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Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals

Abstract

Closely packed nanocrystal systems have been investigated in this thesis with respect to charge separation by charge carrier tunneling. Clustered and layered samples have been analyzed using PL-measurements and SPV-methods. The most important findings are reviewed in the following. A short outlook is also provided for potential further aspects and application of the presented results. The main purpose of this thesis was to find and quantify electronic tunneling transfer in closely packed self-assembled nanocrystal structures presenting quantum mechanical barriers of about 1 nm width. We successfully used hybrid assemblies of CdTe and CdSe nanocrystals where the expected type II alignment between CdTe and CdSe typically leads to a concentration of electrons in CdSe and holes in CdTe nanocrystals. We were able to prove the charge selectivity of the CdTe-CdSe nanocrystal interface which induces charge separation. We mainly investigated the effects related to the electron transfer from CdTe to CdSe nanocrystals. Closely packing was achieved by two independent methods: the disordered colloidal clustering in solution and the layered assembly on dry glass substrates. Both methods lead to an inter-particle distance of about 1 nm of mainly organic material which acts as a tunneling barrier. PL-spectroscopy was applied. The PL-quenching of the  More>>
Publication Date:
Nov 08, 2013
Product Type:
Thesis/Dissertation
Report Number:
INIS-DE-1581
Resource Relation:
Other Information: Diss.
Subject:
36 MATERIALS SCIENCE; ALIGNMENT; CADMIUM SELENIDES; CADMIUM TELLURIDES; CARRIER DENSITY; CHARGE COLLECTION; CRYSTALS; ELECTRON DENSITY; ELECTRON TRANSFER; EMISSION SPECTRA; HOLES; INTERFACES; LAYERS; NANOSTRUCTURES; PHOTOLUMINESCENCE; SCINTILLATION QUENCHING; SOLID CLUSTERS; TUNNEL EFFECT; ULTRAVIOLET SPECTRA; VISIBLE SPECTRA
OSTI ID:
22230938
Research Organizations:
Muenchen Univ. (Germany). Fakultaet fuer Physik
Country of Origin:
Germany
Language:
English
Other Identifying Numbers:
TRN: DE14F1638052023
Availability:
Available from INIS in electronic form
Submitting Site:
DE
Size:
109 page(s)
Announcement Date:
May 22, 2014

Citation Formats

Gross, Dieter Konrad Michael. Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals. Germany: N. p., 2013. Web.
Gross, Dieter Konrad Michael. Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals. Germany.
Gross, Dieter Konrad Michael. 2013. "Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals." Germany.
@misc{etde_22230938,
title = {Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals}
author = {Gross, Dieter Konrad Michael}
abstractNote = {Closely packed nanocrystal systems have been investigated in this thesis with respect to charge separation by charge carrier tunneling. Clustered and layered samples have been analyzed using PL-measurements and SPV-methods. The most important findings are reviewed in the following. A short outlook is also provided for potential further aspects and application of the presented results. The main purpose of this thesis was to find and quantify electronic tunneling transfer in closely packed self-assembled nanocrystal structures presenting quantum mechanical barriers of about 1 nm width. We successfully used hybrid assemblies of CdTe and CdSe nanocrystals where the expected type II alignment between CdTe and CdSe typically leads to a concentration of electrons in CdSe and holes in CdTe nanocrystals. We were able to prove the charge selectivity of the CdTe-CdSe nanocrystal interface which induces charge separation. We mainly investigated the effects related to the electron transfer from CdTe to CdSe nanocrystals. Closely packing was achieved by two independent methods: the disordered colloidal clustering in solution and the layered assembly on dry glass substrates. Both methods lead to an inter-particle distance of about 1 nm of mainly organic material which acts as a tunneling barrier. PL-spectroscopy was applied. The PL-quenching of the CdTe nanocrystals in hybrid assemblies indicates charge separation by electron transfer from CdTe to CdSe nanocrystals. A maximum quenching rate of up to 1/100 ps was measured leading to a significant global PL-quenching of up to about 70 % for the CdTe nanocrystals. It was shown that charge separation dynamics compete with energy transfer dynamics and that charge separation typically dominates. The quantum confinement effect was used to tune the energetic offset between the CdTe and CdSe nanocrystals. We thus observe a correlation of PL-quenching and offset of the energy states for the electron transfer. The investigated PL-quenching vanishes when this offset approaches 0.0 eV. The fact that PL-quenching and its correlation with the energetic offset was observed for both clustered and layered assembly provides a strong indirect indication of charge separation via electron transfer from CdTe to CdSe nanocrystals. The main result of this thesis is the direct proof of the charge separation on the type II interface of CdTe and CdSe nanocrystal layers. SPV-measurements as a direct measurement methode showed clearly the directionality of charge separation since the SPV measures the electric field of the separated charges. Electrons are collected on CdSe nanocrystal layers, holes on CdTe nanocrystal layers. A change in the order between CdSe and CdTe therefore leads to a change in the sign of the SPV-signal. Both SPVspectra and time-resolved SPV-measurements support this finding and showed that the charge selectivity of the CdTe-CdSe interface is unidirectional for the whole excitation spectrum and the entire investigated time range. This indicates that the directionality of the CdTe-CdSe interface is the only dominant charge separation mechanism that was observed. Hence, the type II alignment of the self-assembled nanocrystals used was clearly proven. Introducing an additional barrier between the nanocrystal layers doubled the barrier width so that the SPV-signal is quenched. This is consistent with tunneling transfer which is exponentially dependent on barrier width. Moreover, we learned that both absorption in CdTe and CdSe nanocrystals and the sample thickness contribute to the SPV-signal. Thus, we could observe electron diffusion in CdSe multilayers which was faster than the charge carrier diffusion dynamics in CdTe nanocrystal multilayers. Future research may address the combination of energy transfer dynamics with the charge separation processes presented in this thesis. On the one hand, this may provide a better understanding of their fundamental processes and differentiate between excitonic FRET and electronic Dexter energy transfer. On the other hand, it may pave the way for imitation of the natural photosynthesis where both energy transfer and charge separation are realized on the nanoscale. The nanocrystals may be used as building blocks to replace the organic molecules of natural processes. The closely packed selfassembly of type II aligned nanocrystals may find application in solid state devices such as extremely thin absorber solar cells with surface enhanced substrates. Also colloidal application for water splitting may be an option, where semiconductor nanocrystals may provide both energy transfer and charge separation. The organic barrier around the particles may help to protect the semiconductor nanocrystals against degradation during photo-catalytic water splitting. Moreover, the semiconductor nanocrystals may be used as a tape rule for sensing the relative energetic alignment to other nanoparticles or molecules. The PL-quenching rate correlates with the offset of the energy levels which can be tuned due to the quantum confinement effect. PL-quenching studies may reveal the relative energetic alignment of other nanoparticles when experimental series of their closely packed hybrid assemblies with different nanocrystal sizes are analyzed.}
place = {Germany}
year = {2013}
month = {Nov}
}