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Multi-Component, Co-Deposition of Patterned Films and Nanoparticles via Atmospheric Pressure Plasma CVD

Description:

TECHNOLOGY AREA(S): Materials 

OBJECTIVE: Develop methods to integrate multiple precursor chemistries and engineered nanoparticles into a plasma enhanced chemical vapor deposition (PECVD) system which can operate at room temperature and atmospheric pressure. 

DESCRIPTION: Recent advancements in the field of atmospheric pressure plasma systems, including both afterglow and direct barrier discharge plasmas, have enabled the investigation of thin coatings via plasma enhanced chemical vapor deposition (PECVD), in which electromagnetic fields are used to induce and control gas phase chemical reactions.[1] These systems have demonstrated the ability to treat material surfaces at room temperatures and across several square feet of area, cleaning them or depositing conformal coatings via PECVD with very little thermal damage to even delicate materials or surface microstructures [2-3]. Most of these systems, however, utilize only a single-stream, large area treatment head (typically a slot or showerhead), achieving good lateral uniformity but restricting the ability to controllably mix chemical precursors in the reaction, to pattern deposition on the substrate, or to integrate engineered nanoparticles into the growing films. Significant research efforts in the past two decades within the Department of Defense (DOD), industry, and academia have also resulted in the ability to design and synthesize a broad suite of nanoparticles with tailored optical, chemical, and magnetic properties. Applications include the investigation of biological processes, the targeting of cancer therapies, selective absorption of light in solar cells and sensors, and the control of chemical and mechanical processes in nanoscale composite materials [4]. Significant challenges have arisen, however, in the controlled delivery and integration of these particles into useful coatings on realistic size scales. The Army needs the capability to integrate these two emerging technologies – selective non-equilibrium plasma deposition and engineered nanoparticles – to develop multifunctional, responsive, and adaptable thin film coating systems to enhance soldier and vehicle protection. The ability to independently and selectively react multiple gas-phase precursors would create a new capability for Army materials research – a rapid prototyping foundry – to develop multicomponent/multifunctional coatings with engineered environmental interactions, selective and reconfigurable optical properties, tailored energy-absorbing adhesive surfaces, or conformal coatings to enhance the bioresistance or fire retardancy of fabrics. Independent control of the plasma energy applied to each precursor would allow researchers to selectively produce particular gas phase radicals and then combine them at the substrate, enhancing control over film composition, morphology, and resulting functionality. If in addition the individual flows were laterally constrained, one could create a patterned surface, with control over the composition of each surface feature, integrating polymers, biomaterials, organosiloxanes, or engineered nanoparticles in a multitude of synergistic ways. 

PHASE I: Design concept for delivery of multiple precursor flows to enable the co-deposition of at least 3 separate components (two gas phase plasma reactors, one nanoparticle delivery stream) at atmospheric conditions. The plasma reactors should have independent flow rate control for each individual constituent, and should be able to utilize helium or argon as a primary gas, with the addition of a secondary reactive gas like oxygen at adjustable ratios. If possible, the use of air as a primary gas should also be considered. The concept should include the ability to deliver a flow of dry or wet nanoparticles such as Au to the growing surface during deposition. Demonstrate, build and deliver bench-scale prototype of three-stream system capable of simultaneously depositing 1 micrometer thick organosiloxane coatings and metallic nanoparticles uniformly over an area at least 1” X 1”. 

PHASE II: Build fully-functional prototype system capable of being integrated into an autonomous robotic system and demonstrate continuous, uniform deposition across substrates of varying sizes and shapes, up to 24” X 24”. Include capability to laterally constrain precursor/nanoparticle arrival to areas <5mm in diameter at the point of deposition on the substrate, and demonstrate the ability to deposit small spots, continuous lines, or patterned surfaces with independent incorporation of two PECVD precursors and metallic nanoparticles. Develop integrated process controls for the plasma head and power supplies with a programmable plug and play system that can be operated by both research and industry personnel, or modified by Army personnel to develop custom recipes for particular application areas. 

PHASE III: Follow-on activities are expected to be aggressively pursued by the offeror, namely in seeking opportunities to integrate the hardware, software, and protocols of the developed prototype into commercial systems for the microelectronics and medical communities, as well as defense applications. Such systems would be actively sought by researchers in academia and industry as a means to investigate the functionality of multicomponent thin film systems. 

REFERENCES: 

1: Pappas, D., "Status and Potential of Atmospheric Plasma Processing of Materials", J. Vac. Sci. and Tech. A, 2011, 29, 020801.

2:  Zhang, H. et al., "Deposition of Silicon Oxide by Atmospheric Plasma Jet for Oxygen Diffusion Barrier Applications", Thin Solid Films, 2016, 615, 63-68.

3:  Cavallin, T. et al., "Metal PVD Honey-Combs Coated with TiO2 and Al2O3 via PECVD Suitable for Sensoring Applications", Surf. Coat. And Tech., 2013, 230, 66-72.

4:  Jiang, C. et al., "A Review on the Application of Inorganic Nanoparticles in Chemical Surface Coatings on Metallic Substrates", Royal Soc. Of Chem. ADV, 2017, 7, 7531-7539.Hilt, F. et al, "Efficient Flame Retardant Thin Films Synthesized by Atmospheric Pressure PECVD Through the High Co-deposition Rate if Hexamethyldisiloxane and Triethylphosphate on Polycarbonate and Polyamide-6 Substrates", ACS Appl. Mater. Interfaces, 2016, 8, 12422-12433.

KEYWORDS: Atmospheric Plasma, Hybrid Coatings, Additive Manufacturing, Nanoparticles, Thin-Film Deposition, Soldier Protection, Manufacturing Process, Manufacturing Coatings, Manufacturing Equipment 

CONTACT(S): 

Andres Bujanda 

(410) 306-0680 

andres.a.bujanda.civ@mail.mil 

Derek Demaree 

(410) 306-0840 

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