Luminescent Down-shifting Layer Research Articles

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.

Luminescent boron carbon oxynitride phosphors: a cost-efficient strategy to boost solar cell spectral responsiveness

The incorporation of a Luminescent down-shifting (LDS) layer has emerged as a compelling approach for augmenting the light absorption sensitivity and power conversion efficiency of solar cells, particularly in the short-wavelength light spectrum. In this investigation, we propose the utilization of low-cost, environmentally benign Boron carbon oxynitride (BCNO) phosphors as a viable material for the enhancement of solar radiation absorption in the ultraviolet-blue range. We synthesized BCNO phosphors through a combustion method and conducted a comprehensive analysis of the structural and spectral attributes concerning the impact of temperature. The synthesized boron carbon oxynitride phosphors exhibit a hexagonal boron nitride structure, with an irregular shape and an average particle size of 2447.9 nm. The analysis of photoluminescence spectra reveals that BCNO phosphors effectively capture photons within the 300–500 nm wavelength range and subsequently re-emit them at longer wavelengths. This phenomenon aligns with the overarching goal of optimizing solar cell performance, as it is in the longer wavelength range that solar cells exhibit enhanced efficiency. These findings support the promising potential of BCNO phosphors as a compelling choice for deployment as an LDS layer material on the periphery of solar cells. By facilitating increased photon absorption in the short-wavelength region, BCNO phosphors have the capacity to significantly enhance device performance.

Polyvinyl Chloride-Based Luminescent Downshifting Film with High Flame Retardancy and Excellent UV Resistance for Silicon Solar Cells.

Solar power generation, as a clean energy source, has significant potential for development. This work reports the recent efforts to address the challenge of low power conversion efficiency in photovoltaic devices by proposing the fabrication of a luminescence downshifting layer using polyvinyl chloride (PVC) with added fluorescent dots to enhance light utilization. A photoluminescent microsphere (HCPAM) is synthesized by cross-linking hexachlorocyclotriphosphazene, 2-iminobenzimidazoline, and polyethyleneimine. Low addition of HCPAM can improve the fire safety of PVC films, raising the limiting oxygen index of PVC to 32.4% and reducing the total heat release and smoke production rate values by 14.5% and 42.9%, respectively. Additionally, modified PVC film remains a transparency of 88% and shows down-conversion light properties. When the PVC+1%HCPAM film is applied to the solar cell, the short-circuit current density increases from 42.3 to 43.8mAcm-2, resulting in a 7.0% enhancement in power conversion efficiency. HCPAM also effectively delays the photooxidative aging of PVC, particularly at a 3% content, maintaining the surface morphology and optical properties of PVC samples during ultraviolet aging. This study offers an innovative strategy to enhance the fire and UV-resistant performance of PVC films and expand their applications in protecting and efficiently utilizing photovoltaic devices.

Solar spectral management in space using lanthanide-based downshifting layers

Photovoltaic (PV) cells are still the most used energy generation devices for aerospace applications. Although multijunction solar cells represent the standard commercial technology for powering spacecraft, spacecraft companies are still using Si-based PV cells to decrease the cost of satellites at the expense of efficiency and energy generation losses. One of the limitations on solar energy conversion is the mismatch between the solar spectrum and the absorption of the PV technology in use. Thus, strategies to overcome this have been proposed, namely the use of luminescent downshifting layers (DSLs) which are very promising to shape the incident sunlight. In this sense, downshifting materials with absorption in the UV/blue spectral region have been privileged considering the solar spectrum in space environments (AM0 solar spectrum), in which the UV component is larger than that on Earth surface (AM1.5 solar spectrum). Here, we propose the use of Eu3+-doped di-ureasil organic-inorganic hybrid materials as DSLs to be used on large area Si-based PV cells (∼0.1 m2) for space applications. Electrical measurements on the PV cell, done before and after the deposition of the DSLs, confirm the positive effect of the coatings on the device performance, with a relative increase on the generated electrical power of ∼2.6 %. Here, we report, for the first time, a DSL specifically designed for space applications and with the largest active area reported so far.

Enhancing c-Si Solar Cell Efficiency in the UV Region: Photophysical Insights into the Use of Eu3+ Complexes for Down-Shifting Layer Applications

[Eu(3DPIQC)3] (where DPIQC = 3-(diphenyl phosphoryl)-1-isoquinolinecarboxylate), a luminescent europium complex with antenna ligands, has been carefully embedded within a polyvinyl butyral (PVB) matrix and the resulting material was used to prepare films used as luminescent down-shifting layers (LDSLs) for crystalline Si-based solar cells. The films were characterized using photoluminescence spectroscopy, atomic force spectroscopy (AFM), UV-Vis spectroscopy, and fluorescence microscopy. The AFM analysis shows films with low surface roughness, while fluorescence microscopy revealed that the Eu complex embedded in PVB assumed a spheroidal configuration, a morphology especially beneficial for optical applications. The so-obtained LDSLs were utilized as energy converters in c-Si solar cells to enhance the utilization of high-energy photons, thereby improving their overall efficiency. The determination of photovoltaic parameters carried out before and after the deposition of the LDSLs on the c-Si cells confirms a positive effect on the efficiency of the cell. The Jsc increases from 121.6 mA/cm2 to 124.9 mA/cm2, and the open circuit voltage (Voc) is found to be unrelated to the complex concentration in the films. The fill factor (FF) remains constant with the Eu concentration. The EQE curves indicate an enhancement in the performance of the photovoltaic cells within the UV region of the spectrum for all coated devices. Electrochemical impedance spectroscopy (EIS) was also carried out in order to analyze the effect of the Eu complex in the charge transfer process of the devices.

Improving efficiency of silicon solar cells by integrating SiO2-coated lead-free Cs3Bi2Br9 perovskites quantum dots as luminescence down-shifting layer

Lead-based perovskite quantum dots (QDs) have promising applications in optoelectronic devices, but commercial applications are limited by the potential toxicity and poor stability of lead. Meanwhile, there are lattice, polarity, and thermal expansion coefficient mismatches in integrating semiconductor materials onto the surface of photoelectronic circuit devices, resulting in high-density defects limiting the reliability of photoelectronic devices. Therefore, there is a need to investigate perovskite alternatives that are non-toxic, stable, and can be effectively coupled to silicon photonic circuits. In this paper, lead-free perovskite Cs3Bi2Br9/SiO2 QDs were synthesized. The emission wavelength falls within the 400–560 nm range, exhibiting vibrant blue photoluminescence and demonstrating exceptional air stability for a duration exceeding 60 days. Optical tests and density-functional theory (DFT) calculations show that the silica shell layer effectively binds the electron and hole wave functions, prevents photon-generated carriers from escaping, reduces surface defects, and improves the carrier recombination probability. Meanwhile, using Cs3Bi2Br9/SiO2 QDs as a luminescent down-shifting (LDS) layer in combination with a conventional silicon solar cell, the photovoltaic conversion power was increased by 1.82%. Hence, the core-shell structure is designed by the green environmental protection method to control the improvement of the PL characteristics of QDs, which opens a window for the synthesis of new barrier materials in ethanol and water systems, making the Cs3Bi2Br9/SiO2 QDs have great potential for the application of novel optoelectronic devices in the future.

AgIn5S8/ZnS Quantum Dots for Luminescent Down-Shifting and Antireflective Layer in Enhancing Photovoltaic Performance.

Colloidal AgIn5S8/ZnS quantum dots (QDs) have recently emerged as a promising, efficient, nontoxic, down-shifting material in optoelectronic devices. These QDs exhibit a high photoluminescent quantum yield and offer a range of potential applications, specifically in the field of photovoltaics (PVs) for light management. In this work, we report an eco-friendly method to synthesize AgIn5S8/ZnS QDs and deposit them on commercial silicon solar cells (with an active area of 7.5 cm2), with which the short-circuit current (JSC) enhanced by 1.44% and hence the power conversion efficiency by 2.51%. The enhancements in PV performance are mainly attributable to the improved external quantum efficiency in the ultraviolet region and reduced surface reflectance in the ultraviolet and near-infrared regions. We study the effect of QD concentration on the bifunctions of downshifting and antireflection. The optimal 15 mg/mL QDs blade-coated onto the Si solar cells realize maximum current generation as the reflectance loss in the visible wavelength is compensated by the minimized reflection in the near-infrared region.

Efficiency enhancement of solar cell by using methylammonium lead tribromide/polymethyl methacrylate hybrid film as luminescent down shifting layer

Luminescent down-shifting (LDS) layer was introduced to tackle the issue of poor short-wavelength response of solar cell. Besides LDS effect, coating a LDS layer on the surface of a solar cell leads to a change in surface reflectance. LDS and antireflection (AR) effect are coupled and usually reported as a single effect. For those solar cell with optimized AR, it is difficult to enhance power conversion efficiency (PCE) with the LDS layer due to the variation of reflectance. In this work, we report an obvious PCE enhancement of two mainstream commercial silicon (Si) solar cells with the optimized AR by using methylammonium lead tribromide (MAPbBr3)/polymethyl methacrylate (PMMA) hybrid film as a LDS layer. The used MAPbBr3/PMMA nanoplatelets solutions for LDS layer have an absolute photoluminescent quantum yield of ∼85 % (excited by 350 nm) in air atmosphere for more than 30 days, laying a foundation for the realization of effective LDS effect. Theoretical analysis has separated the AR and LDS effect. It has demonstrated that AR effect has a positive influence on LDS effect, and PMMA plays the key role in the improvement of AR. Experimental studies further elucidated the LDS and AR effect provided by MAPbBr3/PMMA hybrid film. Thanks to this combined effect, the application of MAPbBr3/PMMA hybrid film as a LDS layer on Si heterojunction solar cell yields a PCE gain of 0.3 % absolute and that on passivated emitter and rear cell produces an absolute PCE enhancement of about 0.7 %.

Cesium Copper Halide Perovskite Nanocrystal-Based Photon-Managing Devices for Enhanced Ultraviolet Photon Harvesting.

Space-based solar power harvesting systems with high levels of specific power (the power produced per mass of the mounted photovoltaic cell) are highly desired. In this study, we synthesized high quality lead-free Cs3Cu2Cl5 perovskite nanodisks with efficient ultraviolet (UV) photon absorption, high photoluminescence quantum yields, and a large Stokes shift, which are suitable to serve as photon energy downshifting emitters in the applications of photon-managing devices especially for space solar power harvesting. To demonstrate this possibility, we have fabricated two types of photon-managing devices, i.e., luminescent solar concentrators (LSCs) and luminescent downshifting (LDS) layers. Both experimental results and simulation analyses show that the fabricated LSC and LDS devices exhibit high visible light transmission, low photon scattering and reabsorption energy loss, high UV photon harvesting, and energy conversion after integrating with silicon-based photovoltaic cells. Our research presents a new avenue for utilizing lead-free perovskite nanomaterials in space applications.

Estimating the performance of solar cells with luminescent down-shifting layers

Technological developments for improving the performance of conventional solar cells have become a topic of great interest in recent years. For instance, solar concentrators, new anti-reflective coatings, and Luminescent Down-Shifting Layers (LDS), among different techniques have been used in the past. The latter is an attractive option because an LDS layer has the property of increasing the photon flux density in the appropriate wavelength range on top of a cell device with the possibility of increasing the photo-current density. Then, in this work we focus on the development of a theoretical model to determine the cell´s illumination current density, considering the modified solar spectrum, and taking in account the modified spectral reflectance and transmittance at the upper layers when an optimized LDS layer is inserted on a solar cell. The correct selection of such a layer for a specific solar cell would increase its performance due to the enhanced photon density in the absorption region for which the solar cell has the highest quantum efficiency. As an example, it is shown that a Lu3Al5O12:Ce3+ layer on top of a CdTe solar cell might cause an efficiency increase of around 21%.

Synthesis, photophysical and electrochemical properties of π-conjugated pyrene based down-shifting molecules with fluorinated aryl groups

Pyrene molecule, with excellent photophysical properties (strong absorption cross section, excellent emission properties and a long-excited state lifetime), excellent thermal and photochemical stability, has been widely used as a building block for the synthesis of pyrene-based fluorophores for optoelectronic applications. In this work, we report the synthesis of two series of pyrene–π–A compounds, series I (3–6) and II (10–13), in which nitro, cyano, cyanoacrylonitrile and cyanoacrylic acid as electron acceptor groups are connected to the pyrene core via aryl or fluoroaryl π-conjugating bridges. The incorporation of fluorine atom on the π-extension bridge cause a slightly red-shift at emission wavelength (λem) in solution and polymethylmethacrylate (PMMA) films and increase the Stokes shift due to greater stabilization of molecular orbitals in the excited state, especially for series I. Solvatochromic measurements and theoretical computational studies suggest a higher intramolecular charge transfer in the excited state for series II when compared to series I due to their stronger electron acceptor moieties. All pyrene derivatives are stable and exhibited initial mass loss at temperature above 200 °C. The good photophysical and thermal properties of the synthesized pyrene derivatives, associated with high molar absorption coefficients in the UV spectrum and good fluorescence emission in the range of 430–480 nm (series I) and 505–567 nm (series II) in PMMA films, make them possible candidates for organic light-emitting diode (OLED) and luminescent down-shifting (LDS) layers for stable perovskite solar cells, respectively.

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.

Influence of synthesis parameters of N-doped graphene quantum dots and polymer composite layer on the performance of CIGS solar cells

In this work, N-doped graphene quantum dots (N-GQDs) are used as luminescent downshifting layers, which enhanced the performance of the CIGS solar cells. For providing mechanical strength and chemical stability, a poly(methyl methacrylate) (PMMA) polymer-based matrix is used. However, the PMMA layer creates photoluminescence (PL) quenching, so N-GQDs/PMMA layer is annealed at various temperatures (20–80 °C) to obtain the best performance. These layers were applied on the top of the CIGS solar cells and the performance of the cell is evaluated. The best value of η is obtained for 60 °C. The Jsc and η values are enhanced to 36.03 mA/cm2 and 16.13% from 34.05 mA/cm2 and 14.70%, respectively. Furthermore, the PV cell parameters (photogenerated current density (Jph), shunt resistance (Rsh), series resistance (Rs), diode ideality factor (n), and reverse saturation current density (J0)) were also determined and analyzed to investigate the reduction in losses in the cell.

Vertically-aligned p-n junction Si solar cells with CdTe/CdS luminescent solar convertors

In this work, flat solar cells with vertically aligned p-n junctions are designed. Luminescent down-shifting layers are used for enhancement of the solar cells’ efficiency. The solar cells are fabricated with the architecture of double aligned p-n junctions and contain additional coatings with CdTe/CdS luminescent nanocrystals. Current-voltage characteristics of the solar cells are measured using a solar simulator with a pulsed halogen light source. The influence of the average diameter of the CdTe/CdS nanocrystals in the series of 2.8, 3.6 and 4 nm and related to its emission at the wavelengths of 548, 609, and 642 nm, respectively, on the solar cells’ efficiency is studied and discussed. A flat solar cell with vertically aligned p-n junctions containing luminescent down-shifting layers of the nanocrystals that are 4.0 nm in diameter demonstrates a power conversion efficiency of 9% on an area of 1cm2.

Intrinsic luminescence-downshifting effects of Zn-based Mn-doped nanoparticle layers on Si solar cells

Luminescence downshifting (LDS) effects of Zn-based Mn-doped nanoparticles (NPs) on characteristics of Si solar cells are investigated. ZnSe:Mn/ZnS core-doped core/shell NPs and ZnSe/ZnS:Mn/ZnS shell-doped core/shell/shell NPs are deposited on glass plates using layer-by-layer method. It is found that shell-doped NPs are superior as LDS materials by measuring their optical properties. We deposit LDS layers made of shell-doped NPs on Si cells and measure their internal quantum efficiencies (IQEs) to examine LDS effects separately from the effects of reflection on LDS layers. We find that IQEs for 300–400 nm are more enhanced for cells with thicker LDS layers. IQE at 350 nm is calculated for Si cells with LDS layers coated using an analytical model for the transmittance of downshifted photons into Si cells. IQEs for the respective cells are in qualitative agreement with the measurements.

Recent Advances in Colloidal Quantum Dots or Perovskite Quantum Dots as a Luminescent Downshifting Layer Embedded on Solar Cells.

The solar cell has a poor spectral response in the UV region, which affects its power conversion efficiency (PCE). The utilization of a luminescent downshifting (LDS) layer has been suggested to improve the spectral response of the photovoltaics in the short wavelength region through photoluminescence (PL) conversion and antireflection effects, which then enhance the PCE of the solar cell. Recently, colloidal quantum dots (CQDs) or perovskite quantum dots (PQDs) have been gaining prime importance as an LDS material due to their eminent optical characteristics, such as their wide absorption band, adjustable visible emission, short PL lifetime, and near-unity quantum yields. However, the instability of QDs that occurs under certain air, heat, and moisture conditions limits its commercialization. Thus, in this review, we will focus on the physical and optical characteristics of QDs. Further, we will discuss different synthesis approaches and the stability issues of QDs. Different approaches to improve the stability of QDs will be discussed in detail alongside the recent breakthroughs in QD-based solar cells for various applications and their current challenges. We expect that this review will provide an effective gateway for researchers to fabricate LDS-layer-based solar cells.

Feasibility of Emission-Enhanced CsPbCl3 Quantum Dots Co-Doped with Mn2+ and Er3+ as Luminescent Downshifting Layers in Crystalline Silicon Solar Modules

In order to enhance the photoelectric conversion efficiencies of crystalline silicon (c-Si) solar cells, CsPbCl3 quantum dots (QDs) codoped with Mn2+ and Er3+ (CsPbCl3:Mn2+, Er3+ QDs) were mixed with ethylene–(vinyl acetate) (EVA) to form a film which was used as a luminescent down-shifting (LDS) layer. The LDS layer effectively improved the low utilization of near-ultraviolet light of c-Si solar cells. These CsPbCl3:Mn2+,Er3+ QDs were synthesized via a conventional high-temperature injection method. Mn2+ is the luminescence center, and the incorporation of Er3+ greatly enhances the luminescence intensity of Mn2+. The absolute photoluminescence quantum yield of the QDs dispersed in toluene reached 79.5% when the QDs were synthesized under the optimum conditions, that is, an injection temperature of 180 °C and Pb:Mn:Er preparation molar ratios of 6:4:4. The EVA film embedded with QDs at the optimum concentration (0.9 wt %) was used as an LDS layer for c-Si solar module. The short-circuit current (ISC) and the photoelectric conversion efficiency (η) were increased by 3.42% and 4.02%, respectively, owing to the LDS layer. Moreover, a luminescent solar concentrator (LSC) which was another application of luminescent materials was also demonstrated. For LSC, the relative changes in ISC and η by using the QDs-dispersed EVA film were +14.9% and +18.0%, respectively. These results indicate a feasible application of luminescent downshifting films in solar modules.

Characterization of Luminescent Down-Shifting Spectral Conversion Effects on Silicon Solar Cells with Various Combinations of Eu-Doped Phosphors.

Luminescent down-shifting (LDS) spectral conversion is a feasible approach to enhancing the short-wavelength response of single junction solar cells. This paper presents the optical and electrical characteristics of LDS spectral conversion layers containing a single species or two species of Eu-doped phosphors applied to the front surface of silicon solar cells via spin-on coating. The chemical composition, surface morphology, and fluorescence emission of the LDS layers were respectively characterized using energy-dispersive X-ray analysis, optical imaging, and photoluminescence measurements. We also examined the LDS effects of various phosphors on silicon solar cells in terms of optical reflectance and external quantum efficiency. Finally, we examined the LDS effects of the phosphors on photovoltaic performance by measuring photovoltaic current density–voltage characteristics using an air-mass 1.5 global solar simulator. Compared to the control cell, the application of a single phosphor enhanced efficiency by 17.39% (from 11.14% to 13.07%), whereas the application of two different phosphors enhanced efficiency by 31.63% (from 11.14% to 14.66%).

Bandgap-tuned fluorescent CuGaS2/ZnS core/shell quantum dots for photovoltaic applications

CuGaS2/ZnS quantum dots were investigated for a luminescent downshifting layer and luminescent solar concentrator with a single-crystalline silicon solar module.

Solar spectral management with electrochromic devices including PMMA films doped with biluminescent ionosilicas

The technological potential of poly(methyl methacrylate) (PMMA)-based composite films doped with lanthanide-doped sol–gel derived ionosilicas (IS-Ln) previously proposed for luminescent down-shifting (LDS) and luminescent solar concentrator (LSC) layers connected to photovoltaic (PV) cells is extended here to electrochromic devices (ECDs), targeting the fabrication of single energy harvesting/conversion/management LSC-LDS/PV/ECD systems. These integrated devices have foreseen application in the windows of future zero-energy buildings of smart cities. The proof-of-concept is given with the report of the electro-optical performance of an ECD comprising an optimized electrolyte film composed of PMMA, IS-Nd, and IS-Eu, and the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid. This amorphous electrolyte is stable below 160 °C, exhibits high ionic conductivity (2.13 × 10−4 and 8.76 × 10−4 S cm−1 at room temperature and 44 °C, respectively), and emits in the visible (red color) and near-infrared (NIR) spectral regions. The device demonstrated fast switching speed (50 s) and high transparency in the visible-to-NIR spectral regions (transmittance (T) = 79/96/89/77% at 555/1000/1500/1650 nm in the as-prepared state, respectively). Upon application of ±2.5 V for 200 cycles, at the same wavelengths, the Tbleached/Tcolored values were 44/28, 46/26, 39/20, and 27/9%, respectively, and the coloration efficiency (CE) values CEin/CEout values were −302/+181, −381/+228, −446/+267 and −734/+440 cm2 C−1, respectively.