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At least 19 records

Overcoming efficiency and cost barriers for large-area quantum dot photovoltaics through stable ink engineering

The bottom-up construction of electronics from colloidal quantum dots (CQDs) could innovate nanotechnology manufacturing through printing. However, the unstable and expensive semiconductive CQD inks make the scaling up of CQD electronics challenging. Here, in this study, we develop a strategy for engineering the solution chemistry of lead sulfide (PbS) CQD inks prepared from a low-cost direct synthesis method. By creating an iodine-rich environment in weakly coordinating solvents, we convert the iodoplumbates into functional anions, which condense into a robust surface shell. The fully charged electrostatic surface layer prevents aggregation and epitaxial fusion of CQDs, yielding stable inks. By eliminating the fusion-induced inter-band states, we print a compact CQD film with uniformity in three dimensions, flattened energy landscape and improved carrier transport. We achieved a certified efficiency of 13.40% on 0.04 cm 2 cells, with a 300-fold increase in active area, scaling up to a 12.60 cm 2 module with a certified efficiency of 10%.

14 SOLAR ENERGY↗

Engineering Perovskite Precursor Inks for Scalable Production of High‐Efficiency Perovskite Photovoltaic Modules

Abstract Blade coating of perovskite solar cells (PSCs) and modules has progressed considerably toward the industrial production of perovskite photovoltaics. Developing stable perovskite precursors is critical for achieving uniform coating over large areas. Here, the engineering of a perovskite precursor solution consisting of 2‐methoxyethanol (2‐Me) and 1,3‐dimethyl‐imidazolidinone (DMI) with superior intermediate phase stability that enables scalable production of efficient perovskite solar modules is reported. With this perovskite precursor solution, uniform and pinhole‐less perovskite film is deposited over a large area of > 100 cm 2 and higher‐efficiency PSCs and modules are obtained. The best‐performing unit cell and module with n‐i‐p configuration reach power conversion efficiencies of 23.4% and 20.1%, respectively. Additionally, a series of non‐destructive metrology methods, such as spectroscopic ellipsometry, hyperspectral photoluminescence, electroluminescence, and laser beam‐induced current mapping, are employed to assess and guide the development the blade‐coated perovskite modules. This results show that rational engineering of precursor inks for blade coating is promising for the scalable production of efficient perovskite solar modules.

36 MATERIALS SCIENCE↗

Dry electrodes with a printed cellulose–graphene ink for low-profile strain sensors in electromyography

Dihydrolevoglucosenone, commonly known as Cyrene, is a renewable and fully biodegradable cellulose-waste derived, environmentally friendly solvent, presenting a non-toxic alternative to N-methyl-2-pyrrolidone (NMP). Currently, solution-based processing of graphene and other similar van der Waals solids favor toxic solvents such as NMP, limiting their use for biosensing. However, with the use of Cyrene, bio-compatible printable devices are possible, and studies have already demonstrated its use in temperature and other biosensing methods through screen-printing. Screen-printing unfortunately often requires masks that constrain the minimum acquirable feature size to be above hundreds of centimeters and wastes material, adding to process complexity and cost. Conversely, inkjet-printing is an attractive alternative for the maskless patterning of hierarchically assembled structures, with micron length scales attainable. Graphene's high conductivity positions it ideally for long-wear sensors such as dry electrodes or respiration monitors. Here, we demonstrate the potential of Cyrene-based graphene inks through few-layer inkjet printing on flexible substrates for the first time, to produce non-toxic conductors toward a strain-mediated mechanism for biosensing, used to detect bodily motion for wearable electronics. The challenges overcome in this study include engineering ink chemistry and printing parameters such that Cyrene's relatively high viscosity compared to typical inkjet solvents, still allows for droplet ejection in a conventional material printer, yielding well-resolved clean line-edges in contrast to other solvents that exhibit diffuse line-edges possibly from stray droplets and ink-splashing. Temperature-dependent transport measurements on the inkjet-printed Cyrene-based graphene films showed the conductivity to be largely temperature-invariant but at lower temperatures below 100 K, conductivity decreased, likely as a result of increased inter-membrane separation arising from thermal contraction. Additionally, temperature-dependent Raman spectroscopy showed the red-shift in the G-band, 2D-band and D-band peaks, as temperature increased. As a result, by validating flexion motion detection of the proximal interphalangeal joint demonstrated in this study, our work is the first of its kind to successfully additively manufacture inkjet-printed Cyrene-based graphene strain sensors on flexible substrates for bio-sensing and wearables.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation trajectories of solution-processed perovskite thin films from mixed solvents

The engineering of mixed-solvent formulations and their evaporation conditions are key to reproducible perovskite coatings for high-performance photovoltaics. Here, we report a lumped-parameter evaporation model to predict the evolution of a perovskite ink liquid film over time (solvent ratio, solute concentration, and film thickness). The drying-rate model is validated via in situ film-thickness measurements, and the predicted transient liquid film state is mapped as a process path. These methods allow for the prediction of process sensitivity to local environmental factors and the understanding and visualization of a broader processing parameter space enabled through the coupling of process and ink engineering. Process maps are applied to create a new framework for scalable perovskite coating development with a goal of improving the reproducibility and transferability of perovskite fabrication. This approach is demonstrated with blade-coated FA 0.83 Cs 0.17 PbI 3 photovoltaic devices, improving the photovoltaic conversion efficiency from 17.5% ± 1.7% to 20.3% ± 0.6%.

14 SOLAR ENERGY↗

Eco–Friendly Solvent Engineered CsPbI 2.77 Br 0.23 Ink for Large–Area and Scalable High Performance Perovskite Solar Cells

The performance of large-area perovskite solar cells (PSCs) has been assessed for typical compositions, such as methylammonium lead iodide (MAPbI 3 ), using a blade coater, slot-die coater, solution shearing, ink-jet printing, and thermal evaporation. However, the fabrication of large-area all-inorganic perovskite films is not well developed. This study develops, for the first time, an eco-friendly solvent engineered all-inorganic perovskite ink of dimethyl sulfoxide (DMSO) as a main solvent with the addition of acetonitrile (ACN), 2-methoxyethanol (2-ME), or a mixture of ACN and 2-ME to fabricate large-area CsPbI 2.77 Br 0.23 films with slot-die coater at low temperatures (40–50 °C). The perovskite phase, morphology, defect density, and optoelectrical properties of prepared with different solvent ratios are thoroughly examined and they are correlated with their respective colloidal size distribution and solar cell performance. Here, the optimized slot-die-coated CsPbI 2.77 Br 0.23 perovskite film, which is prepared from the eco-friendly binary solvents dimethyl sulfoxide:acetonitrile (0.8:0.2 v/v), demonstrates an impressive power conversion efficiency (PCE) of 19.05%. Moreover, the device maintains ≈91% of its original PCE after 1 month at 20% relative humidity in the dark. It is believed that this study will accelerate the reliable manufacturing of perovskite devices.

binary and ternary solvent↗

Coaxial Ceramic Direct Ink Writing on Heterogenous and Rough Surfaces: Investigation of Core–Shell Interactions

In this work, coaxial conductor–ceramic direct ink writing enables the printing of sensitive or encapsulated materials onto heterogeneous and rough substrates. While encasing the core fluid within a stiff ceramic shell, continuity may be maintained, even while printing onto conventionally challenging substrates. Here, we report the development of a coaxial ceramic direct ink writing suite and explore coflow interrelationships based on microfluidic principles. A coaxial nozzle is designed to facilitate the coextrusion of an alumina shell, whereas indium–tin-oxide inks constitute the core. In this manner, a core–shell ceramic element may be printed onto rough substrates for future high-temperature applications. Colloidal inks are engineered to provide the required rheological and sintering performance. Moreover, flow simulations in conjunction with microfluidic coflow principles are used to explore the coaxial printing processing space, thus controlling the core–shell architectures. Physical modeling is further used to analyze core deformations and eccentricity. As a result, simulations are validated experimentally, and the analyses are used to deposit coaxial ceramic features onto heterogeneous, high-temperature ceramic substrates.

20 FOSSIL-FUELED POWER PLANTS↗

Impact of controlled prewetting on part formation in binder jet additive manufacturing

Binder jetting is an additive manufacturing process that bonds powder through selectively depositing binder by inkjet printing. The part is then extracted and densified by sintering and/or infiltration. The process offers low costs and fast build rates, but properties can be poor due to residual porosity after sintering. The inkjet printing process may contribute to this residual porosity by creating large pores. The droplet kinetic energy ejects some powder particles from the bed and rearranges others. Particle ejection and rearrangement are theorized to create porous regions in binder-jetted parts. In this work, small amounts of moisture are added to the spread powder before printing and the impact on part formation, part properties, and printing parameters measured with varied droplet spacing, droplet velocity, and print frequency. Moisture is added by applying an atomized fluid mixture to the powder between layer spreading and binder printing. The fluid mixture partially evaporates but leaves a stable residue to increase cohesion and enhance imbibition. Moisture addition to the powder increases the range of droplet spacings for line formation while reducing particle ejection, powder rearrangement, and balling in layer and multilayer parts. Excessive moisture addition decreases the effective saturation of printed lines, but saturation in 3D parts is less impacted. Increased surface roughness in the first few layers of a print was also mitigated with prewetting. Finally, high-speed X-ray imaging verified prewetting reduction in particle ejection and rearrangement.

36 MATERIALS SCIENCE↗

Abstract for CRADA between NETL and the University of Massachusetts Lowell (AGMT-1275)

The demand for printed electronics over conventional electronics is growing each year due to their low costs, low material waste during manufacturing, and compatibility with flexible substrates. The development of inks for printed electronics is a challenge because each printing technology requires different viscosities and curing behaviors to create devices with controlled structures at the micron scale, or smaller. Carbon is a great candidate for fabricating printed electronics devices because it is inexpensive and earth abundant, easily functionalized to impart miscibility with solvent systems, and has electrical properties that can be tuned from insulating to conducting. Despite these advantages, carbons are rarely used for printed electronics because there is a scarcity of inks available for non-contact printing technologies. To address these challenges, the National Energy Technology Laboratory (NETL) will collaborate with the University of Massachusetts Lowell (Participant) through its Printed Electronics Research Collaborative (PERC) to develop engineered carbons and ink formulations optimized specifically for printing radio- and microwave-frequency electronic devices using ink jet, aerosol jet, syringe dispensing, and other additive manufacturing techniques. NETL will process coal, petroleum, and other carbon feedstocks to make engineered carbons with the appropriate composition, microstructure, surface functionalization, and particle morphologies needed to stabilize ink suspensions and impart useful electronic properties to printed devices. The University of Massachusetts Lowell will utilize these engineered carbons to determine which solvent systems and ink additives are needed to achieve the appropriate viscosity, stability, and printability to make useful ink formulations. The University of Massachusetts Lowell will then utilize these inks to manufacture printed resistors and conductors using inkjet, aerosol jet, and syringe dispensing printing methods and will characterize device performance using four-point probe resistivity measurements, contact angle measurements to assess wettability, adhesion evaluation to various substrates, and focused ion beam and scanning electron microscopy for surface and density investigations of printed devices.

36 MATERIALS SCIENCE↗

Persistent polyamorphism in the chiton tooth: From a new biomineral to inks for additive manufacturing

Engineering structures that bridge between elements with disparate mechanical properties are a significant challenge. Organisms reap synergy by creating complex shapes that are intricately graded. For instance, the wear-resistant cusp of the chiton radula tooth works in concert with progressively softer microarchitectural units as the mollusk grazes on and erodes rock. Herein, we focus on the stylus that connects the ultrahard and stiff tooth head to the flexible radula membrane. Using techniques that are especially suited to probe the rich chemistry of iron at high spatial resolution, in particular synchrotron Mössbauer and X-ray absorption spectroscopy, we find that the upper stylus of Cryptochiton stelleri is in fact a mineralized tissue. Remarkably, the inorganic phase is nano disperse santabarbaraite, an amorphous ferric hydroxyphosphate that has not been observed as a biomineral. The presence of two persistent polyamorphic phases, amorphous ferric phosphate and santabarbaraite, in close proximity, is a unique aspect that demonstrates the level of control over phase transformations in C. stelleri dentition. The stylus is a highly graded material in that its mineral content and mechanical properties vary by a factor of 3 to 8 over distances of a few hundred micrometers, seamlessly bridging between the soft radula and the hard tooth head. Furthermore, the use of amorphous phases that are low in iron and high in water content may be key to increasing the specific strength of the stylus. Finally, we show that we can distill these insights into design criteria for inks for additive manufacturing of highly tunable chitosan-based composites.

36 MATERIALS SCIENCE↗

Fabrication of engineered dopant profiles in Er/Lu:YAG transparent laser ceramics via additive manufacturing

Transparent ceramic Er:YAG laser rods were fabricated via the direct ink write (DIW) method with engineered doping profiles featuring an Er-doped core with endcaps and core-clad structures. Laser rods up to 11 cm in length were produced which required development of a scalable process. To achieve this, multiple improvements were implemented, including printing the rods horizontally on a substrate, rather than vertically, eliminating the need for an external support structure and using a sacrificial drying layer to mitigate warping and defects. Highly transparent rods were achieved with optical scatter levels as low as 0.5%/cm (at 543 nm). A small refractive index difference of 5.7 ppm was measured at the interface between the Er-doped core and the Lu-doped endcaps and cladding. These results demonstrate DIW as a straightforward method for making good optical quality laser rods with engineered doping profiles to improve laser performance.

36 MATERIALS SCIENCE↗

3D-Bioprinted Marine Bacteria for the Degradation of Polyhydroxybutyrate Bioplastics

The severe, long-lasting harm caused by plastic pollution to marine ecosystems and coastal economies has led to the development of biodegradable plastics; however, their limited decomposition in marine environments remains a challenge. Here, technologies are presented for creating 3D-bioprinted living materials as a proof of concept for bioplastic degradation, with specific use in marine environments. The approach developed here integrates the halotolerant bioplastic-degrading bacterium Bacillus sp. NRRL B- 14911 into alginate-based bio-ink to print an engineered living material (ELM) termed a “bio-sticker.” Quantification of bacteria viability reveals that bioprinted marine bacteria survive within biostickers for more than 3 weeks. The rate at which the biostickers degrade the bioplastic polyhydroxybutyrate (PHB) can be tuned by altering biosticker biomass concentration, bioplastic concentration, or incubation temperature. Biostickers that are transferred to a different PHB sample still retain high biodegradation activity, demonstrating their reusability. Strain sweep oscillatory tests demonstrate that the biostickers display predominantly viscoelastic behavior. Monotonic tensile tests indicate that the elastic modulus and the adhesion of the biostickers are not negatively impacted by bacteria growth or incubation temperature. This work paves the way for the development of ELMs to facilitate the inclusion of bioplastics within the blue economy, promoting the emergence of more sustainable and ecofriendly materials.

3D bioprinting↗

Fabrication of bulk alumina structures with humidity sensing capabilities using direct ink write technique

Purpose The purpose of this study is to evaluate different 3D structures for humidity sensing that will enable the fabrication of complex geometries with high moisture sensitivity. Design/methodology/approach Humidity sensors based on alumina ceramics were fabricated using direct ink write (DIW) technique. Different engineered surface area, polymer binder ratio and post-processing treatment were considered to increase moisture sensitivity. Findings It was found that the binder ratio plays an important role in controlling the rheology of the paste during printing and determining the pore size after post-processing treatment. The sensibility of the fabricated humidity sensor was investigated by measuring its capacitance response toward relative humidity (RH) varying from 40% to 90% RH at 25°C. It is shown that using 3D lattice design, printed alumina humidity sensor could improve sensitivity up to 31.6 pF/RH%, over an order of magnitude higher than solid alumina. Originality/value Most of the alumina humidity sensors available are films in nature because of manufacturing difficulties, which limited its potential of higher sensitivity, and thus broader applications. In this paper, a novel 3D alumina humidity sensor was fabricated using DIW 3D printing technology.

Engineering↗

Pressure-based process monitoring of direct-ink write material extrusion additive manufacturing

As additive manufacturing (AM) has become a reliable method for creating complex and unique hardware rapidly, the quality assurance of printed parts remains a priority. In situ process monitoring offers an approach for performing quality control while simultaneously minimizing post-production inspection. For extrusion printing processes, direct linkages between extrusion pressure fluctuations and print defects can be established by integrating pressure sensors onto the print head. In this work, the sensitivity of process monitoring is tested using engineered spherical defects. Pressure and force sensors located near an ink reservoir and just before the nozzle are shown to assist in identification of air bubbles, changes in height between the print head and build surface, clogs, and particle aggregates with a detection threshold of 60–70% of the nozzle diameter. Visual evidence of printed bead distortion is quantified using optical image analysis and correlated to pressure measurements. Importantly, this methodology provides an ability to monitor the quality of AM parts produced by extrusion printing methods and can be accomplished using commonly available pressure-sensing equipment.

36 MATERIALS SCIENCE↗

Porous Polymer Structures with Tunable Mechanical Properties Using a Water Emulsion Ink

Recently, the manufacturing of porous polydimethylsiloxane (PDMS) with engineered porosity has gained considerable interest due to its tunable material properties and diverse applications. An innovative approach to control the porosity of PDMS is to use transient liquid phase water to improve its mechanical properties, which has been explored in this work. Adjusting the ratios of deionized water to the PDMS precursor during blending and subsequent curing processes allows for controlled porosity, yielding water emulsion foam with tailored properties. The PDMS-to-water weight ratios were engineered ranging from 100:0 to 10:90, with the 65:35 specimen exhibiting the best mechanical properties with a Young’s Modulus of 1.17 MPa, energy absorption of 0.33 MPa, and compressive strength of 3.50 MPa. This led to a porous sample exhibiting a 31.46% increase in the modulus of elasticity over a bulk PDMS sample. Dowsil SE 1700 was then added, improving the storage capabilities of the precursor. The optimal storage temperature was probed, with -60 °C resulting in great pore stability throughout a three-week duration. The possibility of using these water emulsion foams for paste extrusion additive manufacturing (AM) was also analyzed by implementing a rheological modifier, fumed silica. Fumed silica’s impact on viscosity was examined, revealing that 9 wt% of silica demonstrates optimal rheological behaviors for AM, bearing a viscosity of 10,290 Pa·s while demonstrating shear-thinning and thixotropic behavior. This study suggests that water can be used as pore-formers for PDMS in conjunction with AM to produce engineered materials and structures for aerospace, medical, and defense industries as sensors, microfluidic devices, and lightweight structures.

36 MATERIALS SCIENCE↗

Engineering catalytical electrodes for applications in energy areas

An ink formulation and electrode that enhances hydrogen production, oxygen production, carbon dioxide reduction and other electrocatalytic reactions. Embodiments include an ink formulation with polymer binders having different catalytical precursors and a 3D electrode produced by additive manufacturing from the inventor's ink formulation. Various embodiments of the inventor's apparatus, systems, and methods provide inks that that are 3D-printed into patterns that optimize surface area and flow. The catalytic materials are imbedded into the ink matrix which is then printed into a 3D structure that has architecture that optimizes surface area and flow properties.

Liang, Siwei↗

IPL-Annealed Mixed-Cation Perovskites with Robust Coating Window toward Scalable Manufacturing of Commercial Perovskite Solar Cells

Perovskite solar cells (PSCs) are a promising alternative solar technology, but the technical challenges of (1) stability/durability, (2) efficiency at scale, and (3) manufacturability must be overcome to achieve widespread PSC commercialization. The challenge of balancing solution ink formulation and scalable manufacturing is often overlooked in the literature, where focus is on adopting inks from processes that will not scale. In this study, we apply a classical roll-to-roll manufacturing perspective, utilizing both compositional engineering and intense pulsed light (IPL) annealing, to develop a mixed-cation perovskite ink with a robust coating window that simultaneously solve issues of stability and manufacturability for PSCs. Our method resulted in blade-coated, flexible, mixed-cation PSCs on ITO-PET substrates with a champion power conversion efficiency (PCE) efficiency of 16.7% using IPL annealing of the absorber layer and, to our knowledge, is one of the fastest processing methods for the perovskite layer. This overall reduction in processing time with a stable ink represents an advance toward the scaled production of perovskite solar cells on flexible substrates.

flexible perovskite solar cells↗