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High speed mask-less laser-controlled precision micro-additive manufacture



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Ten, Jyi Sheuan 


A rapid, mask-less deposition technique for writing metal tracks has been developed. The technique was based on laser-induced chemical vapour deposition. The novelty in the technique was the usage of pulsed ultrafast lasers instead of continuous wave lasers in pyrolytic dissociation of the chemical precursor. The motivation of the study was that (1) ultrafast laser pulses have smaller heat affected zones thus the deposition resolution would be higher, (2) the ultrashort pulses are absorbed in most materials (including those transparent to the continuous wave light at the same wavelength) thus the deposition would be compatible with a large range of materials, and (3) the development of higher frequency repetition rate ultrafast lasers would enable higher deposition rates. A deposition system was set-up for the study to investigate the ultrafast laser deposition of tungsten from tungsten hexacarbonyl chemical vapour precursors. A 405 nm laser diode was used for continuous wave deposition experiments that were optimized to achieve the lowest track resistivity. These results were used for comparison with the ultrafast laser track deposition. The usage of the 405 nm laser diode was itself novel and beneficial due to the low capital and running cost, high wall plug efficiency, high device lifetime, and shallower optical penetration depth in silicon substrates compared to green argon ion lasers which were commonly used by other investigators.
The lowest as-deposited track resistivity achieved in the continuous wave laser experiments on silicon dioxide coated silicon was 93±27 µΩ cm (16.6 times bulk tungsten resistivity). This deposition was done with a laser output power of 350 mW, scan speed of 10 µm/s, deposition pressure of 0.5 mBar, substrate temperature of 100 °C and laser spot size of approximately 7 µm. The laser power, scan speed, deposition pressure and substrate temperature were all optimized in this study. By annealing the deposited track with hydrogen at 650 °C for 30 mins, removal of the deposition outside the laser spot was achieved and the overall track resistivity dropped to 66±7 µΩ cm (11.7 times bulk tungsten resistivity). For ultrafast laser deposition of tungsten, spot dwell experiments showed that a thin film of tungsten was first deposited followed by quasi-periodic structures perpendicular to the linear polarization of the laser beam. The wavelength of the periodic structures was approximately half the laser wavelength (λ/2) and was thought to be formed due to interference between the incident laser and scattered surface waves similar to that in laser-induced surface periodic structures. Deposition of the quasi-periodic structures was possible on stainless steel, silicon dioxide coated silicon wafers, borosilicate glass and polyimide films. The thin-films were deposited when the laser was scanned at higher laser speeds such that the number of pulses per spot was lower (η≤11,000) and using a larger focal spot diameter of 33 µm. The lowest track resistivity for the thin-film tracks on silicon dioxide coated silicon wafers was 37±4 µΩ cm (6.7 times bulk tungsten resistivity). This value was achieved without post-deposition annealing and was lower than the annealed track deposited using the continuous wave laser. The ultrafast tungsten thin-film direct write technique was tested for writing metal contacts to single layer graphene on silicon dioxide coated silicon substrates. Without the precursor, the exposure of the graphene to the laser at the deposition parameters damaged the graphene without removing it. This was evidenced by the increase in the Raman D peak of the exposed graphene compared to pristine. The damage threshold was estimated to be 53±7 mJ/cm2 for a scanning speed of 500 µm/s. The deposition threshold of thin-film tungsten on graphene at that speed was lower at 38±8 mJ/cm2. However, no graphene was found when the deposited thin-film tungsten was dissolved in 30 wt% H2O2 that was tested to have no effect on the graphene for the dissolution time of one hour. The graphene likely reacted with the deposited tungsten to form tungsten carbide which was reported to dissolve in H2O2. Tungsten carbide was also found on the tungsten tracks deposited on reduced graphene oxide samples. The contact resistance between tungsten and graphene was measured by both transfer length and four-point probe method with an average value of 4.3±0.4 kΩ µm. This value was higher than reported values using noble metals such as palladium (2.8±0.4 kΩ µm), but lower than reported values using other metals that creates carbides such as nickel (9.3±1.0 kΩ µm). This study opened many potential paths for future work. The main issue to address in the tungsten ultrafast deposition was the deposition outside the laser spot. This prevented uniform deposition in successive tracks close to one another. The ultrafast deposition technique also needs verification using other precursors to understand the precursor requirements for this process. An interesting future study would be a combination with a sulphur source for the direct write of tungsten disulphide, a transition metal dichalcogenide that has a two-dimensional structure similar to graphene. This material has a bandgap and is sought after for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. Initial tests using sulphur micro-flakes on silicon and stainless-steel substrates exposed to the tungsten precursor and ultrafast laser pulses produced multilayer tungsten disulphide as verified in Raman measurements.





O'Neill, William


Mask-less, Laser-induced chemical vapour depostion, LCVD, ultrafast laser, tungsten hexacarbonyl, direct writing, laser induced periodic surface structures, LIPSS, metal on graphene, utrafast laser deposition


Doctor of Philosophy (PhD)

Awarding Institution

University of Cambridge