Liquid-Phase Exfoliation of Two-Dimensional Materials : Applications, deposition methods and printed electronics on paper

Sammanfattning: After the unprecedented success of graphene research, other materials that can also be exfoliated into thin layers, like Transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2), have also become the subjects of extensive studies. As one of the most promising methods for large scale production of such materials, liquid-phase exfoliation (LPE) has also been the subject of extensive research and is maturing as a field to the point that devices using additive manufacturing and printed nanosheets are often reported. The stability of the nanosheets in environmentally friendly solvents, particularly in water, with or without stabilizers, is still a focus of great interest for sustainable and commercial production. In this thesis, different methods of LPE in water with and without stabilizers are investigated and discussed. Stabilizers such as surfactant sodium dodecyl sulfate (SDS) and modified cellulose2-hydroxyethyl cellulose (HEC), were employed. Because waterdoes not have surface energy parameters that match those of2D materials, the dispersions in water do not usually have a high yield. Therefore, to circumvent the use of organic solvents that are known to be able to successfully exfoliate and stabilize nanosheets of two-dimensional materials, this thesis focuses on water as the solution-process medium for exfoliation and the assisting stabilizers used to keep the exfoliated nanomaterials in dispersion with a long half-time. Surfactant-assisted dispersions are discussed together with test-printing resultsusing inkjet to deposit the material. Process parameters for the LPE method using HEC as a stabilizer are presented together with thin nanosheets characterized by Raman spectroscopy. Dispersions using HEC presented the longest half-time among the studied methods, higher than previously reported values for methods using mixed low-boiling-point solvents. Devices using exfoliated nanosheets have been fabricated and presented in the present study. The photoconductivity of MoS2 using a device fabricated with LPE MoS2 nanosheets and the cathodoluminescence of LPE MoS2 are discussed. Although fabricated with mechanically exfoliated nanosheets and not LPE ones, another photodetector fabricated with one of the MoS2 grades used in this thesis is presented to highlight the excellent photoresponse of this material. A method of producing thin nanosheets with-out stabilizers by pre-processing the MoS2 grades withs and papers is introduced. With this method, nanosheets with a lateral size of around 200nm and a concentration around 0.14 g L−1 - that is half the concentration at the same processing conditions in solvent n-methyl pyrrolidone (NMP) - are discussed. Inkjet printing as a deposition method is discussed together with the requirements for the 2D inks. Printed organic electronics using the conductive polymer PEDOT:PSS are compared to those using commercially-available graphene ink, with a focus on printing on paper substrates. In order to bring the thesis into perspective from materials to device fabrication, I study the suitability of inkjet paper substrates for printed electronics, by extensively characterizing the chemical and physical properties of their ink-receiving layers (IRLs) and their impact on the electronic properties of the conductive printed lines.