Self-Assembled InAs/GaAs Quantum Dot Solar Cells

Our work focuses on experimental and theoretical studies aimed at establishing a fundamental understanding of the principal electrical and optical processes governing the operation of quantum dot solar cells (QDSC) and their feasibility for the realization of intermediate band solar cell (IBSC). Uniform performance QD solar cells with high conversion efficiency have been fabricated using carefully calibrated process recipes as the basis of all reliable experimental characterization. The origin for the enhancement of the short circuit current density (Jsc) in QD solar cells was carefully investigated. External quantum efficiency (EQE) measurements were performed as a measure of the below bandgap distribution of transition states. In this work, we found that the incorporation of self-assembled quantum dots (QDs) interrupts the lattice periodicity and introduce a greatly broadened tailing density of states extending from the bandedge towards mid-gap. A below-bandgap density of states (DOS) model with an extended Urbach tail has been developed. In particular, the below-bandgap photocurrent generation has been attributed to transitions via confined energy states and background continuum tailing states. Photoluminescence measurement is used to measure the energy level of the lowest available state and the coupling effect between QD states and background tailing states because it results from a non-equilibrium process. A basic I-V measurement reveals a degradation of the open circuit voltage (Voc) of QD solar cells, which is related to a one sub-bandgap photon absorption process followed by a direct collection of the generated carriers by the external circuit. We have proposed a modified Shockley-Queisser (SQ) model that predicts the degradation of Voc compared with a reference bulk device. Whenever an energy state within the forbidden gap can facilitate additional absorption, it can facilitate recombination as well. If the recombination is non-radiative, it is detrimental to solar cell performance. We have also investigated the QD trapping effects as deep level energy states. Without an efficient carrier extraction pathway, the QDs can indeed function as mobile carriers traps. Since hole energy levels are mostly connected with hole collection under room temperature, the trapping effect is more severe for electrons. We have tried to electron-dope the QDs to exert a repulsive Coulomb force to help improve the carrier collection efficiency. We have experimentally observed a 30% improvement of Jsc for 4e/dot devices compared with 0e/dot devices. Electron-doping helps with better carrier collection efficiency, however, we have also measured a smaller transition probability from valance band to QD states as a direct manifestation of the Pauli Exclusion Principle. The non-linear performance is of particular interest. With the availability of laser with on-resonance and off-resonance excitation energy, we have explored the photocurrent enhancement by a sequential two-photon absorption (2PA) process via the intermediate states. For the first time, we are able to distinguish the nonlinearity effect by 1PA and 2PA process. The observed 2PA current under off-resonant and on-resonant excitation comes from a two-step transition via the tailing states instead of the QD states. However, given the existence of an extended Urbach tail and the small number of photons available for the intermediate states to conduction band transition, the experimental results suggest that with the current material system, the intensity requirement for an observable enhancement of photocurrent via a 2PA process is much higher than what is available from concentrated sun light. In order to realize the IBSC model, a matching transition strength needs to be achieved between valance band to QD states and QD states to conduction band. However, we have experimentally shown that only a negligible amount of signal can be observed at cryogenic temperature via the transition from QD states to conduction band under a broadband IR source excitation. Based on the understanding we have achieved, we found that the existence of the extended tailing density of states together with the large mismatch of the transition strength from VB to QD and from QD to CB, has systematically put into question the feasibility of the IBSC model with QDs.

Essays on Financial Constraints, R&D Investments, and Competition

This dissertation consists of two chapters of theoretical studies that investigate the effect of financial constraints and market competition on research and development (R&D) investments. In the first chapter, I explore the impact of financial constraints on two different types of R&D investments. In the second chapter, I examine the impact of market competition on the relationship between financial constraints and R&D investments. In the first chapter, I develop a dynamic monopoly model to study a firm’s R&D strategy. Contrary to intuition, I show that a financially constrained firm may invest more aggressively in R&D projects than an unconstrained firm. Financial constraints introduce a risk that a firm may run out of money before its project bears fruit, which leads to involuntary termination on an otherwise positive-NPV project. For a company that relies on cash flow from assets in place to keep its R&D project alive, early success can be relatively important. I find that when the discovery process can be expedited by heavier investment (“accelerable” projects), a financially constrained company may find it optimal to “over”-invest in order to raise the probability of project survival. The over-investment will not happen if the project is only “scalable” (investment scales up payoffs). The model generates several testable implications regarding over-investment and project values. In the second chapter, I study the effects of competition on R&D investments in a duopoly framework. Using a homogeneous duopoly model where two unconstrained firms compete head to head in an R&D race, I find that competition has no effect on R&D investment if the project is not accelerable, and the competing firms are not constrained. In a heterogeneous duopoly model where a financially constrained firm competes against an unconstrained firm, I discover interesting strategic interactions that lead to preemption by the constrained firm in equilibrium. The unconstrained competitor responds to its constrained rival’s investment in an inverted-U shape fashion. When the constrained competitor has high cash flow risk, it accelerates the innovation in equilibrium, while the unconstrained firm invests less aggressively and waits for its rival to quit the race due to shortage of funds.