The influence of quantum dot size on the sub-bandgap intraband photocurrent in intermediate band solar cells

The effect of quantum dot (QD) size on the performance of quantum dot intermediate band solar cells is investigated. A numerical model is used to calculate the bound state energy levels and the absorption coefficient of transitions from the ground state to all other states in the conduction band. Comparing with the current state of the art, strong absorption enhancements are found for smaller quantum dots, as well as a better positioning of the energy levels, which is expected to reduce thermal carrier escape. It is concluded that reducing the quantum dot size can increase sub-bandgap photocurrent and improve voltage preservation.

Interstitial Ti for intermediate band formation in Ti-supersaturated silicon

We have analyzed by means of Rutherford backscattering spectrometry (RBS) the Ti lattice location and the degree of crystalline lattice recovery in heavily Ti implanted silicon layers subsequently pulsed laser melted (PLM). Theoretical studies have predicted that Ti should occupy interstitial sites in silicon for a metallic-intermediate band (IB) formation. The analysis of Ti lattice location after PLM processes is a crucial point to evaluate the IB formation that can be clarifyied by means of RBS measurements. After PLM, time-of-flight secondary ion mass spectrometry measurements show that the Ti concentration in the layers is well above the theoretical limit for IB formation. RBS measurements have shown a significant improvement of the lattice quality at the highest PLM energy density studied. The RBS channeling spectra reveals clearly that after PLM processes Ti impurities are mostly occupying interstitial lattice sites.

Guide to intermediate band solar cell research

The intermediate band solar cell (IBSC) is a solar cell that, in order to increase its efficiency over that of single gap solar cells, takes advantage of the absorption of below-bandgap energy photons by means of an intermediate band (IB) located in the semiconductor bandgap. For this process to improve the solar cell performance, the belowbandgap photon absorption has to be effective and the IB cannot limit the open-circuit voltage of the cell. In this paper we provide a guide to the new researcher interested in the idea in order he can quickly become familiar with the concept and updated with the most relevant experimental results.

Effect of concentration on the performance of quantum dot intermediate-band solar cells

Implementation of a high-efficiency quantum dot intermediate-band solar cell (QD-IBSC) must accompany a sufficient photocurrent generation via IB states. The demonstration of a QD-IBSC is presently undergoing two stages. The first is to develop a technology to fabricate high-density QD stacks or a superlattice of low defect density placed within the active region of a p-i-n SC, and the second is to realize half-filled IB states to maximize the photocurrent generation by two-step absorption of sub-bandgap photons. For this, we have investigated the effect of light concentration on the characteristics of QDSCs comprised of multi-layer stacks of self-organized InAs/GaNAs QDs grown with and without impurity doping in molecular beam epitaxy.

Study of the Electrical Behavior in Intermediate Band-Si Junctions

In this study we analyze the electrical behavior of a junction formed by an ultraheavily Ti implanted Si layer processed by a Pulsed Laser Melting (PLM) and the non implanted Si substrate. This electrical behavior exhibits an electrical decoupling effect in this bilayer that we have associated to an Intermediate Band (IB) formation in the Ti supersaturated Si layer. Time-of-flight secondary ion mass spectrometry (ToFSIMS) measurements show a Ti depth profile with concentrations well above the theoretical limit required to the IB formation. Sheet resistance and Hall mobility measurements in the van der Pauw configuration of these bilayers exhibit a clear dependence with the different measurement currents introduced (1menor queA-1mA). We find that the electrical transport properties measured present an electrical decoupling effect in the bilayer as function of the temperature. The dependence of this effect with the injected current could be explained in terms of an additional current flow in the junction from the substrate to the IB layer and in terms of the voltage dependence in the junction with the measurement current.

IBPOWER Project, Intermediate band materials and solar cells for photovoltaics with high efficiency and reduced cost

IBPOWER is a Project awarded under the 7th European Framework Programme that aims to advance research on intermediate band solar cells (IBSCs). These are solar cells conceived to absorb below bandgap energy photons by means of an electronic energy band that is located within the semiconductor bandgap, whilst producing photocurrent with output voltage still limited by the total semiconductor bandgap. IBPOWER employs two basic strategies for implementing the IBSC concept. The first is based on the use of quantum dots, the IB arising from the confined energy levels of the electrons in the dots. Quantum dots have led to devices that demonstrate the physical operation principles of the IB concept and have allowed identification of the problems to be solved to achieve actual high efficiencies. The second approach is based on the creation of bulk intermediate band materials by the insertion of an appropriate impurity into a bulk semiconductor. Under this approach it is expected that, when inserted at high densities, these impurities will find it difficult to capture electrons by producing a breathing mode and will cease behaving as non-radiative recombination centres. Towards this end the following systems are being investigated: a) Mn: In1-xGax N; b) transition metals in GaAs and c) thin films.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Intermediate Band to Conduction Band optical absorption in ZnTe:O

ZnTe doped with high concentrations of oxygen has been proposed in previous works as intermediate band (IB) material for photovoltaic applications. The existence of extra optical transitions related to the presence of an IB has already been demonstrated in this material and it has been possible to measure the absorption coefficient of the transitions from the valence band (VB) to the IB. In this work we present the first measurement of the absorption coefficient associated to transitions from the IB to the conduction band (CB) in ZnTe:O. The samples used are 4 ?m thick ZnTe layers with or without O in a concentration ~ 1019 cm-3, which have been grown on semi-insulating GaAs substrates by molecular beam epitaxy (MBE). The IB-CB absorption coefficient peaks for photon energies ~ 0.4 eV. It is extracted from reflectance and transmittance spectra measured using Fourier Transform Infrared (FTIR) spectroscopy. Under typical FTIR measurement conditions (low light intensity, broadband spectrum) the absorption coefficient in IB-to-CB transitions reaches 700 cm-1. This is much weaker than the one observed for VB-IB absorption. This result is consistent with the fact that the IB is expected to be nearly empty of electrons under equilibrium conditions in ZnTe(:O). The absorption for VB to IB transitions is also observed in the same samples through reflectance measurements performed in the visible range using a monochromator. These measurements are compared with the quantum efficiency (QE) from solar cells fabricated under similar conditions.

InAs/AlGaAs quantum dot intermediate band solar cells with enlarged sub-bandgaps

In the last decade several prototypes of intermediate band solar cells (IBSCs) have been manufactured. So far, most of these prototypes have been based on InAs/GaAs quantum dots (QDs) in order to implement the IB material. The key operation principles of the IB theory are two photon sub-bandgap (SBG) photocurrent, and output voltage preservation, and both have been experimentally demonstrated at low temperature. At room temperature (RT), however, thermal escape/relaxation between the conduction band (CB) and the IB prevents voltage preservation. To improve this situation, we have produced and characterized the first reported InAs/AlGaAs QD-based IBSCs. For an Al content of 25% in the host material, we have measured an activation energy of 361 meV for the thermal carrier escape. This energy is about 250 meV higher than the energies found in the literature for InAs/GaAs QD, and almost 140 meV higher than the activation energy obtained in our previous InAs/GaAs QD-IBSC prototypes including a specifically designed QD capping layer. This high value is responsible for the suppression of the SBG quantum efficiency under monochromatic illumination at around 220 K. We suggest that, if the energy split between the CB and the IB is large enough, activation energies as high as to suppress thermal carrier escape at room temperature (RT) can be achieved. In this respect, the InAs/AlGaAs system offers new possibilities to overcome some of the problems encountered in InAs/GaAs and opens the path for QD-IBSC devices capable of achieving high efficiency at RT.

Estudio teórico de propiedades termodinámicas y optoelectronicas de nuevos materiales fotovoltaicos de banda intermedia = Theoretical study of thermodynamic and optoelectronic properties of new intermediate band photovoltaic materials

Los materiales de banda intermedia han atraido la atención de la comunidad científica en el campo de la energía solar fotovoltaica en los últimos años. Sin embargo, con el objetivo de entender los fundamentos de las células solares de banda intermedia, se debe llevar a cabo un estudio profundo de la características de los materiales. Esto se puede hacer mediante un modelo teórico usando Primeros Principios. A partir de este enfoque se pueden obtener resultados tales como la estructura electrónica y propiedades ópticas, entre otras, de los semiconductores fuertemente dopados y sus precursores. Con el fin de desentrañar las estructuras de estos sistemas electrónicos, esta tesis presenta un estudio termodinámico y optoelectrónico de varios materiales fotovoltaicos. Específicamente se caracterizaron los materiales avanzados de banda intermedia y sus precursores. El estudio se hizo en términos de caracterización teórica de la estructura electrónica, la energética del sistema, entre otros. Además la estabilidad se obtuvo usando configuraciones adaptadas a la simetría del sistema y basado en la combinatoria. Las configuraciones de los sitios ocupados por defectos permiten obtener información sobre un espacio de configuraciones donde las posiciones de los dopantes sustituidos se basan en la simetría del sólido cristalino. El resultado puede ser tratado usando elementos de termodinámica estadística y da información de la estabilidad de todo el espacio simétrico. Además se estudiaron otras características importantes de los semiconductores de base. En concreto, el análisis de las interacciones de van der Waals fueron incluidas en el semiconductor en capas SnS2, y el grado de inversión en el caso de las espinelas [M]In2S4. En este trabajo además realizamos una descripción teórica exhaustiva del sistema CdTe:Bi. Este material de banda-intermedia muestra características que son distintas a las de los otros materiales estudiados. También se analizó el Zn como agente modulador de la posición de las sub-bandas prohibidas en el material de banda-intermedia CuGaS2:Ti. Analizándose además la viabilidad termodinámica de la formación de este compuesto. Finalmente, también se describió el GaN:Cr como material de banda intermedia, en la estructura zinc-blenda y en wurtztite, usando configuraciones de sitios ocupados de acuerdo a la simetría del sistema cristalino del semiconductor de base. Todos los resultados, siempre que fue posible, fueron comparados con los resultados experimentales. ABSTRACT The intermediate-band materials have attracted the attention of the scientific community in the field of the photovoltaics in recent years. Nevertheless, in order to understand the intermediate-band solar cell fundamentals, a profound study of the characteristics of the materials is required. This can be done using theoretical modelling from first-principles. The electronic structure and optical properties of heavily doped semiconductors and their precursor semiconductors are, among others, results that can be obtained from this approach. In order to unravel the structures of these crystalline systems, this thesis presents a thermodynamic and optoelectronic study of several photovoltaic materials. Specifically advanced intermediate-band materials and their precursor semiconductors were characterized. The study was made in terms of theoretical characterization of the electronic structure, energetics among others. The stability was obtained using site-occupancy-disorder configurations adapted to the symmetry of the system and based on combinatorics. The site-occupancy-disorder method allows the formation of a configurational space of substitutional dopant positions based on the symmetry of the crystalline solid. The result, that can be treated using statistical thermodynamics, gives information of the stability of the whole space of symmetry of the crystalline lattice. Furthermore, certain other important characteristics of host semiconductors were studied. Specifically, the van der Waal interactions were included in the SnS2 layered semiconductor, and the inversion degree in cases of [M]In2S4 spinels. In this work we also carried out an exhaustive theoretical description of the CdTe:Bi system. This intermediate-band material shows characteristics that are distinct from those of the other studied intermediate-band materials. In addition, Zn was analysed as a modulator of the positions of the sub-band gaps in the CuGaS2:Ti intermediate-band material. The thermodynamic feasibility of the formation of this compound was also carried out. Finally GaN:Cr intermediate-band material was also described both in the zinc-blende and the wurtztite type structures, using the symmetry-adapted-space of configurations. All results, whenever possible, were compared with experimental results.

Self-organized colloidal quantum dots and metal nanoparticles for plasmon-enhanced intermediate-band solar cells

A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude. In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance. The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

Interband absorption of photons by extended states in intermediate band solar cells

This paper considers sub-bandgap photon absorption in an InAs/GaAs quantum dot matrix. Absorption coefficients are calculated for transitions from the extended states in the valence band to confined states in the conduction band. This completes a previous body of work in which transitions between bound states were calculated. The calculations are based on the empirical k·p Hamiltonian considering the quantum dots as parallelepipeds. The extended states may be only partially extended?in one or two dimensions?or extended in all three dimensions. It is found that extended-to-bound transitions are, in general, weaker than bound-to-bound transitions, and that the former are weaker when the initial state is extended in more coordinates. This study is of direct application to the research of intermediate band solar cells and other semiconductor devices based on light absorption in semiconductors nanostructured with quantum dots.

Experimental verification of intermediate band formation on titanium-implanted silicon

Intermediate band formation on silicon layers for solar cell applications was achieved by titanium implantation and laser annealing. A two-layer heterogeneous system, formed by the implanted layer and by the un-implanted substrate, was formed. In this work, we present for the first time electrical characterization results which show that recombination is suppressed when the Ti concentration is high enough to overcome the Mott limit, in agreement with the intermediate band theory. Clear differences have been observed between samples implanted with doses under or over the Mott limit. Samples implanted under the Mott limit have capacitance values much lower than the un-implanted ones as corresponds to a highly doped semiconductor Schottky junction. However, when the Mott limit is surpassed, the samples have much higher capacitance, revealing that the intermediate band is formed. The capacitance increasing is due to the big amount of charge trapped at the intermediate band, even at low temperatures. Ti deep levels have been measured by admittance spectroscopy. These deep levels are located at energies which vary from 0.20 to 0.28?eV below the conduction band for implantation doses in the range 1013-1014 at./cm2. For doses over the Mott limit, the implanted atoms become nonrecombinant. Capacitance voltage transient technique measurements prove that the fabricated devices consist of two-layers, in which the implanted layer and the substrate behave as an n+/n junction.

Electrical properties of silicon supersaturated with titanium or vanadium for intermediate band material

We have fabricated titanium and vanadium supersaturated silicon layers on top of a silicon substrate by means of ion implantation and pulsed laser melting processes. This procedure has proven to be suitable to fabricate an intermediate band (IB) material, i.e. a semiconductor material with a band of allowed states within the bandgap. Sheet resistance and Hall mobility measurements as a function of the temperature show an unusual behavior that has been well explained in the framework of the IB material theory, supposing that we are dealing with a junction formed by the IB material top layer and the n-Si substrate. Using an analytical model that fits with accuracy the experimental sheet resistance and mobility curves, we have obtained the values of the exponential factor for the thermically activated junction resistance of the bilayer, showing important differences as a function of the implanted element. These results could allow us to engineer the IB properties selecting the implanted element depending on the required properties for a specific application.

The intermediate band approach in the third solar cell generation context

Hydrogenated amorphous silicon thin films were deposited using a high pressure sputtering (HPS) system. In this work, we have studied the composition and optical properties of the films (band-gap, absorption coefficient), and their dependence with the deposition parameters. For films deposited at high pressure (1 mbar), composition measurements show a critical dependence of the purity of the films with the RF power. Films manufactured with RF-power above 80W exhibit good properties for future application, similar to the films deposited by CVD (Chemical Vapor Deposition) for hydrogenated amorphous silicon.