Bijan Movaghar

Unequal Partnership: Asymmetric Roles of Polymeric Donor and Fullerene Acceptor in Generating Free Charge

Natural photosynthetic complexes accomplish the rapid conversion of photoexcitations into spatially separated electrons and holes through precise hierarchical ordering of chromophores and redox centers. In contrast, organic photovoltaic (OPV) cells are poorly ordered, utilize only two different chemical potentials, and the same materials that absorb light must also transport charge; yet, some OPV blends achieve near-perfect quantum efficiency. Here we perform electronic structure calculations on large clusters of functionalized fullerenes of different size and ordering, predicting several features of the charge generation process, outside the framework of conventional theories but clearly observed in ultrafast electro-optical experiments described herein. We show that it is the resonant coupling of photogenerated singlet excitons to a high-energy manifold of fullerene electronic states that enables efficient charge generation, bypassing localized charge-transfer states. In contrast to conventional views, our findings suggest that fullerene cluster size, concentration, and dimensionality control charge generation efficiency, independent of exciton delocalization.

High-detectivity quantum-dot infrared photodetectors grown by metalorganic chemical-vapor deposition

A mid-wavelength infrared photodetector based on InGaAs quantum dots buried in an InGaP matrix and deposited on a GaAs substrate was demonstrated. Its photoresponse at T=77K was measured to be around 4.7μm with a cutoff at 5.5μm. Due to the high peak responsivity of 1.2A∕W and low dark-current noise of the device, a specific peak detectivity of 1.1×1012cmHz1∕2W−1 was achieved at −0.9V bias.

High-detectivity InAs quantum-dot infrared photodetectors grown on InP by metal–organic chemical–vapor deposition

We report a high-detectivity InAs quantum-dot infrared photodetector. The InAs quantum dots were grown by self-assembly on InP substrates via low-pressure metal–organic chemical–vapor deposition. Highly uniform quantum dots with a density of 4×1010cm2 were grown on a GaAs∕InP matrix. Photoresponse was observed at temperatures up to 160 K with a peak of 6.4μm and cutoff of 6.6μm. Very low dark currents and noise currents were obtained by inserting Al0.48In0.52As current blocking layers. The background-limited performance temperature was 100 K. A detectivity of 1.0×1010cmHz1∕2∕W was obtained at 77 K with a bias of −1.1V.

Transport and photodetection in self-assembled semiconductor quantum dots

A great step forward in science and technology was made when it was discovered that lattice mismatch can be used to grow highly ordered, artificial atom-like structures called self-assembled quantum dots. Several groups have in the meantime successfully demonstrated useful infrared photodetection devices which are based on this technology. The new physics is fascinating, and there is no doubt that many new applications will be found when we have developed a better understanding of the underlying physical processes, and in particular when we have learned how to integrate the exciting new developments made in nanoscopic addressing and molecular self-assembly methods with semiconducting dots. In this paper we examine the scientific and technical questions encountered in current state of the art infrared detector technology and suggest ways of overcoming these difficulties. Promoting simple physical pictures, we focus in particular on the problem of high temperature detector operation and discuss the origin of dark current, noise, and photoresponse.

Simple Analytic Description of Collection Efficiency in Organic Photovoltaics

The collection of charge carriers is a fundamental step in the photovoltaic conversion process. In disordered organic films, low mobility and disorder can make collection the performance-limiting step in energy conversion. We derive two analytic relationships for carrier collection efficiency in organic photovoltaics that account for the presence or absence of carrier-selective electrodes. These equations directly include drift and diffusive carrier transport in the device active layers and account for possible losses from Langevin and Shockley-Read-Hall recombination mechanisms. General relationships among carrier mobility, contact selectivity, recombination processes, and organic photovoltaic figures of merit are established. Our results suggest that device collection efficiency remains mobility-limited for many materials systems, and a renewed emphasis should be placed on materials purity.

Quantum Interferences and Electron Transfer in Photosystem I

We have studied the electron transfer occurring in the photosystem I (PSI) reaction center from the special pair to the first iron-sulfur cluster. Electronic structure calculations performed at the DFT level were employed to determine the on-site energies of the fragments comprising PSI, as well as the charge transfer integrals between neighboring pairs. This electronic Hamiltonian was then used to compute the charge transfer dynamics, using the stochastic surrogate Hamiltonian approach to account for the coherent propagation of the electronic density but also for its energy relaxation and decoherence. These simulations give reasonable transfer time ranging from subpicoseconds to nanoseconds and predict coherent oscillations for several picoseconds. Due to these long-lasting coherences, the propagation of the electronic density can be enhanced or inhibited by quantum interferences. The impact of random fluctuations and asymmetries on these interferences is then discussed. Random fluctuations lead to a classical transport where both constructive and destructive quantum interferences are suppressed. Finally it is shown that an energy difference of 0.15 eV between the on-site energies of the phylloquinones leads to a highly efficient electron transfer even in presence of strong random fluctuations.

Polaron formation: Ehrenfest dynamics vs. exact results.

We use a one-dimensional tight binding model with an impurity site characterized by electron-vibration coupling, to describe electron transfer and localization at zero temperature, aiming to examine the process of polaron formation in this system. In particular we focus on comparing a semiclassical approach that describes nuclear motion in this many vibronic-states system on the Ehrenfest dynamics level to a numerically exact fully quantum calculation based on the Bonca-Trugman method [J. Bonča and S. A. Trugman, Phys. Rev. Lett. 75, 2566 (1995)]. In both approaches, thermal relaxation in the nuclear subspace is implemented in equivalent approximate ways: In the Ehrenfest calculation the uncoupled (to the electronic subsystem) motion of the classical (harmonic) oscillator is simply damped as would be implied by coupling to a Markovian zero temperature bath. In the quantum calculation, thermal relaxation is implemented by augmenting the Liouville equation for the oscillator density matrix with kinetic terms that account for the same relaxation. In both cases we calculate the probability to trap the electron by forming a polaron and the probability that it escapes to infinity. Comparing these calculations, we find that while both result in similar long time yields for these processes, the Ehrenfest-dynamics based calculation fails to account for the correct time scale for the polaron formation. This failure results, as usual, from the fact that at the early stage of polaron formation the classical nuclear dynamics takes place on an unphysical average potential surface that reflects the distributed electronic population in the system, while the quantum calculation accounts fully for correlations between the electronic and vibrational subsystems.

Infrared detection from GaInAs/InP nanopillar arrays

We report on the photoresponse from large arrays of 40 nm radius nanopillars with sensitivity in the long-wavelength infrared regime. Using photoluminescence techniques, a peak wavelength blue shift of approximately 5 meV was observed at 30 K from GaInAs/InP nanopillar structures, indicating carrier confinement effects. Responsivity measurements at 30 K indicated peak wavelength response at about 8 µm with responsivity of 420 mA W−1 at −2 V bias. We have also measured the noise and estimated the peak detectivity to be 3 × 108 cm Hz1/2 W−1 at 1 V reverse bias and 30 K. A maximum internal quantum efficiency of 4.5% was derived from experiment. Both the photo and the dark transport have been successfully modelled as processes that involve direct and indirect field-assisted tunnelling as well as thermionic emission. The best agreement with experiment was obtained when allowances were made for the non-uniformity of barrier widths and electric field heating of carriers above the lattice temperature.

High performance InAs quantum dot infrared photodetectors (QDIP) on InP by MOCVD

Inter-subband detectors such as quantum well infrared photodetectors (QWIP) have been widely used in infrared detection. Quantum dot infrared photodetectors (QDIPs) have been predicted to have better performance than QWIPs including higher operation temperature and normal incidence detection. Here we report our recent results of InAs QDIP grown on InP substrate by low-pressure metalorganic chemical vapor deposition (MOCVD). The device structures consist of multiple stacks of InAs quantum dots with InP barriers. High detectivities in the range of 1010cmHz1/2/W were obtained at 77K. The measurements at higher temperatures show better temperature dependent performance than QWIP. However, the performances of QDIPs are still far from the expected. One of the reasons is the low quantum efficiency due to the low fill factor of quantum dots layer. Resonant cavity enhanced QDIP has been studied to increase the quantum efficiency. Different schemes of mirrors using free carrier plasma and distributed Bragg reflector are discussed.

Focal plane arrays based on quantum dot infrared photodetectors

Here we report the first demonstrations of infrared focal plane array (FPA) based on GaAs and InP based quantum dot infrared photodetectors (QDIPs). QDIPs are extension of quantum well infrared photodetectors (QWIPs) and are predicted to outperform QWIPs due to their potential advantages including normally incident absorption, higher responsivity and high temperature operation. Two material systems have been studied: InGaAs/InGaP QDIPs on GaAs substrates and InAs QDIP on InP substrates. An InGaAs/InGaP QDIP has been grown on GaAs substrate by LP-MOCVD. Photoresponse was observed at temperatures up to 200 K with a peak wavelength of 4.7 μm and cutoff wavelength of 5.2 μm. A detectivity of 1.2x1011 cmHz1/2/W was obtained at T=77 K and bias of -0.9 V, which is the highest for QDIPs grown by MOCVD. An InAs QDIP structure has also been grown on InP substrate by LP-MOCVD. Photoresponse of normal incidence was observed at temperature up to 160K with a peak wavelength of 6.4 μm and cutoff wavelength of 6.6 μm. A detectivity of 1.0x1010 cmHz1/2/W was obtained at 77K at biases of -1.1 V, which is the first and highest detectivity reported for QDIP on InP substrate. 256×256 detector arrays were fabricated first time in the world for both the GaAs and InP based QDIPs. Dry etching and indium bump bonding were used to hybridize the arrays to a Litton readout integrated circuit. For the InGaAs/InGaP QDIP FPA, thermal imaging was achieved at temperatures up to 120 K. At T=77K, the noise equivalent temperature difference (NEDT) was measured as 0.509K with a 300K background and f/2.3 optics. For the InP based QDIPs, thermal imaging was achieved at 77 K.