Electronic and Impurity Doping in Colloidal Semiconductor Nanocrystals
Schimpf, Alina M.
MetadataShow full item record
This thesis presents investigations of semiconductor nanocrystals doped with impurity ions, excess charge carriers, or both. The introduction of excess charge carriers into colloidal semiconductor nanocrystals constitutes a longstanding challenge in the development of nanocrystal building blocks for various technologies including solar cells, photovoltaic devices and electroluminescent devices. Chapter 1 discusses methods for electronic doping in semiconductor nanocrystals, focusing on photodoping and aliovent doping strategies. Of the various successful strategies for electronic doping, photodoping is particularly useful as a post-synthetic method for reversible and quantifiable tuning of carrier density. Alternatively, aliovalently doped nanocrystals are attractive due to the great stability of charge carriers. Chapter 2 presents a comparative study of conduction-band electrons in colloidal ZnO nanocrystals added via photodoping or aliovalent doping. The studies show that, although they have very similar spectroscopic properties, the reactivites of the electrons are vastly different, owing to the relative mobilities of their charge-compensating cations. Chapters 3, 4 and 5 present investigations of the ability to add excess electrons to a variety of systems via photodoping. The study in Chapter 3 shows that the maximum number of elecrons that may be added photochemically is dependent on the nanocrystal volume, such that all nanocrystals may be photodoped to the same electron density. Furthermore, the identities of the sacrifical reductant and the charge-compensating cation determine the maximum photodoping density. For the first time, alkyl borohydrides were used as sacrificial reductants to photodope ZnO, leading to much larger carrier densities than previously observed. These findings informed the first demonstration of photodoping in CdE (E= S, Se, Te) nanocrystals, presented in Chapter 4. Chapter 5 presents a combination of photodoping and aliovalent doping in In2O3 nanocrystals to investigate the redox chemistries in In2O3 and ITO nanocrystals. The study shows that all nanocrystals have the same Fermi level, and Sn4+ stabilizes that conduction band to allow accumulation of excess delocalized electrons. Moreover, regardless of Sn4+ doping and therefore of initial carrier density, all nanocrystals have the same number of electrons that may be added photochemically. These results, in conjunction with those presented in Chapters 3 and 4, suggest maximum photodoping density is thermodynamically limited, and is not an intrinsic property of the nanocrystal, nor a result of competition between productive hole-quenching and non-productive Auger recombination in the photoexcited nanocrystals. The ability to reversibly tune the carrier densities in colloidal semiconductor nanocrystals via photodoping allows new photophsyical investigations of electronically doped systems. Chapters 5 and 6 use photodoping to investigate the properties of plasmon resonances in ZnO and In2O3 nanocrystals. Chapter 5 shows that the plasmon energy is affected by both carrier density and Sn4+ doping. Chapter 6 shows that plasmons in ZnO nanocrystals are subject to quantum confinement and therefore may not be understood with a classical Drude picture. The large magnetic exchange interaction between charge carriers and magnetic dopants make diluted magnetic semiconductors (DMSs) particularly attractive for spin-based information processing. Chapter 7 uses pulsed electron paramagnetic resonance (pEPR) spectroscopy to investigate the affect of excess electrons on the Mn2+ spin dynamics in doped ZnO nancorystals, showing that Mn2+ spin relaxation is greatly accelerated by the presence of even one conduction-band electron. Chapter 8 uses pEPR to investigate the intrinsic spin dynamics of Mn2+ in a variety of II-VI colloidal semiconductor nanocrystals. Finally, Chapter 9 shows the ability to tune the effective ¬g value in DMSs at low fields using temperature.¬
- Chemistry