Toward conductive traces: Dip Pen Nanolithography® of silver nanoparticle-based inks

Wang, Hung Ta; Nafday, Omkar A.; Haaheim, Jason; Tevaarwerk, Emma; Amro, Nabil A.; Sanedrin, Raymond G.; Chang, Chih Yang; Ren, F.; Pearton, S. J.

doi:10.1063/1.2995859

Cited by 53 publications

(65 citation statements)

References 14 publications

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“…10 Ink transport in DPN can be facilitated via incorporation of a high-viscosity, high boiling point liquid in the ink. 21,22 The PEG−PPG stabilized Fe(III) tosylate spin-coating solution was therefore a good candidate for developing a DPN writeable ink with the PEG−PPG exhibiting trifunctionality, namely: Fe(III) tosylate stabilization, conductivity enhancement, and ink-thickening.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…IWL-0009−03). The tip was bled of excess ink in a method similar to that previously reported for DPN of liquid inks 21,22 by bringing it in contact with the substrate in several (typically four to five) locations, until deposition of large ∼10 μm "bleed-spots" ceased. One further test array (25 dots of 5 s dwell time) was deposited in order to ensure the system entered a regime of reproducible submicrometer-scale patterning.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…16,17 The ink used consists of a carrier solvent to assist in the transport of a particulate material, and together they deposit onto the substrate via physioadsorption processes. This AFM-based ink deposition process is generally referred to as dip pen nanolithography (DPN) 18 and enables patterning of a wide range of materials ("inks") including small organic molecules, 19 biomolecules, 20 metal nanoparticles, 21,22 and conducting polymers. 23−25 Its range of feature size resolution (from tens of nanometers up to several micrometers), ability to simultaneously pattern multiple inks, 26 upscalability, 27 and versatility in nondestructive lithography on substrates including semiconductors, plastics, biomaterials, and even biological tissue, 28 mean DPN is a promising tool for the nanostructuring of future nanoelectronic devices.…”

Section: ■ Introductionmentioning

confidence: 99%

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Vapor Phase Polymerization of EDOT from Submicrometer Scale Oxidant Patterned by Dip-Pen Nanolithography

et al. 2012

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Some of the most exciting recent advances in conducting polymer synthesis have centered around the method of vapor phase polymerization (VPP) of thin films. However, it is not known whether the VPP process can proceed using significantly reduced volumes of oxidant and therefore be implemented as part of nanolithography approach. Here, we present a strategy for submicrometer scale patterning of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) via in situ VPP. Attolitre (10 -18 L) volumes of oxidant "ink" are controllably deposited using dip-pen nanolithography (DPN). DPN patterning of the oxidant ink is facilitated by the incorporation of an amphiphilic block copolymer thickener, an additive that also assists with stabilization of the oxidant. When exposed to EDOT monomer in a VPP chamber, each deposited feature localizes the synthesis of conducting PEDOT structures of several micrometers down to 250 nm in width. PEDOT patterns are characterized by atomic force microscopy (AFM), conductive AFM, two probe electrical measurement, and micro-Raman spectroscopy, evidencing in situ vapor phase synthesis of conducting polymer at a scale (picogram) which is much smaller than that previously reported. Although the process of VPP on this scale was achieved, we highlight some of the challenges that need to be overcome to make this approach feasible in an applied setting. ABSTRACT: Some of the most exciting recent advances in conducting polymer synthesis have centered around the method of vapor phase polymerization (VPP) of thin films. However, it is not known whether the VPP process can proceed using significantly reduced volumes of oxidant and therefore be implemented as part of nanolithography approach. Here, we present a strategy for submicrometer scale patterning of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) via in situ VPP. Attolitre (10 −18 L) volumes of oxidant "ink" are controllably deposited using dip-pen nanolithography (DPN). DPN patterning of the oxidant ink is facilitated by the incorporation of an amphiphilic block copolymer thickener, an additive that also assists with stabilization of the oxidant. When exposed to EDOT monomer in a VPP chamber, each deposited feature localizes the synthesis of conducting PEDOT structures of several micrometers down to 250 nm in width. PEDOT patterns are characterized by atomic force microscopy (AFM), conductive AFM, two probe electrical measurement, and micro-Raman spectroscopy, evidencing in situ vapor phase synthesis of conducting polymer at a scale (picogram) which is much smaller than that previously reported. Although the process of VPP on this scale was achieved, we highlight some of the challenges that need to be overcome to make this approach feasible in an applied setting.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Vapor Phase Polymerization of EDOT from Submicrometer Scale Oxidant Patterned by Dip-Pen Nanolithography

et al. 2012

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“…The M-Type probes (material Si 3 N 4 , length 107 µm, width 22 µm, spring constant 0.5 N/m) have an ink reservoir etched into the underside of the cantilever, and this holds the ink in place to feed the tip during writing. The tip was bled of excess ink in a method similar to that previously reported for DPN of liquid inks by bringing it in contact with the substrate in several (typically 4-5) locations, until deposition of large ~10 µm 'bleed-spots' ceased [22,23,29]. All patterns were generated using the InkCAD software (v 2.7.1) provided with the Nscriptor system.…”

Section: Patterning Methodologymentioning

confidence: 99%

“…When dissolved in a reducing agent, such as ethylene glycol, the temperature of reduction is lowered significantly [31][32][33]. Ethylene glycol also has a relatively low volatility (boiling point 197 °C), an important parameter for DPN ink formulations [29]. Cho et al have shown that thin films of platinum nanoparticles could be formed by simply drop-casting H 2 PtCl 6 /EG solution onto a substrate heated to 160 °C [32].…”

Section: Ink Developmentmentioning

confidence: 99%

Nanoscale platinum printing on insulating substrates

O’Connell¹,

Higgins²,

Sullivan³

et al. 2013

Nanotechnology

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The deposition of noble metals on soft and/or flexible substrates is vital for several emerging applications including flexible electronics and the fabrication of soft bionic implants. In this paper, we describe a new strategy for the deposition of platinum electrodes on a range of materials, including insulators and flexible polymers. The strategy is enabled by two principle advances: (1) the introduction of a novel, low temperature strategy for reducing chloroplatinic acid to platinum using nitrogen plasma; (2) the development of a chloroplatinic acid based liquid ink formulation, utilizing ethylene glycol as both ink carrier and reducing agent, for versatile printing at nanoscale resolution using dip-pen nanolithography (DPN). The ink formulation has been printed and reduced upon Si, glass, ITO, Ge, PDMS, and Parylene C. The plasma treatment effects reduction of the precursor patterns in situ without subjecting the substrate to destructively high temperatures. Feature size is controlled via dwell time and degree of ink loading, and platinum features with 60 nm dimensions could be routinely achieved on Si. Reduction of the ink to platinum was confirmed by energy dispersive x-ray spectroscopy (EDS) elemental analysis and x-ray diffraction (XRD) measurements. Feature morphology was characterized by optical microscopy, SEM and AFM. The high electrochemical activity of individually printed Pt features was characterized using scanning electrochemical microscopy (SECM). Abstract. The deposition of noble metals on soft and/or flexible substrates is vital for several emerging applications including flexible electronics and the fabrication of soft bionic implants. In this article, we describe a new strategy for the deposition of platinum electrodes on a range of materials, including insulators and flexible polymers. The strategy is enabled by two principle advances: 1) the introduction of a novel, low-temperature strategy for reducing chloroplatinic acid to platinum using nitrogen plasma; 2) the development of a chloroplatinic acid based liquid ink formulation, utilising ethylene glycol as both ink carrier and reducing agent, for versatile printing at nanoscale resolution using dip-pen nanolithography (DPN). The ink formulation has been printed and reduced upon Si, glass, ITO, Ge, PDMS, and Parylene C. The plasma treatment effects reduction of the precursor patterns in situ without subjecting the substrate to destructively high temperatures. Feature size is controlled via dwell time and degree of ink loading, and platinum features with 60 nm dimensions could be routinely achieved on Si. Reduction of the ink to platinum was confirmed by Energy dispersive X-ray spectroscopy (EDS) elemental analysis and X-Ray Diffraction (XRD) measurements. Feature morphology was characterized by optical microscopy, SEM and AFM. The high electrochemical activity of individually printed Pt features was characterized using Scanning Electrochemical Microscopy (SECM).

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Controlled Preparation of Inorganic Nanostructures on Substrates by Dip‐Pen Nanolithography

Sun

Chu

2010

Chemistry An Asian Journal

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Controlled preparation of inorganic nanostructures on substrates is very important for various applications of functional inorganic nanomaterials. Dip-pen nanolithography (DPN), as an atomic force microscopy (AFM) based technique, can directly fabricate nanostructures with precise position and morphology control on the nanometer scale and meanwhile image the produced nanostructures in situ at high resolution. This Focus Review summarizes the challenges and progress in preparing inorganic nanostructures with DPN. The ink and reaction design, morphology and structure control, high-speed lithography, and the application of DPN-generated nanopatterns are all involved. The evolution and development of this technique, its superiorities, and unique properties are also discussed.

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Toward conductive traces: Dip Pen Nanolithography® of silver nanoparticle-based inks

Cited by 53 publications

References 14 publications

Vapor Phase Polymerization of EDOT from Submicrometer Scale Oxidant Patterned by Dip-Pen Nanolithography

Vapor Phase Polymerization of EDOT from Submicrometer Scale Oxidant Patterned by Dip-Pen Nanolithography

Nanoscale platinum printing on insulating substrates

Controlled Preparation of Inorganic Nanostructures on Substrates by Dip‐Pen Nanolithography

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