Impact of MOVPE Environment on Silicon Substrates for III-V-on-Si Multijunction Solar Cells

With the final goal of integrating III-V materials to silicon for tandem solar cells, the influence of the metal-organic vapor phase epitaxy (MOVPE) environment on the minority carrier properties of silicon wafers has been evaluated. These properties will essentially determine the photovoltaic performance of the bottom cell in a III-V-on-Si tandem solar cell device. A comparison of the base minority carrier lifetimes obtained for different thermal processes carried out in a MOVPE reactor on Czochralski silicon wafers has been carried out. The effect of the formation of the emitter by phosphorus diffusion has also been evaluated.

Impact of metal-organic vapor phase epitaxy environment on silicon bulk lifetime for III–V-on-Si multijunction solar cells

With the final goal of integrating III-V materials on silicon substrates for tandem solar cells, the influence of the Metal-Organic Vapor Phase Epitaxy (MOVPE) environment on the minority carrier properties of silicon wafers has been evaluated. These properties will essentially determine the photovoltaic performance of the bottom cell in a III-V-on-Si tandem solar cell. A comparison of the base minority carrier lifetimes obtained for different thermal processes carried out in a MOVPE reactor on Czochralski silicon wafers has been carried out. An important degradation of minority carrier lifetime during the surface preparation (i.e. H2 anneal) has been observed. Three different mechanisms have been proposed for explaining this behavior: 1) the introduction of extrinsic impurities coming from the reactor; 2) the activation of intrinsic lifetime killing impurities coming from the wafer itself; and finally, 3) the formation of crystal defects, which eventually become recombination centers. The effect of the emitter formation by phosphorus diffusion has also been evaluated. In this sense, it has been reported that lifetime can be recovered during the emitter formation either by the effect of the P on extracting impurities, or by the role of the atomic hydrogen on passivating the defects.

Effects of internal luminescence and internal optics on V-oc and J(sc) of III-V solar cells

For solar cells dominated by radiative recombination, the performance can be significantly enhanced by improving the internal optics. Internally radiated photons can be directly emitted from the cell, but if confined by good internal reflectors at the front and back of the cell they can also be re-absorbed with a significant probability. This so-called photon recycling leads to an increase in the equilibrium minority carrier concentration and therefore the open-circuit voltage, Voc. In multijunction cells, the internal luminescence from a particular junction can also be coupled into a lower bandgap junction where it generates photocurrent in addition to the externally generated photocurrent, and affects the overall performance of the tandem. We demonstrate and discuss the implications of a detailed model that we have developed for real, non-idealized solar cells that calculates the external luminescent efficiency, accounting for wavelength-dependent optical properties in each layer, parasitic optical and electrical losses, multiple reflections within the cell and isotropic internal emission. The calculation leads to Voc, and we show data on high quality GaAs cells that agree with the trends in the model as the optics are systematically varied. For multijunction cells the calculation also leads to the luminescent coupling efficiency, and we show data on GaInP/GaAs tandems where the trends also agree as the coupling is systematically varied. In both cases, the effects of the optics are most prominent in cells with good material quality. The model is applicable to any solar cell for which the optical properties of each layer are well-characterized, and can be used to explore a wide phase space of design for single junction and multijunction solar cells.

Improved modeling of photoluminescent and electroluminescent coupling in multijunction solar cells

The performance of tandem stacks of Group III?V multijunction solar cells continues to improve rapidly, both through improved performance of the individual cells in the stack and throughi ncrease in the number of stacked cells. As the radiative efficiency of these individual cells increases, radiative coupling between the stacked cells becomes an increasingly important factor not only in cell design, but also in accurate efficiency measurement and in determining performance of cells and systems under varying spectral conditions in the field. Past modeling has concentrated on electroluminescent coupling between the cells, although photoluminescent coupling is shown to be important for cells operating near their maximum power point voltage or below or when junction defect recombination is significant. Extension of earlier models i sproposed to allow this non-negligible component of luminescent coupling to be included. Therefined model is validated by measurement of the closely related external emission from both single and double junction cells.

Desarrollo de estructuras nanofotonicas de campo cercano para intensificacion localizada de luz en celulas solares de banda intermedia - Near-field nanophotonic structures for localized light enhancement in intermediate band solar cells

This doctoral thesis explores some of the possibilities that near-field optics can bring to photovoltaics, and in particular to quantum-dot intermediate band solar cells (QD-IBSCs). Our main focus is the analytical optimization of the electric field distribution produced in the vicinity of single scattering particles, in order to produce the highest possible absorption enhancement in the photovoltaic medium in their surroundings. Near-field scattering structures have also been fabricated in laboratory, allowing the application of the previously studied theoretical concepts to real devices. We start by looking into the electrostatic scattering regime, which is only applicable to sub-wavelength sized particles. In this regime it was found that metallic nano-spheroids can produce absorption enhancements of about two orders of magnitude on the material in their vicinity, due to their strong plasmonic resonance. The frequency of such resonance can be tuned with the shape of the particles, allowing us to match it with the optimal transition energies of the intermediate band material. Since these metallic nanoparticles (MNPs) are to be inserted inside the cell photovoltaic medium, they should be coated by a thin insulating layer to prevent electron-hole recombination at their surface. This analysis is then generalized, using an analytical separation-of-variables method implemented in Mathematica7.0, to compute scattering by spheroids of any size and material. This code allowed the study of the scattering properties of wavelengthsized particles (mesoscopic regime), and it was verified that in this regime dielectric spheroids perform better than metallic. The light intensity scattered from such dielectric spheroids can have more than two orders of magnitude than the incident intensity, and the focal region in front of the particle can be shaped in several ways by changing the particle geometry and/or material. Experimental work was also performed in this PhD to implement in practice the concepts studied in the analysis of sub-wavelength MNPs. A wet-coating method was developed to self-assemble regular arrays of colloidal MNPs on the surface of several materials, such as silicon wafers, amorphous silicon films, gallium arsenide and glass. A series of thermal and chemical tests have been performed showing what treatments the nanoparticles can withstand for their embedment in a photovoltaic medium. MNPs arrays are then inserted in an amorphous silicon medium to study the effect of their plasmonic near-field enhancement on the absorption spectrum of the material. The self-assembled arrays of MNPs constructed in these experiments inspired a new strategy for fabricating IBSCs using colloidal quantum dots (CQDs). Such CQDs can be deposited in self-assembled monolayers, using procedures similar to those developed for the patterning of colloidal MNPs. The use of CQDs to form the intermediate band presents several important practical and physical advantages relative to the conventional dots epitaxially grown by the Stranski-Krastanov method. Besides, this provides a fast and inexpensive method for patterning binary arrays of QDs and MNPs, envisioned in the theoretical part of this thesis, in which the MNPs act as antennas focusing the light in the QDs and therefore boosting their absorption

Application of photoluminescence and electroluminescence techniques to the characterization of intermediate band solar cells

The intermediatebandsolarcell (IBSC) is a photovoltaic device with a theoretical conversion efficiency limit of 63.2%. In recent years many attempts have been made to fabricate an intermediateband material which behaves as the theory states. One characteristic feature of an IBSC is its luminescence spectrum. In this work the temperature dependence of the photoluminescence (PL) and electroluminescence (EL) spectra of InAs/GaAs QD-IBSCs together with their reference cell have been studied. It is shown that EL measurements provide more reliable information about the behaviour of the IB material inside the IBSC structure than PL measurements. At low temperatures, the EL spectra are consistent with the quasi-Fermi level splits described by the IBSC model, whereas at room temperature they are not. This result is in agreement with previously reported analysis of the quantum efficiency of the solarcells

Radiative thermal escape in intermediate band solar cells

To achieve high efficiency, the intermediate band (IB) solar cell must generate photocurrent from sub-bandgap photons at a voltage higher than that of a single contributing sub-bandgap photon. To achieve the latter, it is necessary that the IB levels be properly isolated from the valence and conduction bands. We prove that this is not the case for IB cells formed with the confined levels of InAs quantum dots (QDs) in GaAs grown so far due to the strong density of internal thermal photons at the transition energies involved. To counteract this, the QD must be smaller.

Transport properties of CuGaSe(2)-based thin-film solar cells as a function of absorber composition

The transport properties of thin-film solar cells based on wide-gap CuGaSe(2) absorbers have been investigated as a function of the bulk [Ga]/[Cu] ratio ranging from 1.01 to 1.33. We find that (i) the recombination processes in devices prepared from absorbers with a composition close to stoichiometry ([Ga]/[Cu] = 1.01) are strongly tunnelling assisted resulting in low recombination activation energies (E(a)) of approx. 0.95 eV in the dark and 1.36 eV under illumination. (ii) With an increasing [Ga]/[Cu] ratio, the transport mechanism changes to be dominated by thermally activated Shockley-Read-Hall recombination with similar E(a) values of approx. 1.52-1.57 eV for bulk [Ga]/[Cu] ratios of 1.12-1.33. The dominant recombination processes take place at the interface between CdS buffer and CuGaSe(2) absorber independently from the absorber composition. The increase of E(a) with the [Ga]/[Cu] ratio correlates with the open circuit voltage and explains the better performance of corresponding solar cells.

Laser-fired contact optimization in c-Si solar cells

In this work we study the optimization of laser-fired contact (LFC) processing parameters, namely laser power and number of pulses, based on the electrical resistance measurement of an aluminum single LFC point. LFC process has been made through four passivation layers that are typically used in c-Si and mc-Si solar cell fabrication: thermally grown silicon oxide (SiO2), deposited phosphorus-doped amorphous silicon carbide (a-SiCx/H(n)), aluminum oxide (Al2O3) and silicon nitride (SiNx/H) films. Values for the LFC resistance normalized by the laser spot area in the range of 0.65–3 mΩ cm2 have been obtained

Modelling of quantum dot solar cells for concentrator PV applications

An equivalent circuit model is applied in order to describe the operation characteristics of quantum dot intermediate band solar cells (QD-IBSCs), which accounts for the recombination paths of the intermediate band (IB) through conduction band (CB), the valence band (VB) through IB, and the VB-CB transition. In this work, fitting of the measured dark J-V curves for QD-IBSCs (QD region being non-doped or direct Si-doped to n-type) and a reference GaAs p-i-n solar cell (no QDs) were carried out using this model in order to extract the diode parameters. The simulation was then performed using the extracted diode parameters to evaluate solar cell characteristics under concentration. In the case of QDSC with Si-doped (hence partially-filled) QDs, a fast recovery of the open-circuit voltage (Voc) was observed in a range of low concentration due to the IB effect. Further, at around 100X concentration, Si-doped QDSC could outperform the reference GaAs p-i-n solar cell if the current source of IB current source were sixteen times to about 10mA/cm2 compared to our present cell.

Triple-Junction Solar Cells for Ultra-High Concentrator Applications

After the successful implementation of a record performing dual-junction solar cell at ultra high concentration, in this paper we present the transition to a triple-junction device. The semiconductor structure of the solar cells is presented and the main changes in respect to a dual-junction design are briefly discussed. Cross-sectional TEM analysis of samples confirms that the quality of the triple-junction structures grown by MOVPE is good, revealing no trace of antiphase disorder, and showing flat, sharp and clear interfaces between the layers. Triple-junction solar cells manufactured on these structures have shown a peak efficiency of 36.2% at 700X, maintaining the efficiency over 35% from 300 to 1200 suns. With some changes in the structure and a fine tuning of its processing, efficiencies close to 40% at 1000 suns are envisaged.

Si(100) versus Ge(100): Watching the interface formation for the growth of III-V-based solar cells on abundant substrates

We investigated the atomic surface properties of differently prepared silicon and germanium (100) surfaces during metal-organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD), in particular the impact of the MOVPE ambient, and applied reflectance anisotropy/difference spectroscopy (RAS/RDS) in our MOVPE reactor to in-situ watch and control the preparation on the atomic length scale for subsequent III-V-nucleation. The technological interest in the predominant opto-electronic properties of III-V-compounds drives the research for their heteroepitaxial integration on more abundant and cheaper standard substrates such as Si(100) or Ge(100). In these cases, a general task must be accomplished successfully, i.e. the growth of polar materials on non-polar substrates and, beyond that, very specific variations such as the individual interface formation and the atomic step structure, have to be controlled. Above all, the method of choice to grow industrial relevant high-performance device structures is MOVPE, not normally compatible with surface and interface sensitive characterization tools, which are commonly based on ultrahigh vacuum (UHV) ambients. A dedicated sample transfer system from MOVPE environment to UHV enabled us to benchmark the optical in-situ spectra with results from various surfaces science instruments without considering disruptive contaminants. X-ray photoelectron spectroscopy (XPS) provided direct observation of different terminations such as arsenic and phosphorous and verified oxide removal under various specific process parameters. Absorption lines in Fourier-transform infrared (FTIR) spectra were used to identify specific stretch modes of coupled hydrides and the polarization dependence of the anti-symmetric stretch modes distinguished different dimer orientations. Scanning tunnelling microscopy (STM) studied the atomic arrangement of dimers and steps and tip-induced H-desorption proved the saturation of dangling bonds after preparati- n. In-situ RAS was employed to display details transiently such as the presence of H on the surface at lower temperatures (T <; 800°C) and the absence of Si-H bonds at elevated annealing temperature and also surface terminations. Ge buffer growth by the use of GeH4 enables the preparation of smooth surfaces and leads to a more pronounced amplitude of the features in the spectra which indicates improvements of the surface quality.

Optimizing Bottom Subcells for III-V-on-Si MultiJunction Solar Cells

Dual-junction solar cells formed by a GaAsP or GaInP top cell and a silicon bottom cell seem to be attractive candidates to materialize the long sought-for integration of III-V materials on silicon for photovoltaic applications. Such integration would offer a cost breakthrough for photovoltaic technology, unifying the low cost of silicon and the efficiency potential of III-V multijunction solar cells. In this study, we analyze several factors influencing the performance of the bottom subcell of this dual-junction, namely, 1) the formation of the emitter as a result of the phosphorus diffusion that takes place during the prenucleation temperature ramp and during the growth of the III-V layers; 2) the degradation in surface morphology during diffusion; and 3) the quality needed for the passivation provided by the GaP layer on the emitter.

Analysis of Chromatic Aberration Effects in Triple-Junction Solar Cells Using Advanced Distributed Models

The consideration of real operating conditions for the design and optimization of a multijunction solar cell receiver-concentrator assembly is indispensable. Such a requirement involves the need for suitable modeling and simulation tools in order to complement the experimental work and circumvent its well-known burdens and restrictions. Three-dimensional distributed models have been demonstrated in the past to be a powerful choice for the analysis of distributed phenomena in single- and dual-junction solar cells, as well as for the design of strategies to minimize the solar cell losses when operating under high concentrations. In this paper, we present the application of these models for the analysis of triple-junction solar cells under real operating conditions. The impact of different chromatic aberration profiles on the short-circuit current of triple-junction solar cells is analyzed in detail using the developed distributed model. Current spreading conditions the impact of a given chromatic aberration profile on the solar cell I-V curve. The focus is put on determining the role of current spreading in the connection between photocurrent profile, subcell voltage and current, and semiconductor layers sheet resistance.

Instrumentation for accelerated life tests of concentrator solar cells

Concentrator photovoltaic is an emergent technology that may be a good economical and efficient alternative for the generation of electricity at a competitive cost. However, the reliability of these new solar cells and systems is still an open issue due to the high-irradiation level they are subjected to as well as the electrical and thermal stresses that they are expected to endure. To evaluate the reliability in a short period of time, accelerated aging tests are essential. Thermal aging tests for concentrator photovoltaic solar cells and systems under illumination are not available because no technical solution to the problem of reaching the working concentration inside a climatic chamber has been available. This work presents an automatic instrumentation system that overcomes the aforementioned limitation. Working conditions have been simulated by forward biasing the solar cells to the current they would handle at the working concentration (in this case, 700 and 1050 times the irradiance at one standard sun). The instrumentation system has been deployed for more than 10 000 h in a thermal aging test for III-V concentrator solar cells, in which the generated power evolution at different temperatures has been monitored. As a result of this test, the acceleration factor has been calculated, thus allowing for the degradation evolution at any temperature in addition to normal working conditions to be obtained.