Highest Efficiency Plasmonic Polycrystalline Silicon Thin-Film Solar Cells by Optimization of Plasmonic Nanoparticle Fabrication

Excitation of surface plasmons in metallic nanoparticles is a promising method for increasing the light absorption in solar cells and hence the cell photocurrent. Comprehensive optimization of a nanoparticle fabrication process for enhanced performance of polycrystalline silicon thin-film solar cells is presented. Three factors were studied: the Ag precursor film thickness, annealing temperature and time. The thickness of the precursor film was 10, 14 and 20 nm; annealing temperature was 190, 200, 230 and 260 °C; and annealing time was varied between 20 and 95 min. Performance enhancement due to light-scattering by nanoparticles was calculated by comparing absorption, short-circuit current density and energy conversion efficiency in solar cells with and without nanoparticles formed under different process conditions. Nanoparticles formed from 14-nm-thick Ag precursor film annealed at 230 °C for 53 min result in the highest absorption enhancement in the 700–1,100 nm wavelength range, in the highest enhancement of total short-circuit current density. The highest photocurrent enhancement was 33.5 %, which was achieved by the cell with the highest absorption enhancement in the 700–1,100 nm range. The plasmonic cell efficiency of 5.32 % was achieved without a back reflector and 5.95 % with the back reflector; which is the highest reported efficiency for plasmonic thin-film solar cells.     

Contribution of LSP Effect to Light Absorption in Thin-Film Crystalline Silicon Solar Cells

Introducing periodic Ag gratings in the rear side of thin-film silicon excites localized surface plasmon (LSP) and Fabry-Perot (FP) effect. These two effects as well as an intrinsic one pass through absorption overlay together and all contribute to the light absorption in silicon. On the basis of electromagnetic field’s linear superposition, the absorptivity caused by LSP effect is separated from the overall absorptivity of a 500-nm-thick silicon and quantized by short current density. Finite difference time domain (FDTD) calculations were performed to obtain the absorptivity of silicon with different Ag grating parameters. The contribution of LSP effect to the light absorption is evaluated by photocurrent ratio and investigated under different Ag grating parameters. It is found that, as LSP effect is excited most intensively, the light absorption of silicon will also be enhanced extremely. By careful design, the overall short current density of silicon is optimized up to 25.4 mA/cm², where the contribution of LSP effect accounts for 38.6 %. Comparing to 14.5 mA/cm² for a reference silicon stack, it increases up to almost 75 %. These results may give design suggestions in implementation of plasmonic solar cell as high efficiency devices.     

Absorption Enhancements in Plasmonic Solar Cells Coated with Metallic Nanoparticles

We find that three mechanisms lead to the absorption enhancements of light in a thin-film amorphous silicon solar cell coated with a periodic array of silver nanoparticles on the rear surface according to our simulation. They are localized surface plasmon modes of the silver nanoparticles, Fabry–Pérot resonant cavity modes and waveguide effects. Each enhancing mechanism can yield a maximum absorption enhancement of over two times at the corresponding resonant wavelengths when the nanoparticles cover 20 % of the solar cell surface, and an average absorption enhancement of up to 57 % can be achieved in the AM 1.5 G solar spectrum. The absorption enhancements can also be tuned in spectrum to optimize the total absorption in a plasmonic solar cell.     

Fluorescent (Au@SiO2)SiC Nanohybrids: Influence of Gold Nanoparticle Diameter and SiC Nanoparticle Surface Density

Gold@silica core–shell nanoparticles were prepared with various gold core diameters (ranging from 20 to 150 nm) and silica thicknesses (ranging from 10 to 30 nm). When the gold diameter is increased, the size dispersion became larger, leading to a broader plasmon band. Then, silicon carbide (SiC) nanoparticles were covalently immobilized onto silica to obtain hybrid (Au@SiO₂) SiC nanoparticles. The absorption properties of these hybrid nanoparticles showed that an excess of SiC nanoparticles in the dispersion can be identified by a strong absorption in the UV region. Compared to SiC reference samples, a blue shift of the fluorescence emission, from 582 to 523 nm, was observed, which was previously attributed to the strong surface modification of SiC when immobilized onto silica. Finally, the influence of several elaboration parameters (gold diameter, silica thickness, SiC concentration) on fluorescence enhancement was investigated. It showed that the highest enhancements were obtained with 10 nm silica thickness, low concentration of SiC nanoparticles, and surprisingly, with a 20-nm gold core diameter. This last result could be attributed to the broad plasmon band of big gold colloids. In this case, SiC emission strongly overlapped gold absorption, leading to possible quenching of SiC fluorescence by energy transfer.     

Optical Modeling of Plasmonic Nanoparticles Enhanced Light Emission of Silicon Light-Emitting Diodes

Significant enhancement of radiative efficiency of thin-film silicon light-emitting diodes achieved by placing the active layer in close proximity to silver (Ag) nanoparticles has been observed. In this paper, optical properties including transmission, reflection, and absorption of a random assembly of Ag nanoparticles are theoretically investigated using the effective medium model. Furthermore, the influence of Ag nanoparticles on light emission of silicon light-emitting diodes is studied by an improved effective mode volume model we propose here. The normalized line shape of dipole oscillation is calculated directly using Lorentz–Drude model without using any approximation. Thus, it results in more accurate calculation of the enhanced Purcell factor in comparison with the conventional approach. We show that an enhancement of radiative efficiency of silicon light-emitting diodes can be achieved by localized surface plasmons on metal nanoparticles. The calculated result of optimal Ag nanoparticle size to enhance light emission of silicon light-emitting diodes at 900 nm wavelength is in very good agreement with those obtained from the experimental result. The model is useful for the design of metallic nanoparticles enhanced light emitters.     

A functional compartmental model of the <Emphasis Type="Italic">Synechocystis</Emphasis> PCC 6803 phycobilisome

In the light-harvesting antenna of the Synechocystis PCC 6803 phycobilisome (PB), the core consists of three cylinders, each composed of four disks, whereas each of the six rods consists of up to three hexamers (Arteni et al., Biochim Biophys Acta 1787(4):272–279, 2009). The rods and core contain phycocyanin and allophycocyanin pigments, respectively. Together these pigments absorb light between 400 and 650 nm. Time-resolved difference absorption spectra from wild-type PB and rod mutants have been measured in different quenching and annihilation conditions. Based upon a global analysis of these data and of published time-resolved emission spectra, a functional compartmental model of the phycobilisome is proposed. The model describes all experiments with a common set of parameters. Three annihilation time constants are estimated, 3, 25, and 147 ps, which represent, respectively, intradisk, interdisk/intracylinder, and intercylinder annihilation. The species-associated difference absorption and emission spectra of two phycocyanin and two allophycocyanin pigments are consistently estimated, as well as all the excitation energy transfer rates. Thus, the wild-type PB containing 396 pigments can be described by a functional compartmental model of 22 compartments. When the interhexamer equilibration within a rod is not taken into account, this can be further simplified to ten compartments, which is the minimal model. In this model, the slowest excitation energy transfer rates are between the core cylinders (time constants 115–145 ps), and between the rods and the core (time constants 68–115 ps).     

Influence of SiO<Subscript>2</Subscript> Spacer Layer Thickness on Performance of Plasmonic Textured Silicon Solar Cell

We investigated the effect of SiO₂ spacer layer thickness between the textured silicon surface and silver nanoparticles (Ag NPs) on solar cell performance using quantum efficiency analysis. Separation of Ag NPs from high index silicon with SiO₂ layer led to modified absorption and scattering cross-sections due to graded refractive index medium. The forward scattering from Ag NPs is very sensitive to SiO₂ layer thickness in plasmonic silicon cell performance due to the evanescent character of generated near-fields around the NPs. With the optimized ～30–40 nm SiO₂ spacer layer, we observed an enhancement of solar cell efficiency from ～8.7 to ～10 %, which is due to the photocurrent enhancement in the off-resonance surface plasmon region. We also estimated minority carrier diffusion lengths (L _eff) from internal quantum efficiency data, which are also sensitive to SiO₂ spacer layer thickness. We observed that the L _eff values are enhanced from ～356 to ～420 μm after placing Ag NPs on ～40 nm spacer layer due to improved forward (angular) scattering of light from the Ag NPs into silicon.     

Abiotic Photophosphorylation Model Based on Abiogenic Flavin and Pteridine Pigments

A model for abiotic photophosphorylation of adenosine diphosphate by orthophosphate with the formation of adenosine triphosphate was studied. The model was based on the photochemical activity of the abiogenic conjugates of pigments with the polymeric material formed after thermolysis of amino acid mixtures. The pigments formed showed different fluorescence parameters depending on the composition of the mixture of amino acid precursors. Thermolysis of the mixture of glutamic acid, glycine, and lysine (8:3:1) resulted in a predominant formation of a pigment fraction which had the fluorescence maximum at 525 nm and the excitation band maxima at 260, 375, and 450 nm and was identified as flavin. When glycine in the initial mixture was replaced with alanine, a product formed whose fluorescence parameters were typical to pteridines (excitation maximum at 350 nm, emission maximum at 440 nm). When irradiated with the quasi-monochromatic light (over the range 325–525 nm), microspheres in which flavin pigments were prevailing showed a maximum photophosphorylating activity at 375 and 450 nm, and pteridine-containing chromoproteinoid microspheres were most active at 350 nm. The positions and the relative height of maxima in the action spectra correlate with those in the excitation spectra of the pigments, which point to the involvement of abiogenic flavins and pteridines in photophosphorylation.     

Surface Plasmon Enhancement of Optical Absorption in Thin-Film Silicon Solar Cells

Strong electromagnetic field enhancement that occurs under conditions of the surface plasmon excitation in metallic nanoparticles deposited on a semiconductor surface is a very efficient and promising tool for increasing the optical absorption within semiconductor solar cells and, hence, their photocurrent response. The enhancement of the optical absorption in thin-film silicon solar cells via the excitation of localized surface plasmons in spherical silver nanoparticles is investigated. Using the effective medium model, the effect of the nanoparticle size and the surface coverage on that enhancement is analyzed. The optimum configuration and the nanoparticle parameters leading to the maximum enhancement in the optical absorption and the photocurrent response in a single p-n junction silicon cell are obtained. The effect of coupling between the silicon layer and the surface plasmon fields on the efficiency of the above enhancement is quantified as well.     

Wavelength-dependent photodamage to <Emphasis Type="Italic">Chlorella</Emphasis> investigated with a new type of multi-color PAM chlorophyll fluorometer

A new type of multi-color PAM chlorophyll fluorometer (Schreiber et al. 2012) was applied for measurements of photodamage to photosystem II (PS II) in optically thin suspensions of Chlorella (200 μg Chl l^?1) in the presence of 1 mM lincomycin. An action spectrum of the relative decrease of F _v/F _m in the 440–625 nm range was measured, which not only showed the expected high activity in the blue, but at a lower level also substantial activity above 540 nm. With the same dilute suspension, a PS II absorption spectrum was derived via measurements of the O-I₁ rise kinetics induced by differently colored strong light at defined incident quantum flux densities. After normalization of the two spectra at 625 nm, the relative extent of photodamage at 440–480 nm proved substantially higher than absorption by PS II, whereas the two spectra were close to identical in the 540–625 nm range. Hence, overall photodamage to PS II appears to consist of two components, one of which is due to light absorbed by PS II pigments, whereas the other one is likely to involve direct light absorption by Mn in the oxygen-evolving complex (Hakala et al. Biochim Biophys Acta 1706:68–80, 2005). Based on this rationale, an action spectrum of the Mn mechanism of photodamage was deconvoluted from the overall action spectrum, declining steeply above 480 nm. An almost identical Mn-spectrum was derived by another approach with the PAR of the various colors being adjusted to give identical rates of PS II turnover, PAR _II. The tentative, basic assumption of negligibly small contribution of the Mn mechanism to photodamage above 540 nm was supported by supplementary measurements using an external 665 nm lamp. 665 nm not only gave about two times PS II turnover as compared to 625 nm, but also about two times photodamage.     

Excitation energy transfer in phycobiliproteins of the cyanobacterium <Emphasis Type="Italic">Acaryochloris marina</Emphasis> investigated by spectral hole burning

The cyanobacterium Acaryochloris marina developed two types of antenna complexes, which contain chlorophyll-d (Chl d) and phycocyanobilin (PCB) as light-harvesting pigment molecules, respectively. The latter membrane-extrinsic complexes are denoted as phycobiliproteins (PBPs). Spectral hole burning was employed to study excitation energy transfer and electron–phonon coupling in PBPs. The data reveal a rich spectral substructure with a total of four low-energy electronic states whose absorption bands peak at 633, 644, 654, and at about 673 nm. The electronic states at ~633 and 644 nm can be tentatively attributed to phycocyanin (PC) and allophycocyanin (APC), respectively. The remaining low-energy electronic states including the terminal emitter at 673 nm may be associated with different isoforms of PC, APC, or the linker protein. Furthermore, the hole burning data reveal a large number of excited state vibrational frequencies, which are characteristic for the chromophore PCB. In summary, the results are in good agreement with the low-energy level structure of PBPs and electron–phonon coupling parameters reported by Gryliuk et al. (BBA 1837:1490–1499, 2014) based on difference fluorescence line-narrowing experiments.     

Optical Confinements in Correlated Spectral Characteristics of Vertically Aligned Silicon Nanometric Wires Followed by a Facile Fabrication Thereof

Nanometric wires, in particular, vertically aligned silicon nanowires, possess a huge prospect in current thin film solar cell technologies. A bottom-up process to acquire vertically aligned silicon nanowire (Si-NW) on c-Si wafer was demonstrated and characterized. A well coverage of Si-NWs on c-Si, ca. 6.5 × 10⁸/cm², was obtained. SEM micrograph confirmed a variation in Si-NW size in length as well as in diameter. On the other hand, inherent optical characteristics of nanometric wires define the performance of such nanowire-based thin film solar cell. Therefore, key factors, such as absorption profile, energy flow, electromagnetic (EM) field, and generation rate distribution in typical model, “Si-NW on c-Si slab,” have been observed at different wavelengths of solar spectrum. A single Si-NW of cylindrical shape was modelled on c-Si and optimized to elucidate the aforementioned characteristics. Light absorption at 700 nm was found to be the best in this scenario, and therefore, EM field and Poynting vector distribution were simulated at the same wavelength. It was revealed that at 700 nm, strongest sites of EM field and energy flow became more available and confined. Exciton generation rate was found to be distributed and confined all the way down to the bottom of the wire. A correlated phenomenon such as optical confinements in spectral characteristics in nanoscale is elucidated. Such a focused prediction in spectral optical characteristics and facile fabrication route is indispensable in optoelectronics as well as nanowire-based advanced electronic design.     

Influence of Femtosecond Laser Ablated Silver Nanoparticles on the Nonlinear Optical Properties of Basic Fuchsin dye

We investigate the linear and nonlinear optical properties of Basic Fuchsin influenced by femtosecond laser ablated silver nanoparticles in deionised water. Single beam z-scan technique using a Q-switched Nd:YAG laser (Spectra PhysicsLAB-1760, 532 nm, 7 ns, 10 Hz) is used for the present study. Quenching of fluorescence is observed in the presence of silver nanoparticles. Transmission electron microscopic observation reveals that the nanoparticles are spherical in shape, with an average size of 7 nm. The samples show self-defocusing nonlinearity and better nonlinear absorption behavior in the presence of silver sol. The nonlinear absorption varies with varying input fluence and concentration. The results show that the variations in the nonlinear parameters are also due to the surface plasmon resonance of silver nanoparticles. The nonlinearity of the dye is increased in the presence of silver nanoparticles, which makes the material suitable for various photonic and optoelectronic applications.     

Solid and Hollow Gold Nanostructures for Nanomedicine: Comparison of Photothermal Properties

The photothermal properties of solid and hollow gold nanostructures represented by colloidal solutions of spherical nanoparticles, nanoshells, and nanocages upon irradiation with a 100 mW 808 nm continuous-wave laser for the first time were experimentally compared under identical optical density and nanoparticle concentration conditions. Accompanying computer modeling of light absorption by the studied gold nanostructures revealed the general parameters influencing the photothermal efficiency, which is of significance for nanomedical applications. The spectral position of localized plasmonic excitations of the studied nanostructures ranged from 518 nm for solid gold nanoparticles to 718 nm for gold nanocages, which provided a possibility to observe a direct influence of the wavelength proximity between the localized surface plasmon resonance and laser line on the heat generation capability of the nanostructures. As a result, the best photothermal efficiency was registered for gold nanocages, which proves them as an efficient photothermal treatment agent and a possible candidate to build a nanocarrier platform for drug delivery with a controlled release. Light absorption modeling demonstrated an existence of optimal wall thickness for gold nanoshells that should lead to the maximum photothermal efficiency when irradiated with 808 nm light, which varied from about 0.1 to 0.4 in units of external nanoshell radius with an increase of the wall porosity. Additionally, computer modeling results show that increased wall porosity should lead to enhanced photothermal efficiency of polydisperse colloidal solutions of hollow gold nanostructures.     

Plasmonic Au-MoO<Subscript>3</Subscript> Colloidal Nanoparticles by Reduction of HAuCl<Subscript>4</Subscript> by Blue MoO<Subscript>x</Subscript> Nanosheets and Observation of the Gasochromic Property

Defective colloids of blue MoO_x nanosheets were prepared by anodizing exfoliation method in water. This colloidal solution exhibits an optical plasmonic absorption band in the infrared region at about 760 nm. Merely mixing HAuCl₄ solution with the MoO_x leads to loss of the blue color, decaying of 760 nm plasmonic peak and simultaneous formation of the gold plasmon absorption peak at 550–570 nm. Some spectral variations in gold plasmonic peak and MoO_x optical band gap were observed for Mo:Au ratio of 10:1, 20:1, 30:1, and 40:1. The size of the gold nanoparticles was in the 5–6 nm range with fcc crystalline structure. X-ray photoelectron spectroscopy (XPS) revealed that the initial solution contains Mo⁵⁺ states and hydroxyl groups, which after reduction, hydroxyl groups are eliminated and the Mo⁵⁺ states converted to Mo⁶⁺. The obtained Au-MoO₃ colloids have a gasochromic property in which they are colored back to blue in the presence of hydrogen gas and the molybdenum oxide absorption peak recovered again. Furthermore, it was observed that both gold and Mo oxide plasmonic peaks redshift by insertion of hydrogen gas which is attributed to change in solution refractive index and formation of defect concentration.     

The probabilities of one- and multi-track events for modeling radiation-induced cell kill

In view of the clinical importance of hypofractionated radiotherapy, track models which are based on multi-hit events are currently reinvestigated. These models are often criticized, because it is believed that the probability of multi-track hits is negligible. In this work, the probabilities for one- and multi-track events are determined for different biological targets. The obtained probabilities can be used with nano-dosimetric cluster size distributions to obtain the parameters of track models. We quantitatively determined the probabilities for one- and multi-track events for 100, 500 and 1000 keV electrons, respectively. It is assumed that the single tracks are statistically independent and follow a Poisson distribution. Three different biological targets were investigated: (1) a DNA strand (2 nm scale); (2) two adjacent chromatin fibers (60 nm); and (3) fiber loops (300 nm). It was shown that the probabilities for one- and multi-track events are increasing with energy, size of the sensitive target structure, and dose. For a 2 × 2 × 2 nm³ target, one-track events are around 10,000 times more frequent than multi-track events. If the size of the sensitive structure is increased to 100–300 nm, the probabilities for one- and multi-track events are of the same order of magnitude. It was shown that target theories can play a role for describing radiation-induced cell death if the targets are of the size of two adjacent chromatin fibers or fiber loops. The obtained probabilities can be used together with the nano-dosimetric cluster size distributions to determine model parameters for target theories.     

Surface Plasmon Polariton Band Gap-Enabled Plasmonic Mach–Zehnder Interferometer: Design,Analysis, and Application

In this paper, we propose a design for surface plasmon polariton band gap (SPPBG)-enabled plasmonic Mach–Zehnder interferometer (PMZI) comprising of array of silver nanorods embedded upright into silicon on insulator (SOI) substrate and analyze its potential in sensing, intended for cancer therapy. Periodic arrangement of nanorods embedded into SOI substrate grants strong spatial confinement and assist waveguidance to the propagating plasmon mode due to the SPPBG effect. This arrayed system triggers local field enhancement promoting sensing proficiency of the device and is assessed in terms of wavelength and phase shift. Proposed design of SPPBG-enabled PMZI sensor is successfully employed for detection and classification of various cancerous cells. The structural parameters of PMZI are optimized in compliance with the plasmonic band gap in the range of 400–800 nm yielding exceptionally high sensitivity at input wavelength of 633 nm. Volumetric analysis of the analyte reveals that very small analyte volume of the order of 10^?15 cc is sufficient to yield significant phase shift. Phase shift obtained for the breast adenocarcinoma and blood cancer cell lines are 1.2357radian and 0.3351radian, respectively, which read very high value of phase shifts to identify extremely small changes in refractive index of the analyte. Figure of merit calculated thereby expose impressive device performance outdoing preceding plasmonic sensors leading to validation of proposed ultra-compact-sensitive PMZI design.     

Optical Properties of Core–Shell Gold–Silver and Silver–Gold Nanoparticles for Near UV and Visible Radiation Wavelengths

Modeling of optical properties of spherical core–shell gold–silver and silver–gold nanoparticles (NPs) was carried out based on extended Mie theory for radiation wavelengths in the range 300?≤?λ?≤?650 nm. Efficiency factors of absorption, scattering, and extinction of radiation by core–shell NPs in the range of the radii 5–100 nm and in the range of shell thicknesses 0–40 nm were calculated. Results show the nonlinear dependences of optical properties of core–shell gold–silver and silver–gold nanoparticles on radiation wavelengths, core radii, and shell thicknesses. These results can be applied for photonic technologies of nanoparticles.     

Plasmonic Core–Shell Nanowires for Enhanced Second-Harmonic Generation

We demonstrate the synthesis and characterization of core–shell nanowires consisting of a non-centrosymmetric KNbO₃ core and a gold shell. This type of nanostructure combines the nonlinear optical properties of the core and the plasmonic resonance of the shell in the near infrared spectral range. We report successful spectroscopic measurements on coated single wires to characterize the resonant behavior of the gold shell. We present a theoretical model based on the electrostatic approximation to estimate the enhancement of second-harmonic generation in a nanowire due to the shell. It suggests a possible enhancement factor of up to 4,000 for a system with a nanoshell of 16 nm thickness at a wavelength of 900 nm.