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The bulk photovoltaic effect (BPVE) leads to directed photo-currents and photo-voltages in bulk materials. Unlike photo-voltages in p-n junction solar cells that are limited by carrier recombination to values below the bandgap energy of the absorbing material, the BPVE photo-voltages have been shown to greatly exceed the bandgap energy. Therefore the BPVE is not subject to the Shockley-Queisser limit for sunlight to electricity conversion in single junction solar cells and experimental claims of efficiencies beyond this limit have been made. Here, we show that BPVE energy conversion efficiencies are, in practice, orders of magnitude below the Shockley-Queisser limit of single junction solar cells and are subject to different, more stringent limits. The name BPVE stands for two different fundamental effects, the shift current and the injection current. In both of these, the voltage bias necessary to produce electrical energy, accelerates both, intrinsic and photo-generated, carriers. We discuss how energy conservation alone fundamentally limits the BPVE to a bandgap-dependent value that exceeds the Shockley Queisser limit only for very small bandgaps. Yet, small bandgap materials have a large number of intrinsic carriers, leading to high conductivity which suppresses the photo-voltage. We discuss further how slightly more stringent fundamental limits for injection (ballistic) currents may be derived from the trade-off between high resistivity, needed for a high voltage, and long ballistic transport length, needed for a high current. We also explain how erroneous experimental and theoretical claims of high efficiency have arisen. Finally, we calculate the energy conversion efficiency for an example 2D material that has been suggested as candidate material for high efficiency BPVE based solar cells and show that the efficiency is very similar to the efficiency of known 3D materials., Comment: 23 pages, 6 figures

Si$_x$Ge$_{1-x-y}$Sn$_y$ ternary alloys are a candidate material system for use in solar cells and other optoelectronic devices. We report on the direct transition energies and structural properties of Ge-rich Si$_x$Ge$_{1-x-y}$Sn$_y$ alloys with six different compositions up to 10 % Si and 3 % Sn, lattice-matched to Ge or GaAs substrates. The direct transitions occurring between 0.9 and 5.0 eV were investigated using spectroscopic ellipsometry (SE), and the resulting data was used to obtain the dielectric functions of the Si$_x$Ge$_{1-x-y}$Sn$_y$n layer by fitting a multi-layer model. Values for the $E_0$, $E_1$, $\Delta_1$, $E_0'$ and $E_2$ transition energies were then found by differentiating these dielectric functions to extract the locations of critical points. Structurally, the composition of the samples was measured using energy-dispersive X-ray measurements (EDX). The lattice constants predicted from these compositions are in good agreement with reciprocal space maps obtained through X-ray diffraction (XRD). The results confirm that a 1 eV direct absorption edge can be achieved using relatively low Si and Sn fractions ($<$ 10 % and $<$ 3 % respectively), while the higher-energy critical points show smaller shifts relative to Ge and match results previously observed or predicted in the literature., Comment: 11 pages, 9 figures

We present a combined experimental and theoretical analysis of the evolution of the near-band gap electronic and optical properties of Si$_{x}$Ge$_{1-x-y}$Sn$_{y}$ alloys lattice-matched to Ge and GaAs substrates. We perform photoreflectance (PR) and photoluminescence (PL) measurements on Si$_{x}$Ge$_{1-x-y}$Sn$_{y}$ epitaxial layers grown via chemical vapour deposition, for Si (Sn) compositions up to $x =$ 9.6% ($y =$ 2.5%). Our measurements indicate the presence of an indirect fundamental band gap, with PL observed $\approx$ 200-250 meV lower in energy than the direct $E_0$ transition identified by PR measurements. The measured PL is Ge-like, suggesting that the alloy conduction band (CB) edge is primarily derived from the Ge L-point CB minimum. Interpretation of the PR and PL measurements is supported by atomistic electronic structure calculations. Effective alloy band structures calculated via density functional theory confirm the presence of an indirect fundamental band gap, and reveal the origin of the observed inhomogeneous broadening of the measured optical spectra as being alloy-induced band hybridisation occurring close in energy to the CB edge. To analyze the evolution of the band gap, semi-empirical tight-binding (TB) calculations are employed to enable calculations for large supercell sizes. TB calculations reveal that the alloy CB edge is hybridized in nature, consisting at low Si and Sn compositions of an admixture of Ge L-, $\Gamma$- and X-point CB edge states, and confirm that the alloy CB edge retains primarily Ge L-point CB edge character. Our experimental measurements and theoretical calculations confirm a direct transition energy close to 1 eV in magnitude for Si and Sn compositions $x =$ 6.8 - 9.6% and $y =$ 1.6 - 2.2%., Comment: Main: 16 pages, 8 figures. Supplemental material: 15 pages, 10 figures

Hot carrier solar cells promise theoretical power conversion efficiencies far beyond the single junction limit. However, practical implementations of hot carrier solar cells have lagged far behind those theoretical predictions. Reciprocity relations for electro-luminescence from conventional single junction solar cells have been extremely successful in driving their efficiency ever closer to the theoretical limits. In this work, we discuss how the signatures of a functioning hot carrier device should manifest experimentally in electro-luminescence and dark $I-V$ characteristics. Hot carrier properties lead to deviations from the Shockley diode equation that is typical for conventional single junction solar cells. These deviations are directly linked to an increase in temperature of the carriers and therefore the temperature measured from electro-luminescence spectra. We also elucidate how the behaviour of hot carrier solar cells in the dark depends on whether Auger processes play a significant role, revealing a stark contrast between the regime of negligible Auger recombination (carrier conservation model) and dominant Auger recombination (Impact Ionization model) for hot carrier solar cells., Comment: 11 pages, 8 figures

Concentrator Photovoltaic (CPV) systems use high efficiency multi-junction solar cells with efficiencies >40%, but the module efficiency is often much lower. The increased complexity of a CPV module, with optics, receiver and the tracker gives an increased probability that faults will arise during the operational lifetime. In addition, a location like India has varied atmospheric conditions that further complicates the diagnosis of faults. It is therefore important to decouple effects due to the external environment (such as the atmosphere) from effects due to the degradation of the module. By applying a computer model to outdoor CPV test data in Bangalore, India we have established a method to assess the performance of the CPV module and finally we present a method to diagnose faults in the module., Comment: 7 pages, 12 figures