Efficiency Of Nonradiative Energy Transfer Research Articles

Paper-Thin Al-Catalyzed Si Nanowire Solar Cells and Efficiency Enhancement by Hybrid Nanostructures with Mn-Doped Perovskite Nanocrystals

The use of thin silicon (Si) wafers and streamlined fabrication methods that can be scaled up without compromising device efficiency is a key strategy for realizing low-cost and flexible solar cells. Herein, aluminum (Al)-catalyzed Si nanowires (NWs) formed by vapor–liquid–solid growth on paper-thin polished and etched Si(111) wafers of 100 and 60 μm thickness with high proficiency for minimizing interfacial defects and light absorption loss have been accomplished. Successfully addressing the major challenge of rapid Al catalyst oxidation by ex situ and uncomplicated growth conditions allows for the potential to scale up the process while preventing the formation of deep-level traps resulting from catalyst contamination. The Si NWs formed on the nanowave surface of a thin etched Si wafer evidence comparable light absorbance and low interfacial defects to those grown on thin polished and traditional Si wafers. Fabrication of thin Si NW solar cells with a homojunction p+–p–n–n+ structure toward the enhanced power conversion efficiency (PCE) by hybrid nanostructures with manganese-doped cesium lead chloride (CsPb0.81Mn0.19Cl3) perovskite nanocrystals (NCs) using a simple drop-casting method has been explicitly explained. The precise tuning of the energy band and NC size enabled a significant radiative energy transfer by matching the light absorption range of NCs with a high Stokes shift in the luminescence spectrum and the spectral response range of underlying Si solar cells. The nonradiative energy transfer efficiency of NCs and an NC amount infiltration on homojunction Si NW solar cells for maximizing PCE enhancement were examined. The effective photon-harvesting architectures of NWs and NCs together with efficient energy transfers and surface passivation from NCs to the underlying homojunction Si NW solar cells could capably enhance PCE up to a 9% level. These results exhibited the potential for feasible low-cost and large-scale fabrication techniques with lower consumption of raw materials for future photovoltaic applications.

Gadolinium oxide single crystals: Optical properties and radiation resistance

Large-size high optical quality Gd2O3 single crystals were grown from solution at T = 1145 °C by Czochralski method. XRD analysis showed that the crystal structure is characterized by a single cubic phase (С-phase). Absorption spectra and luminescence properties of Gd2O3 doped with impurity Tb3+ ion were studied. The absorption spectrum is determined by electronic transitions in Gd3+ ion (spectral region of 245–315 nm) and interband electron transitions below 240 nm. Intraconfigurational radiative f-f transitions from 5D4 level in Tb3+ ion are clearly manifested upon both UV- and X-ray excitation. At the same time, 6PJ → 8S7/2 radiative transitions in Gd3+ ions are completely absent. This fact indicates high efficiency of nonradiative energy transfer from Gd3+ to Tb3+ ions. Thermo-luminescent spectroscopy shows the absence of charge carrier trapping centers, which proves the perfection of its crystal structure. The crystal under study shows high radiation resistance to high-energy (E = 10 MeV, D = 105 kGy) electron beam. However, the effects of irradiation appear only in the photoluminescence excitation spectra and thermally stimulated luminescence.

High-efficiency plasmonic luminescent solar concentrators based on thiol-ene polymer

Advances in solar energy harvesting technology require innovative approaches to meet the growing energy demand. In this work, we exploit the plasmonic interaction of metal nanoparticles with fluorophores to improve the optical performance of luminescent solar concentrators (LSCs). The plasmonic luminescent solar concentrators (PLSCs) with dimensions of 5 cm × 5 cm × 0.5 cm containing CsPbBr3 quantum dots (QDs) and gold nanoparticles (Au NPs) are fabricated, characterized, and evaluated systematically. As the Au NPs concentration increases, the optical performance of PLSCs exhibits, first enhancement, and then diminishment. When the Au NPs concentration is 2 × 10−4 wt%, the optimal external quantum efficiency, optical conversion efficiency, and power conversion efficiency of the PLSC reach 1.58%, 2.90%, and 0.437%, respectively. At higher concentrations of Au NPs, the non-radiative energy transfer from the CsPbBr3 QDs to the Au NPs leads to a decrease of the emission, which can be confirmed by the decreasing lifetime of the QDs. The overall optical performance of PLSCs depends on two competing effects, excitation rate and non-radiative energy transfer efficiency. Furthermore, the PLSC demonstrate the good aesthetic quality as an excellent substitute for commercial glass. We anticipate that the high optical conversion efficiency of PLSCs based on thiol-ene polymer would shed light on future application in LSCs.

Novel Design of 0D Nanoparticles-2D Transition-Metal Dichalcogenides Heterostructured Devices for High-Performance Optical and Gas-Sensing Applications

Two-dimensional Transition metal dichalcogenides (TMDCs), have now attracted much attention due to their unique layered structure and physical properties. Up to date, several studies have demonstrated monolayered and few-layered TMDC-based photodetectors with good stability, photo-switching time and broadband detectivity from UV to infrared light region. However, the reported responsivity is not as high as the theoretical expectation, indicating that the light absorption is limited by the atomic thickness of 2D-TMDCs and could still be improved. To overcome the drawback of low absorption in 2D TMDC materials, previous reports have revealed several strategies to enhance the electric field and light-harvesting in these atomically thin TMDC layers by hybridizing plasmonic noble-metal nanoparticles, such as Pt, Au and Ag, to facilitate the light-matter interaction at the surface of semiconductors. In this regard, we aim to combine highly absorptive CuInS2(CIS) nanocrystals with noble metal nanoparticles as the photosensitizer to enhance the intrinsic absorptivity and promote the performance of MoS2-based photodetectors. The interests of noble nanocrystals such as platinum and gold are featured for their distinctive properties of the carrier transportation and the storage when combined with semiconductor materials. The strategy described here acts as a perspective to significantly improve the performance of MoS2-based photodetectors with outstanding detection responsivity with selectable wavelengths by further controlling the size and material of the decorated CIS nanocrystals.In addition to optical sensing, TMDCs have also been developed as a promising candidate for gas-molecule detection. Different from commercial metal oxide gas sensors, TMDCs as sensing materials can be operated at room temperature with good performance, increasing its reliability for future industrial applications. Nevertheless, the relatively low response and long response/recovery time are the main drawbacks of these promising devices. Therefore, we proposed the approach to successfully increase the surface area of TMDCs by a one-step synthesis from WO3 into three-dimensional (3D) WS2 nanowalls through a rapid heating and rapid cooling process. Moreover, the combination of CdS/ZnS or CdSe/ZnS core/shell quantum dots (QDs) with different emission wavelengths and WS2 nanowalls will further improve the performance of WS2-based photodetector devices, including 3.5~4.7 times photocurrent enhancement and shorter response time. The remarkable results of the QD-WS2 hybrid devices to the high non-radiative energy transfer (NRET) efficiency between QDs and our nanostructured material are caused by the spectral overlap between the emission of QDs as the donors and the absorption of WS2 as the acceptors. Additionally, the outstanding NO2 gas-sensing properties of QDs/WS2 devices were demonstrated with a remarkably low detection limit down to 50 ppb with a fast response time of 26.8 s, contributed by tremendous local p-n junctions generated from p-type WS2 nanowalls and n-type CdSe-ZnS QDs in this hybrid system.Our strategies to combine 0D nanoparticles or quantum dots and 2D TMDC materials can significantly enhance the optical sensing and gas molecule sensing properties compared to pristine TMDC-based devices, resulting from the efficient charge or energy transfer between the multi-dimension material system and the creation of local p-n junctions. Moreover, the scalability of these hybrid nanostructures allows our devices to exhibit much more possibilities in advanced multifunctional applications.

Elucidating the Size-dependent FRET Efficiency in Interfacially Engineered Quantum Dots Attached to PBSA Sunscreen.

Applying sunscreen on human skin provides photoprotection against the harmful ultraviolet (UV) radiation of the sun. Sunscreen absorbs UV radiations and dissipates the absorbed energy through various radiative and nonradiative pathways. The attachment of functionalized quantum dots (QDs) to the sunscreen component is a novel idea to enhance the absorption cross-section of UV radiations. Therefore, the attachment of the sunscreen component to the ligand functionalized biocompatible QDs and the absorbed energy transfer from sunscreen to the QDs could work as a model system to overall improve the efficiency of the sunscreen. This study elucidates the mechanism of size-dependent Förster resonance energy transfer (FRET) efficiency and its rate between 2-phenylbenzimidazole-5-sulfonic acid (PBSA) and mercaptoacetic acid (MAA) functionalized CdS QDs. In the PBSA-QDs dyad, the PBSA (donor) dissipates UV-absorbed energy to the CdS QDs (acceptor). Following excitation at 306 nm, the steady-state photoluminescence (SSPL) and time-resolved photoluminescence (TRPL) techniques measurements demonstrate that both the nonradiative energy transfer efficiency and rate are QDs size-dependent in addition to donor-acceptor distance, and suggest that bigger sized-QDs result in an increase of the FRET efficiency.

Light Capture and Energy Conversion in Plasmonic-Polymeric Hybrid Nanoelectrodes

Plasmonic nanomaterials have absorption cross-sections exceeding other classes of materials but dephase quickly into their dielectric environment. In this work, plasmonic-polymeric nanoantenna-reactor systems are hybridized to increase the electron-hole pair lifetime through interfacial redistribution. The electron-hole pair can then be extracted to drive catalysis as the selected polymeric acceptor, a metallophthalocyanine, has been shown to catalysis O2 and CO2 reduction efficiently. Single particle spectroelectrochemistry was used to characterize the energy transfer efficiencies of the hybrid structures by recording the surface plasmon resonance energy linewidth change during in situ polymerization. The electrochemical polymerization is selective and photoenhanced on the surface of the gold nanorods. We complement resonance energy transfer efficiencies calculated from single particle changes in linewidth with calculations from excitation polarization-dependent photoluminescence measurements. Non-radiative energy transfer efficiencies up to 50% are achieved for plasmonic-polymeric nano-antenna reactors. The understanding of interfacial transfer pathways between plasmonic-polymeric materials will lead to control and tunability of scalable hybrid nanoelectrodes.

Plasmon Energy Transfer in Hybrid Nanoantennas.

Plasmonic metal nanoparticles exhibit large dipole moments upon photoexcitation and have the potential to induce electronic transitions in nearby materials, but fast internal relaxation has to date limited the spatial range and efficiency of plasmonic mediated processes. In this work, we use photo-electrochemistry to synthesize hybrid nanoantennas comprised of plasmonic nanoparticles with photoconductive polymer coatings. We demonstrate that the formation of the conductive polymer is selective to the nanoparticles and that polymerization is enhanced by photoexcitation. In situ spectroscopy and simulations support a mechanism in which up to 50% efficiency of nonradiative energy transfer is achieved. These hybrid nanoantennas combine the unmatched light-harvesting properties of a plasmonic antenna with the similarly unmatched device processability of a polymer shell.

Exciton recycling via InP quantum dot funnels for luminescent solar concentrators

Luminescent solar concentrators (LSC) absorb large-area solar radiation and guide down-converted emission to solar cells for electricity production. Quantum dots (QDs) have been widely engineered at device and quantum dot levels for LSCs. Here, we demonstrate cascaded energy transfer and exciton recycling at nanoassembly level for LSCs. The graded structure composed of different sized toxic-heavy-metal-free InP/ZnS core/shell QDs incorporated on copper doped InP QDs, facilitating exciton routing toward narrow band gap QDs at a high nonradiative energy transfer efficiency of 66%. At the final stage of non-radiative energy transfer, the photogenerated holes make ultrafast electronic transitions to copper-induced mid-gap states for radiative recombination in the near-infrared. The exciton recycling facilitates a photoluminescence quantum yield increase of 34% and 61% in comparison with semi-graded and ungraded energy profiles, respectively. Thanks to the suppressed reabsorption and enhanced photoluminescence quantum yield, the graded LSC achieved an optical quantum efficiency of 22.2%. Hence, engineering at nanoassembly level combined with nonradiative energy transfer and exciton funneling offer promise for efficient solar energy harvesting.

Design of Core-Shell Quantum Dots-3D WS2 Nanowall Hybrid Nanostructures with High-Performance Bifunctional Sensing Applications.

Transition metal dichalcogenides (TMDCs) have recently attracted a tremendous amount of attention owing to their superior optical and electrical properties as well as the interesting and various nanostructures that are created by different synthesis processes. However, the atomic thickness of TMDCs limits the light absorption and results in the weak performance of optoelectronic devices, such as photodetectors. Here, we demonstrate the approach to increase the surface area of TMDCs by a one-step synthesis process of TMDC nanowalls from WOx into three-dimensional (3D) WS2 nanowalls. By utilizing a rapid heating and rapid cooling process, the formation of 3D nanowalls with a height of approximately 150 nm standing perpendicularly on top of the substrate can be achieved. The combination of core-shell colloidal quantum dots (QDs) with three different emission wavelengths and 3D WS2 nanowalls further improves the performance of WS2-based photodetector devices, including a photocurrent enhancement of 320-470% and shorter response time. The significant results of the core-shell QD-WS2 hybrid devices can be contributed by the high nonradiative energy transfer efficiency between core-shell QDs and the nanostructured material, which is caused by the spectral overlap between the emission of core-shell QDs and the absorption of WS2. Besides, outstanding NO2 gas-sensing performance of core-shell QDs/WS2 devices can be achieved with an extremely low detection limit of 50 ppb and a fast response time of 26.8 s because of local p-n junctions generated by p-type 3D WS2 nanowalls and n-type core-shell CdSe-ZnS QDs. Our work successfully reveals the energy transfer phenomenon in core-shell QD-WS2 hybrid devices and shows great potential in commercial multifunctional sensing applications.

Enhancing Nonradiative Energy Transfer between Nitridized Carbon Quantum Dots and Monolayer WS2

Two-dimensional (2D) monolayer (1L) transition metal dichalcogenides (TMDs) suffer from low absorption in the visible light region. Nonradiative energy transfer (NRET) is an effective method to enhance such absorption, which, as shown in this study, can be accomplished by using surface nitridized carbon quantum dots (CQDs). The optical absorption and photoluminescence (PL) of CQDs in the visible light region can be greatly enhanced by increasing the level of nitridization. The nitridized CQDs exhibit weak p-type doping but strong PL quenching in contact with vapor transport (VT)-deposited 1L-WS2. Owing to the good overlap between the fluorescence and absorption spectra for CQDs and 1L-WS2, an interactive NRET process reduces the PL lifetimes of both CQDs and 1L-WS2. The NRET efficiency can be greatly enhanced by up to 73% for samples coated with CQDs of increasing surface nitridization.

NIR-Light-Driven Generation of Reactive Oxygen Species Using Ru(II)-Decorated Lipid-Encapsulated Upconverting Nanoparticles.

The biological application of ruthenium anticancer prodrugs for photodynamic therapy (PDT) and photoactivated chemotherapy (PACT) is restricted by the need to use poorly penetrating high-energy photons for their activation, i.e., typically blue or green light. Upconverting nanoparticles (UCNPs), which produce high-energy light under near-infrared (NIR) excitation, may solve this issue, provided that the coupling between the UCNP surface and the Ru prodrug is optimized to produce stable nanoconjugates with efficient energy transfer from the UCNP to the ruthenium complex. Herein, we report on the synthesis and photochemistry of the two structurally related ruthenium(II) polypyridyl complexes [Ru(bpy)2(5)](PF6)2 ([1](PF6)2) and [Ru(bpy)2(6)](PF6)2 ([2](PF6)2), where bpy = 2,2-bipyridine, 5 is 5,6-bis(dodecyloxy)-2,9-dimethyl-1,10-phenanthroline, and 6 is 5,6-bis(dodecyloxy)-1,10-phenanthroline. [1](PF6)2 is photolabile as a result of the steric strain induced by ligand 5, but the irradiation of [1](PF6)2 in solution leads to the nonselective and slow photosubstitution of one of its three ligands, making it a poor PACT compound. On the other hand, [2](PF6)2 is an efficient and photostable PDT photosensitizer. The water-dispersible, negatively charged nanoconjugate UCNP@lipid/[2] was prepared by the encapsulation of 44 nm diameter NaYF4:Yb3+,Tm3+ UCNPs in a mixture of 1,2-dioleoyl-sn-glycero-3-phosphate and 1,2-dioleoyl-sn-glycero-3-phosphocholine phospholipids, cholesterol, and the amphiphilic complex [2](PF6)2. A nonradiative energy transfer efficiency of 12% between the Tm3+ ions in the UCNP and the Ru2+ acceptor [2]2+ was found using time-resolved emission spectroscopy. Under irradiation with NIR light (969 nm), UCNP@lipid/[2] was found to produce reactive oxygen species (ROS), as judged by the oxidation of the nonspecific ROS probe 2′,7′-dichlorodihydrofluorescein (DCFH2–). Determination of the type of ROS produced was precluded by the negative surface charge of the nanoconjugate, which resulted in the electrostatic repulsion of the more specific but also negatively charged 1O2 probe tetrasodium 9,10-anthracenediyl-bis(methylene)dimalonate (Na4(ADMBMA)).

Photophysical Properties of Upconverting Nanoparticle-Phthalocyanine Complexes.

Interaction between upconverting nanoparticles and aluminum octacarboxyphthalocyanine was studied. The efficiency of non-radiative energy transfer from the nanoparticles to phthalocyanine increased with the number of phthalocyanine molecules adsorbed on the nanoparticle, but only up to a certain limit. Further increase in the phthalocyanine concentration resulted in a decrease of its sensitized fluorescence due to the dimerization of dye molecules on the nanoparticle surface. When subjected to infrared irradiation, phthalocyanine molecules in the hybrid complex generated singlet oxygen. The observed effects are of interest in regard to the targeted search for new components of efficient third-generation hybrid photosensitizers.

Dependence of Photocurrent Enhancements in Hybrid Quantum Dot-MoS2 Devices on Quantum Dot Emission Wavelength

The spectral dependence of nonradiative energy transfer (NRET) from three spectrally different quantum dot (QD) ensembles to monolayer MoS2 is reported. The QDs with peak emission wavelengths of 450, 530, and 630 nm induce large photocurrent enhancements in the hybrid devices with monolayer MoS2 islands grown by chemical vapor deposition (CVD). NRET efficiencies of over 90% are observed for each of the QD-MoS2 hybrids, with 3-fold to 6-fold photocurrent enhancements, depending on the spectral overlap between the QDs and the monolayer MoS2. We find good agreement between the trends obtained from the NRET rate and the spectral overlap function showing evidence for a Förster-like energy transfer mechanism in these CdSeS/ZnS QD-MoS2 devices.

Energy transfer in upconversion nanoparticles – phthalocyanine hybrid complexes

In this work, we have studied the interaction between upconversion nanoparticles, and aluminum octacarboxyphthalocyanine in water solutions. It was shown that the self-assembled hybrid complexes are stable in water and NaCl solutions. The efficiency of nonradiative energy transfer from nanoparticles to the aluminum phthalocyanines increases with the number of phthalocyanine molecules in solution, but phthalocyanine sensitized fluorescence decreases due to phthalocyanine dimerization process. Also, singlet oxygen was generated by the phthalocyanine in the hybrid complex under infrared laser irradiation. The detected effects are of interest from the point of view of the directional search of components for a hybrid, highly efficient photosensitizers.

Dependence of Photocurrent Enhancements in Quantum Dot (QD)‐Sensitized MoS2 Devices on MoS2 Film Properties

AbstractThis report demonstrates highly efficient nonradiative energy transfer (NRET) from alloyed CdSeS/ZnS semiconductor nanocrystal quantum dots (QDs) to MoS2 films of varying layer thicknesses, including pristine monolayers, mixed monolayer/bilayer, polycrystalline bilayers, and bulk‐like thicknesses, with NRET efficiencies of over 90%. Large‐area MoS2 films are grown on Si/SiO2 substrates by chemical vapor deposition. Despite the ultrahigh NRET efficiencies there is no distinct increase in the MoS2 photoluminescence intensity. However, by studying the optoelectronic properties of the MoS2 devices before and after adding the QD sensitizing layer photocurrent enhancements as large as ≈14‐fold for pristine monolayer devices are observed, with enhancements on the order of ≈2‐fold for MoS2 devices of mixed monolayer and bilayer thicknesses. For the polycrystalline bilayer and bulk‐like MoS2 devices there is almost no increase in the photocurrent after adding the QDs. Industrially scalable techniques are specifically utilized to fabricate the samples studied in this report, demonstrating the viability of this hybrid structure for commercial photodetector or light harvesting applications.

Spectral and kinetic features of nonradiative energy transfer in hybrid associates of colloidal quantum dots and organic dyes

The features of nonradiative resonance energy transfer in hybrid associates of colloidal CdS quantum dots (QDs) with molecules of a thiazine dye and J-aggregates of a carbocyanine dye are discussed. The case of an inhomogeneously broadened recombination band of donor (CdS QDs) luminescence is considered. We detected spectral-selective quenching of recombination luminescence of colloidal CdS QDs in association with organic dyes. The maximum of quenching occurs in the region of absorption of the acceptor (organic dye molecule). It is shown using the time-correlated single photon counting technique that the lifetime of the QD luminescence decreases synchronously with the quenching of the luminescence, but only at the wavelengths falling in the region of absorption of the dye. Based on the concept of a donor–acceptor nature of emission of CdS QDs, the dependence of the efficiency of nonradiative energy transfer on the luminescence wavelength is analyzed taking into account the Poisson distribution of its quenchers.

Nonradiative energy transfer in planar systems based on structurally different fluorophores

In the multilayer systems where monolayers of donor and acceptor fluorophores of different chemical structure are separated by an inert layer, the dependence of nonradiative energy transfer efficiency on the distance between the planar components of a donor–acceptor couple has a maximum at a finite nonzero thickness of the separating layer.

Near band gap luminescence in hybrid organic-inorganic structures based on sputtered GaN nanorods

Novel hybrid organic-inorganic nanostructures fabricated to utilize non-radiative resonant energy transfer mechanism are considered to be extremely attractive for a variety of light emitters for down converting of ultaviolet light and for photovoltaic applications since they can be much more efficient compared to devices grown with common design. Organic-inorganic hybrid structures based on green polyfluorene (F8BT) and GaN (0001) nanorods grown by magnetron sputtering on Si (111) substrates are studied. In such nanorods, stacking faults can form periodic polymorphic quantum wells characterized by bright luminescence. In difference to GaN exciton emission, the recombination rate for the stacking fault related emission increases in the presence of polyfluorene film, which can be understood in terms of Förster interaction mechanism. From comparison of dynamic properties of the stacking fault related luminescence in the hybrid structures and in the bare GaN nanorods, the pumping efficiency of non-radiative resonant energy transfer in hybrids was estimated to be as high as 35% at low temperatures.

Polarized white light from hybrid organic/III-nitrides grating structures

Highly polarised white light emission from a hybrid organic/inorganic device has been achieved. The hybrid devices are fabricated by means of combining blue InGaN-based multiple quantum wells (MQWs) with a one-dimensional (1D) grating structure and down-conversion F8BT yellow light emitting polymer. The 1D grating structure converts the blue emission from unpolarised to highly polarised; Highly polarised yellow emission has been achieved from the F8BT polymer filled and aligned along the periodic nano-channels of the grating structure as a result of enhanced nano-confinement. Optical polarization measurements show that our device demonstrates a polarization degree of up to 43% for the smallest nano-channel width. Furthermore, the hybrid device with such a grating structure allows us to achieve an optimum relative orientation between the dipoles in the donor (i.e., InGaN/GaN MQWs) and the diploes in the acceptor (i.e., the F8BT), maximizing the efficiency of non-radiative energy transfer (NRET) between the donor and the acceptor. Time–resolved micro photoluminescence measurements show a 2.5 times enhancement in the NRET efficiency, giving a maximal NRET efficiency of 90%. It is worth highlighting that the approach developed paves the way for the fabrication of highly polarized white light emitters.

The effect of ionic strength on spectral properties of quantum dots and aluminum phthalocyanine complexes

The effect of ionic strength on spectral properties of negatively charged semiconductor (CdSe/ZnS) nanocrystals (quantum dots, QDs) and polycationic aluminum phthalocyanines (PCs) is considered. A QD/PC complex, formed via self-assembly, remains stable throughout a wide range of ionic strength values of a solution and [PC]/[QD] concentration ratio. The efficiency of nonradiative energy transfer from QDs to PCs rises with an increase in the ionic strength of solution. The fluorescence amplification factor of PC reduces with an increase in number of PC molecules in a complex with a quantum dot, reaching negative values at high [PC]/[QD] ratios. This is probably due to the decrease in the effect of energy migration on the total PC fluorescence upon its own significant absorption ability of a large number of acceptors. These effects are of interest to develop selection principles of components for hybrid complexes stabilized with electrostatic interaction.