Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.

Interplay Between Structure, Stoichiometry, and Electron Transfer Dynamics in SILAR-based Quantum Dot-Sensitized Oxides

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor–acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.

Quantum transport and integrability of the Anderson model for a quantum dot with multiple leads

We show that an Anderson Hamiltonian describing a quantum dot connected to multiple leads is integrable. A general expression for the nonlinear conductance is obtained by combining the Bethe ansatz exact solution with Landauer-Buttiker theory. In the Kondo regime, a closed form expression is given for the matrix conductance at zero temperature and when all the leads are close to the symmetric point. A bias-induced splitting of the Kondo resonance is possible for three or more leads. Specifically, for N leads, with each at a different chemical potential, there can be N-1 Kondo peaks in the conductance.

Entangled two-photon source using biexciton emission of an asymmetric quantum dot in a cavity

A semiconductor based scheme has been proposed for generating entangled photon pairs from the radiative decay of an electrically pumped biexciton in a quantum dot. Symmetric dots produce polarization entanglement, but experimentally realized asymmetric dots produce photons entangled in both polarization and frequency. In this work, we investigate the possibility of erasing the “which-path” information contained in the frequencies of the photons produced by asymmetric quantum dots to recover polarization-entangled photons. We consider a biexciton with nondegenerate intermediate excitonic states in a leaky optical cavity with pairs of degenerate cavity modes close to the nondegenerate exciton transition frequencies. An open quantum system approach is used to compute the polarization entanglement of the two-photon state after it escapes from the cavity, measured by the visibility of two-photon interference fringes. We explicitly relate the two-photon visibility to the degree of the Bell-inequality violation, deriving a threshold at which Bell-inequality violations will be observed. Our results show that an ideal cavity will produce maximally polarization-entangled photon pairs, and even a nonideal cavity will produce partially entangled photon pairs capable of violating a Bell-inequality.

Tunable molecular resonances of a double quantum dot Aharonov-Bohm interferometer

We investigate resonant tunnelling through molecular states of an Aharonov-Bohm (AB) interferometer composed of two coupled quantum dots. The conductance of the system shows two resonances associated with the bonding and the antibonding quantum states. We predict that the two resonances are composed of a Breit-Wigner resonance and a Fano resonance, of which the widths and Fano factor depend on the AB phase very sensitively. Further, we point out that the bonding properties, such as the covalent and ionic bonding, can be identified by the AB oscillations.

Coherent charge and spin transfer in a quantum dot coupled to a mesoscopic ring

We study the effect of coherent charge and spin fluctuations in a mesoscopic device composed of a quantum dot and an Aharonov-Bohm ring. We show that, while the charge fluctuations suppress the persistent current algebraically as a function of the level spacing of the ring, the spin fluctuations give rise to a completely different behavior. We discuss the origin of this difference in relation to the peculiar nature of the ground state in the Kondo limit. (C) 2003 Elsevier B.V. All rights reserved.

Nanotossicologia dei quantum dot di CdS in linee cellulari umane

Le nanotecnologie sono un settore emergente in rapida crescita, come dimostra l'esplosione del mercato dei prodotti ad esso collegati. I quantum dot di cadmio solfuro (CdS QD) sono ampiamente utilizzati per la produzione di materiali semiconduttori e dispositivi optoelettronici; tuttavia, non sono ancora completamente chiari gli effetti di questi nanomateriali sulla salute umana. Questo lavoro di dottorato si pone l'obbiettivo di definire il potenziale citotossico e genotossico dei CdS QD in linee cellulari umane e definirne il meccanismo implicato. A questo scopo, essendo il fegato uno dei principali organi di accumulo del cadmio e dei nanomateriali a base di cadmio, è stata utilizzata la linea cellulare HepG2 derivante da un epatocarcinoma umano. È stato evidenziato, in seguito all'assorbimento, da parte delle cellule, dei CdS QD, un effetto citotossico, con conseguente modulazione dell'espressione genica di una serie di geni coinvolti sia nei processi di rescue (autofagia, risposta allo stress) sia in quelli di morte cellulare programmata. È stato, inoltre, dimostrata l'assenza di un rilevante effetto genotossico dipendente da questi nanomateriali. Infine, è stato osservato che cellule esposte ai CdS QD presentano mitocondri con un potenziale di membrana alterato, con conseguente alterazione della funzionalità di tale organello, pur conservando l'integrità del DNA mitocondriale.

A simple, sensitive and selective quantum-dot-based western blot method for the simultaneous detection of multiple targets from cell lysates

Quantum dots (Qdots) are fluorescent nanoparticles that have great potential as detection agents in biological applications. Their optical properties, including photostability and narrow, symmetrical emission bands with large Stokes shifts, and the potential for multiplexing of many different colours, give them significant advantages over traditionally used fluorescent dyes. Here, we report the straightforward generation of stable, covalent quantum dot-protein A/G bioconjugates that will be able to bind to almost any IgG antibody, and therefore can be used in many applications. An additional advantage is that the requirement for a secondary antibody is removed, simplifying experimental design. To demonstrate their use, we show their application in multiplexed western blotting. The sensitivity of Qdot conjugates is found to be superior to fluorescent dyes, and comparable to, or potentially better than, enhanced chemiluminescence. We show a true biological validation using a four-colour multiplexed western blot against a complex cell lysate background, and have significantly improved previously reported non-specific binding of the Qdots to cellular proteins.

Synthesis and evaluation of novel ligands for quantum dot stabilisation and polymerisation studies

This thesis describes the design and synthesis of a variety of functionalised phosphine oxides and sulfides, based on the structure of trioctylphosphine oxide, synthesised for the purpose of surface modification of quantum dots. The ability of the ligands to modify the surface chemistry via displacement of the original hexadecylamine capping layer of quantum dots was evaluated. Finally the surface modified quantum dots were investigated for enhancement in their inherent properties and improved compatibility with the various applications for which they were initially designed. Upon the commencement of research involving quantum dots it became apparent that more information on their behaviour and interaction with the environment was required. The limits of the inherent stability of hexadecylamine capped quantum dots were investigated by exposure to a number of different environments. The effect upon the stability of the quantum dots was monitored by changes in the photoluminescence ability of their cores. Subtle differences between different batches of quantum dots were observed and the necessity to account for these in future applications noted. Lastly the displacement of the original hexadecylamine coating with the "designer" functionalised ligands was evaluated to produce a set of conditions that would result in the best possible surface modification. A general procedure was elucidated however it was discovered that each displacement still required slight adjustment by consideration of the other factors such as the difference in ligand structure and the individuality of the various batches of quantum dots. This thesis also describes a procedure for the addition of a protective layer to the surface of quantum dots by cross-linking the functionalised ligands bound to the surface via an acyclic diene metathesis polymerisation. A detailed description of the problems encountered in the analysis of these materials combined with the use of novel techniques such as diffusion ordered spectroscopy is provided as a means to overcome the limitations encountered. Finally a demonstration of the superior stability, upon exposure to a range of aggressive environments of these protected materials compared with those before cross-linking provided physical proof of the cross-linking process and the advantages of the cross-linking modification. Finally this thesis includes the presentation of initial work into the production of luminescent nanocrystal encoded resin beads for the specific use in solid phase combinatorial chemistry. Demonstration of the successful covalent incorporation of quantum dots into the polymeric matrices of non-functionalised and functionalised resin beads is described. Finally by preliminary work to address and overcome the possible limitations that may be encountered in the production and general employment of these materials in combinatorial techniques is given.

Filter assisted wavelength conversion with quantum-dot SOAs

The nonlinear operation regimes of quantum-dot semiconductor optical amplifiers (QD-SOAs) are investigated and the ideal filter providing the best all-optical wavelength conversion efficiency is derived theoretically. Results are confirmed by experiments with Q2-factors amounting to 16 dB.

Quantum-dot mode-locked lasers with dual-mode optical injection

Quantum-dot mode-locked lasers are injection-locked by coherent two-tone master sources. Spectral tuning, significantly improved time-bandwidth product, and low jitter are demonstrated without deterioration of the pulse properties.

Dynamics of quantum-dot mode-locked lasers with optical injection

We present the dynamics of quantum-dot passively mode-locked semiconductor lasers under optical injection. We discuss the benefits of various configurations of the master source including single, dual, and multiple coherent frequency sources. In particular, we demonstrate that optical injection can improve the properties of the slave laser in terms of time-bandwidth product, optical linewidth, and timing jitter.

Quantum-dot mode-locked lasers with dual-mode optical injection

Quantum-dot mode-locked lasers are injection-locked by coherent two-tone master sources. Spectral tuning, significantly improved time-bandwidth product, and low jitter are demonstrated without deterioration of the pulse properties.

Tunable master-oscillator power-amplifier based on chirped quantum-dot structures

A broadly tunable master-oscillator power-amplifier (MOPA) picosecond optical pulse source is demonstrated, consisting of an external cavity passively mode-locked laser diode with a tapered semiconductor amplifier. By employing chirped quantum-dot structures on both the oscillator's gain chip and amplifier, a wide tunability range between 1187 and 1283 nm is achieved. Under mode-locked operation, the highest output peak power of 4.39 W is achieved from the MOPA, corresponding to a peak power spectral density of 31.4 dBm/nm. © 1989-2012 IEEE.

202nm continuous tuning from high-power external-cavity InAs/GaAs quantum-dot laser

Record broadly tunable high-power external cavity InAs/GaAs quantum-dot diode laser is demonstrated. A maximum output power of 455mW and a side-mode suppression ratio >45dB in the central part of the tuning range are achieved. ©2010 IEEE.