Aruna Ivaturi

Optimizing infrared to near infrared upconversion quantum yield of β-NaYF4:Er3+ in fluoropolymer matrix for photovoltaic devices

The present study reports for the first time the optimization of the infrared (1523 nm) to near-infrared (980 nm) upconversion quantum yield (UC-QY) of hexagonal trivalent erbium doped sodium yttrium fluoride (β-NaYF4:Er3+) in a perfluorocyclobutane (PFCB) host matrix under monochromatic excitation. Maximum internal and external UC-QYs of 8.4% ± 0.8% and 6.5% ± 0.7%, respectively, have been achieved for 1523 nm excitation of 970 ± 43 Wm−2 for an optimum Er3+ concentration of 25 mol% and a phosphor concentration of 84.9 w/w% in the matrix. These results correspond to normalized internal and external efficiencies of 0.86 ± 0.12 cm2 W−1 and 0.67 ± 0.10 cm2 W−1, respectively. These are the highest values ever reported for β-NaYF4:Er3+ under monochromatic excitation. The special characteristics of both the UC phosphor β-NaYF4:Er3+ and the PFCB matrix give rise to this outstanding property. Detailed power and time dependent luminescence measurements reveal energy transfer upconversion as the dominant UC mechanism.

Ultra-high photoluminescent quantum yield of β-NaYF4: 10% Er3+ via broadband excitation of upconversion for photovoltaic devices.

The upconversion photoluminescent quantum yield (PLQY) of erbium-doped hexagonal sodium yttrium fluoride (β-NaYF(4): 10% Er(3+) was measured under broadband excitation with full width half maxima ranging from 12 to 80 nm. A novel method was developed to increase the bandwidth of excitation, while remaining independent of power via normalization to the air mass 1.5 direct solar spectrum. The measurements reveal that by broadening the excitation spectrum a higher PLQY can be achieved at lower solar concentrations. The highest PLQY of 16.2 ± 0.5% was achieved at 2270 ± 100 mW mm(-2) and is the highest ever measured.

SFX as a low-cost ‘Spiro’ hole-transport material for efficient perovskite solar cells

Four spiro[fluorene-9,9′-xanthene] (SFX) derivatives, SFX-TAD, SFX-TCz, SFX-TPTZ and SFX-MeOTAD have been synthesized for use as hole-transport materials and fully characterized by 1H/13C NMR spectroscopy, mass spectrometry, XRD and DSC. Their thermal, optical and electrochemical properties were investigated. The use of different substituents affects the highest occupied molecular orbital (HOMO) energy level proving the versatility of the central core towards the facile and low-cost preparation of spiro-hole-transport materials. Among the synthesized SFX derivatives, SFX-MeOTAD was employed as hole-transporting material (HTM) and the performance tested in perovskite solar cells with device architecture glass/FTO/compact TiO2/mesoporous Al2O3/CH3NH3PbI3−xClx/HTM/Au. SFX-MeOTAD gave a comparable efficiency to spiro-MeOTAD, demonstrating great potential for use of the SFX family as cost effective and versatile hole conductors facilitating commercialization of perovskite solar cells (PSCs).

Spray deposited copper zinc tin sulphide (Cu2ZnSnS4) film as a counter electrode in dye sensitized solar cells.

Stoichiometric thin films of Cu2ZnSnS4 (CZTS) were deposited by the spray technique on a FTO coated glass substrate, with post-annealing in a H2S environment to improve the film properties. CZTS films were used as a counter electrode (CE) in Dye-Sensitized Solar Cells (DSCs) with N719 dye and an iodine electrolyte. The DSC of 0.25 cm(2) area using a CE of CZTS film annealed in a H2S environment under AM 1.5G illumination (100 mW cm(-2)) exhibited a short circuit current density (JSC) = 18.63 mA cm(-2), an open circuit voltage (VOC) = 0.65 V and a fill factor (FF) = 0.53, resulting in an overall power conversion efficiency (PCE) = 6.4%. While the DSC using as deposited CZTS film as a CE showed the PCE = 3.7% with JSC = 13.38 mA cm(-2), VOC = 0.57 V and FF = 0.48. Thus, the spray deposited CZTS films can play an important role as a CE in the large area DSC fabrication.

Upconverter Silicon Solar Cell Devices for Efficient Utilization of Sub-Band-Gap Photons Under Concentrated Solar Radiation

Upconversion (UC) of sub-band-gap photons has the potential to increase the efficiency of solar cells significantly. We realized an upconverter solar cell device, by attaching an upconverter layer of β-NaYF4 doped with 25% Er3+ embedded in the polymer perfluorocyclobutyl to the rear side of a bifacial silicon solar cell. We determined the external quantum efficiency of such upconverter solar cell devices under broad-band sub-band-gap excitation. Under consideration of spectral mismatch, we calculated the expected increase of the short-circuit current density due to UC under the air mass 1.5 global illumination. We determined an enhancement of 2.2 mA/cm2 for a spectral excitation band ranging from 1450 to 1600 nm and a comparatively low solar concentration of 78 suns. Subsequently, a system of concentrator lens and upconverter solar cell device was characterized with a solar simulator. We determined an increase of the short-circuit current density due to UC of sub-band-gap photons of 13.1 mA/cm2 under a concentration of 210 suns. This corresponds to a potential relative increase of the solar cell efficiency of 0.19%.

'Donor-free' oligo(3-hexylthiophene) dyes for efficient dye-sensitized solar cells

The common trend in designing dyes for use in DSSCs with iodide-based electrolyte is based on a donor–π spacer–acceptor (D–π–A) architecture. Here, we report two ‘donor-free’ cyanoacrylic end-functionalized oligo(3-hexylthiophene) dyes (5T and 6T). Despite having no donor group, both dyes show reversible first oxidation process. Both 5T and 6T have n-hexyl alkyl chains to retard aggregation at different positions as well as different numbers of thiophene moieties. However, the dyes showed similar absorption properties and redox potentials. The DSSCs based on these dyes give power conversion efficiencies of more than 7%, although a significant difference in the VOC and FF has been observed. Using electrochemical impedance spectroscopy, this is attributed to the presence of more trap states when 6T attaches to TiO2 and modifies the surface, mainly affecting the fill factor. Overall, these dyes introduce a new and effective design concept for liquid-electrolyte DSSC sensitisers.

Enhanced up-conversion for photovoltaics via concentrating integrated optics

Concentrating optics are integrated into up-conversion photovoltaic (UC-PV) devices to independently concentrate sub-band-gap photons on the up-conversion layer, without affecting the full solar concentration on the overlying solar cell. The UC-PV devices consist of silicon solar cells optimized for up-conversion, coupled with tapered and parabolic dielectric concentrators, and hexagonal sodium yttrium fluoride (β-NaYF₄) up-converter doped with 25% trivalent erbium (Er³⁺). A normalized external quantum efficiency of 1.75x10⁻² cm²/W and 3.38x10⁻² cm²/W was obtained for the UC-PV device utilizing tapered and parabolic concentrators respectively. Although low to moderate concentration was shown to maximize UC, higher concentration lead to saturation and reduced external quantum efficiency. The presented work highlights some of the implications associated with the development of UC-PV devices and designates a substantial step for integration in concentrating PV.

The influence of 1D, meso- and crystal structures on charge transport and recombination in solid-state dye-sensitized solar cells

We have prepared single crystalline SnO2 and ZnO nanowires and polycrystalline TiO2 nanotubes (1D networks) as well as nanoparticle-based films (3D networks) from the same materials to be used as photoanodes for solid-state dye-sensitized solar cells. In general, superior photovoltaic performance can be achieved from devices based on 3-dimensional networks, mostly due to their higher short circuit currents. To further characterize the fabricated devices, the electronic properties of the different networks were measured via the transient photocurrent and photovoltage decay techniques. Nanowire-based devices exhibit extremely high, light independent electron transport rates while recombination dynamics remain unchanged. This indicates, contrary to expectations, a decoupling of transport and recombination dynamics. For typical nanoparticle-based photoanodes, the devices are usually considered electron-limited due to the poor electron transport through nanocrystalline titania networks. In the case of the nanowire-based devices, the system becomes limited by the organic hole transporter used. In the case of polycrystalline TiO2 nanotube-based devices, we observe lower transport rates and higher recombination dynamics than their nanoparticle-based counterparts, suggesting that in order to improve the electron transport properties of solid-state dye-sensitized solar cells, single crystalline structures should be used. These findings should aid future design of photoanodes based on nanowires or porous semiconductors with extended crystallinity to be used in dye-sensitized solar cells.

Manipulating hybrid structures of polymer/ a-Si for thin film solar cells

A series of uniform polymer/amorphous silicon hybrid structures have been fabricated by means of solution-casting for polymer and radio frequency excited plasma enhanced chemical vapour deposition for amorphous silicon (a-Si:H). Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) functioned as a photoactive donor, while the silicon layer acted as an acceptor. It is found that matching the hole mobility of the polymer to the electron mobility of amorphous silicon is critical to improve the photovoltaic performance from hybrid cells. A three-layer p-i-n structure of ITO/PEDOT:PSS(200 nm)/i-Si(450 nm)/n-Si(200 nm)/Al with a power conversion efficiency of 4.78% under a standard test condition was achieved.

Measurement procedure for absolute broadband infrared up-conversion photoluminescent quantum yields: Correcting for absorption/re-emission

The internal photoluminescent quantum yield (iPLQY)--defined as the ratio of emitted photons to those absorbed--is an important parameter in the evaluation and application of luminescent materials. The iPLQY is rarely reported due to the complexities in the calibration of such a measurement. Herein, an experimental method is proposed to correct for re-emission, which leads to an underestimation of the absorption under broadband excitation. Although traditionally the iPLQY is measured using monochromatic sources for linear materials, this advancement is necessary for nonlinear materials with wavelength dependent iPLQY, such as the application of up-conversion to solar energy harvesting. The method requires an additional measurement of the emission line shape that overlaps with the excitation and absorption spectra. Through scaling of the emission spectrum, at the long wavelength edge where an overlap of excitation does not occur, it is possible to better estimate the value of iPLQY. The method has been evaluated for a range of nonlinear material concentrations and under various irradiances to analyze the necessity and boundary conditions that favor the proposed method. Use of this refined method is important for a reliable measurement of iPLQY under a broad illumination source such as the Sun.