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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., 11 pages, 8 figures

The hot-phonon bottleneck effect in lead-halide perovskites (APbX3) prolongs the cooling period of hot charge carriers, an effect that could be used in the next-generation photovoltaics devices. Using ultrafast optical characterization and first-principle calculations, four kinds of lead-halide perovskites (A=FA+/MA+/Cs+, X=I−/Br−) are compared in this study to reveal the carrier-phonon dynamics within. Here we show a stronger phonon bottleneck effect in hybrid perovskites than in their inorganic counterparts. Compared with the caesium-based system, a 10 times slower carrier-phonon relaxation rate is observed in FAPbI3. The up-conversion of low-energy phonons is proposed to be responsible for the bottleneck effect. The presence of organic cations introduces overlapping phonon branches and facilitates the up-transition of low-energy modes. The blocking of phonon propagation associated with an ultralow thermal conductivity of the material also increases the overall up-conversion efficiency. This result also suggests a new and general method for achieving long-lived hot carriers in materials., Slow cooling of hot charge carriers in lead halide perovskite could be used in photovoltaics devices. Here, Yang et al. study hot carrier dynamics by transient absorption spectroscopy. They relate the phonon bottleneck to the up-conversion of low-energy phonons, facilitated by the presence of organic cations.

Compared to traditional pn-junction photovoltaics, hot carrier solar cells offer potentially higher efficiency by extracting work from the kinetic energy of photogenerated 'hot carriers' before they cool to the lattice temperature. Hot carrier solar cells have been demonstrated in high-bandgap ferroelectric insulators and GaAs/AlGaAs heterostructures, but so far not in low-bandgap materials, where the potential efficiency gain is highest. Recently, a high open-circuit voltage was demonstrated in an illuminated wurtzite InAs nanowire with a low bandgap of 0.39 eV, and was interpreted in terms of a photothermoelectric effect. Here, we point out that this device is a hot carrier solar cell and discuss its performance in those terms. In the demonstrated devices, InP heterostructures are used as energy filters in order to thermoelectrically harvest the energy of hot electrons photogenerated in InAs absorber segments. The obtained photovoltage depends on the heterostructure design of the energy filter and is therefore tunable. By using a high-resistance, thermionic barrier, an open-circuit voltage is obtained that is in excess of the Shockley-Queisser limit. These results provide generalizable insight into how to realize high voltage hot carrier solar cells in low-bandgap materials, and therefore are a step towards the demonstration of higher efficiency hot carrier solar cells.

As an important step towards the realisation of silicon-based tandem solar cells using silicon quantum dots embedded in a silicon dioxide (SiO2) matrix, single-junction silicon quantum dot (Si QD) solar cells on quartz substrates have been fabricated. The total thickness of the solar cell material is 420 nm. The cells contain 4 nm diameter Si quantum dots. The impacts of post-metallisation treatments such as phosphoric acid (H3PO4) etching, nitrogen (N2) gas anneal and forming gas (Ar: H2) anneal on the cells’ electrical and photovoltaic properties are investigated. The Si QD solar cells studied in this work have achieved an open circuit voltage of 410 mV after various processes. Parameters extracted from dark I–V, light I–V and circular transfer length measurement (CTLM) suggest limiting mechanism in the Si QD solar cell operation and possible approaches for further improvement.

EPJ Photovoltaics 2, 25001 (2011). doi:10.1051/epjpv/2011024, Published by EDP Sciences, Les Ulis

25th European Photovoltaic Solar Energy Conference and Exhibition / 5th World Conference on Photovoltaic Energy Conversion, 6-10 September 2010, Valencia, Spain; 182-190, Silicon quantum dot (Si QD) solar cells offer the potential to tune the effective band gap, through quantum confinement, and allow fabrication of optimised tandem devices in one growth run in a thin film process. Previous work in our group has shown how such cells can be fabricated by sputtering of thin layers of silicon rich oxide sandwiched between a stoichiometric oxide that on annealing crystallise to form Si QDs of uniform and controllable size. Doping multilayers with P and B allows formation of a rectifying junction with an effective band gap of 1.8eV, which can give an open circuit voltage (VOC) of almost 500mV. However, the doping behaviour of P and B in these QD materials is not well understood. In addition P and B have big but opposite effects on QD crystallisation, with P (B) forming larger (smaller) QDs than for undoped material. Two possible models for the doping mechanisms in these materials are explored: one relying on doping of a sub-oxide region around the Si QDs and the other based on the differing nucleation effects of P and B. In addition initial results on heterointerfaces in the QD superstructure are assessed as a means to improve vertical current transport, and the effects of hydrogenation on improving VOC by passivating defects. Routes to incorporating these explanations for doping and other structural improvements are discussed as means of optimising the performance of these Si QD cells.

Doping of Si quantum dots is important in the field of Si quantum dots-based solar cells. Structural, optical and electrical properties of Si QDs formed as multilayers in a SiO 2 matrix with various phosphorus (P) concentrations introduced during the sputtering process were investigated for its potential application in all-silicon quantum dot tandem solar cells. The formation of Si quantum dots was confirmed by transmission electron microscopy. The addition of phosphorus was observed to modify Si crystallization, though the phosphorus concentration was found to have little effect on quantum dot size. Secondary ion mass spectroscopy results indicate minimal phosphorus diffusion from Si QDs layers to adjacent SiO 2 layers during high-temperature annealing. Resistivity is significantly decreased by phosphorus doping. Resistivity of slightly phosphorus-doped (0.1 at% P) films is seven orders of magnitude lower than that of intrinsic films. Dark resistivity and activation energy measurements indicate the existence of an optimal phosphorus concentration. The photoluminescence intensity increases with the phosphorus concentration, indicating a tendency towards radiative recombination in the doped films. These results can provide optimal condition for future Si quantum dots-based solar cells.

Promise of Si nanocrystals highly depends on tailoring their behaviour through doping. Phosphorus-doped silicon nanocrystals embedded in a silicon dioxide matrix have been realized by a co-sputtering process. The effects of phosphorus-doping on the properties of Si nanocrystals are investigated. Phosphorus diffuses from P–P and/or P–Si to P–O upon high temperature annealing. The dominant X-ray photoelectron spectroscopy P 2p signal attributable to Si–P and/or P–P (130 eV) at 1100 °C indicates that the phosphorus may exist inside Si nanocrystals. It is found that existence of phosphorus enhances phase separation of silicon rich oxide and thereby Si crystallization. In addition, phosphorus has a considerable effect on the optical absorption and photoluminescence properties as a function of annealing temperature.

We report work progress on the growth of Si quantum dots in different matrices for future photovoltaic applications. The work reported here seeks to engineer a wide-bandgap silicon-based thin-film material by using quantum confinement in silicon quantum dots and to utilize this in complete thin-film silicon-based tandem cell, without the constraints of lattice matching, but which nonetheless gives an enhanced efficiency through the increased spectral collection efficiency. Coherent-sized quantum dots, dispersed in a matrix of silicon carbide, nitride, or oxide, were fabricated by precipitation of Si-rich material deposited by reactive sputtering or PECVD. Bandgap opening of Si QDs in nitride is more blue-shifted than that of Si QD in oxide, while clear evidence of quantum confinement in Si quantum dots in carbide was hard to obtain, probably due to many surface and defect states. The PL decay shows that the lifetimes vary from 10 to 70 microseconds for diameter of 3.4 nm dot with increasing detection wavelength.

Hot Carrier solar cells have long been recognized as an attractive contender in the search for high efficiency photovoltaic devices but their fabrication requires solution of two important material challenges: finding materials with drastically reduced carrier cooling rates and realization of selective energy contacts to extract the photogenerated carriers. This paper is concerned with the problem of absorber phononic engineering to reduce carrier cooling rates. The physics of carrier cooling is explored and experimental data of other authors are discussed with a view to assessing the potential of state-of-the art nanostructured materials for PV conversion. A tentative initial calculation based on the thermalisation in these nanostructures and assuming all other aspects as ideal, gives 54% efficiency at 2500suns as compared to 54% for no thermalisation at all. Phononic band gap engineering to further reduce carrier cooling or bring down the threshold concentration is discussed.

Double barrier Quantum Dot structures are potential candidates for Energy Selective Contacts for Hot Carrier Solar Cells. Silicon QD in SiO2 matrix is studied for its energy selectivity using a two dimensional model. The impact of the disorders- configurational, morphological, thickness variations of the SiO2 barriers- on conductance and selectivity of the structure is studied. Application of an external electric field modifies the confinement potential and thus the resonant properties of the structure. The impact of the applied electric field on the properties of the energy selective contact is also studied in this paper.

Ge nanocrystals were fabricated in Si3N4 matrix by rf (radio frequency) magnetron sputtering, followed by post-annealing in a conventional tube furnace filled with N2. Ge content was varied between 30-50vol% in Ge-rich silicon nitride (GRN) layer with variation of annealing temperature between 600-900 °C were applied to study the crystallization properties. The structure of the Ge nanocrystals was studied by Raman spectroscopy, glancing incidence x-ray diffraction (GIXRD) and transmission electron microscope (TEM). The composition and bonding status of Ge nanocrystals was confirmed by x-ray photoelectron spectroscopy (XPS). TEM images, Raman and XRD results show that the crystallization transition is dependent on temperature and Ge content. Crystals in 50vol% annealed at 900 °C were found as partially oxidized with 2at% of oxygen during the annealing process. This was shown by the XPS result. However, absorption measurement did not show evidence of quantum confinement of the Ge crystals.

To search a suitable material candidate for “all-Si” tandem solar cell, a hybrid super-lattice structure consisting 30 periods of alternating amorphous Si0.7C0.3 (5 nm) layers and ultra-thin Si3N4 barrier layers (0.2-2.0 nm) has been deposited by magnetron sputtering with subsequent annealing by a rapid thermal annealing (RTA) process. Structural and electrical characterization of the layered film was carried out after annealing. 8 nm barrier layer thickness is proven to be able to provide sufficient structural confinement even after high temperature annealing. Increased resistivity was measured for the overall multi-layer structure, resulting from the incorporation of the Si3N4 barrier layers hence likely suppressing carrier transport and further electron hopping is proven the main transportation mechanism.

The concept of third-generation photovoltaics is to significantly increase device efficiencies whilst still using thin-film processes and abundant non-toxic materials. A strong potential approach is to fabricate tandem cells using thin-film deposition that can optimise collection of energy in a series of cells with decreasing band gap stacked on top of each other. Quantum dot materials, in which Si quantum dots (QDs) are embedded in a dielectric matrix, offer the potential to tune the effective band gap, through quantum confinement, and allow fabrication of optimised tandem solar cell devices in one growth run in a thin-film process. Such cells can be fabricated by sputtering of thin layers of silicon rich oxide sandwiched between a stoichiometric oxide that on annealing crystallise to form Si QDs of uniform and controllable size. For approximately 2-nm diameter QDs, these result in an effective band gap of 1.8 eV. Introduction of phosphorous or boron during the growth of the multilayers results in doping and a rectifying junction, which demonstrates photovoltaic behaviour with an open circuit voltage (VOC) of almost 500 mV. However, the doping behaviour of P and B in these QD materials is not well understood. A modified modulation doping model for the doping mechanisms in these materials is discussed which relies on doping of a sub-oxide region around the Si QDs.

In this paper, a positive effect of rapid thermal annealing (RTA) technique has been researched and compared with conventional furnace annealing for Si nanocrystalline in silicon carbide (SiC) matrix system. Amorphous Si-rich SiC layer has been deposited by co-sputtering in different Si concentrations (50 to approximately 80 v%). Si nanocrystals (Si-NC) containing different grain sizes have been fabricated within the SiC matrix under two different annealing conditions: furnace annealing and RTA both at 1,100°C. HRTEM image clearly reveals both Si and SiC-NC formed in the films. Much better "degree of crystallization" of Si-NC can be achieved in RTA than furnace annealing from the research of GIXRD and Raman analysis, especially in high-Si-concentration situation. Differences from the two annealing procedures and the crystallization mechanism have been discussed based on the experimental results.