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Applications of 3D printing that range from temporary medical devices to environmentally responsible manufacturing would benefit from printable resins that yield polymers with controllable material properties and degradation behavior. Towards this goal, poly(β-amino ester) (PBAE)-diacrylate resins were investigated due to the wide range of available chemistries and tunable material properties. PBAE-diacrylate resins were synthesized from hydrophilic and hydrophobic chemistries and with varying electron densities on the ester bond to provide control over degradation. Hydrophilic PBAE-diacrylates led to degradation behaviors characteristic of bulk degradation while hydrophobic PBAE-diacrylates led to degradation behaviors dominated initially by surface degradation and then transitioned to bulk degradation. Depending on chemistry, the crosslinked PBAE-polymers exhibited a range of degradation times under accelerated conditions, from complete mass loss in 90 min to minimal mass loss at 45 days. Patterned features with 55 μm resolution were achieved across all resins, but their fidelity was dependent on PBAE-diacrylate molecular weight, reactivity, and printing parameters. In summary, simple chemical modifications in the PBAE-diacrylate resins coupled with projection microstereolithography enables high resolution 3D printed parts with similar architectures and initial properties, but widely different degradation rates and behaviors.

A high-performance holographic recording medium was developed based on a unique combination of photoinitiated thiol–ene click chemistry and functional, linear polymers used as binders. Allyl reacti...

Semicrystalline polymeric materials possessing extraordinary mechanical properties were rapidly fabricated using light from low viscosity liquids at room temperature. Unlike conventional photopolymerizations which form crosslinked networks, this material is a noncrosslinked polymer which renders it meltable and intrinsically reprocessable. This introduces a new class of high performance, recyclable materials applicable for light-based additive manufacturing.

The electric potential, electric field, and charge density of a monolayer of MoS2 have been quantitatively measured at atomic-scale resolution. This has been performed by off-axis electron holography using a double aberration-corrected transmission electron microscope operated at 80 kV and a low electron beam current density. Using this low dose rate and acceleration voltage, the specimen damage is limited during imaging. In order to improve the sensitivity of the measurement, a series of holograms have been acquired. Instabilities of the microscope such as the drifts of the specimen, biprism, and optical aberrations during the acquisition have been corrected by data processing. Phase images of the MoS2 monolayer have been acquired with a sensitivity of 2π/698 rad associated with a spatial resolution of 2.4 A. The improvement in the signal-to-noise ratio allows the charge density to be directly calculated from the phase images using Poisson's equation. Density functional theory simulations of the potential and charge density of this MoS2 monolayer were performed for comparison to the experiment. The experimental measurements and simulations are consistent with each other, and notably, the charge density in a sulfur monovacancy (VS) site is shown.

3D printing is transforming traditional processing methods for applications ranging from tissue engineering to optics. To fulfill its maximum potential, 3D printing requires a robust technique for producing structures with precise three-dimensional (x, y and z) control of mechanical properties. Previous efforts to realize such spatial control of modulus within 3D printed parts have largely focused on low-resolution (mm to cm scale) multi-material processes and grayscale approaches that spatially vary the modulus in the x-y plane and energy dose-based (E = I(0) t(exp)) models that do not account for the resin’s sub-linear response to irradiation intensity. Here, we demonstrate a novel approach for through-thickness (z) voxelated control of mechanical properties within a single-material, monolithic part. Control over the local modulus is enabled by a predictive model that incorporates the observed non-reciprocal dose response of the material. The model is validated by an application of atomic force microscopy to map the through-thickness modulus on multi-layered 3D parts. Overall, both smooth gradations (30 MPa change over ≈75 μm) and sharp step-changes (30 MPa change over ≈5 μm) in modulus are realized in poly(ethylene glycol) diacrylate based 3D constructs, paving the way for advancements in tissue engineering, stimuli-responsive 4D printing and graded metamaterials.

Implantable electrophoretic drug delivery devices have shown promise for applications ranging from treating pathologies such as epilepsy and cancer to regulating plant physiology. Upon applying a voltage, the devices electrophoretically transport charged drug molecules across an ion‐conducting membrane out to the local implanted area. This solvent‐flow‐free “dry” delivery enables controlled drug release with minimal pressure increase at the outlet. However, a major challenge these devices face is limiting drug leakage in their idle state. Here, a method of reducing passive drug leakage through the choice of the drug co‐ion is presented. By switching acetylcholine's associated co‐ion from chloride to carboxylate co‐ions as well as sulfopropyl acrylate‐based polyanions, steady‐state drug leakage rate is reduced up to sevenfold with minimal effect on the active drug delivery rate. Numerical simulations further illustrate the potential of this method and offer guidance for new material systems to suppress passive drug leakage in electrophoretic drug delivery devices., Drug leakage is a safety concern for long‐term implantable electrophoretic drug delivery devices. In this work, co‐ion engineering is proposed as a clinically viable method to drastically reduce drug leakage rate, without any sacrifices on the device active performance. The co‐ion engineering method is drug‐independent and can be readily applied to existing electrophoretic drug delivery devices.

Photopolymers formed from the family of thiol-X “click” reactions notably form sulfur-containing thioether linkages. While sulfur-containing materials are conventionally expected to result in high ...

With high contrast optical images, it is possible to write sub-diffraction limited features over large areas. The dimensions of these super-resolved lithographic features are a function of optical contrast and total dose. Writing uniform subwavelength features requires uniform dose, and therefore uniform recording intensity. Patterns written with Gaussian beams exhibit large linewidth variation within each exposure field, and we mitigate this by incorporating a refractive beam shaper. A beam shaper does improve uniformity; however, intensity noise remains an issue. To mitigate intensity noise, we show that it is possible to scan the beam while recording without washing out the interference pattern. This is accomplished with an interferometer that incorporated a diffraction grating as a beam splitter. To first order, this design is insensitive to beam pointing. That is, as pointing angle changes, the interference fringe positions remain fixed while the beam position moves. Scanning over the resist averages out intensity noise, dramatically improving uniformity. We demonstrate both experimentally and with models, linewidth variation across a field written with different recording strategies. Linewidth from a Gaussian recording beam varies by 32% center to beam waist. With the inclusion of refractive beam shaping, linewidth uniformity can be brought down to 13%. By incorporating scanning with beam shaping, linewidth uniformity can be further reduced to as low as 4%.

Although the angular distribution of noise gratings in holographic photopolymer is understood to arise from Bragg matching, the details of scatter strength and dynamics are not fully understood. This confounds development of materials and recording techniques that minimize haze. Here, the kinetics are studied using a multi-physics numerical approach coupling diffraction of light from the dynamic material including scatter centers, reactions of chemical species initiated by this light, diffusion and swelling of these constituents, and the formation of the refractive index from the resulting composition. The approach is validated in the case of two-beam transmission holography by comparison to traditional harmonic series and rigorous coupled-mode approaches. Two beam holography in the presence of scatter is then used to study haze development. This reveals that haze due to weak noise gratings grows significantly above initial scatter only in reaction-limited materials, consistent with proposed Bragg-matched amplification mechanisms. Amplified haze is found to be proportional to initial scatter, quantifying the impact of clean sample fabrication. Conversely, haze is found to grow super-linearly with sample thickness, illustrating the significant challenge for applications requiring low haze in large thickness.

This work introduces a rapid and facile approach to predictably control integration between two materials with divergent properties. Programmed integration between photopolymerizable soft and stiff hydrogels was investigated for their promise in applications such as tissue engineering where heterogeneous properties are often desired. Spatial control afforded by grayscale 3D printing was leveraged to define regions at the interface that permit diffusive transport of a second material in-filled into the 3D printed part. The printing parameters (i.e., effective exposure dose) for the resin were correlated directly to mesh size to achieve controlled diffusion. Applying this information to grayscale exposures led to a range of distances over which integration was achieved with high fidelity. A prescribed finite distance of integration between soft and stiff hydrogels led to a 33% increase in strain to failure under tensile testing and eliminated failure at the interface. The feasibility of this approach was demonstrated in a layer-by-layer 3D printed part fabricated by stereolithography, which was subsequently infilled with a soft hydrogel containing osteoblastic cells. In summary, this approach holds promise for applications where integration of multiple materials and living cells is needed by allowing precise control over integration and reducing mechanical failure at contrasting material interfaces.

Transparent substrates introduce challenges in optical metrology, recording, and microscopy. Backside reflections reduce signal to noise, are recorded as artifacts, or introduce spurious signals. These reflections often need to be suppressed, but large angular and spectral bandwidths preclude the use of anti-reflection (AR) coatings. Using elastomeric materials doped with optical absorbers, we detail a method and a materials set for temporary suppression of Fresnel reflections for multiple substrates spanning wide spectral and angular bandwidths. Tuning the refractive index of the elastomer to match a substrate minimizes reflection and the addition of different absorptive dopants allow for either broadband or wavelength-selective reflection suppression. As performance is limited only by the index mismatch, both spectral and angular performances significantly exceed those of AR coatings. We demonstrate reflection suppression in excess of 30 dB spanning a bandwidth over 500 nm. After use, these light traps may be removed and reused without damaging the substrate.

Volumetric additive manufacturing (VAM) forms complete 3D objects in a single photocuring operation without layering defects, enabling 3D printed polymer parts with mechanical properties similar to their bulk material counterparts. This study presents the first report of VAM-printed thiol-ene resins. With well-ordered molecular networks, thiol-ene chemistry accesses polymer materials with a wide range of mechanical properties, moving VAM beyond the limitations of commonly used acrylate formulations. Since free-radical thiol-ene polymerization is not inhibited by oxygen, the nonlinear threshold response required in VAM is introduced by incorporating 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as a radical scavenger. Tuning of the reaction kinetics is accomplished by balancing inhibitor and initiator content. Coupling this with quantitative measurements of the absorbed volumetric optical dose allows control of polymer conversion and gelation during printing. Importantly, this work thereby establishes the first comprehensive framework for spatial-temporal control over volumetric energy distribution, demonstrating structures 3D printed in thiol-ene resin by means of tomographic volumetric VAM. Mechanical characterization of this thiol-ene system, with varied ratios of isocyanurate and triethylene glycol monomers, reveals highly tunable mechanical response far more versatile than identical acrylate-based resins. This broadens the range of materials and properties available for VAM, taking another step toward high-performance printed polymers.

Understanding the three-dimensional (3D) mechanical and chemical properties of distinctly different, adjacent biological tissues is crucial to mimicking their complex properties with materials. 3D printing is a technique often employed to spatially control the distribution of the biomaterials, such as hydrogels, of interest, but it is difficult to print both mechanically robust (high modulus and toughness) and biocompatible (low modulus) hydrogels in a single structure. Moreover, due to the fast diffusion of mobile species during printing and nonequilibrium swelling conditions of low-solids-content hydrogels, it is challenging to form the high-fidelity structures required to mimic tissues. Here a predictive transport and swelling model is presented to model these effects and then is used to compensate for these effects during printing. This model is validated experimentally by photopatterning spatially distinct hydrogel elastic moduli using a single photo-tunable poly(ethylene glycol) (PEG) pre-polymer solution by sequentially patterning and in-diffusing fresh pre-polymer for further polymerization.

The thermal radiative properties of glazing materials are fundamental inputs for evaluating the energetic performance and thermal behaviour of buildings. These properties are required for many practical applications ranging from infra-red thermography to building performance simulation and thermal comfort evaluations. Soda–lime–silica glass is the most widely used glass, worldwide, for glazing and the derivation of its thermal and optical properties are the subject of this work. Based on experimentally acquired spectral reference measurement data for soda-lime glass, the complex-valued Fresnel equations are solved and Monte-Carlo integration is carried out over the black-body spectrum, as well as over the hemisphere. These calculations are performed for various radiative temperatures to establish their temperature dependencies, and additionally the temperature-dependent transmittance of soda-lime glass was analysed. By applying a non-linear optimisation algorithm, computationally efficient practical fitting formulae for the angular reflectivity, emissivity and absorptivity are derived. All equations are numerically solved with a high degree of accuracy. The determination of the hemispherical total emissivity for this type of glass confirms the current accepted value (∼0.2%) originally derived by Rubin (1985). A simple yet robust experimental design, based on thermography, is used to validate the results of the numerical reflectivity model. Additionally, we provide angular functions, fitting functions and additional constants that were hitherto unavailable. The practical benefits of the fitting formulae provided are considerable in relation to modelling the reflection of thermal radiation on glazed surfaces, and are demonstrated in two case-study applications in the appendix.

Volumetric 3D printing motivated by computed axial lithography enables rapid printing of homogeneous parts but requires a high dimensionality gradient-descent optimization to calculate image sets. Here we introduce a new, simpler approach to image-computation that algebraically optimizes a model of the printed object, significantly improving print accuracy of complex parts under imperfect material and optical precision by improving optical dose contrast between the target and surrounding regions. Quality metrics for volumetric printing are defined and shown to be significantly improved by the new algorithm. The approach is extended beyond binary printing to grayscale control of conversion to enable functionally graded materials. The flexibility of the technique is digitally demonstrated with realistic projector point spread functions, printing around occluding structures, printing with restricted angular range, and incorporation of materials chemistry such as inhibition. Finally, simulations show that the method facilitates new printing modalities such as printing into flat, rather than cylindrical packages to extend the applications of volumetric printing.

Successful 3D scaffold designs for musculoskeletal tissue engineering necessitate full consideration of the form and function of the tissues of interest. When designing structures for engineering cartilage and osteochondral tissues, one must reconcile the need to develop a mechanically robust system that maintains the health of cells embedded in the scaffold. In this work, we present an approach that decouples the mechanical and biochemical needs and allows for the independent development of the structural and cellular niches in a scaffold. Using the highly tuned capabilities of digital light processing-based stereolithography, structures with complex architectures are achieved over a range of effective porosities and moduli. The 3D printed structure is infilled with mesenchymal stem cells and soft biomimetic hydrogels, which are specifically formulated with extracellular matrix analogs and tethered growth factors to provide selected biochemical cues for the guided differentiation towards chondrogenesis and osteogenesis. We demonstrate the ability to utilize these structures to (a) infill a focal chondral defect and mitigate macroscopic and cellular level changes in the cartilage surrounding the defect, and (b) support the development of a stratified multi-tissue scaffold for osteochondral tissue engineering.

Biofabrication allows for the templating of structural features in materials on cellularly-relevant size scales, enabling the generation of tissue-like structures with controlled form and function. This is particularly relevant for growing organoids, where the application of biochemical and biomechanical stimuli can be used to guide the assembly and differentiation of stem cells and form architectures similar to the parent tissue or organ. Recently, ablative laser-scanning techniques was used to create 3D overhang features in collagen hydrogels at size scales of 10–100 µm and supported the crypt-villus architecture in intestinal organoids. As a complementary method, providing advantages for high-throughput patterning, we printed thioester functionalized poly(ethylene glycol) (PEG) elastomers using digital light processing (DLP) and created sacrificial, 3D shapes that could be molded into soft (G′ < 1000 Pa) hydrogel substrates. Specifically, three-arm 1.3 kDa PEG thiol and three-arm 1.6 kDa PEG norbornene, containing internal thioester groups, were photopolymerized to yield degradable elastomers. When incubated in a solution of 300 mM 2-mercaptoethanol (pH 9.0), 1 mm thick 10 mm diameter elastomer discs degraded in µm, resolutions of 22 ± 5 µm, and overhang structures as small as 50 µm, were printed on the order of minutes. These sacrificial thioester molds with physiologically relevant features were cast-molded into Matrigel and subsequently degraded to create patterned void spaces with high fidelity. Intestinal stem cells (ISCs) cultured on the patterned Matrigel matrices formed confluent monolayers that conformed to the underlying pattern. DLP printed sacrificial thioester elastomer constructs provide a robust and rapid method to fabricate arrays of 3D organoid-sized features in soft tissue culture substrates and should enable investigations into the effect of epithelial geometry and spacing on the growth and differentiation of ISCs.

We present a sample preparation method for cryo-electron microscopy (cryo-EM) that requires only 320 nL of sample to prepare a cryo-EM grid, depending on the protocol used. The sample is applied and spread on the grid by a microcapillary. The procedure does not involve any blotting steps, and realtime monitoring allows the water film thickness to be assessed and decreased to an optimum value prior to vitrification. We demonstrate that the method is suitable for high-resolution cryo-EM and will enable alternative electron microscopy approaches, such as single-cell visual proteomics. (C) 2016 The Author(s). Published by Elsevier Inc.

Two-stage holographic photopolymers capable of high refractive index modulation (Δn) on the order of 10–2 enable the fabrication of a myriad of optical elements. While there are commercial products available that meet these requirements, researchers often want the flexibility to customize both the form factor of the samples as well as the mechanical and chemical properties for their specific applications. We present a novel high refractive index acrylate writing monomer in a low refractive index urethane matrix as a model material for customization for optical applications. We discuss the achievable Δn of this custom monomer, 1,3-bis(phenylthio)-2-propyl acrylate (BPTPA) in the urethane matrix as a function of solubility, along with a comparison to a commercially available high refractive index monomer, 2,4,6- tribromophenyl acrylate. Formulations with BPTPA exhibit a peak-to-mean Δn ≈ 0.029 in transmission holograms without any obvious deficiencies in transparency, color, or scatter. This writing monomer and the synthetic processes present a promising platform for the fabrication of high-performance holographic photopolymers for a wide range of research applications.

We show the design and fabrication of high diffraction efficiency, optically recorded gradient-index Fresnel lenses in a two-stage photopolymer. A design analysis reveals that lens f/# is limited by the material refractive index contrast, motivating use of recent high-contrast polymers. The number of pixels required for the optical exposure is typically well beyond available spatial light-modulator resolutions, motivating the use of a photolithographic mask. We use a dithered binary chrome mask with 9000×9000 pixels of 2.5 μm diameter to write lenses up to 23 mm in diameter. Lenses down to f/44 with 76% diffraction efficiency and f/79 with 83% diffraction efficiency are demonstrated.

A predominant challenge in tissue engineering is the need of a robust technique for producing structures with precise three-dimensional control of mechanical properties. In an effort to understand how to control the mechanical and chemical properties of materials patterned using stereolithography, this study focuses on the development of a model that allows for orthogonally programmable elastic modulus and geometry in a 3D hydrogel structure. In this study, we use pediatric physeal tissue engineering as a model application. Pediatric physeal injuries can be detrimental to children because damaged cartilage within the physis can lead to assymetric growth arrest. A challenge related to physeal tissue regeneration is the presence of three distinct zones within the physis or growth plate, where cells evolve differently and are known to be sensitive to the mechanical environment. We use a poly(ethylene glycol) diacrylate based photopolymerization chain-growth reaction with a modulus that can range from 600KPa to 39 MPa to spatially control the mechanical properties in our 3D parts and match the growth plate tissue environment. We apply Fourier transform infrared spectroscopy (FTIR) to quantify the degree of monomer conversion over time and intensity, while comparing it with a mechanical model that relates conversion to modulus. To evaluate the spatially controlled mechanical properties in printed structures, nanoindentation is performed to extract the modulus in each biomimetic zone. In this work we present the implementation of both a gradual change in mechanical properties, as well as a step function in 3D scaffolds on the order of 100 microns. This work enables predictive models of structural properties that can be translated into tissue engineering microstructures that match the native biomechanical environment of any tissue.

We show the design and fabrication of high diffraction efficiency, optically recorded gradient-index Fresnel lenses in a two-stage photopolymer. A design analysis reveals that lens f/# is limited by the material refractive index contrast, motivating use of recent high contrast polymers. The number of pixels required for the optical exposure is typically well beyond available spatial light modulator resolutions, motivating the use of a photolithographic mask. Thus, we present a photolithographic technique by which a single exposure into a self-developing photopolymer can directly print single custom high efficiency DOEs with freeform phase profiles, in contrast to holographic optical elements that are limited to the interference of two propagating fields. We use a dithered binary chrome mask with 9000 x 9000 pixels of 2.5 μm diameter to write lenses up to 23 mm in diameter. Lenses down to f/44 with 76% diffraction efficiency and f/79 with 83% diffraction efficiency are demonstrated.

We demonstrate the formation of shape-programmed, glassy origami structures using a single-layer photopolymer with two mechanically distinct phases. The latent origami pattern consisting of rigid, high cross-link density panels and flexible, low cross-link density creases is fabricated using a series of photomask exposures. Strong optical absorption of the polymer formulation creates depth-wise gradients in the cross-link density of the creases, enforcing directed folding which enables programming of both mountain and valley folds within the same sheet. These multiple photomask patterns can be sequentially applied because the sheet remains flat until immersed into a photopolymerizable monomer solution that differentially swells the polymer to fold and form the origami structure. After folding, a uniform photoexposure polymerizes the absorbed solution, permanently fixing the shape of the folded structure while simultaneously increasing the modulus of the folds. This approach creates sharp folds by mimicking the stiff panels and flexible creases of paper origami while overcoming the traditional trade-off of self-actuated materials that require low modulus for folding and high modulus for mechanical robustness. Using this process, we demonstrate a waterbomb base capable of supporting 1500 times its own weight.

We demonstrate switchable, thin film diffractive optical gratings and Fresnel zone plate lenses fabricated using a micro-patterned electrochromic polymer and gel electrolyte. Electrochemically switching the conductive polymer PEDOT:PSS causes the patterned layer to change between a low-absorption to high absorption state, acting as an amplitude diffractive optical element. The switchable lens and gratings were fabricated using a lithographically patterned electrochromic polymer, a gel electrolyte, and an ITO-coated glass substrate. Within an applied voltage of −1 V to 1 V, the diffraction efficiency of the switchable lens can be varied 4.1-fold between the ‘on’ and ‘off’ states. Due to their low actuation voltage and biocompatibility, electrochemically actuated diffractive optics have potential applications in low power and implantable biomedical devices.

Organic electrochemical transistors (OECTs) are transistors that can have extrinsic transconductances as high as 400 S m-1 , but they typically have response times on the order of 1 ms or longer. These response speeds are limited by ion transport. It is shown that OECTs can exceed the ionic response speed by a factor of 30 when operated in a high-speed bias regime.

Diffusive photopolymers are an area of intense recent materials development, spurred by interest in holographic data storage, display holography, and custom diffractive optical elements, among other applications. This review examines a range of photopolymer formulations of academic and commercial interest, and places their design strategies in context via quantitative analysis of the recording fidelity, maximum refractive index change and the degree to which they achieve this limit. Finally, this analysis is extended to estimate the scope of achievable future performance improvements. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1021–1035.

Current hydrogels used for tissue engineering are limited to a single range of mechanical properties within the replicated tissue construct. We show that repeated in-swelling by a single hydrogel pre-cursor solution into an existing polymerized hydrogel followed by photo-exposure increases hydrogel mechanical properties. The process is demonstrated with a photo-clickable thiol-ene hydrogel using a biocompatible precursor solution of poly(ethylene glycol) dithiol and 8-arm poly(ethylene glycol) functionalized with norbornene. The polymer fraction in the precursor solution was varied by 5, 10, and 20 percent by weight and an off-stoichiometric ratio of thiol : ene was used, leaving free enes available for subsequent reaction. Multiple swelling and exposure cycles for the same precursor solution were performed. The compressive modulus increased by a factor between three and ten (formulation dependent), while volume swelling ratio decreased by a factor of two, consistent with increased crosslink density. The modified hydrogels also demonstrate increased toughness by fracturing at compressive forces five times greater than the initial hydrogel. We attribute the increased toughness to subsequent increases in crosslink density created by the repeated photopolymerization of in-swollen macromer. This technique demonstrates the ability to significantly modify hydrogel network properties by exploiting swelling and polymerization processes that can be applied to traditional three-dimensional printing systems to spatially control local mechanical properties.

With a host of new materials being investigated as active layers in organic electrochemical transistors (OECTs), several advantageous characteristics can be utilized to improve transduction and circuit level performance for biosensing applications. Here, the subthreshold region of operation of one recently reported high performing OECT material, poly(2‐(3,3′‐bis(2‐(2‐(2‐methoxyethoxy)ethoxy)ethoxy)‐[2,2′‐bithiophen]‐5‐yl)thieno[3,2‐b]thiophene), p(g2T‐TT) is investigated. The material's high subthreshold slope (SS) is exploited for high voltage gain and low power consumption. An ≈5× improvement in voltage gain (A V) for devices engineered for equal output current and 370× lower power consumption in the subthreshold region, in comparison to operation in the higher transconductance (g m), superthreshold region usually reported in the literature, are reported. Electrophysiological sensing is demonstrated using the subthreshold regime of p(g2T‐TT) devices and it is suggested that operation in this regime enables low power, enhanced sensing for a broad range of bioelectronic applications. Finally, the accessibility of the subthreshold regime of p(g2T‐TT) is evaluated in comparison with the prototypical poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and the role of material design in achieving favorable properties for subthreshold operation is discussed.

3D printing hydrogels via stereolithography is a promising system for the creation of regenerative medical implants. However, the mechanical and chemical properties of materials patterned using stereolithography-based printing techniques are largely unknown. In an effort to understand how optical propagation, polymerization, and transport dynamics result in material mechanical property distribution, this study focuses on the axial (depth) characterization of single-layer printed materials as a function of light intensity, exposure time and absorption depth. We use a poly(ethylene glycol) diacrylate based photopolymerization chain-growth reaction with an approximate bulk modulus of 39 MPa to explore this phenomenon. Fourier transform infrared spectroscopy (FTIR) is employed to quantify the degree of monomer conversion over time and intensity, while comparing it with a Beer-Lambert model that describes the effect of Tinuvin CarboProtect, the neutral absorber in our material on conversion as a function of depth. To evaluate the mechanical properties of the printed materials, compression testing is performed on each sample to extract the bulk modulus and to map conversion as a function of exposure time by fitting the force-displacement curves of each condition to the Hertz model for a quantitative comparison of material stiffness. This study aims to understand material and mechanical property distribution in a single layer, and use this understanding to create a predictive model of these properties, as well as decrease the scale of the distribution with the implementation of a novel post-cure technique. This work enables predictive models of microscopic polymer properties that can be translated into improved macroscopic structural properties to form a robust polymer network for tissue engineering microstructures.

Applying a technique borrowed from super-resolution microscopy to photolithography, we achieve critical dimensions well below the diffraction limit. Exposing photoresist in the far-field, over a broad area, we can demonstrate dimensions as small as λ/7. In this paper, we show that conventional i-line photoresists exposed with this technique, along with modified processing, are capable of supporting features as small as 50 nm, and possibly smaller. We consider the necessary requirements to achieve sub-diffraction dimensions, detail a simple model for photoresist development, and show its use in predicting the minimum attainable feature size. Finally, we characterize two commercial photoresists, and compare the resulting features to those of the model.

Holographic photopolymers capable of high refractive index modulations (Δn) on the order of 10-2 are integral for the fabrication of functional holographic optical elements (HOEs) for use in a range of optical applications. A novel high refractive index liquid writing monomer suitable for two-stage photopolymer systems was designed and synthesized. This monomer exhibits facile synthetic procedure, low viscosity, high refractive index as well as excellent solubility in a low refractive index urethane matrix. The solubility limit, refractive index change and reaction kinetics/conversion were studied against a commercial reference high refractive index monomer, 2,4,6-tribromophenyl acrylate (TBPA). Superior performance in solubility to TBPA is shown with similar reaction kinetics and final conversion as confirmed by realtime Fourier transform infrared spectroscopy (FTIR) and real-time monitoring of diffraction grating growth. We demonstrate the ability to load substantial amounts of these writing monomers enabling a straightforward path to higher achievable Δn values (peak-to-mean Δn ~ 0.03) without sacrificing optical properties (transparency, color or scatter) as validated through recording ~100% efficiency volume transmission holograms in sub-15 μm thick films.

Precise direct-write lithography of 3D waveguides or diffractive structures within the volume of a photosensitive material is hindered by the lack of metrology that can yield predictive models for the micron-scale refractive index profile in response to a range of exposure conditions. We apply the transport of intensity equation in conjunction with confocal reflection microscopy to capture the complete spatial frequency spectrum of isolated 10 μm-scale gradient-refractive index structures written by single-photon direct-write laser lithography. The model material, a high-performance two-component photopolymer, is found to be linear, integrating, and described by a single master dose response function. The sharp saturation of this function is used to demonstrate nearly binary, flat-topped waveguide profiles in response to a Gaussian focus.

International audience; Quantitative characterization of electrically active dopants and surface charges in nano-objects is challenging, since most characterization techniques using electrons [1–3], ions [4] or field ionization effects [5–7] study the chemical presence of dopants, which are not necessarily electrically active. We perform cathodoluminescence and voltage contrast experiments on a contacted and biased ZnO nanowire with a Schottky contact and measure the depletion length as a function of reverse bias. We compare these results with state-of-the-art off-axis electron holography in combination with electrical in situ biasing on the same nanowire. The extension of the depletion length under bias observed in scanning electron microscopy based techniques is unusual as it follows a linear rather than square root dependence, and is therefore difficult to model by bulk equations or finite element simulations. In contrast, the analysis of the axial depletion length observed by holography may be compared with three-dimensional simulations, which allows estimating an n-doping level of 1 × $10^{18}$ $cm^{−3}$ and negative sidewall surface charge of 2.5 × $10^{12}$ $cm^{−2}$ of the nanowire, resulting in a radial surface depletion to a depth of 36 nm. We found excellent agreement between the simulated diameter of the undepleted core and the active thickness observed in the experimental data. By combining TEM holography experiments and finite element simulation of the NW electrostatics, the bulk-like character of the nanowire core is revealed.

International audience; Organic electrochemical transistors (OECTs) are promising transducers for biointerfacing due to their high transconductance, biocompatibility, and availability in a variety of form factors. Most OECTs reported to date, however, utilize rather large channels, limiting the transistor performance and resulting in a low transistor density. This is typically a consequence of limitations associated with traditional fabrication methods and with 2D substrates. Here, the fabrication and characterization of OECTs with vertically stacked contacts, which overcome these limitations, is reported. The resulting vertical transistors exhibit a reduced footprint, increased intrinsic transconductance of up to 57 mS, and a geometry-normalized transconductance of 814 S m−1. The fabrication process is straightforward and compatible with sensitive organic materials, and allows exceptional control over the transistor channel length. This novel 3D fabrication method is particularly suited for applications where high density is needed, such as in implantable devices.

Holographic photopolymers capable of high refractive index modulation (Δn) on the order of 10-2 are integral for the fabrication of functional holographic optical elements that are useful in a myriad of optical applications. In particular, to address the deficiency of suitable high refractive index writing monomers for use in two-stage holographic formulations, here we report a novel high refractive index writing monomer, 1,3-bis(phenylthio)-2-propyl acrylate (BPTPA), simultaneously possessing enhanced solubility in a low refractive index (n = 1.47) urethane matrix. When examined in comparison to a widely used high refractive index monomer, 2,4,6-tribromophenyl acrylate, BPTPA exhibited superior solubility in a stage 1 urethane matrix of approximately 50% with a 20% higher refractive index increase per unit amount of the writing monomer for stage 2 polymerizations. Formulations with 60 wt % loading of BPTPA exhibit a peak-to-mean holographic Δn ≈ 0.029 without obvious deficiencies in transparency, color, or scatter. To the best of our knowledge, this value is the highest reported in the peer-reviewed literature for a transmission hologram. The capabilities and versatility of BPTPA-based formulations are demonstrated at varying length scales via demonstrative refractive index gradient structure examples including direct laser write, projection mask lithography of a 1″ diameter Fresnel lens, and ∼100% diffraction efficiency volume transmission holograms with a 1 μm fringe spacing in 11 μm thick samples.

Freestanding substrates with high refractive index modulation, good oxygen resistance, and low volume shrinkage are critical in photolithography for the purpose of high density data storage, image patterning and anticounterfeiting. Herein, we demonstrate a novel paradigm of direct holographic image patterning via the radical-mediated thiol–yne click reaction subsequent to the base-catalyzed thiol-Michael addition reaction. With the benefit of a newly synthesized alkyne monomer, 9-(2-((2-(prop-2-yn-1-yloxy)ethyl)thio)ethyl)-9H-carbazole (POETEC), holograms with as high as 96% diffraction efficiency, refractive index modulation of 0.0036, dynamic range of 5.6 per 200 μm and volume shrinkage of 1.1%, are successfully patterned in an aerobic environment. Uniquely and distinctly, an inhibitor is unnecessary to prevent the initiation of the sequential reaction in this framework.

Damage to articular cartilage can over time cause degeneration to the tissue surrounding the injury. To address this problem, scaffolds that prevent degeneration and promote neotissue growth are needed. We introduce a new hybrid scaffold that combines a stereolithography-based three-dimensional printed support structure with an injectable and photopolymerizable hydrogel for delivering cells to treat focal chondral defects. In this proof of concept study, we demonstrate the ability to a) infill the support structure with an injectable hydrogel precursor solution, b) incorporate cartilage cells during infilling using a degradable hydrogel that promotes neotissue deposition, and c) minimize damage to the surrounding cartilage when the hybrid scaffold is placed in situ in a focal chondral defect in an osteochondral plug that is cultured under mechanical loading. With the ability to independently control the properties of the structure and the injectable hydrogel, this hybrid scaffold approach holds promise for treating chondral defects.

Optically-driven diffusion of high refractive index molecules within a transparent thermoset polymer matrix is a promising platform for hybrid optics that combines a wide range of optical structures from large scale holograms to micron-scale gradient index waveguides in a single integrated optical system. Design of such a system requires characterization of the optical response of the material at a wide range of spatial scales and intensities. While holographic analysis of the photopolymers is appropriate to probe the smaller spatial scales and lower intensity optical response, quantitative phase mapping of isolated structures is needed to probe the response to the higher intensities and lower spatial frequencies used in direct write lithography of waveguides. We apply the transport of intensity equation (TIE) to demonstrate quantitative refractive index measurements of 10 μm-scale localized gradient index structures written into diffusive photopolymer materials using both single- and two-photon polymerization. These quantitative measurements allow us to study the effect of different exposure conditions and material parameters such as writing beam power, exposure time, and wt% loading of the writing monomer on the overall profile of the refractive index structure. We use these measurements to probe the time scales over which diffusion is significant, and take advantage of the diffusion of monomer with a multiple-write scheme that achieves a peak refractive index contrast of 0.025.

Two-beam holographic exposure and subsequent monitoring of the time-dependent first-order Bragg diffraction is a common method for investigating the refractive index response of holographic photopolymers for a range of input writing conditions. The experimental set up is straightforward, and Kogelnik’s well-known coupled wave theory (CWT)[1] can be used to separate measurements of the change in index of refraction (Δn) and the thickness of transmission and reflection holograms. However, CWT assumes that the hologram is written and read out with a plane wave and that the hologram is uniform in both the transverse and depth dimensions, assumptions that are rarely valid in practical holographic testing. The effect of deviations from these assumptions on the measured thickness and Δn become more pronounced for over-modulated exposures. As commercial and research polymers reach refractive index modulations on the order of 10-2, even relatively thin (< 20 μm thick) transmission volume holograms become overmodulated. Peak Δn measurements for material analysis must be carefully evaluated in this regime. We present a study of the effects of the finite Gaussian write and read beams on the CWT analysis of photopolymer materials and discuss what intuition this can give us about the effect other non-uniformities, such as mechanical stresses and significant absorption of the write beam, will have on the analysis of the maximum attainable refractive index in a material system. We use this analysis to study a model high Δn two-stage photopolymer holographic material using both transmission and reflection holograms.

We present a general strategy for characterizing the reaction and diffusion kinetics of polymeric holographic recording media by which key processes are decoupled and independently measured. The separate processes are combined into a predictive model that is shown to make accurate quantitative predictions of index response over three orders of exposure dose (~1 to ~10 3 mJ/cm 2 ) and feature size (0.35 to 500 microns) for a model material similar to commercial media. Several critical performance concepts also emerge from the model, including a prediction of a formulation’s maximum potential index response, insight into why a particular material may not achieve this maximum and the process that limits the recording resolution.

Many new materials emerging are strictly two dimensional (2D), often only one or two monolayers thick. They include transition metal dichalcogenides, such as MoS2 , and graphene. Graphene in particular appears to have many potential applications. Typically the crystalline film without contamination is of interest. Therefore, a reliable method is needed to routinely evaluate the quality of the synthesized samples. Here, we present one such candidate method that utilizes standard electron diffraction and low/medium magnification imaging in a rudimentary transmission electron microscope. The electron irradiation dose is very low thus reducing electron irradiation damage of the investigated samples. As an example, the method was applied to the evaluation of as-grown graphene sample quality and a study on heating-induced change in graphene. It can be used to evaluate the volume and areal ratio of crystalline to noncrystalline component. The method is amiable to automated film quality evaluation.

Applying a technique from super-resolution microscopy to photolithography, we achieve feature sizes below the diffraction limit. Using conventional i-line photoresists exposed with near UV, we demonstrate individual feature sizes below 100 nm.

Orthogonal, sequential “click” reactions were implemented to yield novel polymeric substrates with the ability to record holographic data. The base-catalyzed thiol–acrylate Michael “click” reaction was implemented to yield a writable, stage 1 polymeric substrate with glass transition temperatures (Tg) ranging from 0 to −26 °C and rubbery storage moduli (E′) from 11.1 to 0.3 MPa. The loosely cross-linked matrix also contained a novel high refractive index monomer 9-(2,3-bis(allyloxy)propyl)-9H-carbazole (BAPC) that did not participate in the thiol–Michael reaction but allowed for large index gradients to be developed within the network upon subsequent exposure to coherent laser beams and initiation of the radical-mediated thiol–ene reaction. The holographic gratings were recorded with 96% diffraction efficiency and ca. 2.4 cm/mJ of light sensitivity in 2 s under a 405 nm exposure with an intensity of 20 mW/cm2. Subsequent to pattern formation, via a thiol–allyl radical “click” photopolymerization initiated...

Background: Resolution enhancement combined with multiple patterning enables photolithography to write patterns with both feature size and spacing below the diffraction limit. Continued resolution enhancement at i-line will enable an older generation of lithographic tools to reach resolutions typically achieved using deep UV (DUV). Aim: A demonstration and deterministic model of large critical dimension enhancement at i-line. In addition to enhanced resolution, the technique must also achieve high repeatability and low line edge roughness (LER), while using commercial resists. Approach: Overexposing photoresist with high-contrast interference nulls leads to subwavelength critical dimensions. Starting with a theoretical analysis of the technique, we consider limits imposed by optics, linewidth scaling rates, and LER. This analysis shows that low LER and deterministic linewidth control are both readily achievable. Results: We demonstrate large area, i-line patterning of features with 50-nm linewidth, without the aid of subsequent trim or etch and with LER of 5 nm. Linewidth is shown to scale with dose as predicted from the optical model, independent of photoresist. Conclusions: These dimensions are similar to what may be achieved using scanning near-field, DUV, or e-beam lithography, yet achieved with far-field near UV exposures over a large area. Deterministic linewidth control and low LER make this process viable for fabrication at length scales well below those typically achieved with i-line tools.

There are distinct advantages to designing polymer systems that afford two distinct sets of material properties– an intermediate polymer that would enable optimum handling and processing of the material, while maintaining the ability to tune in different, fi nal polymer properties that enable the optimal functioning of the material. In this study, by designing a series of non-stoichiometric thiol-acrylate systems, a polymer network is initially formed via a base catalyzed Michael addition reaction that proceeds stoichiometrically via the thiol-acrylate “click” reaction. This self-limiting reaction results in a polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. These two stage reactive thiol-acrylate networks that have intermediate stage rubbery moduli and glass transition temperatures that range from 0.5 MPa and − 10 ° C to 22 MPa and 22 ° C, respectively, are formulated and characterized. The same polymer networks can then attain glass transition temperatures that range from 5 ° C to 195 ° C and rubbery moduli of up to 200 MPa after the subsequent photocuring stage. The two stage reactive networks formed by varying the stoichiometric ratios of the thiol and acrylate monomers were shown to perform as substrates for three specifi c applications: shape memory polymers, impression materials, and as optical materials for writing refractive index patterns.

Theoretical predictions and experimental results show that the carrier mobility in conjugated polymers depends on carrier concentration. However, existing models for organic electrochemical transistors (OECTs) assume uniform carrier mobility along the transistor channel despite variations in carrier concentration. Here, a model incorporating disorder-induced nonuniform mobility is developed to describe the steady-state behavior of OECTs. This model is tested using in situ optical measurements of an OECT channel to decouple the mobility and carrier concentration contributions to channel conductivity. It is found that unlike existing models, the nonuniform mobility model agrees with these measurements. Furthermore, it is found that the model matches current–voltage data over a wide range of device geometries and two different device architectures. Finally, it is shown that a 120% improvement of transconductance can be obtained by operating a sensor according to device parameters given by the nonuniform mobility model rather than those extracted from an existing model that assumes a uniform mobility. Ultimately, the model presented allows more accurate measurement of material properties via transistor characterization. This will enable better-informed material optimization, development of more accurate transient models for OECTs, and more effective use of OECTs made from existing materials.