The Optoelectronic Properties of Nanoparticles from First Principles Calculations /

Saved in:
Bibliographic Details
Author / Creator:Brawand, Nicholas Peter, author.
Ann Arbor : ProQuest Dissertations & Theses, 2017
Description:1 electronic resource (186 pages)
Format: E-Resource Dissertations
Local Note:School code: 0330
URL for this record:
Hidden Bibliographic Details
Other authors / contributors:University of Chicago. degree granting institution.
Notes:Advisors: Giulia Galli Committee members: Dmitri Talapin; Juan de Pablo.
Dissertation Abstracts International, Volume: 78-12(E), Section: B.
Summary:The tunable optoelectronic properties of nanoparticles through the modification of their size, shape, and surface chemistry, make them promising platforms for numerous applications, including electronic and solar conversion devices. However, the rational design and optimization of nanostructured materials remain open challenges, e.g. due to difficulties in controlling and reproducing synthetic processes and in precise atomic-scale characterization. Hence, the need for accurate theoretical predictions, which can complement and help interpret experiments and provide insight into the underlying physical properties of nanostructured materials. This dissertation focuses on the development and application of first principles calculations to predict the optoelectronic properties of nanoparticles. Novel methods based on density functional theory are developed, implemented, and applied to predict both optical and charge transport properties.
In particular, the generalization of dielectric dependent hybrid functionals to finite systems is introduced and shown to yield highly accurate electronic structure properties of molecules and nanoparticles, including photoemission and absorption properties. In addition, an implementation of constrained density functional theory is discussed, for the calculation of hopping transport in nanoparticle systems. The implementation was verified against literature results and compared against other methods used to compute transport properties, showing that some methods used in the literature give unphysical results for thermally disordered systems. Furthermore, the constrained density functional theory implementation was coupled to the self-consistent image charge method, making it possible to include image charge effects self-consistently when predicting charge transport properties of nanoparticles near interfaces.
The methods developed in this dissertation were then applied to study the optoelectronic and transport properties of specific systems, in particular, silicon and lead chalcogenide nanoparticles. In the case of Si, blinking in oxidized Si nanoparticles was addressed. Si dangling bonds at the surface were found to introduce defect states which, depending on their charge and local stress conditions, may give rise to ON and OFF states responsible for exponential blinking statistics. We also investigated, engineering of band edge positions of nanoparticles through post-synthetic surface chemistry modification, with a focus on lead chalcogenides. In collaboration with experiment, we demonstrated how band edge positions of lead sulfide nanoparticles can be tuned by over 2.0 eV. We established a clear relationship between ligand dipole moments and nanoparticle band edge shifts which can be used to engineer nanoparticles for optoelectronic applications.
Calculations of transport properties focused on charge transfer in silicon and lead chalcogenide nanoparticles. Si nanoparticles with deep defects and shallow impurities were investigated, showing that shallow defects may be more detrimental to charge transport than previously assumed. In the case of lead chalcogenide nanoparticles, hydrogen was found to form complexes with defects which can be used to remove potentially detrimental charge traps in nanoparticle solids. The methods and results presented in this dissertation are expected to help guide engineering of nanoparticles for future device applications.