Edward Van Keuren

Endohedral fullerenes for organic photovoltaic devices

So far, one of the fundamental limitations of organic photovoltaic (OPV) device power conversion efficiencies (PCEs) has been the low voltage output caused by a molecular orbital mismatch between the donor polymer and acceptor molecules. Here, we present a means of addressing the low voltage output by introducing novel trimetallic nitride endohedral fullerenes (TNEFs) as acceptor materials for use in photovoltaic devices. TNEFs were discovered in 1999 by Stevenson et al. ; for the first time derivatives of the TNEF acceptor, Lu(3)N@C(80), are synthesized and integrated into OPV devices. The reduced energy offset of the molecular orbitals of Lu(3)N@C(80) to the donor, poly(3-hexyl)thiophene (P3HT), reduces energy losses in the charge transfer process and increases the open circuit voltage (Voc) to 260 mV above reference devices made with [6,6]-phenyl-C(61)-butyric methyl ester (C(60)-PCBM) acceptor. PCEs >4% have been observed using P3HT as the donor material. This work clears a path towards higher PCEs in OPV devices by demonstrating that high-yield charge separation can occur with OPV systems that have a reduced donor/acceptor lowest unoccupied molecular orbital energy offset.

A three-dimensional wide-angle BPM for optical waveguide structures

Algorithms for effective modeling of optical propagation in three- dimensional waveguide structures are critical for the design of photonic devices. We present a three-dimensional (3-D) wide-angle beam propagation method (WA-BPM) using Hoekstras scheme. A sparse matrix algebraic equation is formed and solved using iterative methods. The applicability, accuracy and effectiveness of our method are demonstrated by applying it to simulations of wide-angle beam propagation, along with a technique for shifting the simulation window to reduce the dimension of the numerical equation and a threshold technique to further ensure its convergence. These techniques can ensure the implementation of iterative methods for waveguide structures by relaxing the convergence problem, which will further enable us to develop higher-order 3-D WA-BPMs based on Padé approximant operators.

Wavelength dependence of the third-order nonlinear optical properties of a polythiophene/selenophene derivative film

The third-order nonlinear optical properties of a hybrid polymer film containing substituted thiophene rings copolymerized with unsubstituted selenophene were measured using the Z-scan technique. Large, resonantly enhanced third-order nonlinearities were found at wavelengths on the low-energy side of the absorption band. In contrast to the results on a similar copolymer film incorporating only thiophene, a strong two-photon absorption appeared in the near infrared. The imaginary part of the third-order susceptibility can be adequately explained as saturation of an exciton band, while the origin of the large negative real part is unknown.

Nonlinear refractive indices of polydiacetylene microcrystals

Polydiacetylene microcrystals in a water suspension or a polymer matrix were prepared by a simple precipitation procedure in order to obtain a thin samples with good optical quality maintaining the characteristics of crystalline materials. The nonlinear refraction, n2, and nonlinear absorption, (beta) , around the exciton peak were measured by z-scan method using a tunable picosecond laser. The signs of the n2 are positive/negative at wavelengths shorter/longer than the exciton peak and strong saturable absorption, which (beta) is negative, are observed around the peak. The largest n2 was obtained to be plus 0.024 cm2/GW (Re(chi (3) equals plus 1.4 multiplied by 10-9 esu) at 640 nm for a gelatin composite film containing 24 wt percent of polydiacetylene microcrystals.

Coalescence of Single Photons Emitted by Disparate Single-Photon Sources: The Example of InAs Quantum Dots and Parametric Down-Conversion Sources

Single photons produced by fundamentally dissimilar physical processes will in general not be indistinguishable. We show how photons produced from a quantum dot and by parametric down-conversion in a nonlinear crystal can be manipulated to be indistinguishable. The measured two-photon coalescence probability is 16%, and is limited by quantum-dot decoherence. Temporal filtering to the quantum-dot coherence time and accounting for detector time response increases this to 61% while retaining 25% of the events. This technique can connect different elements in a scalable quantum network.

Photoreversible optical nonlinearities of polymeric films containing spiropyran with long alkyl chains

It was demonstrated that the third‐order optical nonlinearity of polymer films could be reversibly controlled by the photochromic conversion and following J‐aggregate formation of spiropyran embedded in an inert polymer matrix. Patterns consisting of areas with high and low third‐order nonlinear optical activities were prepared by imagewise exposure of the photochromic films followed by thermal treatment to form thermally stable J aggregates of photoinduced merocyanine in the exposed area. This system could be useful in developing new unconventional optical devices based on optical nonlinearities, including new types of spatial light modulators.

Phthalocyanine Nanoparticle Formation in Supersaturated Solutions

Self-organization of molecules in solution is an important natural and synthetic process, in particular for the preparation of nanomaterials. However, the mechanism of growth for solution-based nanoparticle formation is not always well understood. We present results that clarify these mechanisms in solutions of magnesium phthalocyanine in which the self-organization is induced by addition of a miscible nonsolvent. From simultaneous measurements of the sizes of the growing nanoparticles by photon correlation spectroscopy and the molecular concentration by absorption and fluorescence spectroscopy, we have found that the particles do not grow by molecular diffusion to the surfaces. These results suggest the importance of unstable clusters in the growth process. We also observed a strong dependence of the particle size on the initial concentration which we attribute to effects of the curvature of the solubility curve.

Thermal ablation of PMMA for water release using a microheater

A new approach was developed in this work to ablate a micropore through a polymethylmethacrylate (PMMA) layer using a microheater for the on-demand release of water stored in a microreservoir. The size of the ablated micropore in the PMMA capping layer is mainly governed by the heater temperature profile and ablation time. Furthermore, the molten PMMA resulting from the heating energy tends to retract away from the micropore location, taking away the gold heater lines from the pore area. This prevents the possibility of any gold traces blocking the flow of water released from within the microreservoir. Simulation was conducted to find temperature profiles on the surface of the microheater, and the results were used to interpret the phenomena observed in the ablation process. Simulation was also conducted for the case when the microreservoir was filled with water. In addition, two alternative ablation materials, unexposed SU-8 and polydimethylsiloxane (PDMS), were examined as possible microreservoir capping layers. The approach developed has potential applications in microfluidic systems to release encapsulated fluids in a controllable manner.

Magnetic nanobeads as potential contrast agents for magnetic resonance imaging.

Metal-oxo clusters have been used as building blocks to form hybrid nanomaterials and evaluated as potential MRI contrast agents. We have synthesized a biocompatible copolymer based on a water stable, nontoxic, mixed-metal-oxo cluster, Mn8Fe4O12(L)16(H2O)4, where L is acetate or vinyl benzoic acid, and styrene. The cluster alone was screened by NMR for relaxivity and was found to be a promising T2 contrast agent, with r1 = 2.3 mM(-1) s(-1) and r2 = 29.5 mM(-1) s(-1). Initial cell studies on two human prostate cancer cell lines, DU-145 and LNCap, reveal that the cluster has low cytotoxicity and may be potentially used in vivo. The metal-oxo cluster Mn8Fe4(VBA)16 (VBA = vinyl benzoic acid) can be copolymerized with styrene under miniemulsion conditions. Miniemulsion allows for the formation of nanometer-sized paramagnetic beads (~80 nm diameter), which were also evaluated as a contrast agent for MRI. These highly monodispersed, hybrid nanoparticles have enhanced properties, with the option for surface functionalization, making them a promising tool for biomedicine. Interestingly, both relaxivity measurements and MRI studies show that embedding the Mn8Fe4 core within a polymer matrix decreases r2 effects with little effect on r1, resulting in a positive T1 contrast enhancement.

A simple three dimensional wide-angle beam propagation method

The development of three dimensional (3-D) waveguide structures for chip scale planar lightwave circuits (PLCs) is hampered by the lack of effective 3-D wide-angle (WA) beam propagation methods (BPMs). We present a simple 3-D wide-angle beam propagation method (WA-BPM) using Hoekstras scheme along with a new 3-D wave equation splitting method. The applicability, accuracy and effectiveness of our method are demonstrated by applying it to simulations of wide-angle beam propagation and comparing them with analytical solutions.