Date of Award

12-2015

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Materials Science and Engineering

Advisor

Richardson, Kathleen

Committee Member

Luzinov, Igor

Committee Member

Kornev, Konstantin

Committee Member

Ballato, John

Committee Member

Jacobsohn, Luiz G

Abstract

Chalcogenide glasses (ChGs) are well-known for their optical properties, making them ideal candidates for emerging applications of mid-infrared microphotonic devices, such as lab-on-a-chip chemical sensing devices, which currently demand additional flexibility in processing and materials available to realize new device designs. Solution-derived processing of ChG films, initially developed in the 1980s by Chern and Lauks, has consisted mainly of spin-coating and offers unique advantages over the more traditional physical vapor deposition techniques. In the present effort, the nanoparticles of interest are luminescent quantum dots (QDs), which can be used as an on-chip source of light for a planar chemical sensing device. Prior efforts of QD incorporation have exposed limitations of spin-coating of ChG solutions, namely QD aggregation and material waste, along with incompatibility with larger scale manufacturing methods such roll-to-roll processing. This dissertation has evaluated electrospray (ES) as an alternative method of solution-derived chalcogenide glass film deposition. While employed in other materials systems, deposition of optical quality ChG films via electrospray has not been previously attempted, nor have parameters until now, been defined. This study has defined pre-cursor solution chemistry, electrospray jet process parameters required for formation of stable films, annealing protocols and resulting film attributes, yielding important correlations needed to realize high optical quality films. Electrosprayed films attributes were compared to those seen for spin coating and trade-offs in processing route and resulting quality, were identified. Optical properties of importance to device applications were defined, including surface roughness, refractive index, and infrared transmission. The use of a serpentine path of the spray over the substrate was demonstrated to obtain uniform thickness, blanket films, and demonstrates process compatibility with roll-to-roll processing whereby (theoretically) 100% of starting solution can be utilized in a continuous process. The present effort has shown that electrospray offers the advantage of spatially defined, localized deposition, which enables direct 2-D and 3-D printing, though with limited (unoptimized) spatial resolution on the order of millimeters. Knowledge of processing protocols were exploited to fabricate multi-layer films from two different glass compositions to yield an effective refractive index gradient (GRIN). GRIN coatings were fabricated and refractive index variations were predicted. The advantages of electrospray deposition were also explored for the enhancement of quantum dot doping in ChG films. A hypothesis whereby electrospray would enable deposition of films based on consolidation of many, single QD doped aerosol droplets was developed and evaluated. Experimental validation of this premise in CdSe and PbS doped ChG films was shown, indicating that electrospray offers a kinetic barrier to QD movement preventing aggregation from occurring, not seen in spin-coating. Two types of organic ligands were found to enhance dispersion of QDs in amine solvents, octadecylamine and mercaptopropionic acid. Utilizing TEM characterization, evidence that electrospray may be more suitable than spin-coating for the dispersion of QDs in solution-derived ChG films was confirmed. However, the ultimate effectiveness of this approach was limited due to the ability to quantify direct loading levels of the QD and surrounding glass matrix. This work demonstrates that electrospray offers additional flexibility over spin-coating and other evaporation methods for the deposition of ChG coatings. Electrospray processing of doped and undoped ChG solutions for microphotonic applications has been shown as a viable alternative in the processing and material toolbox where spatially defined index and dopant control is required.

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Engineering Commons

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