Jun.-Prof. Dr. Lola González-García

Soft electronic devices enable new types of products for an ergonomic interaction of humans with a digital environment. The inkjet (droplet on demand) printing of electrically conductive ink on soft substrates such as paper, textile, and polymers is a promising route for the prototyping and small-scale production of soft electronics that is efficient, cost-saving, and provides a rapid turnaround due to its fully digital workflow. The choice of materials and processing parameters is challenging, however, due to the combined complexity of metal-containing inks, their dynamics during droplet ejection, the active role of the porous substrate, and possible post-deposition steps. This review focuses on recent developments in inkjet printing of metal inks onto soft, porous substrates and their applications. The first section discusses the general principles in the inkjet printing of metal inks, including drop formation and jetting, wetting, and post treatment processes. The second section deals with the effect that the porosity of substrates has on the drying, diffusion, and adhesion of inks. Finally, current challenges and achievements of inkjet-printed, metal-containing inks are discussed.

We report on the dilution-induced agglomeration of ultrathin gold nanowires (AuNWs) into regular bundles. Wires with a metal core diameter of 1.6–1.7 nm surrounded by a ligand shell of oleylamine formed stable colloids in n-hexane and cyclohexane. Dilution with pure solvent induced the self-assembly into bundles with a regular, hexagonal cross-section. Small-angle X-ray scattering and thermogravimetric analysis indicated that bundles formed only if the ligand shell was sufficiently sparse. Dilution with pure solvent shifts the chemical equilibrium and reduces the ligand density, thus enabling agglomeration. We show that agglomeration is driven not by van der Waals forces but by the depletion forces of linearly shaped molecules. Linear solvent molecules or small amounts of unbound ligand align normal to the nanowire if the ligand shell is sparse. The resulting reduction in entropy creates a driving force for the AuNWs to bundle such that the low-entropy domains overlap and the overall entropy is increased. Dilution-induced nanowire bundling is thus explained as a combined effect of ligand desorption and destabilization by depletion.

Abstract A new type of hybrid core–shell nanoparticle dielectric that is suitable for inkjet printing is introduced. Gold cores (dcore ≈ 4.5 nm diameter) are covalently grafted with thiol-terminated polystyrene (Mn = 11000 Da and Mn = 5000 Da) and used as inks to spin-coat and inkjet-print dielectric films. The dielectric layers have metal volume fractions of 5 to 21 vol% with either random or face-centered-cubic structures depending on the polymer length and grafting density. Films with 21 vol% metal have dielectric constants of 50@1 Hz. Structural and electrical characterization using transmission electron microscopy, small-angle X-ray scattering, and impedance spectroscopy indicates that classical random capacitor–resistor network models partially describe this hybrid material but fail at high metal fractions, where the covalently attached shell prevents percolation and ensures high dielectric constants without the risk of dielectric breakdown. A comparison of disordered to ordered films indicates that the network structure affects dielectric properties less than the metal content. The applicability of the new dielectric material is demonstrated by formulating inkjet inks and printing devices. An inkjet-printed capacitor with an area of 0.79 mm2 and a 17 nm thick dielectric had a capacitance of 2.2±0.1 nF@1 kHz.

We examine network formation and percolation of carbon black by means of Monte Carlo simulations and experiments. In the simulation, we model carbon black by rigid aggregates of impenetrable spheres, which we obtain by diffusion-limited aggregation. To determine the input parameters for the simulation, we experimentally characterize the micro-structure and size distribution of carbon black aggregates. We then simulate suspensions of aggregates and determine the percolation threshold as a function of the aggregate size distribution. We observe a quasi-universal relation between the percolation threshold and a weighted average radius of gyration of the aggregate ensemble. Higher order moments of the size distribution do not have an effect on the percolation threshold. We conclude further that the concentration of large carbon black aggregates has a stronger influence on the percolation threshold than the concentration of small aggregates. In the experiment, we disperse the carbon black in a polymer matrix and measure the conductivity of the composite. We successfully test the hypotheses drawn from simulation by comparing composites prepared with the same type of carbon black before and after ball milling, i.e., on changing only the distribution of aggregate sizes in the composites.

We describe the gram-scale synthesis of hybrid gold nanoparticles with a shell of conductive polymers. A large-scale synthesis of hexadecyltrimethylammonium bromide (CTAB)-capped gold nanoparticles (AuNP@CTAB) was followed by ligand exchange with conductive polymers based on thiophene in a 10 L reactor equipped with a jacket to ensure a constant temperature of 40 °C and a mechanical stirrer. Slow and controlled reduction of the gold precursors and the presence of small amounts of silver nitrate are revealed to be the critical synthesis variables to obtain particles with a sufficiently narrow size distribution. Batches of approximately 10 g of faceted AuNP@CTAB with tunable average particle sizes from 54 to 85 nm were obtained per batch. Ligand exchange with poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) in the same reactor then yielded hybrid Au@PEDOT:PSS nanoparticles. They were used to formulate sinter-free inks for the inkjet printing of conductive structures without the need for a sintering step.

Hybrid electronic materials combine inorganic metals and semiconductors with π-conjugated polymers. The orientation of the polymer molecules in relation to the inorganic components is crucial for electrical material properties and device performance, but little is known of the configuration of π-conjugated polymers that bind to inorganic surfaces. Highly curved surfaces are common when using nanoscale components, for example, metal nanocrystal cores covered with conductive polymers. It is important to understand their effect on molecular arrangement. Here, we compare the molecular structures and electrical conductivities of well-defined nanoscale gold spheres and rods with shells of the covalently bound polythiophene PTEBS (poly[2-(3-thienyl)-ethyloxy-4-butylsulfonate]). We prepared aqueous sinter-free inks from the particles and printed them. The particles formed highly conductive films immediately after drying. Films with spherical metal cores consistently had 40% lower conductivities than films based on nanorods. Raman and X-ray photoelectron spectroscopy revealed differences in the gold–sulfur bonds of PTEBS on rods and spheres. The fractions of bond sulfur groups implied differences in the alignment of PTEBS with the surface. More polymer molecules were bound in an edge-on configuration on spheres than on rods, where almost all polymers aligned “face-on” with the metal surface. This leads to different interface resistances: gold–polythiophene–gold interfaces between rods with π–π-tacked face-on PTEBS apparently foster electron transport along the surface-normal direction, while edge-on PTEBS does not. Molecular confinement thus increases the conductivity of hybrid inks based on highly curved nanostructures.

Abstract Conductive inkjet printing with metal nanoparticles is irreversible because the particles are sintered into a continuous metal film. The resulting structures are difficult to remove or repair and prone to cracking. Here, a hybrid ink is used to obviate the sintering step and print interconnected particle networks that become highly conductive immediately after drying. It is shown that reversible conductive printing is possible on low-cost cardboard samples after applying standard paper industry coats that are adapted in terms of surface energy and porosity. The conductivity of the printed films approaches that of sintered standard inks on the same substrate, but the mobility of the hybrid particle film makes them less sensitive to cracks during bending and folding of the substrate. Damages that occur can be partially repaired by wetting the film such that particle mobility is increased and particles move to bridge insulating gaps in the film. It is demonstrated that the conductive material can be recovered from the cardboard at the end of its life time and be redispersed to recycle the particles and reuse them in conductive inks.

We studied the concentration-dependent agglomeration of apolar nanoparticles in different solvents. Octanethiol-stabilized gold nanoparticles (AuNPs) in evaporating liquid droplets were observed in situ using small-angle X-ray scattering. Concurrent analysis of liquid volume and particle agglomeration provided time-dependent absolute concentrations of free and agglomerated particles. All dispersions underwent an initial stage where the particle concentration increased but no agglomerates formed. Subsequently, agglomeration started at concentrations that varied by several orders of magnitude for different solvents. While agglomerates grew, the concentration of the dispersed particles remained at a constant “colloidal solubility” in most solvents. We consistently found that the colloidal stability of AuNPs decreased as cyclohexane > heptane > nonane > decane > toluene and suggest that details of the molecular interactions between solvent and ligand shell set this order.

Gold nanorods (AuNRs) with conductive polymer shells are interesting colloidal building blocks for electronics. Hybrid particles with AuNR cores and poly(3,4-ethylenedioxythiophene) or polystyrene sulfonate (PEDOT:PSS) shells were prepared as stable aqueous dispersions. Film formation during the drying of such dispersions is known to affect the electric conductivity of the material. We observed the mechanisms of drying in thin, spray-coated films with grazing incidence small-angle X-ray scattering (GISAXS). A sparse, uniform monolayer formed because the anisotropic shape of the AuNR inhibited “coffee-ring” effects. We used generalized two-dimensional correlation (2DC) spectroscopy to analyze the GISAXS data and to decipher the microscopic structure formation of the film during drying. Four major scattering peaks were attributed to porous PEDOT, PSS, Au, and the substrate layer. Their time-dependent intensity indicated the sequence of film formation: AuNR with mobile shells arranged on the substrate first, PEDOT and then PSS dried sequentially around the gold core. We discuss the final phase-separation of PEDOT:PSS on the hybrid rods. ER

Metal grids with submicron line diameters are optically transparent, mechanically flexible, and suitable materials for transparent and flexible electronics. Printing such narrow lines with dilute metal nanoparticle inks is challenging because it requires percolation throughout the particle packing. Here, we print fully connected submicron lines of 3.2 nm diameter gold nanoparticles and vary the organic ligand shell to study the relation between colloidal interactions, ligand binding to the metal core, and conductivity of the printed lines. We find that particles with repulsive potentials aid the formation of continuous lines, but the required long ligand molecules impede conductivity and need to be removed after printing. Weakly bound alkylamines provided sufficient interparticle repulsion and were easy to remove with a soft plasma treatment after printing, so that grids with a transparencies above 90% and a conductivity of 150 Ω sq–1 could be printed.