Film formation from plasma-enabled surface-catalyzed dehalogenative coupling of a small organic molecule

Hartl, Hugo; Guo, Yafei; Ostrikov, Kostya Ken; Xian, Yuezhong; Zheng, Jie; Li, Xingguo; Fairfull‐Smith, Kathryn E.; MacLeod, Jennifer

doi:10.1039/c8ra08920e

Cited by 11 publications

(35 citation statements)

References 53 publications

(45 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The dissociation and creation of free metal cations is followed by their reduction to crystalline metal by electrons from the plasma or secondary electrons emitted from the film (in the case of the ion beam experiments). The volatile anions can possibly be removed by a plasma‐enabled dehalogenative coupling reaction . In support of a reducing species such as electrons also playing a role in addition to the ions, the conversion of different metal salts was found to correlate more strongly with their reduction potentials than their bond strengths, and the metal salts that could not be converted did in some cases have bond dissociation energies that are actually lower than those of the metals salts that could be converted …”

Section: Resultsmentioning

confidence: 99%

A New Class of Low‐Temperature Plasma‐Activated, Inorganic Salt‐Based Particle‐Free Inks for Inkjet Printing Metals

Sui

Dai

Liu

et al. 2019

Adv Materials Technologies

View full text Add to dashboard Cite

tailor the properties of the printed device for each specific application.Currently, printing approaches such as inkjet printing have been limited to a small number of metals because of the inks that are composed of either nano particles or metal-organics. Metal nano particlebased inks are characterized by high metal loading which lead to low contact resistances. However, the inks are prone to agglomeration because of the high particle densities and the high sur face free energy of nanoparticles. For this reason, a number of steps are required to synthesize dispersed and printable inks, including the addition of organic capping groups such as poly(Nvinyl 2pyrrolidone) to sterically stabilize the particles. [9] The interactions between the organics and the metal nanoparticle surface are material specific and most studies have focused on Ag, [10] Au, [11] and Cu. [12] Alternatively, metalloorganic decomposition (MOD) inks composed of molecular metal-organic compounds are particlefree, reducing nozzle clogging, and free of the organic capping groups. [13] A drawback, though, is that these compounds are not readily available and must be carefully designed and syn thesized so that they are stable before and during printing near ambient temperatures, while still capable of being decomposed to produce metallic structures at slightly elevated temperatures. [14] Overall, MOD has focused on Ag, with an increasing number of studies only recently emerging on other metals such as Cu. [12] In addition to the limited number of metals, printing has also been restricted to a few substrates that can withstand relatively high temperatures because of a heating step, referred to gener ally as sintering, that is carried out after printing. In the case of metal nanoparticlebased inks, heating is required to remove the organic capping groups and fuse the metal nanoparticles to form percolating electrically conductive structures. [15] For MOD inks, the heating activates decomposition of the metal-organic compound which leads to release of the organic groups and metal nanoparticle nucleation and growth. [16] Recently, alter native approaches to heating such as chemical, [17] electrical, [18] photonic, [10,19] laser, [20] plasma, [21] and microwave [15,22] have been reported to lower the thermal loading; however, the effec tiveness of these methods varies considerably. [23] Inkjet printing is rapidly emerging as a means to fabricate low-cost electronic devices; however, its widespread adoption is hindered by the complexity of the inks and the relatively high processing temperatures, limiting it to only a few metals and substrates. A new approach for inkjet printing is described, based on commercially available, particle-free inks formulated from inorganic metal salts and their subsequent low-temperature conversion to metallic structures by a non-equilibrium, inert gas plasma. This single, general method is demonstrated for a library of metals including gold (Au), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), lead (Pb), bismut...

show abstract

Section: Resultsmentioning

confidence: 99%

A New Class of Low‐Temperature Plasma‐Activated, Inorganic Salt‐Based Particle‐Free Inks for Inkjet Printing Metals

Sui

Dai

Liu

et al. 2019

Adv Materials Technologies

View full text Add to dashboard Cite

show abstract

“…Control experiment to demonstrate the crucial role of electrons in the reduction process: schematics of plasma reduction by plasma jet (a) without mesh and (b) with grounded mesh to filter out electron interaction; photos of plasma treatment (c) without mesh and (e) showing reduced metal pattern related to (a) and (c); (f) no reduction shown treated through grounded mesh to reveal importance of electrons in metal reduction process The dehalogenation reaction (Fig. 22) (Hartl, et al, 2019) is another interesting example of plasma on-surface reactions. Similarly to Lee et al , N2 -plasma was applied to a liquid source sprayed surface.…”

Section: On-surface Reactionsmentioning

confidence: 99%

“…Similarly to Lee et al , N2 -plasma was applied to a liquid source sprayed surface. In this application, atmospheric-pressure plasma treatment is thought to be promoting a metal-catalysed surface reaction that cleaves carbon-halogen (C-X) bonds in the presence of a transition metal (Hartl, et al, 2019). Due to the low dissociation energy of the C-X bond, catalytic cleaving may happen through the plasma-assisted Ullmann reaction, where copper acts as a catalyst for C-X bond dissociation and induces subsequent aryl-aryl coupling.…”

Section: On-surface Reactionsmentioning

confidence: 99%

“…Schematic to represent the plasma-catalytic dehalogenation process (Hartl, et al, 2019) Plasma has the unique benefit of non-equilibrium characteristics, containing high energy electrons at low gas temperature whilst also containing high-density reactive radicals. This makes it highly suitable for assisting conventional printing technology, which often faces challenges in dealing with various nontraditional substrates or 3D objects.…”

Section: Fig 22mentioning

confidence: 99%

“…The optical microscope images in Figure 33 show tailored morphologies through a catalyzed reaction of small molecules 1,2,4-trichlorobenzene (TCB), as was briefly mentioned in section 3.4. It is thought that the monomer molecule was dissociated by the plasma into reactive fragments, which then crosslinked to form an oligomeric/polymeric product that formed a thin film on the substrate (Hartl, et al, 2019). The surface wettability was influenced by the plasma parameters, with high-dose plasmas leading to a strongly hydrophobic surface with water contact angles up to 130°.…”

Section: Fig 32mentioning

confidence: 99%

See 2 more Smart Citations

Plasma-digital nexus: plasma nanotechnology for the digital manufacturing age

Hong

Murphy

Ashford

et al. 2020

Rev. Mod. Plasma Phys.

View full text Add to dashboard Cite

Digital transformation in manufacturing is one of the key megatrends in the development of global economy and society. Three-dimensional (3D) printing is a transformative digital technology poised to disrupt manufacturing and supply chains across major industries. Here we critically examine relevant insights into current and emerging applications of plasma nanotechnology in printing, including 3D printing. Plasma devices operated at atmospheric pressure coupled with printing processes may help strengthen 3D printing as an emerging fabrication technology that morphs diverse metal powders, polymers, plastics and other materials into digitally designed 3D shapes and patterns. We discuss how plasma applications may help overcome current limitations of 3D printing in various fields, e.g. limitations of sculpting composite materials, lack of mechanical strength and the need for postprocessing. Our key focus is on the challenges, opportunities and physical mechanisms of the use of 3D printing in nano-manufacturing, defined as the fabrication of nanoscale building blocks, such as nanoparticles and nanomaterials; their assembly into higher-order (micro-scale) structures; and the integration of these structures into larger (macro-) scale devices and systems by controlling energy and matter at nanoscale. Moreover, we discuss the physico-chemical mechanisms that result in highlyconformal deposition of nanostructured materials onto 3D surfaces with microscopic (and possibly nanoscale) control of textures and inter-layer cross-linking, without the need for additional heating. We further highlight the arising opportunities for plasma nanotechnology to synergize with the emerging digital transformation platforms in surface micro-and nano-structuring using polymers, metals, metallic alloys, and other materials. These new findings in plasma-digital nanoscale fabrication may lead to a new digital manufacturing platform suitable for a number of cutting-edge applications in electronic, sensing and energy devices.

show abstract

Versatile, Rapid, and Plasma‐Assisted Synthesis of Cuprous Halide Composites at Room Temperature and Pressure

Hartl

Ostrikov

MacLeod

2021

Adv Materials Technologies

Self Cite

View full text Add to dashboard Cite

the hole concentration in CuI 1−x Br x can be controlled by modifying the stoichiometric ratio of the halides, demonstrating that these binary halides are promising candidates for tailored electronic properties in next-generation devices. [8] In addition to the compositional variation, disorderrelated effects contribute to the changes in the electronic and optical structure in these solid solutions. [9] With these electronic applications in mind, the synthesis of CuX films has become a hot topic in recent years, with a focus on chemical vapor deposition [10][11][12] and vacuum deposition techniques such as molecular beam epitaxy, [13,14] reactive sputtering, [15] and thermal evaporation. [8,16,17] At the same time, the cuprous halides are promising candidates for other applications, such as the use of CuBr in sensing, [18][19][20] or the use of CuCl as cathode in Mg primary batteries. [21] The growth of CuX on copper is also of interest for batteries, as CuCl/ Cu anodes are being investigated for use in lithium ion batteries (LIBs), [21][22][23] and LIBs comprising an anode made from Cu foam covered with a CuBr-and Br-doped graphene-like film exhibit dendrite-free operation and an increased cycling stability. [24] This ever-expanding suite of applications means that it is of considerable interest to identify new approaches to CuX synthesis. One outstanding challenge is integrating CuX into composite films, where only a limited amount of work has been done. For example, a polyvinyl alcohol (PVA)/CuI composite material, in which the inorganic crystals were synthesized directly within the polymer matrix through the reduction of CuCl 2 by NaI in aqueous PVA solution, has shown promise for photovoltaic applications. [25] Similarly, a polypyrrole/CuI composite film synthesized through a one-pot approach, demonstrated electrochemical sensing properties. [26] Composite films comprising inorganic nanoparticles within a polymer matrix provide advantages for certain applications, where their contrasting and/or complementary properties can create synergistic benefits. [27] Here, we demonstrate a versatile, single-step approach to synthesizing an array of CuX composite films. The process involves deposition of a halogen-containing liquid organic precursor onto a metal substrate, and subsequent application of a dielectric barrier discharge (DBD) plasma. DBD plasma creates a reactive environment, in which electrons, ions, ultraviolet radiation, and free radicals can contribute to reactions in suitable precursor molecules. [28] We have previously shown that exposure to DBD plasma causes cleaving of the CCl bonds Cuprous halides (CuX) are transparent semiconductors with a range of appealing characteristics, and with targeted applications in electronics, energy storage, and sensing. Here, it is demonstrated that CuX films can be formed at room temperature and atmospheric pressure using a rapid, plasma-based approach. Crystalline CuX products are formed using dielectric barrier discharge plasma to react liquid small-molecule precu...

show abstract

Film formation from plasma-enabled surface-catalyzed dehalogenative coupling of a small organic molecule

Abstract: New surface coating pathway by plasma-enabled surface-catalyzed reaction, offering control of surface chemistry, wettability and roughness.

Cited by 11 publications

References 53 publications

A New Class of Low‐Temperature Plasma‐Activated, Inorganic Salt‐Based Particle‐Free Inks for Inkjet Printing Metals

A New Class of Low‐Temperature Plasma‐Activated, Inorganic Salt‐Based Particle‐Free Inks for Inkjet Printing Metals

Plasma-digital nexus: plasma nanotechnology for the digital manufacturing age

Versatile, Rapid, and Plasma‐Assisted Synthesis of Cuprous Halide Composites at Room Temperature and Pressure

Contact Info

Product

Resources

About