M. C. Hanna

Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers

We calculate the maximum power conversion efficiency for conversion of solar radiation to electrical power or to a flux of chemical free energy for the case of hydrogen production from water photoelectrolysis. We consider several types of ideal absorbers where absorption of one photon can produce more than one electron-hole pair that are based on semiconductor quantum dots with efficient multiple exciton generation (MEG) or molecules that undergo efficient singlet fission (SF). Using a detailed balance model with 1 sun AM1.5G illumination, we find that for single gap photovoltaic (PV) devices the maximum efficiency increases from 33.7% for cells with no carrier multiplication to 44.4% for cells with carrier multiplication. We also find that the maximum efficiency of an ideal two gap tandem PV device increases from 45.7% to 47.7% when carrier multiplication absorbers are used in the top and bottom cells. For an ideal water electrolysis two gap tandem device, the maximum conversion efficiency is 46.0% using...

Comparing organic to inorganic photovoltaic cells: Theory, experiment, and simulation

Charge carriers are photogenerated with very different spatial distributions in conventional inorganic photovoltaic (IPV) cells and in organic photovoltaic (OPV or excitonic) cells. This leads to a fundamental, and often overlooked, mechanistic difference between them. Carriers are generated primarily at the exciton-dissociating heterointerface in OPV cells, resulting in the production of electrons in one phase and holes in the other—the two carrier types are thus already separated across the interface upon photogeneration in OPV cells, giving rise to a powerful chemical potential energy gradient ∇μhv that promotes the photovoltaic effect. This occurs also in high-surface-area OPV cells, although their description is more complex. In contrast, both carrier types are photogenerated together throughout the bulk in IPV cells: ∇μhv then drives both electrons and holes in the same direction through the same phase; efficient carrier separation therefore requires a built-in equilibrium electrical potential energ...

Comparing Multiple Exciton Generation in Quantum Dots To Impact Ionization in Bulk Semiconductors: Implications for Enhancement of Solar Energy Conversion

Multiple exciton generation (MEG) in quantum dots (QDs) and impact ionization (II) in bulk semiconductors are processes that describe producing more than one electron-hole pair per absorbed photon. We derive expressions for the proper way to compare MEG in QDs with II in bulk semiconductors and argue that there are important differences in the photophysics between bulk semiconductors and QDs. Our analysis demonstrates that the fundamental unit of energy required to produce each electron-hole pair in a given QD is the band gap energy. We find that the efficiency of the multiplication process increases by at least 2 in PbSe QDs compared to bulk PbSe, while the competition between cooling and multiplication favors multiplication by a factor of 3 in QDs. We also demonstrate that power conversion efficiencies in QD solar cells exhibiting MEG can greatly exceed conversion efficiencies of their bulk counterparts, especially if the MEG threshold energy can be reduced toward twice the QD band gap energy, which requires a further increase in the MEG efficiency. Finally, we discuss the research challenges associated with achieving the maximum benefit of MEG in solar energy conversion since we show the threshold and efficiency are mathematically related.

n-Type Transition Metal Oxide as a Hole Extraction Layer in PbS Quantum Dot Solar Cells

The n-type transition metal oxides (TMO) consisting of molybdenum oxide (MoO(x)) and vanadium oxide (V(2)O(x)) are used as an efficient hole extraction layer (HEL) in heterojunction ZnO/PbS quantum dot solar cells (QDSC). A 4.4% NREL-certified device based on the MoO(x) HEL is reported with Al as the back contact material, representing a more than 65% efficiency improvement compared with the case of Au contacting the PbS quantum dot (QD) layer directly. We find the acting mechanism of the hole extraction layer to be a dipole formed at the MoO(x) and PbS interface enhancing band bending to allow efficient hole extraction from the valence band of the PbS layer by MoO(x). The carrier transport to the metal anode is likely enhanced through shallow gap states in the MoO(x) layer.

Determining the Internal Quantum Efficiency of PbSe Nanocrystal Solar Cells with the Aid of an Optical Model

We determine the internal quantum efficiency (IQE) of the active layer of PbSe nanocrystal (NC) back-contact Schottky solar cells by combining external quantum efficiency (EQE) and total reflectance measurements with an optical model of the device stack. The model is parametrized with the complex index of refraction of each layer in the stack as calculated from ellipsometry data. Good agreement between the experimental and modeled reflectance spectra permits a quantitative estimate of the fraction of incident light absorbed by the NC films at each wavelength, thereby yielding well-constrained QE spectra for photons absorbed only by the NCs. Using a series of devices fabricated from 5.1+/-0.4 nm diameter PbSe NCs, we show that thin NC cells achieve an EQE and an active layer IQE as high as 60+/-5% and 80+/-7%, respectively, while the QE of devices with NC layers thicker than about 150 nm falls, particularly in the blue, because of progressively greater light absorption in the field-free region of the films and enhanced recombination overall. Our results demonstrate that interference effects must be taken into account in order to calculate accurate optical generation profiles and IQE spectra for these thin film solar cells. The mixed modeling/experimental approach described here is a rigorous and powerful way to determine if multiple exciton generation (MEG) photocurrent is collected by devices with EQE<100%. On the basis of the magnitudes and shapes of the IQE spectra, we conclude that the 1,2-ethanedithiol treated NC devices studied here do not produce appreciable MEG photocurrent.

Surface photovoltage spectroscopy of quantum wells and superlattices

Surface photovoltage spectroscopy (SPS) has been employed to monitor optical transitions in quantum well and superlattice structures at room temperature. Excellent agreement is found between theoretical predictions of heavy hole and electron energy level positions and the observed transitions. The results show that using this technique, the complete band diagram of the quantum structure may be constructed. SPS emerges as a powerful tool capable of monitoring optical transitions above the lowest one in a simple to interpret, contactless, and nondestructive way.

Composition dependence of Raman intensity of the nitrogen localized vibrational mode in GaAs1-xNx

We have investigated the nitrogen-localized vibrational mode (LVM) Raman intensity and its frequency (ωLVM) as a function of nitrogen concentration in GaAs1−xNx (x⩽0.04) at 300 K. The normalized Raman intensity of nitrogen LVM with respect to that of GaAs–LO phonon as well as ωLVM exhibits a remarkable linear dependence on the nitrogen concentration for x⩽0.03. This provides excellent calibration to determine nitrogen composition not only in the ternary alloy GaAs1−xNx but also in the quaternaries such as Ga1−yInyAs1−xNx.

TWO COLOR BLINKING OF SINGLE STRAIN-INDUCED GAAS QUANTUM DOTS

In this letter we report on a temporal instability in the ground and excited state luminescence of a single strain-induced quantum dot. Using a microscopic photoluminescence technique, we record spectra from a single strain-induced quantum dot in the GaAs/(AlGa)As material system. On a time scale of seconds the luminescence shows an increase and decrease in intensity with an increase of the ground state luminescence correlating with a decrease in the excited state luminescence intensity and vice versa. We term the observed effect two color blinking.

Characterization of MOCVD lateral epitaxial overgrown III-V semiconductor layers on GaAs substrates

We have studied the lateral epitaxial overgrowth by MOCVD of a variety of highly mismatched III-V semiconductors on GaAs substrates. For [001] substrates we determined the oxide stripe orientation that gives the maximum lateral growth rate to be /spl sim/ 25/sup o/ from [110]. We successfully achieved that lateral overgrowth of In/sub x/Ga/sub 1-x/As alloys on GaAs and found that the use of Bi as a surfactant led to an improvement in the morphology and luminescence uniformity. The studies have been extended to the lateral epitaxial overgrowth of InAs, GaP, and InP.

Initiation and evolution of phase separation in heteroepitaxial InAlAs films

We have investigated the initiation and evolution of phase separation in heteroepitaxial InAlAs films. In misfit-free InAlAs layers, cross-sectional scanning tunneling microscopy (XSTM) reveals the presence of isotropic nanometer-sized clusters. For lattice-mismatched InAlAs layers with 1.2% misfit, quasiperiodic contrast modulations perpendicular to the growth direction are apparent. Interestingly, these lateral modulations are apparently initiated within the first few bilayers of film growth, and both the amplitude and wavelength of the modulations increase with film thickness. The saturation value of the modulation wavelength determined from XSTM coincides with the lateral superlattice period determined from (002) x-ray reciprocal space maps, suggesting that the lateral modulation wavelength represents a periodic composition variation. Together, these results suggest that phase separation in the heteroepitaxial InAlAs thin-film system is a misfit-driven kinetic process initiated by random compositional nonuniformities, which later develop into coupled compositional and surface morphological variations.