Timothy W. Schmidt

Improving the light-harvesting of amorphous silicon solar cells with photochemical upconversion

Single-threshold solar cells are fundamentally limited by their ability to harvest only those photons above a certain energy. Harvesting below-threshold photons and re-radiating this energy at a shorter wavelength would thus boost the efficiency of such devices. We report an increase in light harvesting efficiency of a hydrogenated amorphous silicon (a-Si:H) thin-film solar cell due to a rear upconvertor based on sensitized triplet–triplet-annihilation in organic molecules. Low energy light in the range 600–750 nm is converted to 550–600 nm light due to the incoherent photochemical process. A peak efficiency enhancement of (1.0 ± 0.2)% at 720 nm is measured under irradiation equivalent to (48 ± 3) suns (AM1.5). We discuss the pathways to be explored in adapting photochemical UC for application in various single threshold devices.

Photochemical upconversion: present status and prospects for its application to solar energy conversion

All photovoltaic solar cells transmit photons with energies below the absorption threshold (bandgap) of the absorber material, which are therefore usually lost for the purpose of solar energy conversion. Upconversion (UC) devices can harvest this unused sub-threshold light behind the solar cell, and create one higher energy photon out of (at least) two transmitted photons. This higher energy photon is radiated back towards the solar cell, thus expanding the utilization of the solar spectrum. Key requirements for UC units are a broad absorption and high UC quantum yield under low-intensity incoherent illumination, as relevant to solar energy conversion devices, as well as long term photostability. Upconversion by triplet–triplet annihilation (TTA) in organic chromophores has proven to fulfil the first two basic requirements, and first proof-of-concept applications in photovoltaic conversion as well as photo(electro)chemical energy storage have been demonstrated. Here we review the basic concept of TTA-UC and its application in the field of solar energy harvesting, and assess the challenges and prospects for its large-scale application, including the long term photostability of TTA upconversion materials.

Dye-Sensitized Solar Cell with Integrated Triplet-Triplet Annihilation Upconversion System.

Photon upconversion (UC) by triplet-triplet annihilation (TTA-UC) is employed in order to enhance the response of solar cells to sub-bandgap light. Here, we present the first report of an integrated photovoltaic device, combining a dye-sensitized solar cell (DSC) and TTA-UC system. The integrated device displays enhanced current under sub-bandgap illumination, resulting in a figure of merit (FoM) under low concentration (3 suns), which is competitive with the best values recorded to date for nonintegrated systems. Thus, we demonstrate both the compatibility of DSC and TTA-UC and a viable method for device integration.

Photochemical Upconversion: The Primacy of Kinetics

Incoherent photochemical upconversion is a process by which low-energy light can be converted into a higher-energy form with promising applications in solar energy conversion and storage, photocatalysis, biological imaging, and photochemical drug activation. Despite intensive research in recent years, there remains an underappreciation of the chemical kinetics that controls the efficiency of the upconversion process. Here, we provide a brief overview of research into photochemical upconversion and provide a tutorial to guide the design of efficient upconversion compositions. We further provide our perspective on where this area of research is heading and how very efficient systems will be developed.

A molecular approach to the intermediate band solar cell: The symmetric case

Molecular materials may overcome some of the difficulties for making an intermediate band solar cell by storing energy in long-lived triplet states. Both the problems of fast nonradiative interband relaxation and selective photon absorption can be solved by this approach. A practical implementation of the molecular intermediate band solar cell is considered with a symmetric band alignment, resting on a proven triplet-triplet annihilation process. The limiting power conversion efficiency for this system exceeds that of a single bandgap device over a broad range, peaking at 40.6% for 1.9eV under 1 sun illumination.

Oscillator strengths and radiative lifetimes for C2: Swan, Ballik-Ramsay, Phillips, and dΠg3←cΣu+3 systems

High level ab initio calculations, using multireference configuration interaction (MRCI) techniques, have been carried out to investigate the spectroscopic properties of the singlet AΠu1←XΣg+1 Phillips, the triplet dΠg3←aΣu3 Swan, the bΣg−3←aΠu3 Ballik-Ramsay, and the dΠg3←cΣu+3 transitions of C2. The MRCI expansions are based on full-valence complete active space self-consistent-field reference states and utilize the aug-cc-pV6Z basis set to resolve valence electron correlation. Core and core-valence correlations and scalar relativistic energy corrections were also incorporated in the computed potential energy surfaces. Nonadiabatic and spin-orbit effects were explored and found to be of negligible importance in the calculations. Harmonic frequencies and rotational constants are typically within 0.1% of experiment. The calculated radiative lifetimes compare very well with the available experimental data. Oscillator strengths are reported for all systems: fv′v″, where 0⩽v⩽5.

Photochemical Upconversion Enhanced Solar Cells: Effect of a Back Reflector

Photochemical upconversion is applied to a hydrogenated amorphous silicon solar cell in the presence of a back-scattering layer. A custom-synthesized porphyrin was utilized as the sensitizer species, with rubrene as the emitter. Under a bias of 24 suns, a peak external quantum efficiency (EQE) enhancement of ~2 % was observed at a wavelength of 720 nm. Without the scattering layer, the EQE enhancement was half this value, indicating that the effect of the back-scatterer is to double the efficacy of the upconverting device. The results represent an upconversion figure of merit of 3.5 × 10–4 mA cm–2 sun–2, which is the highest reported to date.

Line strengths and updated molecular constants for the C2 Swan system

Abstract New rotational line strengths for the C2 Swan system ( d Π g 3 – a Π u 3 ) have been calculated for vibrational bands with v ′ = 0 – 10 and v ″ = 0 – 9 , and J values up to J=34–96, using previous observations in 33 vibrational bands. Line positions from several sources were combined with the results from recent deperturbation studies of the v ′ = 4 and v ′ = 6 levels, and a weighted global least squares fit was performed. The updated molecular constants are reported. The line strengths are based on a recent ab initio calculation of the transition dipole moment function. A line list has been made available, including observed and calculated line positions, Einstein A coefficients and oscillator strengths (f-values). The line list will be useful for astronomers, combustion scientists and materials scientists who utilize C2 Swan spectra. Einstein A coefficients and f-values were also calculated for the vibrational bands of the Swan system.

Spectroscopic Observation of the Resonance-Stabilized 1-Phenylpropargyl Radical

The gas-phase laser-induced fluorescence (LIF) spectrum of a 1-phenylpropargyl radical has been identified in the region 20,800-22,000 cm(-1) in a free jet. The radical was produced from discharges of hydrocarbons including benzene. Disregarding C2, C3, and CH, this radical appears as the most strongly fluorescing product in a visible wavelength two-dimensional fluorescence excitation-emission spectrum of a jet-cooled benzene discharge. The structure of the carrier was elucidated by measurement of a matching resonant two-color two-photon ionization spectrum at m/z = 115 and density functional theory. The assignment was proven conclusively by observation of the same excitation spectrum from a low-current discharge of 3-phenyl-1-propyne. The apparent great abundance of the 1-phenylpropargyl radical in discharges of benzene and, more importantly, 1-hexyne may further underpin the proposed importance of the propargyl radical in the formation of complex hydrocarbons in combustion and circumstellar environments.

Entropically driven photochemical upconversion.

Conventional photochemical upconversion (UC) through homo-geneous triplet-triplet annihilation (TTA) is subject to several enthalpic losses that limit the UC margin. Here, we address one of these losses: the triplet energy transfer (TET) from the sensitizer to the emitter molecules. Usually, the triplet energy level of the emitter is set below that of the sensitizer. In our system, the triplet energy level of the emitter exceeds that of the sensitizer by ∼600 cm(-1). Choosing suitable concentrations for the sensitizer and emitter molecules, we can exploit entropy as a driving force for the migration of triplet excitation from the sensitizer to the emitter manifolds. Thereby we obtain a new record for the peak-to-peak TTA-UC energy margin of 0.94 eV. A modified Stern-Volmer analysis yields a TET rate constant of 2.0 × 10(7) M(-1) s(-1). Despite being relatively inefficient, the upconverted fluorescence is easily visible to the naked eye with irradiation intensities as low as 2 W cm(-2).