated, SWNTs are known to undergo a bandgap shift transition (BST), which effectively changes the nanotube dielectric environment. Here, we show that the entire spectrum of excitonic resonances blue shifts under this transition, with excited states showing larger shifts, approaching 100 meV for a 1 nm diameter nanotube. The excitonic binding energy, Coulomb self-energy correction, and dielectric shift under the BST are estimated. Analysis of this blue shift reveals the dominant effect of dielectric screening on SWNT excitonic states.

Reduced number of homogalacturonan domains in pectins of an Arabidopsis mutant enhances the flexibility of the polymer.

Pectins are a family of highly complex multifunctional cell wall polysaccharides. Little is known on the relation between pectin structure, hydrodynamic properties, and cellular function. In this study, we took advantage of the Arabidopsis pectin mutant quasimodo2 (qua2), which specifically lacks half of its homogalacturonan blocks, to study the relationship between the amount of homogalacturonan blocks and the hydrodynamic properties of pectins. It was first shown that, in qua2 pectins, homogalacturonans had maintained the same size as those in the wild type. The persistence lengths of isolated homogalacturonan and rhamnogalacturonan-I blocks were then measured and it was shown that homogalacturonan was over 4-fold more rigid than rhamnogalacturonan-I. WT and qua2 pectins were next compared and it appeared that the specific reduction of the number of homogalacturonan blocks leads to an increased flexibility of qua2 pectins. These results show for the first time how mutant pectins can be used to demonstrate the opposite influence of rhamnogalacturonan-I and homogalacturonan blocks on the hydrodynamic properties of pectins.

Charge contrast imaging of suspended nanotubes by scanning electron microscopy.

A method of rapidly identifying and imaging suspended nanotubes by scanning electron microscopy is reported. Nanotubes are visible in high contrast and even at low magnification. The contrast can be explained by considering the effect that the charge on the nanotube has on the substrate. The proposed mechanism is general and should apply to any charged nanostructure in proximity to a surface or interface. This represents a new contrast mechanism in scanning electron microscopy.

Photoluminescence imaging of suspended single-walled carbon nanotubes.

Single-walled carbon nanotubes (SWNTs) suspended in air over trenches are imaged using their intrinsic near-infrared (NIR) photoluminescence (1.0-1.6 microm). Far-field emission from extended suspended lengths (approximately 50 microm) is both spatially and spectrally resolved, and SWNTs are classified based on the spatial uniformity of their emission intensity and emission wavelength. In a few cases, emission assigned to different (n,m) species is observed along the same suspended segment. Most SWNTs imaged on millisecond time scales show steady emission, but a few fluctuate and suffer a reduction of intensity. The quantum efficiency is dramatically higher than that in previous reports and is estimated at 7%, a value that is precise but subject to corrections because of assumptions about absorption and coherence.

Swelling behavior and controlled release of theophylline and sulfamethoxazole drugs in beta-lactoglobulin protein gels obtained by phase separation in water/ethanol mixture.

Physically cross-linked beta-lactoglobulin (BLG) protein gels containing theophylline and sulfamethoxazole low molecular weight drugs were prepared in 50% ethanol solution at pH 8 and two protein concentrations (6 and 7% (w/v)). Swelling behavior of cylindrical gels showed that, irrespective of the hydrated or dehydrated state of the gel, the rate of swelling was the highest in water. When the gels were exposed to water, they first showed a swelling phase in which their weight increased 3 and 30 times for hydrated and dehydrated gels, respectively, due to absorption of water, followed by a dissolution phase. The absorption of solvent was however considerably reduced when the gels were exposed to aqueous buffer solutions. The release behavior of both theophylline and sulfamethoxazole drugs from BLG gels was achieved in a time window ranging from 6 to 24 h. The drug release depended mainly on the solubility of the drugs and the physical state of the gel (hydrated or dry form). Analysis of drug release profiles using the model of Peppas showed that diffusion through hydrated gels was governed by a Fickian process whereas diffusion through dehydrated gels was governed partly by the swelling capacities of the gel but also by the structural rearrangements inside the network occurring during dehydration step. By a judicious selection of protein concentration, hydrated or dehydrated gel state, drug release may be modulated to be engineered suitable for pharmaceutical as well as cosmetics and food applications.

Structure determination of the 1/1 alpha/beta mixed lactose by X-ray powder diffraction.

The mixed form of alpha/beta lactose was obtained by heating amorphous alpha-lactose at 443 K. NMR spectroscopy determined the stoichiometry of this mixed compound to be 1/1. The X-ray powder diffraction pattern was recorded at room temperature with a sensitive curved detector (CPS 120). The structure was solved by real-space methods (simulated annealing) followed by Rietveld refinements with soft constraints on bond lengths and bond angles. The H atoms of the hydroxyl groups were localized by minimization of the crystalline energy. The cell of 1/1 alpha/beta lactose is triclinic with the space group P1 and contains two molecules (one molecule of each anomer). The crystalline cohesion is achieved by networks of O-H...O hydrogen bonds. The width of the Bragg peaks is interpreted through a microstructural approach in terms of isotropic strain effects and anisotropic size effects.

Ab initio structure determination of the high-temperature phase of anhydrous caffeine by X-ray powder diffraction.

The high-temperature phase I of anhydrous caffeine was obtained by heating and annealing the purified commercial form II at 450 K. This phase I can be maintained at low temperature in a metastable state. A powder X-ray diffraction pattern was recorded at 278 K with a laboratory diffractometer equipped with an INEL curved position-sensitive detector CPS120. Phase I is dynamically orientationally disordered (the so-called plastic phase). The Rietveld refinements were achieved with rigid-body constraints. It was assumed that on each site, a molecule can adopt three preferential orientations with equal occupation probability. Under a deep undercooling of phase I, below 250 K, the metastable state enters in a glassy crystal state.

Structure determination of the stable anhydrous phase of alpha-lactose from X-ray powder diffraction.

The stable anhydrous form of alpha-lactose has been obtained by the dehydration of alpha-lactose monohydrate in methanol. An X-ray powder diffraction pattern was recorded at room temperature with a laboratory diffractometer equipped with an INEL curved sensitive detector CPS120. The starting structural model of this form was found by a Monte-Carlo simulated annealing method. The structure was obtained through Rietveld refinements and the minimization of crystalline energy for the localization of the H atoms of the hydroxyl groups. Soft restraints were applied to bond lengths and angles. Networks of O-H...O hydrogen bonds account for the crystalline cohesion. A comparison is made between the hydrogen-bond networks of this form and those of the monohydrate and hygroscopic anhydrous forms of alpha-lactose.