Laser-assisted chemical liquid-phase deposition of metals for micro- and optoelectronics

• Main Author: Kordás, K. (Krisztián)
• Format: Doctoral Thesis
• Language: English
• Published: University of Oulu 2002
• Subjects: metallization; optical fiber; polyimide; porous silicon; printed circuit board
• Online Access: http://urn.fi/urn:isbn:9514266862; http://nbn-resolving.de/urn:isbn:9514266862

Abstract The demands toward the development of simple and cost-effective fabrication methods of metallic structures with high lateral resolution on different substrates - applied in many fields of technology, such as in microelectronics, optoelectronics, micromechanics as well as in sensor and actuator applications - gave the idea to perform this research. Due to its simplicity, laser-assisted chemical liquid-phase deposition (LCLD) has been investigated and applied for the metallization of surfaces having practical importance (Si, GaAs, SiO2, Si3N4, etc.) since the beginning of the 80s. By the invention of novel substrates (polyimide, porous silicon), it was adequate to work out new precursors or just adopt old ones and optimise LCLD in order to fabricate metallic micro-patterns upon these materials for various purposes. According to the motivations mentioned above, LCLD was utilized for the fabrication of palladium (Pd) micro-patterns on polyimide (PI), polyimide/copper flexible printed circuit boards (PCBs), fused silica (SiO2) and silicon (Si). The selective metallization of porous silicon (PS) has been carried out with nickel (Ni). Depending on the types of lasers, either the focusing (Ar+ laser beam) or diaphragm projection (KrF and XeCl excimer laser pulses) method was employed. In the course of the work, various precursors of the corresponding metals have been investigated and utilized. In the beginning, the pyrolytic decomposition of palladium-amine complex ions ([Pd(NH3)4]2+) on PI by a scanned and focused Ar+ laser beam was optimised and discussed. Thick (up to several micrometers) and narrow (~ 10 μm) Pd conductor lines with electrical conductivity close to that of the bulk were obtained. In the continuation of these investigations, the precursor was developed further. [Pd(NH3)4]2+ was mixed with the solution of formaldehyde (HCOH) in order to induce the reduction of the metal complex ions. To our knowledge, we were the first - so far - who applied this solution and described the reaction. With the proper choice of the laser parameters, thin Pd films as catalyst layers for electroless copper plating were deposited utilizing Ar+ and excimer lasers as well. The chemically plated copper deposits - upon the obtained Pd film - have excellent electrical and good mechanical properties. In the second part of the thesis, three practical applications (metallization of via holes drilled in PI/Cu flexible PCBs, end-mirror fabrication on single-mode optical fibers, and carbon nanotube growth on Pd activated Si and Si/SiO2 substrates) of Pd LCLD were realized. The previously presented [Pd(NH3)4]2+ and [Pd(NH3)4]2+/HCOH precursors were employed for creating the catalyst Pd layers for the carbon nanotube chemical vapor-phase deposition and for the autocatalytic electroless chemical copper plating, respectively. Finally, a simple novel method was introduced for the area-selective metallization of PS. Since the surface of PS reduces spontaneously most metals from their aqueous solutions, it is difficult to realize localized metal deposition from liquid-phase precursors on it. We proposed the application of a stable Ni plating bath from which the metal deposits only when the PS is irradiated with photons having wavelength shorter than 689 nm, thus making possible an area-selective laser-assisted metal deposition. The deposited metal structures and patterns were analysed by field emission scanning electron microscopy (FESEM) equipped with energy dispersive spectrometer (EDS), by the milling and imaging modes of a focused ion beam system (FIB), optical microscopy, profilometry, resistance, and by reflectance measurements.