Development of CMOS-Compatible, Microwave-Assisted Solution Processing of Nanostructured Zine Ferrite Films for Gigahertz Circuits
The development of radio frequency integrated circuits (RFICs), especially the dream of integrating analog, digital and radio frequency (RF) components on the same chip that is commonly known as System-on-a-Chip (SoC), is crucial to mobile communications of the future. Such SoC approach offers enhanced performance, greater reliability, and substantially less power consumption of integrated circuits while reducing overall physical size and thus manufacturing cost. However, the progress has been stalled by the lack of miniaturized inductor elements. Rise of unwanted parasitic effects limits down-scaling of the inductor structures and leaves the use of magnetic coating as a viable and attractive option to enhance the inductance and thus inductance density. It is also essential to shift from perm alloy and other amorphous alloys to ferrites and hex ferrites as the core material because of their very high electrical resistivity so as to keep losses in check, a criterion that cannot be compromised on in GHz frequency applications. This is viable, however, only if the integration of the magnetic core (film), particularly a ferrite film, is fully compatible with the CMOS fabrication process. Various approaches have been taken to meet this requirement, including investigations of employing layers of ferrite materials to envelop the inductor loop. However, the deposition of thin films of ferrites, whether by PVD or CVD, usually calls for the deposited ferrite layer to be annealed at an elevated temperature to crystallize the layer so that its magnetic characteristics are appropriate for the optimum performance of the circuit element. Such annealing is incompatible with CMOS process flow required for aggressive device geometries, as the inductor element is added after the active semiconductor circuit is processed, and any exposure of the processed circuit to elevated temperatures risks disturbing precise doping profiles employed and the integrity of the inter-layer dielectrics. What is called for is a low-temperature process for the deposition of a ferrite layer on top of the patterned inductor element – a layer of thickness such that most of the fringe field is encapsulated – while ensuring that the layer comprises crystallites of uniform size that leads to uniform magnetic behaviour. Recognizing the difficulty of meeting the various stringent requirements, it has recently been remarked that such a goal is a formidable challenge. In an attempt to address this challenge, in this work, we have adopted a counter-intuitive approach - the deposition of the desired ferrite composition on a processed die (that contains the inductor structures along with active semiconductor circuits) by immersing it into a chemical (reactant) solution, followed by a brief irradiation of microwave frequency. However, to identify the desired ferrite composition and the appropriate recipe to deposit them, a systematic effort had to be made first, to understand the inter-relationship between synthesis process, structure of resulting material, and its physical and chemical properties. Therefore, at the beginning, a general introduction in which key concepts related to the magnetic-core inductors, the microwave-irradiation-assisted synthesis of nanostructures, the ‗state of the art‘ in the field of integration of appropriate magnetic material to the RFICs, are all outlined. As a proof of concept, microwave-irradiation-assisted solution-based deposition of zinc ferrite thin films on the technologically important Si (100) substrate is demonstrated. The highlight of the process is the use of only non-toxic metal organic precursors and aqua-alcoholic solvents for the synthesis, which is complete in 10 minutes @< 100 °C, without any poisonous by-products. Effects of various process parameters such as solute concentrations, surfactant types, and their concentrations are investigated. A wide range of deposition rates (10 - 2000 nm/min) has been achieved by tweaking the process parameters. The simultaneous formation of zinc ferrite nanocrystallites (ZFNC) along with deposition of thin film is the hallmark of this synthesis technique. Unlike its bulk counterpart, both film and powder are found upon investigation to be rich in magnetic behavior– owing to plausible cationic distribution in the crystal lattice, induced by the inherently quick and far-from-equilibrium nature of the process. The accurate estimation of magnetic characteristics in film is, however, found to be difficult due to the high substrate-to-film mass ratio. The simultaneously prepared ZFNC is examined to arrive at the optimized process recipe that imparts the desired magnetic properties to the zinc ferrite system. The crystallographic cationic distribution in zinc ferrite powder is, however, difficult to study due to the nanoscale dimension of the as prepared material. To enable crystal growth, slow and rapid annealing in air at two different temperatures are employed. The effects of these annealing schemes on various attributes (magnetic properties in particular) are studied. Rapid annealing turns out to be an interesting pathway to promote rapid grain-growth without disturbing the crystallographic site occupancies. The presence of inversion, i.e., the amount of Fe3+ in the ‗A‘-sites in the spinel structure that ideally is zero in normal spinel structure of zinc ferrite, is evident in all annealed ZFNC, as determined by Riveted analysis. Such partially inverted ZFNC exhibits soft magnetic behavior with high saturation magnetization, which can easily be ―tuned‖ by choosing appropriate annealing conditions. However, a few unique strategic modifications to the same microwave-irradiation-assisted solution-based synthesis technique are tried for the formation of nanocrystalline powder with desired sizes and properties without the necessity of anneal. The approach eventually appears to pave a way for the formation of oriented structures of zinc ferrite. The effects of anneal, nevertheless, are studied with the help of neutron powder diffractometry and magnetic measurements. The magnetic ordering at various temperatures is analyzed and connected to the magnetic measurements. The study shows that long-range magnetic ordering, present even at room temperate, originates from the distribution of cations in the partially inverted spinel structures, induced by the rapid and kinetically driven microwave synthesis. Keeping the mild nature (<200 °C) of the processing in mind, a large degree of inversion (~0.5) is a surprise and results in a very high saturation magnetization, as much as 30 emu/g at room temperature (paramagnetic in bulk), in the ZFNC system. Based on the knowledge of process-structure-property interrelationship, a recipe for the deposition of ferrite thin films by the microwave-assisted deposition technique is optimized. Successful deposition of smooth and uniform zinc ferrite thin films on various substrates is, then, demonstrated. The mystery behind the strong adherence of the film to the substrate - an unexpected outcome of a low-temperature process - is probed by XPS and the formation of silicates at the interface is identified as the probable reason. The uniformity and consistency of film composition is also examined in this chapter. Another salient feature of the process is its capability to coat any complex geometry conformally, allowing the possibility of depositing the material in a way to ―wrap around‖ the three-dimensional inductor structures of RF-CMOS. Integration of nanostructure zinc ferrite thin films onto on-chip spiral inductor structures has been demonstrated successfully. The magnetic-core inductors so obtained exhibit the highest inductance density (700 nH/mm2) and the highest Q factor (~20), reported to date, operate at 5 GHz and above, by far the highest reported to date. An increase in inductance density of as much as 20% was achieved with the use of just 1 µm thick film of zinc ferrite covering only the ―top‖ of the spiral structure, i.e., up to 20% of chip real estate can potentially be freed to provide additional functionality. The microwave-assisted solution-based deposition process described in this thesis is meant for ‗post-CMOS‘ processing, wherein the film deposited on some specific electronic components can add desired functionality to or improve the performance of a component (circuit) underneath. However, the effect of such ‗post-CMOS‘ processing on the active MOS devices, interconnects, and even inter-layer-dielectrics fabricated prior to the deposition has to be mild enough to leave the performance of delicate MOS characteristics intact. Such CMOS-compatibility of the present deposition process has been tested with a satisfactorily positive result.
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