Tailoring Morphology and Structure of Inkjet‐Printed Liquid‐Crystalline Semiconductor/Insulating Polymer Blends for High‐Stability Organic Transistors

Inkjet printing of semiconducting polymers is desirable for realizing low‐cost, large‐area printed electronics. However, sequential inkjet printing methods often suffer from nozzle clogging because the solubility of semiconducting polymers in organic solvents is limited. Here, it is demonstrated that the addition of an insulating polymer to a semiconducting polymer ink greatly enhances the solubility and stability of the ink, leading to the stable ejection of ink droplets. This bicomponent blend comprising a liquid‐crystalline semiconducting copolymer, poly(didodecylquaterthiophene‐alt‐didodecylbithiazole) (PQTBTz‐C12), and an insulating commodity polymer, polystyrene, is extremely useful as a semiconducting layer in organic field‐effect transistors (OFETs), providing fine control over the phase‐separated morphology and structure of the inkjet‐printed film. Tailoring the solubility‐induced phase separation of the two components leads to a bilayer structure consisting of a polystyrene layer on the top and a highly crystalline PQTBTz‐C12 layer on the bottom. The blend film is used as the semiconducting layer in OFETs, reducing the semiconductor content to several tens of pictograms in a single device without degrading the device performance. Furthermore, OFETs based on the PQTBTz‐C12/polystyrene film exhibit much greater environmental and electrical stabilities compared to the films prepared from homo PQTBTz‐C12, mainly due to the self‐encapsulated structure of the blend film.     

Development,characterization, and processing of thin and thick inkjet-printed dielectric films

This work introduces the material and electrical characterization of two dielectric inks for use with inkjet printing fabrication and the realization of fully-printed multilayer electronic structures. The dielectric inks are categorized by the thickness of their per-layer profiles, where SU-8 polymer and poly(4-vinylphenol)-based solutions are utilized to realize thick (>4 μm) and thin (< 400 nm) inkjet-printed dielectric films, respectively. The material formulations for each ink are outlined in detail in order to achieve the desired viscosity and surface tension for optimal printing with a Dimatix inkjet printing system. Once printability and processing techniques are tuned and established, various material and electrical characterizations are performed, including printed profile measurement, multilayer profile tendencies, thermal reflow processing, UV-ozone surface energy modification, relative permittivity extraction, leakage current density, and dielectric breakdown voltage. Finally, the demonstration of fully-printed post-processed on-chip capacitors utilizing both thin and thick dielectric inks in conjunction with a silver nanoparticle-based metallic ink is presented and compared with other inkjet-printed capacitors.     

Surface Charge Reversal Method for High‐Resolution Inkjet Printing of Functional Water‐Based Inks

Printed electronics is a rapidly growing area of research being explored for the manufacture of large‐area and cost‐effective electronic devices by the patterned application of functional inks. There are challenges associated with processing the inks compatible with inkjet printing technology and developing efficient methods to successfully obtain the desired features, particularly when it comes to metal and metal–organic complex inks. Here, a reliable method is developed to achieve a sophisticated microstructured pattern using the inkjet printing technique assisted by a surface charge reversal effect. In addition, a procedure is formulated to obtain good quality, stable metal–organic water‐based inks compatible with salts of a variety of transition metals and rare earths, without the need for additional volatile solvents. A feasible and water‐based ink formulation combined with a simple and noninvasive surface charge reversal treatment constitutes a major step toward the manufacture of high‐resolution, inorganic patterned thin films on hydrophobic substrates using inkjet printing. These outcomes lead to the path of effective fusion of inorganic and organic heterointerfaces by simples designing and printing.     

A transition solvent strategy to print polymer:fullerene films using halogen-free solvents for solar cell applications

Inkjet printing is a mask-less non-contact deposition technique that is potentially suited for prototyping and manufacturing of thin-film polymer organic semiconductor devices from digital images. However new strategies are needed to achieve films with good macromorphology (i.e., high-fidelity footprint and uniform cross-section) and nanomorphology on unstructured substrates using a conventional ink-jet. Here we report a new transition solvent strategy to provide the desired film macromorphology and ultrafine nanomorphology in regioregular poly(3-hexylthiophene):phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) model films, without using chlorinated solvents. This strategy employs a good volatile solvent in combination with a miscible poor solvent that is much less volatile, which is the reverse of the usual low−high boiling-point solvent method. The good solvent suppresses premature aggregation in the ink head. Its removal by evaporation on the substrate leaves the poor solvent that triggers early π-stacking ordering and/or gelation of the polymer matrix that immobilizes the printed fluid on the substrate, suppressing both contact-line depinning and evaporation-induced solvent flow effects. The resultant donor–acceptor nanomorphology is further improved by vacuum drying at an optimal rate that avoids bubble formation. We have systematically characterized P3HT:PCBM films deposited with different solvents and platen temperatures to identify key macro- and nano-morphology determining processes. High-performance printed P3HT:PCBM solar cells were realized. These findings are applicable also to other printing and coating techniques based on low-viscosity inks.     

Correlating dilute solvent interactions to morphology and OPV device performance

Solvent additives have been explored as a reliable way to control the morphology in bulk-heterojunction (BHJ) layers for improved device performance. We show that the choice of solvent additives has direct implications on morphological evolution, i.e. poly(3-hexylthiophene) (P3HT): [6,6]-phenyl C61-butyric acid methyl ester (PCBM) BHJ films processed with a small amount of 1,8-diiodooctane or 1-chloronaphthalene have more crystalline PCBM domains compared to crystalline P3HT domains, while the opposite is true for films cast with nitrobenzene additive and films cast purely from chlorobenzene. The BHJ film cross-links when annealed at 300 °C in the presence of 1,8-diiodooctane. Cross-linking is found to occur even in pristine P3HT and PCBM films annealed under similar conditions. NMR spectroscopy is presented as a viable technique for quantitative analysis of the amount of solvents left in the BHJ films before and after heat treatment. Despite differences in the ways the additives affect the morphology of the BHJ layer, device performance remained stable over 300 h for all additives tested.     

Formulation and processing of novel conductive solution inks in continuous inkjet printing of 3-D electric circuits

One of the greatest challenges for the inkjet printing electrical circuits is formulation and processing of conductive inks. In the present investigation, two different formulations of particle-free conductive solutions are introduced that are low in cost, easy to deposit, and possess good electrical properties. A novel aqueous solution consisting of silver nitrate and additives is initially described. This solution demonstrates excellent adherence to glass and polymers and has an electrical resistivity only 2.9 times that of bulk silver after curing. A metallo-organic decomposition (MOD) ink is subsequently introduced. This ink produces a close-packed silver crystal microstructure after low-temperature thermolysis and subsequent high-temperature annealing. The electrical conductance of the final consolidated trace produced with the MOD ink is very close to bulk silver. In addition, the traces produced with the MOD material exhibit excellent wear and fracture resistance. When utilized in a specialized continuous inkjet (CIJ) printing technology system, both particle-free solution inks are able to produce conductive traces in three dimensions. The importance of three-dimensional (3-D) printing of conductive traces is finally discussed in relation to the broad range of applications in the freeform fabrication industry.     

Universally applicable small-molecule co-host ink formulation for inkjet printing red,green, and blue phosphorescent organic light-emitting diodes

For organic light-emitting diodes (OLEDs), inkjet printing technology is being developed as an alternative to the traditional vacuum evaporation, because of its precise patterning, high-efficient material utilization, large-area compatibility and low-cost. In this work, we report a universal ink formulation of small-molecule co-host and binary solvents for red, green and blue phosphorescent OLEDs. Moreover, the effect of hole-transporting layers on the ink spreading, film uniformity and exciton confinement ability is investigated. Furthermore, a large-area (170 mm × 170 mm) and homogeneous light-emitting film is inkjet-printed. Finally, red, green and blue OLEDs are successfully constructed using these optimized ink formulations on the solvent resistance hole-transporting layer. This work can reduce the complexity to adjust the host materials and solvents for different color inks, and could be applied in large-area and low-cost OLED displays with high resolution.     

Effect of Trace Solvent on the Morphology of P3HT:PCBM Bulk Heterojunction Solar Cells

The performance of bulk‐heterojunction (BHJ) solar cells is strongly correlated with the nanoscale structure of the active layer. Various processing techniques have been explored to improve the nanoscale morphology of the BHJ layer, e.g., by varying the casting solvent, thermal annealing, solvent annealing, and solvent additives. This paper highlights the role of residual solvent in the “dried” BHJ layer, and the effect of residual solvents on PCBM diffusion and ultimately the stability of the morphology. We show that solvent is retained within the BHJ film despite prolonged heat treatment, leading to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM agglomerates. The addition of a small volume fraction of nitrobenzene to the casting solution inhibits the diffusion of PCBM in the dry film, resulting in smaller PCBM agglomerates, and improves the fill factor of the BHJ device to 0.61 without further tempering. The addition of nitrobenzene also increases the P3HT crystalline content, while increasing the onset temperature for melting of P3HT side chains and backbone. The melting temperature for PCBM is also higher with the nitrobenzene additive present.     

Efficient,large area organic photovoltaic modules with active layers processed with non-halogenated solvents in air

Organic photovoltaic (OPV) modules with excellent power conversion efficiencies of 4.20% and 5.87% were obtained with blends of novel low bandgap polymers, POD2T-DTBT and PDTBT-alt-TT, respectively, with PCBM as the active layers. Large area polymer:PCBM blend films were deposited by blade coating with high film uniformity, fast processing speed, and low material consumption, without the need for an inert atmosphere. With the requirements of future manufacturing in mind, the effects of air exposure on the active layers and the substitution of chlorinated solvents for polymer processing were investigated. While the decline of V_oc due to air exposure was recovered by appropriate treatment of the completed devices, FF and J_sc were significantly affected due to interfacial effects, indicating that air exposure should be limited in duration. Active layers of POD2T-DTBT:PCBM processed with less toxic, non-halogenated mixed solvents, comprising non-polar o-xylene with small amounts of polar additive, showed a fine, interpenetrating nanofibrous network that facilitates charge transport in bulk heterojunction photovoltaic cells. The performance of POD2T-DTBT:PCBM photovoltaic cells and modules processed with the new ink formulations were on par with that obtained with chlorinated solvents, with the modules exhibiting impressive power conversion efficiencies above 4%. The results indicated that POD2T-DTBT was an outstanding candidate for future OPV production due to its high performance, processibility in different ink formulations and compatibility with the large area coating techniques.     

Rheological characterization of liquid electrolytes for drop-on-demand inkjet printing

Physico-chemical properties of inkjet printing liquids significantly affect the quality of print-out, thus being the key parameter in the performance of printed electronic device (PEDs). Complex hydrodynamic interactions that inks are subjected to in an inkjet printing device has an influence on their rheological response, thus final drop formation, jetting, and drying kinetics. This paper provides a systematic comparison of three PED electrolytes based on different solvents i.e. Sulfolane, 3-Methoxypropionitrile and Acetonitrile that gave them different physico-chemical properties. Rheological properties of printed electrolytes were found to strongly influence the quality of print-outs, which is investigated both optically and morphologically. Best printing results were obtained with the sulfolane-based electrolyte that has the most uniform temperature and shear rate dependent rheological behavior as well as the lowest evaporation rate. By carefully controlling the printing temperature window, it is possible to subject PED electrolytes to higher shearing viscosity profiles while avoiding undesirable dilatant behavior which results in clogged printing nozzles and disrupted droplet trajectory.     

Dispersion control of Ag nanoparticles in bulk-heterojunction for efficient organic photovoltaic devices

This research focuses on the effect of different capping agents on Ag nanoparticles (NPs), for the improved efficiency of organic photovoltaic cells. Ag NPs were produced by solution chemistry of the polyol process, and then successfully capped with oleylamine (OA), polyvinylpyrrolidone (PVP), or thiol terminated polystyrene (PS-SH), as proven by FT-IR spectra. These Ag NPs with different capping agents were finally embedded in the photoactive layer of poly(3-hexylthiophene):6,6-phenyl-C61 butyric acid methyl ester (P3HT:PCBM) bulk heterojunction solar cells. Because of the presence of a suitable capping agent that prevents aggregation, the dispersity of the Ag NPs in organic solvent was significantly improved, in the sequence of OA, PVP, and PS-SH. The photovoltaic cells exhibit increased performance from 3.11% to 3.49%, at an optimized blend ratio of Ag NPs (2.5 wt%) capped with PS-SH. This enhancement is mainly attributed to the improved short circuit current (increased from 8.49 mA/cm² to 9.29 mA/cm²) and extinction with effective light scattering, caused by improved dispersion of the Ag NPs in BHJ films, through reducing unwanted particle aggregation.     

Ion‐Conductive,Viscosity‐Tunable Hexagonal Boron Nitride Nanosheet Inks

Liquid‐phase exfoliation of layered solids holds promise for the scalable production of 2D nanosheets. When combined with suitable solvents and stabilizing polymers, the rheology of the resulting nanosheet dispersions can be tuned for a variety of additive manufacturing methods. While significant progress is made in the development of electrically conductive nanosheet inks, minimal effort is applied to ion‐conductive nanosheet inks despite their central role in energy storage applications. Here, the formulation of viscosity‐tunable hexagonal boron nitride (hBN) inks compatible with a wide range of printing methods that span the spectrum from low‐viscosity inkjet printing to high‐viscosity blade coating is demonstrated. The inks are prepared by liquid‐phase exfoliation with ethyl cellulose as the polymer dispersant and stabilizer. Thermal annealing of the printed structures volatilizes the polymer, resulting in a porous microstructure and the formation of a nanoscale carbonaceous coating on the hBN nanosheets, which promotes high wettability to battery electrolytes. The final result is a printed hBN nanosheet film that possesses high ionic conductivity, chemical and thermal stability, and electrically insulating character, which are ideal characteristics for printable battery components such as separators. Indeed, lithium‐ion battery cells based on printed hBN separators reveal enhanced electrochemical performance that exceeds commercial polymer separators.     

High-brightness perovskite quantum dot light-emitting devices using inkjet printing

The performance of perovskite quantum dot light-emitting diodes (PeQLEDs) has been rapidly enhanced recently, but the devices are still stuck in the stage of using small-scale solution processes, such as spin-coating. In this work, we report the realization of high performance PeQLEDs by using inkjet printing technique. We demonstrate the preparation of a printable perovskite quantum dot ink by using a hybrid solvent consisting of high boiling solvent dodecane and low boiling solvent n-octane. A universal strategy for eliminating coffee rings during inkjet printing of perovskite inks is developed based on the modulation of ink formulation, and the stacking model of perovskite quantum dot in a pixel pit structure is proposed. The inkjet-printed PeLEDs exhibit a low turn-on voltage of 2.7 V, a brightness of 10992 cd/m² at 6.6 V and a maximum current efficiency of 8.67 cd/A, which is by far the highest value reported for inkjet-printed PeLEDs. The results pave a way for future realization of high performance pixelated PeLED displays with inkjet printing technique.     

谈喷印机喷印工艺与油墨性能的关系

喷印机的喷印过程中,喷印质量直接受油墨性能和喷印工艺参数的影响。本文从喷印机的实用性出发,主要分析探讨了在保证喷印质量的情况下喷印工艺参数的设定与油墨性能的相互关系,并对喷印工艺参数的设定和油墨的使用提出了一些量化指标,为使用者在选择油墨及对油墨性能进行调整和改善提供一定的参考依据,对喷印机的实际应用也有着一定的指导意义。     

Polymer solar cells based on inkjet-printed PEDOT:PSS layer

In this article, we have demonstrated solar cell performance of the inkjet-printed PEDOT:PSS layer and the roles of additives in device efficiency. The newly proposed PEDOT:PSS inks with additives of glycerol and surfactant show the improved surface morphology and high conductivity resulting in the enhanced photovoltaic performance. Using the optimized ink formulation of PEDOT:PSS, we have demonstrated a 3.16% efficient solar cell with an inkjet printing.     

Polysiloxane Inks for Multimaterial 3d Printing of High-Permittivity Dielectric Elastomers

Dielectric elastomer transducers (DET) are promising candidates for electrically-driven soft robotics. However, the high viscosity and low yield stress of DET formulations prohibit 3D printing, the most common manufacturing method for designer soft actuators. DET inks optimized for direct ink writing (DIW) produce elastomers with high stiffness and mechanical losses, diminishing the utility of DET actuators. To address the antagonistic nature of processing and performance constraints, principles of capillary suspensions are used to engineer DIW DET inks. By blending two immiscible polysiloxane liquids with a filler, a capillary ink suspension is obtained, in which the ink rheology can be tuned independently of the elastomer electromechanical properties. Rheometry is performed to measure and optimize processibility as a function of filler and secondary liquid fraction. Including polar polysiloxanes as the secondary liquid produces a printed elastomer exhibiting a four-fold permittivity increase over commercial polydimethylsiloxane. The characterization and multimaterial printing into layered DET devices demonstrates that the immiscible capillary suspension improves the processability of the inks and enhances the properties of the elastomers, enabling actuation of the devices at comparatively low voltages. It is anticipated that this formulation approach will allow soft robotics to harness the full potential of DETs.     

All-solution processed organic solar cells with top illumination

All-solution processed organic solar cells with inverted device architecture were demonstrated. Devices contain opaque bottom electrodes and semitransparent top electrodes, resulting in top illuminated devices. Nanoparticles-based Ag ink was used for inkjet printing both top and bottom electrodes. Semi-transparent top electrode consists of high conductivity PEDOT:PSS and Ag current collecting grids. Printed electrodes were compared to evaporated Ag electrodes (both top and bottom) and to ITO electrode in terms of transmittance, roughness, sheet resistance and device performance. All-solution processed devices with top illumination have average PCE of 2.4%, using P3HT:PCBM as photoactive layer. Top-illuminated devices with inverted architecture and bottom-illuminated device with conventional architecture, containing the identical layers, but in the reverse sequence, were then compared. Performed studies have revealed an advantage of inverted cell architecture.     

Time‐Dependent Morphology Evolution by Annealing Processes on Polymer:Fullerene Blend Solar Cells

Changes in the nanoscale morphologies of the blend films of poly (3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), for high‐performance bulk‐heterojunction (BHJ) solar cells, are compared and investigated for two annealing treatments with different morphology evolution time scales, having special consideration for the diffusion and aggregation of PCBM molecules. An annealing condition with relatively fast diffusion and aggregation of the PCBM molecules during P3HT crystallization results in poor BHJ morphology because of prevention of the formation of the more elongated P3HT crystals. However, an annealing condition, accelerating PCBM diffusion after the formation of a well‐ordered morphology, results in a relatively stable morphology with less destruction of crystalline P3HT. Based on these results, an effective strategy for determining an optimized annealing treatment is suggested that considers the effect of relative kinetics on the crystallization of the components for a blend film with a new BHJ materials pair, upon which BHJ solar cells are based.     

谈喷印机喷印工艺与油墨性能的关系

在喷印机的喷印过程中,喷印质量直接受油墨性能和喷印工艺的影响。本文从喷印机的实用性出发,主要分析探讨了在保证喷印质量的情况下喷印工艺参数的设定与油墨性能的相互关系,并对喷印工艺参数的设定和油墨的使用提出了一些量化指标,为使用者在选择油墨及对油墨性能进行调整和改善提供一定的参考依据,对喷印机的实际应用也有着一定的指导意义。     

All-inkjet-printed dissolved oxygen sensors on flexible plastic substrates

Inkjet printing is a promising alternative manufacturing method to conventional standard microfabrication techniques for the development of flexible and low-cost devices. Although the use of inkjet printing for the deposition of selected materials for the development of sensor devices has been reported many times in literature, it is still a challenge and a potential route towards commercialization to completely manufacture sensor devices with inkjet technology. In this work is demonstrated the fabrication of a functional low-cost dissolved oxygen (DO) amperometric sensor with feature sizes in the micrometer range using inkjet printing. All the required technological steps for the fabrication of a complete electrochemical three electrodes system are discussed in detail. The working and counter electrodes have been printed using a gold nanoparticle ink, whereas a silver nanoparticle ink was used to print a pseudo-reference electrode. Both inks are commercially available and can be sintered at low temperatures, starting already at 120 °C, which allows the use of plastic substrates. In addition, a printable SU8 ink formulation cured by UV is applied as passivation layer in the sensor device. Finally, as the performance of analytical methods strongly depends on the working electrode material, is demonstrated the electrochemical feasibility of this printed DO sensor, which shows a linear response in the range between 0 and 8 mg L⁻¹ of DO, and affords a detection limit of 0.11 mg L⁻¹, and a sensitivity of 0.03 μA L mg⁻¹. The use of flexible plastic substrates and biocompatible inks, and the rapid prototyping and low-cost of the fabricated sensors, makes that the proposed manufacturing approach opens new opportunities in the field of biological and medical sensor applications.