Electrospray deposition (ESD) applies a high voltage to liquids flowing through narrow capillaries to produce monodisperse generations of droplets down to hundreds of nanometers in diameter, each carrying a small amount of the delivered solute. This deposition method has been combined with insulated stencil masks for fabricating micropatterns by spraying solutions containing nanoparticles, polymers, or biomaterials. To optimize the fabrication process for micro-coatings, a self-limiting electrospray deposition (SLED) method has recently been developed. Here, we combine SLED with a pre-existing patterned polymer film to study SLED’s fundamental behavior in a bilayer geometry. SLED has been observed when glassy insulating materials are sprayed onto conductive substrates, where a thickness-limited film forms as charge accumulates and repels the arrival of additional charged droplets. In this study, polystyrene (PS), Parylene C, and SU-8 thin films of varying thickness on silicon are utilized as insulated spraying substrates. Polyvinylpyrrolidone (PVP), a thermoplastic polymer is sprayed below its glass transition temperature (Tg) to investigate the SLED behavior on the pre-deposited insulating films. Furthermore, to examine the effects of in-plane confinement on the spray, a microhole array patterned onto the PS thin film by laser dewetting was sprayed with dyed PVP in the SLED mode. This was then extended to an unmasked electrode array showing that masked SLED and laser dewetting could be used to target microscale regions of conventionally-patterned electronics.

No abstract

Thermocapillary dewetting of liquids and molten films has recently emerged as a viable alternative to conventional microprocessing methods. As this thermal gradient-induced mechanism is universal, it can be applied to any material. This work explores the sequential dewetting of materials with varying melting points, including polymers and metals, to create aligned morphologies. The variation in melting point allows for the dewetting of single layers at a time or mobility-limited simultaneous dewetting. As a result, a variety of multimaterial structures can be produced with built-in alignment, such as arrays of concentric circles, lines with periodic segmentation, or islands on holes. This approach employs photothermal methods to induce the necessary thermal gradient, manipulating several variables in order to influence the consequent structures. Adjusting laser power and light intensity allows for the control of temperature for selective dewetting of films; altering beam size and exposure time affects the extent of dewetting in terms of diameter size; overlap effects and simultaneous dewetting can result in complex architectures. This controlled writing of patterns also presents a technique to create both masks at low temperatures for conductive multilayers as well as templates for electrospray deposition.

Focused laser spike (FLaSk) excitation has been demonstrated as a reliable technique for the patterning of micro-to-nanoscale features locally by thermocapillary shear of thin films. Recent work on polymer thin films has revealed that overlapping laser scans can leverage coupled thermal and fluid effects to create subwavelength patterns. Compared to polymeric films, metallic thin films possess both a lower melt viscosity and higher surface tension. Here, we investigate overlapping effects in the dewetting of ∼15 nm gold thin films on borosilicate and quartz glass substrates with a 532 nm continuous wave laser. During this process, FLaSk initiates capillary and thermocapillary dewetting simultaneously. Further, the low oxidation potential and high vapor pressure of gold lead to nonequilibrium vaporization during heating. Since the parameters of overlapping scans control the amount of material that is heated and to what temperature it is heated, selection of laser power, scanning distance, writing speed, and numerical aperture results in particles with different sizes and spacing deposited on the writing substrates or a positioned superstrate through a laser-induced localized physical vapor deposition (LILPVD) process. If the laser parameters are selected within a specific working range, uniform or periodic particle distributions can be repeatably deposited in this fashion, which can then be used as seeds for nanomaterial growth. In addition, if the substrate melts during FLaSk, the viscous force of the liquid-on-liquid dewetting broadens the range of patterning conditions by resisting the motion of the gold leading to more uniform particles over a large range of parameters.

<p>Electrospray deposition (ESD) applies a high voltage to liquids flowing through narrow capillaries to produce monodisperse generations of droplets down to hundreds of nanometers in diameter, each carrying a small amount of the delivered solute. This deposition method has been combined with insulated stencil masks for fabricating micropatterns by spraying solutions containing nanoparticles, polymers, or biomaterials. To optimize the fabrication process for micro-coatings, a self-limiting electrospray deposition (SLED) method has recently been developed. Here, we combine SLED with a pre-existing patterned polymer film to study SLED’s fundamental behavior in a bilayer geometry. SLED has been observed when glassy insulating materials are sprayed onto conductive substrates, where a thickness-limited film forms as charge accumulates and repels the arrival of additional charged droplets. In this study, polystyrene (PS), Parylene C, and SU-8 thin films of varying thickness on silicon are utilized as insulated spraying substrates. Polyvinylpyrrolidone (PVP), a thermoplastic polymer is sprayed below its glass transition temperature (T_g) to investigate the SLED behavior on the pre-deposited insulating films. Furthermore, to examine the effects of in-plane confinement on the spray, a microhole array patterned onto the PS thin film by laser dewetting was sprayed with dyed PVP in the SLED mode. This was then extended to an unmasked electrode array showing that masked SLED and laser dewetting could be used to target microscale regions of conventionally patterned electronics.</p>