Understanding the Potential of Light Absorption in Dots-in-Host Semiconductors.

The outstanding physical properties of dots-in-host (QD@Host) hetero semiconductors demand detailed methods to fundamentally understand the best routes to optimize their potentialities for different applications. In this work, a 4-band k.p-based method was developed for rock-salt quantum dots (QDs) that describes the complete optical properties of arbitrary QD@Host systems, trailblazing the way for the full optoelectronic analysis of quantum-structured solar cells. Starting with the determination of the QD bandgap and validation against well-established literature results, the electron transition rate is then computed and analyzed against the main system parameters. This is followed by a multiparameter optimization, considering intermediate band solar cells as a promising application, where the best QD configuration was determined, together with the corresponding QD@Host absorption spectrum, in view of attaining the theoretical maximum efficiency (∼50%) of this photovoltaic technology. The results show the creation of pronounced sub-bandgap absorption due to the electronic transitions from/to the quantum-confined states, which enables a much broader exploitation of the sunlight spectrum.

Photonic-Enhanced Perovskite Solar Cells: Tailoring Color and Light Capture.

The current exponential growth of solar electricity technologies toward consumer-oriented applications, as in building- or vehicle-integrated photovoltaics (B/VIPV), is calling for improved solar cells, not only in cost-effectiveness, but also with better adaptability and aesthetics. Here, using perovskite solar cells (PSCs) as test bed, we demonstrate an unprecedented photonic method to generate any color on a cell layout, while also increasing PV efficiency. To this end, photonic surface features were designed for PSCs, which filled the dual purpose of light-trapping (LT) and modulation of reflected light interference. A variety of geometries, from simple gratings to complex semispheroids, were optically optimized for two of the most challenging colors, magenta and green, while assuring the generation of their maximum feasible photocurrent. The best results corresponded to a current density of 22.07 mA/cm2, obtained for the magenta solar cell with top domes, exhibiting an increase of 6.68%, relative to an optimized planar reference cell. In turn, the same type of geometry was able to generate the leading green cell, with up to 21.40 mA/cm2 (a relative increase of 3.44%). Additionally, the uniformity of the optical output of the optimal solar cells was tested under a range of incident light angles, between 0◦ and 60◦, where the current density suffered relative losses only down to 6.65%.

Photon shifting and trapping in perovskite solar cells for improved efficiency and stability.

Advanced light management techniques can enhance the sunlight absorption of perovskite solar cells (PSCs). When located at the front, they may act as a UV barrier, which is paramount for protecting the perovskite layer against UV-enabled degradation. Although it was recently shown that photonic structures such as Escher-like patterns could approach the theoretical Lambertian-limit of light trapping, it remains challenging to also implement UV protection properties for these diffractive structures while maintaining broadband absorption gains. Here, we propose a checkerboard (CB) tile pattern with designated UV photon conversion capability. Through a combined optical and electrical modeling approach, this photonic structure can increase photocurrent and power conversion efficiency in ultrathin PSCs by 25.9% and 28.2%, respectively. We further introduce a luminescent down-shifting encapsulant that converts the UV irradiation into Visible photons matching the solar cell absorption spectrum. To this end, experimentally obtained absorption and emission profiles of state-of-the-art down-shifting materials (i.e., lanthanide-based organic-inorganic hybrids) are used to predict potential gains from harnessing the UV energy. We demonstrate that at least 94% of the impinging UV radiation can be effectively converted into the Visible spectral range. Photonic protection from high-energy photons contributes to the market deployment of perovskite solar cell technology, and may become crucial for Space applications under AM0 illumination. By combining light trapping with luminescent downshifting layers, this work unravels a potential photonic solution to overcome UV degradation in PSCs while circumventing optical losses in ultrathin cells, thus improving both performance and stability.

Surface modification of halide perovskite using EDTA-complexed SnO2 as electron transport layer in high performance solar cells.

The long-term performance of metal halide perovskite solar cells (PSCs) can be significantly improved by tuning the surface characteristics of the perovskite layers. Herein, low-temperature-processed ethylenediaminetetraacetic acid (EDTA)-complexed SnO2 (E-SnO2) is successfully employed as an electron transport layer (ETL) in PSCs, enhancing the efficiency and stability of the devices. The effects of EDTA treatment on SnO2 are investigated for different concentrations: comparing the solar cells' response with 15%-2.5% SnO2 and E-SnO2 based ETLs, and it was found that 7.5% E-SnO2 provided the best results. The improved surface properties of the perovskite layer on E-SnO2 are attributed to the presence of small amount of PbI2 which contributes to passivate the defects at the grain boundaries and films' surface. However, for the excess PbI2 based devices, photocurrent dropped, which could be attributed to the generation of shallow traps due to excess PbI2. The better alignment between the Fermi level of E-SnO2 and the conduction band of perovskite is another favorable aspect that enables increased open-circuit potential (VOC), from 0.82 V to 1.015 V, yielding a stabilized power conversion efficiency of 15.51%. This complex ETL strategy presented here demonstrates the enormous potential of E-SnO2 as selective contact to enhance the perovskite layer properties and thereby allow stable and high-efficiency PSCs.

Solar fuels design: Porous cathodes modeling for electrochemical carbon dioxide reduction in aqueous electrolytes.

The reduction of carbon dioxide emissions is crucial to reduce the atmospheric greenhouse effect, fighting climate change and global warming. Electrochemical CO2 reduction is one of the most promising carbon capture and utilization technologies, that can be powered by solar energy and used to make added-value chemicals and green fuels, providing grid-stability, energy security, and environmental benefits. A two-dimensional finite-elements model for porous electrodes was developed and validated against experimental data, allowing the design and performance improvement of a porous zinc cathode morphology and its operational conditions for an electrolyzer producing syngas via the co-electrolysis of CO2 and water. Porosity, pore length, fiber geometric shape, inlet pressure, system temperature, and catholyte flow rate were explored, and these parameters were thoroughly tuned by using the smart-search Nelder-Mead's multi-parameter optimization algorithm to achieve pronouncedly higher, industrial-relevant current density values than those previously reported, up to 263.6 mA/cm2 at an applied potential of -1.1 V vs. RHE.

MXene-Enhanced Nanoscale Photoconduction in Perovskite Solar Cells Revealed by Conductive Atomic Force Microscopy.

The use of MXene materials in perovskite solar cells (PSCs) has received significant interest due to their distinct features that result from the termination of functional groups and the oxidation of MXene. Herein, we have used photoconductive atomic force microscopy (pcAFM) to map the local (nanoscale) photovoltaic performances of the Ti3C2Tx MXene nanosheet-integrated TiO2 (MXene@TiO2) electron transport layer-based PSCs to determine the influence of the treatment on the microscopic charge flow inside the devices. At different applied voltages, the morphology and current have been simultaneously measured with nanoscale resolution from the top surfaces of the solar cells without back contacts. The PSCs based on MXene@TiO2 exhibit more enhanced current flow across the grains than the only TiO2-based PSCs. At zero applied bias, the average local photocurrent for MXene-integrated PSCs is several times higher than the reference PSCs and decreases gradually when the positive bias is increased until the open circuit voltage. Considerable differences were also observed in the short circuit current among different locations that appear identical in AFM topography. Our findings reveal the potential of MXene-integrated ETLs to enhance the nanoscale photoconduction and inherent characteristics of the active layers, thereby improving the performance of the polycrystalline photovoltaic devices.

Parylene-Sealed Perovskite Nanocrystals Down-Shifting Layer for Luminescent Spectral Matching in Thin Film Photovoltaics.

The present contribution aims to enhance solar cells' performance via the development of advanced luminescent down-shifting based on encapsulated nanostructured perovskite materials. Here, thin films of inorganic lead halide (CsPbBr3) perovskite nanocrystal luminophores were synthetized, by hot-injection, deposited on glass substrates by spin-coating, and encapsulated with parylene type C, via chemical vapor deposition, to protect and stabilize the films. The optical properties of these thin films were characterized by absorption, emission and 2D contour spectra, their structure by X-ray diffraction and X-ray photoelectron spectroscopy, and the morphology by Scanning Transmission Electron microscopy. I-V curve and spectral response nanocrystalline silicon photovoltaic (nc-Si:H PV) cells were studied in the absence and presence of the perovskite and parylene luminescent down-shifting layers. The incorporation of the CsPbBr3 nanocrystals and their encapsulation with the parylene type C polymeric coating led to an increase in the current generated and the spectral response of the PV cells in the regime of the nanocrystals' fluorescence emission. A 3.1% increase in the short circuit current density and a 5.6% increase in the power conversion efficiency were observed.

Copper-Arsenic-Sulfide Thin-Films from Local Raw Materials Deposited via RF Co-Sputtering for Photovoltaics.

The inexorable increase of energy demand and the efficiency bottleneck of monocrystalline silicon solar cell technology is promoting the research and development of alternative photovoltaic materials. Copper-arsenic-sulfide (CAS) compounds are still rather unexplored in the literature, yet they have been regarded as promising candidates for use as p-type absorber in solar cells, owing to their broad raw material availability, suitable bandgap and high absorption coefficient. Here, a comprehensive study is presented on the structural and optoelectronic properties of CAS thin-films deposited via radio-frequency magnetron co-sputtering, using a commercial Cu target together with a Cu-As-S target with material obtained from local resources, specifically from mines in the Portuguese region of the Iberian Pyrite Belt. Raman and X-ray diffraction analysis confirm that the use of two targets results in films with pronounced stoichiometry gradients, suggesting a transition from amorphous CAS compounds to crystalline djurleite (Cu31S16), with the increasing proximity to the Cu target. Resistivity values from 4.7 mΩ·cm to 17.4 Ω·cm are obtained, being the lowest resistive films, those with pronounced sub-bandgap free-carrier absorption. The bandgap values range from 2.20 to 2.65 eV, indicating promising application as wide-bandgap semiconductors in third-generation (e.g., multi-junction) photovoltaic devices.

Colloidal Lithography for Photovoltaics: An Attractive Route for Light Management.

The pursuit of ever-more efficient, reliable, and affordable solar cells has pushed the development of nano/micro-technological solutions capable of boosting photovoltaic (PV) performance without significantly increasing costs. One of the most relevant solutions is based on light management via photonic wavelength-sized structures, as these enable pronounced efficiency improvements by reducing reflection and by trapping the light inside the devices. Furthermore, optimized microstructured coatings allow self-cleaning functionality via effective water repulsion, which reduces the accumulation of dust and particles that cause shading. Nevertheless, when it comes to market deployment, nano/micro-patterning strategies can only find application in the PV industry if their integration does not require high additional costs or delays in high-throughput solar cell manufacturing. As such, colloidal lithography (CL) is considered the preferential structuring method for PV, as it is an inexpensive and highly scalable soft-patterning technique allowing nanoscopic precision over indefinitely large areas. Tuning specific parameters, such as the size of colloids, shape, monodispersity, and final arrangement, CL enables the production of various templates/masks for different purposes and applications. This review intends to compile several recent high-profile works on this subject and how they can influence the future of solar electricity.

Optimal-Enhanced Solar Cell Ultra-thinning with Broadband Nanophotonic Light Capture.

Recent trends in photovoltaics demand ever-thin solar cells to allow deployment in consumer-oriented products requiring low-cost and mechanically flexible devices. For this, nanophotonic elements in the wave-optics regime are highly promising, as they capture and trap light in the cells' absorber, enabling its thickness reduction while improving its efficiency. Here, novel wavelength-sized photonic structures were computationally optimized toward maximum broadband light absorption. Thin-film silicon cells were the test bed to determine the best performing parameters and study their optical effects. Pronounced photocurrent enhancements, up to 37%, 27%, and 48%, respectively, in ultra-thin (100- and 300-nm-thick) amorphous, and thin (1.5-?m) crystalline silicon cells are demonstrated with honeycomb arrays of semi-spheroidal dome or void-like elements patterned on the cells' front. Also importantly, key advantages in the electrical performance are anticipated, since the photonic nano/micro-nanostructures do not increase the cell roughness, therefore not contributing to recombination, which is a crucial drawback in state-of-the-art light-trapping approaches.

Experimental quantification of useful and parasitic absorption of light in plasmon-enhanced thin silicon films for solar cells application.

A combination of photocurrent and photothermal spectroscopic techniques is applied to experimentally quantify the useful and parasitic absorption of light in thin hydrogenated microcrystalline silicon (µc-Si:H) films incorporating optimized metal nanoparticle arrays, located at the rear surface, for improved light trapping via resonant plasmonic scattering. The photothermal technique accounts for the total absorptance and the photocurrent signal accounts only for the photons absorbed in the µc-Si:H layer (useful absorptance); therefore, the method allows for independent quantification of the useful and parasitic absorptance of the plasmonic (or any other) light trapping structure. We demonstrate that with a 0.9 µm thick absorber layer the optical losses related to the plasmonic light trapping in the whole structure are insignificant below 730 nm, above which they increase rapidly with increasing illumination wavelength. An average useful absorption of 43% and an average parasitic absorption of 19% over 400-1100 nm wavelength range is measured for µc-Si:H films deposited on optimized self-assembled Ag nanoparticles coupled with a flat mirror (plasmonic back reflector). For this sample, we demonstrate a significant broadband enhancement of the useful absorption resulting in the achievement of 91% of the maximum theoretical Lambertian limit of absorption.

Broadband light trapping in thin film solar cells with self-organized plasmonic nano-colloids.

The intense light scattered from metal nanoparticles sustaining surface plasmons makes them attractive for light trapping in photovoltaic applications. However, a strong resonant response from nanoparticle ensembles can only be obtained if the particles have monodisperse physical properties. Presently, the chemical synthesis of colloidal nanoparticles is the method that produces the highest monodispersion in geometry and material quality, with the added benefits of being low-temperature, low-cost, easily scalable and of allowing control of the surface coverage of the deposited particles. In this paper, novel plasmonic back-reflector structures were developed using spherical gold colloids with appropriate dimensions for pronounced far-field scattering. The plasmonic back reflectors are incorporated in the rear contact of thin film n-i-p nanocrystalline silicon solar cells to boost their photocurrent generation via optical path length enhancement inside the silicon layer. The quantum efficiency spectra of the devices revealed a remarkable broadband enhancement, resulting from both light scattering from the metal nanoparticles and improved light incoupling caused by the hemispherical corrugations at the cells' front surface formed from the deposition of material over the spherically shaped colloids.

Highly efficient nanoplasmonic SERS on cardboard packaging substrates.

This work reports on highly efficient surface enhanced Raman spectroscopy (SERS) constructed on low-cost, fully recyclable and highly reproducible cardboard plates, which are commonly used as disposable packaging material. The active optical component is based on plasmonic silver nanoparticle structures separated from the metal surface of the cardboard by a nanoscale dielectric gap. The SERS response of the silver (Ag) nanoparticles of various shapes and sizes were systematically investigated, and a Raman enhancement factor higher than 106 for rhodamine 6G detection was achieved. The spectral matching of the plasmonic resonance for maximum Raman enhancement with the optimal local electric field enhancement produced by 60 nm-sized Ag NPs predicted by the electromagnetic simulations reinforces the outstanding results achieved. Furthermore, the nanoplasmonic SERS substrate exhibited high reproducibility and stability. The SERS signals showed that the intensity variation was less than 5%, and the SERS performance could be maintained for up to at least 6 months.

Broadband photocurrent enhancement in a-Si:H solar cells with plasmonic back reflectors.

Plasmonic light trapping in thin film silicon solar cells is a promising route to achieve high efficiency with reduced volumes of semiconductor material. In this paper, we study the enhancement in the opto-electronic performance of thin a-Si:H solar cells due to the light scattering effects of plasmonic back reflectors (PBRs), composed of self-assembled silver nanoparticles (NPs), incorporated on the cells' rear contact. The optical properties of the PBRs are investigated according to the morphology of the NPs, which can be tuned by the fabrication parameters. By analyzing sets of solar cells built on distinct PBRs we show that the photocurrent enhancement achieved in the a-Si:H light trapping window (600 - 800 nm) stays in linear relation with the PBRs diffuse reflection. The best-performing PBRs allow a pronounced broadband photocurrent enhancement in the cells which is attributed not only to the plasmon-assisted light scattering from the NPs but also to the front surface texture originated from the conformal growth of the cell material over the particles. As a result, remarkably high values of J(sc) and V(oc) are achieved in comparison to those previously reported in the literature for the same type of devices.

Colloidal plasmonic back reflectors for light trapping in solar cells.

A novel type of plasmonic light trapping structure is presented in this paper, composed of metal nanoparticles synthesized in colloidal solution and self-assembled in uniform long-range arrays using a wet-coating method. The high monodispersion in size and spherical shape of the gold colloids used in this work allows a precise match between their measured optical properties and electromagnetic simulations performed with Mie theory, and enables the full exploitation of their collective resonant plasmonic behavior for light-scattering applications. The colloidal arrays are integrated in plasmonic back reflector (PBR) structures aimed for light trapping in thin film solar cells. The PBRs exhibit high diffuse reflectance (up to 75%) in the red and near-infrared spectrum, which can pronouncedly enhance the near-bandgap photocurrent generated by the cells. Furthermore, the colloidal PBRs are fabricated by low-temperature (<120 °C) processes that allow their implementation, as a final step of the cell construction, in typical commercial thin film devices generally fabricated in a superstrate configuration.

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.

Self-assembled silver nanoparticles for plasmon-enhanced solar cell back reflectors: correlation between structural and optical properties.

The spectra of localized surface plasmon resonances (LSPRs) in self-assembled silver nanoparticles (NPs), prepared by solid-state dewetting of thin films, are discussed in terms of their structural properties. We summarize the dependences of size and shape of NPs on the fabrication conditions with a proposed structural-phase diagram. It was found that the surface coverage distribution and the mean surface coverage (SC) size were the most appropriate statistical parameters to describe the correlation between the morphology and the optical properties of the nanostructures. The results are interpreted with theoretical predictions based on Mie theory. The broadband scattering efficiency of LSPRs in the nanostructures is discussed towards application as plasmon-enhanced back reflectors in thin-film solar cells.

Light concentration in the near-field of dielectric spheroidal particles with mesoscopic sizes.

This paper presents a numerical study of the light focusing properties of dielectric spheroids with sizes comparable to the illuminating wavelength. An analytical separation-of-variables method is used to determine the electric field distribution inside and in the near-field outside the particles. An optimization algorithm was implemented in the method to determine the particles' physical parameters that maximize the forward scattered light in the near-field region. It is found that such scatterers can exhibit pronounced electric intensity enhancement (above 100 times the incident intensity) in their close vicinity, or along wide focal regions extending to 10 times the wavelength. The results reveal the potential of wavelength-sized spheroids to manipulate light beyond the limitations of macroscopic geometrical optics. This can be of interest for several applications, such as light management in photovoltaics.

Brownian dynamics simulations of single-wall carbon nanotube separation by type using dielectrophoresis.

We theoretically investigate the separation of individualized metallic and semiconducting single-wall carbon nanotubes (SWNTs) in a dielectrophoretic (DEP) flow device. The SWNT motion is simulated by a Brownian dynamics (BD) algorithm, which includes the translational and rotational effects of hydrodynamic, Brownian, dielectrophoretic, and electrophoretic forces. The device geometry is chosen to be a coaxial cylinder because it yields effective flow throughput, the DEP and flow fields are orthogonal to each other, and all the fields can be described analytically everywhere. We construct a flow-DEP phase map showing different regimes, depending on the relative magnitudes of the forces in play. The BD code is combined with an optimization algorithm that searches for the conditions that maximize the separation performance. The optimization results show that a 99% sorting performance can be achieved with typical SWNT parameters by operating in a region of the phase map where the metallic SWNTs completely orient with the field, whereas the semiconducting SWNTs partially flow-align.