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Surface-relief diffraction gratings' optimization for plasmonic enhancements in thin-film solar cells
Abstract
Methodical and intensive surface plasmon (SP) excitation trials were carried out on various dielectric-metal interfaces to optimize plasmonic photocurrent enhancements in organic P3HT-PCBM photovoltaic thin films. The SPs were optically excited via the diffraction grating method using single, crossed, and parallel grating schemes, with trials yielding optimal grating and film thickness parameters. Photocurrent enhancements up to 355% were demonstrated with TM-polarized incident light on single and parallel grating structures, while both TM and TE-polarized incident light enhancements were present on crossed grating structures. When compared with the photocurrent enhancements seen on single gratings, those seen on parallel gratings were comparable in magnitude but were shown over a broader optical band. This broadening of the optical band was due to the simultaneous SP excitations by the two superimposed gratings in the parallel scheme. Copyright © 2012 John Wiley & Sons, Ltd.
... Surface plasmons have been used in a large number of applications ranging from enhancements in the properties of solar cells [13] and biosensors [14] to studying film growth and interface characteristics [15]. Tuning the incident light wavelength at which a SP occurs can offer several advantages to practical applications. ...
... A diffraction grating was then inscribed on the azobenzene layer using a 532-nm Coherent Verdi V5 diode-pumped laser and a Lloyd mirror setup [13]. Gratings with pitches 615 nm and 635 nm were inscribed on different PLZT substrates with a laser irradiance of 870 mW/cm 2 for an exposure time of 375 seconds, which yielded grating depths of approximately 150 nm, as measured with the Atomic Force Miscroscope (AFM). ...
... For a flat metal/dielectric interface, the SP wavelength SP is given by the following equation [13]: ...
Real-time surface plasmon modulation was achieved by electrically varying the pitch of a nanoscale surface relief diffraction grating inscribed on an azobenzene thin film covered with a layer of silver. The azobenzene film was spin coated on an electrostrictive Lead Lanthanum Zirconate Titanate (PLZT) ceramic substrate and a combination of DC bias and AC electric fields were applied longitudinally on the PLZT ceramic causing a change in the grating’s pitch as well as the surface plasmon’s resonance wavelength. This method permits extremely accurate control of the surface plasmon wavelength for tunable optics applications.
... Their precise excitation conditions and ability to enhance the light's electromagnetic field has found applications ranging from bio-sensing [1], organic light emitting diodes (OLEDs) [2], and on-chip spectrometers [3]. However, one of their most promising uses may be in increasing the efficiency of thin film solar cells [4]. Light-induced SPs allow for more efficient photon absorption without increasing the thickness of the photoactive layer. ...
... After fabrication, each grating was sputter-coated with 60 nm of silver using a Bal-Tec SCD-050 sputter coater. The silver layer was previously shown to take the same shape of the underlying grating, creating a metallic sinusoidal grating on top of the azobenzene grating [4]. ...
Large-scale linear diffraction gratings with gradually varying pitch were photo-inscribed onto the surface of azobenzene thin films using a 532 nm laser and a modified Lloyd mirror set-up. By placing a cylindrical lens in front of the direct half of the inscribing beam, gratings with a chirping rate as high as 12.9 nm/mm were produced. Subsequently, when these chirped-pitch gratings were coated with silver, over three-fold bandwidth increase was observed in the surface plasmon transmission peaks at FWHM, when compared to constant-pitch gratings. This was made possible due to the simultaneous excitation of surface plasmon resonance in a band of light wavelengths.
... Other studies have been done on the angular dependence of this SPR polarization conversion in azobenzene crossed SRGs, and the results of light momentum transfer in between the gratings were explained in terms of the two-dimensional SPR wave vectors. 26,27 This SPR approach in crossed SRGs (CSRGs) is remarkable, since when placed in between crossed polarizers, light transmitted through a CSRG will be zero except in the narrow bandwidth where the SPR conversion has occurred. ...
... where θ is the incidence angle, m is an integer, and Λ is the grating pitch. 27 At normal incidence, equating eqs 2 and 3 allows solving for the light wavelength where the surface plasmon occurs (λ SPR ), which is given by ...
We present an original, low-cost nanoplasmonic (bio)sensor based on crossed surface relief gratings (CSRGs) generated from orthogonally superimposed surface relief gratings (SRGs) on gold-coated azo-glass substrate. This surface plasmon resonance (SPR)-based sensing approach is unique, since the light transmitted through a CSRG is zero except in the narrow bandwidth where the SPR conversion occurs, enabling quantitative monitoring of, only, the plasmonic signal from bio-molecular interactions in real-time. We validated the individual SRG plasmonic signature of CSRGs by observing their respective SPR excitation peaks, and tested them to detect both bulk and near-surface refractive index (RI) changes. Compared to simple SRGs, CSRGs portray a much-improved sensitivity of 647.8 nm/RIU, a resolution in the order of 10⁻⁵ RIU, and a figure of merit (FOM) of 14 for bulk RI-change sensing. We also demonstrate their ability to perform as biosensors, through the detection and monitoring of near-surface bio-molecular interactions in real-time, a first for CSRGs. The minimum detectable concentration of biotin-streptavidin binding events was 8.3 nM. Due to their sensing abilities, low-cost (<10 cents/unit), easiness of fabrication and inherent suitability for integration with microfluidics, we anticipate that CSRGs will stand as strong candidates in the portable diagnostics arena.
... [2][3][4] SRG typically occur when a material containing azobenzene moieties is irradiated with two interfering coherent laser beams, upon which the molecular motion causes the formation of peaks and troughs in the surface of the material which mimic the interference pattern. 5 Several applications have been proposed for SRG, including resonant waveguide filters, 6 plasmonic biosensors, 7 DNAtunable dye laser, 8 organic light emitting diodes, 9 light-harvesting structures for photovoltaic cells, 10,11 as well as many other applications. 12 As most simple azobenzene derivatives readily crystallize, studies of their photophysical behavior in the solid state use materials where the chromophores are either dispersed in or bonded to polymers, 1,13,14 or incorporated into small molecules that can readily form glassy phases. ...
Azobenzene-containing materials exhibit various photomechanical properties, including the formation of surface relief gratings (SRG) when irradiated with two interfering laser beams. In a recent study, a novel glass-forming derivative of Disperse Red 1 (DR1) with a mexylaminotriazine group was synthesized in high yield with a simple and efficient procedure, and showed the ability to form high-quality amorphous thin films with a high resistance to crystallization. Irradiation of films of this material yielded SRG with growth rates comparable to other reported azo materials. Herein, a series of closely related molecular glasses containing azobenzene chromophores with various absorption maxima ranging from 410 to 570 nm were synthesized, and their physical and photomechanical properties were studied. All materials studied showed the ability to form stable glassy phases, and irradiation with lasers emitting at various wavelengths allowed to perform a comparative study of SRG growth within a series of analogous chromophores.
... [3][4][5] Photoinduced SRG have been targeted for several applications, including holographic data storage, 6,7 distributed feedback lasers, 8 optical sensors and coupling devices, 9,10 and light harvesting structures for photovoltaic cells. 11,12 While initial studies on the solid-state photophysical behavior of azobenzene-based materials were performed using polymers, 13,14 small molecules possess several advantages, being monodisperse species, they are typically easier to purify, characterize and process, and show more reproducibility in their behavior. [15][16][17][18][19][20] However, the challenge with small molecules is ensuring that they can form amorphous thin lms, and not crystallize over time. ...
Materials containing azobenzene chromophores exhibit photomechanical behaviors, including the formation of surface relief gratings (SRG) caused by irradiation with two interfering laser beams. While azo-functionalized polymers were extensively studied, small molecules offer the advantage of being monodisperse species, which translates into easier synthesis and purification, as well as more uniform behavior. A drawback is that they tend to crystallize and do not always form high-quality thin films. Glass-forming compounds incorporating azobenzene were previously synthesized in several synthetic steps and in low yield. Herein, a Disperse Red 1 (DR1) functionalized with a mexylaminotriazine group is synthesized in 94% yield using a simple and straightforward procedure. It shows both the ability to form extremely stable glassy phases, and the ability to form SRG in the solid state with growth rates and grating heights closely similar to DR1-functionalized polymers.
In solar-assisted steam generators, simultaneously realizing high sunlight absorption and water transportation is a significant challenge. In this study, inspired by natural transpiration and the hierarchical architecture of artificial origami, we developed a three-dimensional (3D) graphene oxide-based solar steam generator (GOSG), which delicately designed and constructed via direct writing-based 3D printing coupled with freeze-drying. The obtained GOSG features a rippled upper surface decorated by stomata-like pores, while its substructures comprise hierarchical biomimetic structures with vertically orientated vessels-like channels serving as the basic capillary tubes for water transportation. Benefiting from the elaborate multi-scale structure design and the chemical modification of oxygenic functional groups, the as-printed 3D GOSG realizes the synergistic integration of improved performances, including wide spectra sunlight absorption, rapid water transportation, heat localization, and vapor evaporation. In the systematic investigation of the solar-thermal conversion processes, the GOSG device showed a superior efficiency of up to 94.5% under illumination as large as 1 kW·m-2, which is greater than those of most reported systems. The water desalination and sewage treatment abilities of the GOSG were further validated, demonstrating its multifunctional applications. Moreover, the prototype device tested for solar-assisted steam generation at an outdoor site demonstrated excellent mechanical robustness, cyclic durability, and diverse applicability, indicating the great potential of the GOSG as a high-efficiency, customizable, and scalable solar steam generator. These outstanding properties of the GOSG confirm that the combination of composition modification and structure optimization in a multi-scale design is an effective strategy for significantly improving the solar steam generation performance.
Due to the compromise between exciton diffusion length and light absorption, the active layer thickness of organic solar cells (OSCs) is limited. As we all know, embedding metal nanostructures into OSCs can improve the performance of OSCs by triggering surface plasma resonance, scattering, and other effect without increasing the physical thickness of light trapping layer. Besides, the plasma response and other roles will distinguish when metal nanostructures are embedded into different position of OSCs, which are equally important to the performance of OSCs. In this paper, the enhancement mechanisms of various metal nanostructures in different layers of OSCs are summarized from the electricity and optics aspects. This review also further highlights the progress of plasma effect and their working mechanism in OSCs, and it is expected to provide more perspective of plasma effect for performance enhancement of OSCs.
Precise control over molecular movement is of fundamental and practical importance in physics, biology, and chemistry. At nanoscale, the peculiar functioning principles and the synthesis of individual molecular actuators and machines has been the subject of intense investigations and debates over the past 60 years. In this review, we focus on the design of collective motions that are achieved by integrating, in space and time, several or many of these individual mechanical units together. In particular, we provide an in-depth look at the intermolecular couplings used to physically connect a number of artificial mechanically active molecular units such as photochromic molecular switches, nanomachines based on mechanical bonds, molecular rotors, and light-powered rotary motors. We highlight the various functioning principles that can lead to their collective motion at various length scales. We also emphasize how their synchronized, or desynchronized, mechanical behavior can lead to emerging functional properties and to their implementation into new active devices and materials.
In the present work, we use the photoinduced mass transport in thin films containing azobenzene derivatives to manipulate matter at the nanoscopic scale. First, we develop a simple method to elaborate periodic arrays of metal structures with adjustable plasmonic properties. The dispersion diagrams of the surface plasmons are measured and exhibit, as expected, the opening of an energy bandgap and of an unusual momentum-gap. The latter arises from the interaction of the plasmon modes of the two interfaces on either side of the metal film. Near-field measurements show the localization of the plasmon-enhanced optical field on the periodic structure, in agreement with calculations by RCWA. Second, we demonstrate the optical control of the displacement of nanoparticles, both metallic and dielectric, on the surface of an azobenzene-containing thin film. Displacement over several microns is observed with the direction controlled by the light polarization. This provides a new toolkit to manipulate nanoparticles at the nanoscale and gives deeper insight into the mechanisms at the origin of the photoinduced mass transport in azobenzene-containing films.
A thermo-optical process was developed for the erasure of surface relief gratings (SRG) inscribed on various films of mexylaminotriazine molecular glasses functionalized with different azobenzene chromophores, as well as azobenzene polymer films. Irradiation of the samples with a CO2 laser beam causes localized heating of the soda lime substrate, which is then transferred to the azobenzene films, causing complete erasure of the gratings while the temperature of each film was monitored in real time. The erasure temperature has been found to be strongly correlated with the respective glass transition temperatures (Tg) of the materials. Therefore, complete and partial all-optical erasure of gratings was successfully demonstrated and occurred in under a minute for azobenzene molecular glasses and under 3 minutes for azo-polymer films. Finally, gratings were shown to erase in specific patterns through the use of a metallic mask.
The surface plasmon resonance (SPR) effect of metal nanoparticles (MNPs) is effectively applied on polymer solar cells (PSCs) to improve power conversion efficiency (PCE). However, universality of the reported results mainly focused on utilizing single type of MNPs to enhance light absorption only in specific narrow wavelength range. Herein, a surface-energy-induced dual MNPs plasmon resonance by thermally evaporating method was presented to achieve the absorption enhancement in wider range. The differences of surface energy between silver (Ag), gold (Au), and tungsten trioxide (WO3) compared by contact angle images enable Ag and Au prefer to respectively aggregate into isolated islands rather than films at the initial stage of the evaporation process, which was clearly demonstrated in the atom force microscopy (AFM) measurement. The sum of plasmon-enhanced wavelength range induced by both Ag NPs (350-450 nm) and Au NPs (450-600 nm) almost cover the whole absorption spectra of active layer, which compatibly contribute a significant efficiency improvement from 4.57±0.16 % to 6.55 ±0.12 % compared to the one without MNPs. Besides, steady state photoluminescence (PL) measurements provide a strong evidence that the SPR induced by the Ag-Au NPs increase the intensity of light absorption. Finally, ultraviolet photoelectron spectroscopy (UPS) reveals that doping Au and Ag causes upper shift of both the work function and valence band of WO3, which is directly related to holes collection ability. We believe the surface-energy-induced dual plasmon resonance enhancement by simple thermally evaporating technique might pave the way toward higher-efficiency PSCs.
The optical properties of thin-film layers are described by the complex index-of-refraction (N) and are commonly measured using spectroscopic ellipsometry. Once determined, they can be used to predict the optical reflection and transmission from films of any thickness. Fitting of the spectroscopic ellipsometry data for thin-film polymers and polymer-blends is difficult because numerous numerical assumptions are necessary and optical birefringence must be accounted for. Ellipsometric fitting techniques fail for thin films with strong absorption and high surface roughness. The authors present a simple method to measure N, perpendicular to the sample plane, of optically homogeneous films using a UV/Vis spectrometer and partial transmission substrates.
The surface of an azoaromatic polymer film is optically altered to produce local highly efficient diffraction gratings. The gratings obtained are stable but can be erased by heating the polymer above its glass transition temperature and no permanent damage of the film is observed. Multiple gratings can be simultaneously written and gratings can be overwritten. Atomic force microscopy was used to investigate the gratings produced on the surfaces. Possible mechanisms responsible for the surface alteration are discussed.
Surface plasmons are waves that propagate along the surface of a conductor. By altering the structure of a metal's surface, the properties of surface plasmons—in particular their interaction with light—can be tailored, which offers the potential for developing new types of photonic device. This could lead to miniaturized photonic circuits with length scales that are much smaller than those currently achieved. Surface plasmons are being explored for their potential in subwavelength optics, data storage, light generation, microscopy and bio-photonics.
A new method of exciting nonradiative surface plasma waves (SPW) on smooth surfaces, causing also a new phenomena in total reflexion, is described. Since the phase velocity of the SPW at a metal-vacuum surface is smaller than the velocity of light in vacuum, these waves cannot be excited by light striking the surface, provided that this is perfectly smooth.However, if a prism is brought near to the metal vacuum-interface, the SPW can be excited optically by the evanescent wave present in total reflection. The excitation is seen as a strong decrease in reflection for the transverse magnetic light and for a special angle of incidence. The method allows of an accurate evaluation of the dispersion of these waves. The experimental results on a silver-vacuum surface are compared with the theory of metal optics and are found to agree within the errors of the optical constants.
We demonstrate enhanced power conversion efficiency in organic photovoltaic (OPV) cells incorporated into a plasmonic nanocavity array. The nanocavity array is formed between a patterned Ag anode and an unpatterned Al cathode. This structure leads to the confinement of optical energy and enhanced absorption in the OPV. Devices characterized under simulated solar illumination show a 3.2-fold increase in power conversion efficiency compared to OPVs with unpatterned Ag anodes. The observed enhancement is also reflected in the external quantum efficiency, and the spectral response is consistent with optical finite-difference time-domain simulations of the structure.
We theoretically investigate and compare the influence of square silver gratings and one-dimensional photonic crystal (1D PC) based nanostructures on the light absorption of organic solar cells with a thin active layer. We show that, by integrating the grating inside the active layer, excited localized surface plasmon modes may cause strong field enhancement at the interface between the grating and the active layer, which results in broadband absorption enhancement of up to 23.4%. Apart from using silver gratings, we show that patterning a 1D PC on top of the device may also result in a comparable broadband absorption enhancement of 18.9%. The enhancement is due to light scattering of the 1D PC, coupling the incoming light into 1D PC Bloch and surface plasmon resonance modes.
A 260 nm layer of organic bulk heterojunction blend of the polymer poly(3-hexylthiophene) (P3HT) and the fullerene [6,6]-phenyl C61-butyric (PCBM) was spin-coated in between aluminum and gold electrodes, respectively, on top of a laser inscribed azo polymer surface-relief diffraction grating. Angle-dependent surface plasmons (SPs) with a large band gap were observed in the normalized photocurrent by the P3HT-PCBM layer as a function of wavelength. The SP-induced photocurrents were also investigated as a function of the grating depth and spacing.
A polarization conversion of linearly polarized light incident on a cross-corrugated metal surface may occur due to the optical energy exchange between the surface plasmon (SP) resonances at the metal-dielectric interface. In this paper, the angular and wavelength dependence of the SP-induced polarization conversion was studied in transmission as a function of the grating pitch of two perpendicular surface relief diffraction gratings. A theoretical model based on graphical representations in momentum space of the traveling light beam through the specimen was developed and successfully applied to the experimental results.
We have developed a liquid crystal (LC) device that is totally
controlled using light. The initial alignment is made by optically
buffing the azopolymer film with two coherent argon laser beams. Surface
relief gratings have been optically induced on an assembled cell filled
with LC. A single linearly polarized argon laser beam is then employed
to irradiate the sample and photoinduce a twisted alignment structure.
This can then be erased by a circularly polarized beam. The alignment
information can also be erased by heating to the glass transition
temperature of the azopolymer film
Beginning from low level concepts the basic understanding for the optical excitation of surface plasmons is developed. Prism coupling using the attenuated total reflection technique is discussed as well as the less traditional grating coupling technique. A brief discussion of some recent developments using twisted gratings is also presented. Finally a short summary of the potential device applications is given.
To enhance solar harvesting in organic solar cells, uniform-sized metal nanoparticles of ~13 nm were incorporated to the device via pulse-current electrodeposition, which is a kind of simple and quick solution process that can control the density and size of metal nanoparticles. By incorporating plasmonic Ag nanoparticles on surface modified transparent electrodes, overall power conversion efficiency was increased from 3.05% to 3.69%, mainly resulting from the improved photocurrent density as a result of enhanced absorption of the photoactive conjugate polymer due to the high electromagnetic field strength in the vicinity of the excited surface plasmons.
The authors demonstrate the triggering of surface plasmons at the interface of a metal grating and a photovoltaic bulk heterojunction blend of alternating polyfluorenes and a fullerene derivative. An increased absorption originating from surface plasmon resonances is confirmed by experimental reflection studies and theoretical modeling. Plasmonic resonances are further confirmed to influence the extracted photocurrent from devices. More current is generated at the wavelength position of the plasmon resonance peak. High conductivity polymer electrodes are used to build inverted sandwich structures with top anode and bottom metal grating, facilitating for triggering and characterization of the surface plasmon effects.
We look at four length scales associated with the surface plasmon–polariton (SPP) modes in the visible and near-infrared. We examine some of the consequences of these length scales for exploiting surface plasmon–polariton modes as a means to provide sub-wavelength optics. The four length scales discussed are the SPP wavelength, the SPP propagation distance, and the penetration depths of the field associated with the SPP into the dielectric and metal media that bound the interface that supports the SPP. Length scales spanning seven orders of magnitude, from nanometres to centimetres, are of relevance to SPPs. This paper concludes by identifying some of the challenges that lie ahead.
Polymer-based photovoltaic cells, with periodic sub-micrometer structures as an efficient light-trapping scheme, are investigated to improve the performance of organic solar cells based on poly(3-hexylthiophene) and 1-(3-methoxycarbonyl)propyl-1-phenyl-(6,6)C61. A soft lithographic approach that uses photoresponsive azo polymer films as masters and poly(dimethylsiloxane) as stamps is used to form surface relief gratings (SRGs) on the active layers. The effect of periodic gratings on solar cell performance is precisely investigated according to various grating conditions such as period, depth, and dimension. The solar cells with 1D and 2D SRGs present improved incident-photon-to-current conversion efficiencies and an overall increase in power conversion efficiencies, primarily resulting from the enhancement of short-circuit current density, indicating that periodic structures induce further photon absorption in the active film.
Volume birefringence or surface relief gratings are optically inscribed on the surface of azopolymer thin films using polarized
light from a moderate power laser. The inscription is done in a one step process and the images are stable over extended periods
of time. Multiple holographic images can be written locally and these erasable sub-wavelength structures are used to produce
a variety of optical devices.
Plasmonic phenomenon inside the materials composing an organic solar cell based on a photoactive poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylenevinylene):(6,6)-phenyl-C61-butyric-acid-methyl ester (MEH-PPV:PCBM) bulk heterojunction is studied using Finite Difference Time Domain (FDTD) method calculations and the modeling results are compared with experimental results.Enhanced absorptance of light up to 50% is experimentally obtained in a 50-nm-thick blend layer including spin-coated silver nanospheres with a diameter of 40 nm. FDTD calculations based on the design of 2D-grating of nanoparticles confirm the high values of absorptance. Spatial distributions of electromagnetic field power density in the structures show confinement of the power at the interface or in the vicinity of the nanoparticles depending on the wavelength and on the preferential directions.
One limiting factor to the efficiency of the bulk heterojunction solar cell is the weak absorbance of the thin photoactive layer. The thickness is restricted by the small charge carrier mobility. Two cell concepts—light trapping with diffraction gratings and buried nano-electrodes—were investigated. Optical simulations based on rigorous coupled wave analysis were performed with supporting experiments in order to evaluate the concept of an embossed diffraction grating in the active polymer film. An increased absorptance in the active layer is calculated for transversal electric polarisation. High losses in the corrugated aluminium electrode in transversal magnetic polarisation would require a displacement of the corrugated boundary between two dielectrics. The second approach is based on vertical nano-electrodes. The planar semi-transparent electrode is substituted by comb-like array of electrodes embedded in the photoactive polymer blend. The potential of this approach is discussed and initial experimental results are presented.
In P3HT:PCBM based organic solar cells we propose and demonstrate numerically plasmonic backcontact grating architectures for strong optical absorption enhanced in both transverse-magnetic and transverse-electric polarizations. Even when the active material is partially replaced by the metallic grating (without increasing the active layer film thickness), we show computationally that the light absorption in thin-film P3HT:PCBM is increased by a maximum factor of ~21% considering both polarizations under AM1.5G solar radiation and over a half-maximum incidence angle of 45° (where the enhancement drops to its half) compared to the same cell without a grating. This backcontact grating outperforms the typical plasmonic grating placed in PEDOT:PSS layer.
Compilación de las propiedades físicas de los materiales usados en los distintos tipos de láseres y sistemas ópticos. Materiales ópticos contenido: Materiales cristalinos; Vidrios; Materiales de polímeros (plásticos ópticos); Metales; Líquidos; Gases; Apéndices.
Surface plasmons (SPs) are generated on a doubly corrugated gold-covered surface. The corrugations were obtained by direct holographic inscription of surface relief gratings on an azopolymer film. This method permits the superposition of multiple surface profiles with easy control of the grating spacing. One grating is inscribed to act as coupler for the incident light to the SP and a second grating is inscribed to generate a gap in the SP dispersion curve. The coupling and the gap can be observed by measuring the reflectivity of the gold surface as a function of the angle of incidence and the wavelength of the probe beam.
Described are the resonance effects associated with surface plasmon excitation (the excitation of evanescent electro-magnetic surface waves) which occur when light is reflected from metal gratings and rough surfaces.
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