NH_3 Plasma Surface Treatments of Engineering Fluoropolymers: A Way to Enhance Adhesion of Ni or Cu Thin Films Deposited by Electroless Plating

This paper describes the electroless Ni or Cu plating of some fiuoropolymer substrates through a tin-free activation process. Materials subjected to surface metallization are commercial Teflon() FEP, Nafion(), ACLAR() and LaRCTM-CP1 thin films which have recently gained a large scientific and technological interest due to their excellent thermal, chemical, mechanical and dielectric properties. The original approach implemented in the present work involves: (i)the grafting of nitrogen-containing functionalities on the polymer surfaces through plasma treatments in ammonia, (ii) the direct catalysis of the so-modified surfaces via their immersion in a simple acidic PdCl2 solution (i.e. without using a prior surface sensitization in an acidic SnCl2 solution), and finally (iii) the electroless metallization itself. However, prior to the immersion in the industrial plating baths, the chemical reduction of the Pd+2 species (species covalently tethered on the nitrogen-containing groups) to metallic palladium (PdO) is shown to be a key factor in catalyzing the electroless deposition initiation. This is made by immersion in an hypophosphite (H2PO2-) solution. Wettability measurements and X-ray photoelectron spectroscopy (XPS) experiments are used to characterize every surface modification step of the developed process. A cross-hatch tape test was used to asses the adhesion strength of the electroless films that is shown qualitatively good. In addition, a fragmentation test was developed in combination with electrical measurements. Its use allows to distinguish different adhesion levels at the metal/polymer interface and to evidence the influence of some processing parameters.

Direct Ni Electroless Metallization of Poly(etherimide) without Using Palladium as a Catalyst

Nickel or copper electroless metallization of polymers needs the grafting of a catalyst (palladium in the Pd(0) oxidation state) on the substrate surface to be coated. Our previous works on this topic [1-5] have allowed to develop a simple, tin-free method to attach Pd(+2) species from a palladium chloride (PdCl2) solution on any insulating surface and subsequently to reduce them, in the wet way, into the Pd(0) oxidation state. This Pd(0) state of the catalyst allows an instantaneous initiation of the Ni or Cu deposit by immersion in a plating bath. As palladium is an expensive chemical, it appears interesting to replace it by Ni(0) or Cu(0) species which are catalysts of their own ion reduction. Concerning the direct Ni electroless plating, the polymer surface (PI) was made catalytic for the electroless process by deposition (spin- coating or dipping) of an ultra-thin film of an organic nickel salt in an alcoholic solution. The chemical reduction of this salt, checked by XPS, was performed by chemical or photochemical ways and by plasma. Under these conditions, the initiation, by autocatalysis, of the Ni film deposition in an industrial plating bath was immediate i.e. without any initiation time. The film obtained was homogeneous, dense, bright, well-adhering up to thicknesses reaching