Fabrication and characterizations of PCDTBT: PC71BM bulk heterojunction solar cell using air brush coating method

Organic solar cells have been significantly attracted due to the need to develop an inexpensive clean and sustainable renewable energy source. We report on the fabrication of poly [N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)]/[6, 6]-phenyl-C₇₁-butyric acid methyl ester blend active layer using airbrush spray-coating method in mixed solvents. Optical absorption of the active layers was analyzed using UV–visible spectral studies in the wavelength range from 300 to 800 nm. The surface morphology of the active layers deposited with different parameters (spraying time and substrate-nozzle distance) was examined using atomic force microscopy. The current density–voltage (J–V) characteristics of photovoltaic cells were measured under the illumination of simulated solar light with 100 mW cm^?2 (AM 1.5G) by an Oriel 1000 W solar simulator. The power conversion efficiency of the solar cell is more than 5 %.     

Photovoltaic properties of low-band-gap fluorene-based donor-acceptor copolymers

The photovoltaic properties of three fluorene-thiophene-based donor-acceptor copolymers with low band gap and reasonably high hole mobility were studied in copolymer/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk-heterojunction photovoltaic cells. The copolymers were poly[2,7-(9,9′-dihexylfluorene)-alt-2,3-dimethyl-5,7-dithien-2-yl-quinoxaline] (PFDDTQ) (band gap = 1.94 eV; mobility = 2.83 × 10^− 5 cm² V^− 1 s^− 1), poly[2,7-(9,9′-dihexylfluorene)-alt-4,7-dithien-2-yl-2,1,3-benzothiadiazole] (PFDTBT) (band gap = 1.82 eV; mobility = 4.71 × 10^− 5 cm² V^− 1 s^− 1) and poly[2,7-(9,9′-dihexylfluorene)-alt-2,3-dimethyl-5,7-dithien-2-yl-thieno[3,4-b] pyrazine] (PFDDTTP) (band gap = 1.68 eV; mobility = 1.18 × 10^− 4 cm² V^− 1 s^− 1). The order in the short-circuit current density and power-conversion efficiency of the photovoltaic cells was PFDTBT > PFDDTQ > PFDDTTP, which contradicted the order in the band gap and mobility. The short-circuit current density and power-conversion efficiency (PCE) coincided instead with the order in the mobility of the copolymer/PCBM blend, where the mobility was increased for PFDTBT and PFDDTQ owing to the charge transfer with PCBM, but was decreased for PFDDTTP due to phase separation resulting from the strong intermolecular interactions of PFDDTTP. With its high blended mobility and low band gap, PFDTBT achieved a PCE of 1.1%.     

Photoinduced charge transfer and efficient solar energy conversion in a blend of a red polyfluorene copolymer with CdSe nanoparticles

We present measurements of charge transfer and the photovoltaic effect in a blend of the alternating polyfluorene copolymer poly(2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)) with branched CdSe nanoparticles. Quasi-steady-state photoinduced absorption measurements identified a long-lived charged species that formed after photoexcitation at room temperature. Photovoltaic devices based on this blend system showed a spectral response extending to 650 nm and gave a solar power conversion efficiency of 2.4% under Air Mass 1.5 Global (AM1.5G) conditions.     

Characterization of spray-coating methods for conjugated polymer blend thin films

We examine the characteristics and functionality of conjugated polymer thin films, based on blends of poly(9,9-dioctylfluorene-2,7-diyl-co-bis-N,NN′-(4-butylphenyl)-bis-N,N′-phenyl-1,4-phenylenediamine) (PFB) and poly(9,9-dioctylfluorene-2,7-diyl-co-benzothiadiazole) (F8BT), using a spray-coating deposition technique suitable for large areas. The morphological properties of these blend films are studied in detail by atomic force microscopy (AFM) methods, showing that favourable results, in terms of layer deposition rate and uniformity, can be achieved using a 5:1 blend of o-dichlorobenzene and chlorobenzene as the solvent medium. A photoluminescence quenching efficiency of above 80 % is also observed in such blend films. As a feasibility study, prototypical photovoltaic devices exhibit open circuit voltages of up to 1.0 V under testing, and solar power conversion efficiencies in the 0.1–1 % order of magnitude; metrics which are comparable with those reported for spin-coated cells of the same active blend and device architecture.     

White polymer light-emitting diodes based on poly(2-(4′-(diphenylamino)phenylenevinyl)-1,4-phenylene-alt-9,9-n-dihexylfluorene-2,7-diyl) doped with a poly(p-phenylene vinylene) derivative

Efficient white polymer light-emitting diodes based on the polymer blend of poly(2-(4′-(diphenylamino)phenylenevinyl)-1,4-phenylene-alt-9,9-n-dihexylfluorene-2,7-diyl) doped with poly{2-[3′,5′-bis(2?-ethylhexyloxy) benzyloxy]-1,4-phenylenevinylene}-co-poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) were fabricated. The electroluminescence (EL) spectrum is easily controlled by changing the dopant concentration. A white light emission was realized on the device with the dopant concentration of 0.194‰ and the emission light is less sensitive to the applied voltage in a wide voltage range. The maximum luminance and the maximum EL efficiency of the single-layer device were 2330 cd/m² and 0.29 cd/A, respectively. By introducing an Alq₃ layer as an electron transporting and hole blocking layer, the overall performance of the double layer device was dramatically improved, the maximum luminance and the maximum EL efficiency reached 3300 cd/m² and 2.37 cd/A, respectively.     

Fourier transform photocurrent spectroscopy applied to a broad variety of electronically active thin films (silicon, carbon, organics)

Steady state and low frequency photocurrent spectroscopies have proved as a valuable tool for investigation of many different semiconductors, used for example as an absorber in photovoltaic solar cells or in the large area sensors. Fourier transform photocurrent spectroscopy (FTPS), described here, exhibits advantages as a high sensitivity (we demonstrate dynamical range up to 9 orders of magnitude of the optical absorption coefficient, connected with the absorption process leading to free carriers; or sensitivity for dopant detection better than 1 part-per-billion), fast acquisition of data (it can be of the order of seconds) or high resolution (under more lengthy acquisition of data). Results on amorphous silicon, microcrystalline silicon, diamond layers, nanocrystalline diamond and very thin organic films, as poly(2-methoxy-5-(3′,7′-dimethyl-octyloxy))-p-phenylene-vinylene (MDMO-PPV), regioregular poly(3-hexylthiophene (P3HT) and their blends with (6,6)-phenyl-C61-butyric-acid (PCBM) are reported, together with the results measured on various thin film silicon or polymer solar cells.     

Sequential processing: control of nanomorphology in bulk heterojunction solar cells

Bulk heterojunction organic photovoltaic devices based on poly[N-9'-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole) (PCDTBT)/[6,6]-phenyl C(70) butyric acid methyl ester (PC(70)BM) can be successfully fabricated by a sequential solution deposition process. When the top layer is deposited from an appropriate cosolvent, the PC(70)BM penetrates a predeposited bottom layer of PCDTBT during the spin-casting process, resulting in an interdiffused structure with a layer-evolved bulk heterojunction (LE-BHJ) nanomorphology. The PCDTBT:PC(70)BM LE-BHJ solar cells prepared with an optimized cosolvent ratio have comparable power conversion efficiency to the conventional BHJ solar cells. The nanomorphology of the optimized PCDTBT:PC(70)BM LE-BHJ mixture was found to have better vertical connectivity than the conventional BHJ material.     

Molecular design of copolymers based on polyfluorene derivatives for Bulk-heterojunction-type solar cells

Poly{[2,7-(9,9′-dihexylfluorene)]-alt-[4,7-di(thiophen-2-yl)benzo[c][1, 2, 5]thiadiazole]} (PFDTBT) with low band gap was reported as an intriguing and promising donor in Bulk-heterojunction-type solar cells. In this paper, based on the structure of PFDTBT, three new kinds of donor materials: poly{[2,7-(9,9′-dihexylfluorene)]-alt-[4,7-di(thiophen-2-yl)-[1, 2, 5]thiadiazolo[3,4-d]pyridazine]} (PFDTTDP), poly{[2,7-(9,9′-dihexyloxyfluorene)]-alt-[4,7-di(thiophen-2-yl)-[1, 2, 5]thiadiazolo[3,4-d]pyridazine]} (POFDTTDP), and poly{[2,6-(4,4-dihexyl)-4H-cyclopenta[2,1-b;3,4-b’]-dithiophene)-alt-[4-(1,3,4-thiadiazol-2-yl)-7-(thiophen-2-yl)-[1, 2, 5]thiadiazolo[3,4-d]pyridazine]} (PCPTTTDP), were designed and computed by density function theory (DFT). The electronic, optical and photovoltaic properties, and charge transport rates were investigated. The reorganization energies for holes and electrons are around 0.11 and 0.08 eV, respectively. It indicates that PFDTTDP, POFDTTDP, and PCPTTTDP are good candidates for donor material. Especially, when 6,6-phenyl-C61-butyric acid methyl ester (PC₆₁BM) functions as acceptor, PCPTTTDP has the most appropriate highest occupied molecular orbital and lowest unoccupied molecular orbital energy, and has the broadest absorption in the near-infrared region.     

The effect of helium plasma etching on polymer-based optoelectronic devices

In this paper the optoelectronic performance of selectively patterned conjugated polymers in light emitting diodes (LEDs) and photodetectors was examined. Polymers were patterned via a dry, non-reactive ion etching process using helium plasma. The polymers studied were the light-emitting poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and poly[9,9-di-(2′-ethylhexyl)fluorenyl-2,7-diyl], and the conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate). The electroluminescent spectra of etched and unetched LEDs are almost identical. There is no correlation between He-ion etching times and LED emission spectra changes. The MEH-PPV-based photodetectors show no decrease in external quantum efficiencies due to increased etch times. Results show that using helium plasma is effective at etching these polymers at predictable rates from selected areas without damaging the working device.     

Spontaneous stratification in composite films consisting of conjugated polymers and neat C60 prepared by electrophoretic deposition

The morphology of composite films consisting of conjugated polymers and C₆₀ prepared by electrophoretic deposition (EPD) has been studied. While C₆₀ exists as nanocrystals uniformly embedded in the composite films based on poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene], a spontaneous stratification of the composite films into polymer-C₆₀-mixture and C₆₀-microcrystal layers is observed in the films based on a polyfluorene derivative, poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-{2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene}]. The results suggest that EPD can be a useful tool for controlling the morphology of bulk heterojunction systems for organic photocells.     

Blue electroluminescent materials based on 2,7-distyrylfluorene for organic light-emitting diodes

A series of blue fluorescent 9,9-diethyl-2,7-distyryl-9H-fluorene derivatives with various capping moieties such as diphenylamino; diphenylphosphino; triphenylsilyl; phenoxy; phenylmercapto; phenylselenoxy; and triphenymethyl groups were synthesized using the Honor-Emmons reaction. The highest occupied molecular orbital-lowest unoccupied molecular orbital energy levels were characterized with a photoelectron spectrometer and rationalized with quantum mechanical density functional theory calculations. The electroluminescent properties were explored through the fabrication of multilayer devices with a structure of Indium-tin-oxide/N,N′-diphenyl-N,N′-(1-napthyl)-(1,1′-phenyl)-4,4′-diamine/2-methyl-9,10-di(2-naphthyl)anthracene:blue dopants (5-15 wt.%)/4,7-diphenyl-1,10-phenanthroline/lithium quinolate/Al. All devices, except that using NPh₂, exhibited a Commission Internationale de I'Eclairage (CIE) y value less than 0.19. The best luminous efficiency of 3.87 cd/A and external quantum efficiency of 2.65% at 20 mA/cm² were obtained in a device comprising the 4-phenylsulfanyl capped 9,9-diethyl-2,7-distyrylfluorene derivative with CIE coordinates (0.16, 0.18).     

The synergistic effect of nanocrystal integration and process optimization on solar cell efficiency

This paper investigates the roles of semiconducting single-walled carbon nanotubes (SWNTs) and metallic SWNTs in the SWNT/poly(3-hexylthiophene) (P3HT)-based photovoltaic conversion system. SWNTs containing different fractions of semiconducting nanotubes were conjugated with P3HT by virtue of π-π interaction. The energy transfer and carrier transport mechanisms in the photovoltaic composites were experimentally investigated by optical absorption spectroscopy, photoluminescence spectroscopy and carrier mobility measurements. At low loading of SWNTs, a high percentage of semiconducting nanotubes result in diminished non-radiative decay of exciton and lower carrier mobility, causing higher open circuit voltage and lower photocurrent. At an optimized morphology, SWNT/P3HT/phenyl-C61-butyric acid methyl ester (PCBM) hybrid-based solar cells demonstrated much higher photocurrent than a reference solar cell (P3HT:PCBM) due to the improved carrier mobility. Further thermal annealing of the devices significantly increased the open circuit voltage to 610?mV, resulting in an 80% increase of power conversion efficiency in comparison to the reference solar cell. These results are expected to lay a foundation for the integration of various nanocrystals into solar cells for efficient photovoltaic conversion.     

Surface plasmon enhanced fluorescence of cationic conjugated polymer on periodic nanoarrays

The fluorescence from conjugated polymer assembled onto lithographically fabricated gold nanoarrays using genetically engineered peptides as molecular linkers is studied. A 16-fold increase in the photoluminescence of the conjugated polymer is observed when assembled on the optimized nanostructures due to surface plasmon enhanced fluorescence. This is achieved using a water-soluble cationic conjugated polymer, poly[(9,9-bis(6'-((N,N,N-trimethylammonium)hexyl)-2,7-fluorene)-co-4,7-di-2-thienyl-2,1,3-benzothiadiazole] dibromide (PFDBT-N(+)), systematically tuning the vertical distance of PFDBT-N(+) from the gold nanopillar surface using solid-specific peptide linkers and horizontally optimizing the localized surface plasmon resonance by varying the geometric arrangements of the patterned metal nanoarrays. The diameter and tip-to-tip spacing of the nanopillars along with vertically tuning the distance of PFDBT-N(+) from the nanopillar affected the observed fluorescence enhancements. The collective optical properties of conjugated polymers combined with the photonic properties of nanoparticles provide a new means in the development of metal enhanced hybrid nanomaterials for biotechnology.     

Photovoltaic performance of ruthenium complex dye associated with number and position of carboxyl groups on bipyridine ligands

A series of ruthenium complex dyes with different number and position of carboxyl groups on bipyridine ligands, such as Ru(4-carboxyl-4′-methyl-2,2′-bipyridine)(4,4′-dimethyl-2,2′- bipyridine)(NCS)₂ (denoted as Ru1A), Ru(4-carboxyl-4′-methyl-2,2′-bipyridine)₂(NCS)₂ (Ru11A), Ru(4,4′-dicarboxyl-2,2′-bipyridine)(4,4′-dimethyl-2,2′-bipyridine)(NCS)₂ (Ru2A), and Ru(4-carboxyl-4′-methyl-2,2′-bipyridine)(4,4′-dicarboxyl-2,2′-bipyridine)(NCS)₂ (Ru3A) were synthesized and compared with Ru(4,4′-dicarboxyl-2,2′-bipyridine)₂ (NCS)₂, commonly known as N3 dye for the adsorption behavior on the TiO₂ surface and photovoltaic properties of dye-sensitized solar cells. The experimental results show that the tilt angle of ruthenium dyes on the TiO₂ surface which is dependent on the number and position of their carboxyl groups strongly affected the photovoltaic performance.     

A unified description of current-voltage characteristics in organic and hybrid photovoltaics under low light intensity

We develop a simple model that can explain the current-voltage ( J- V) curves of excitonic photovoltaic solar cells, spanning polymer:polymer, polymer:fullerene, and polymer:nanocrystal devices. We show that by subtracting out the dark current, we can explain apparent intensity-dependent characteristics and thus identify geminate recombination as the dominant loss mechanism and establish its electric field dependence. We present an analytic fit to the J- V curves of all measured devices based on a single fitted parameter, the electric field required to split 50% of geminate charge pairs, which we term the critical field. Devices of different material combinations and morphologies can all be described by this method and yield critical fields varying between >1 x 10(8) V/m for blends of poly(9,9'-dioctylfluorene- co-bis- N, N'-(4-butylphenyl)-bis- N, N'-phenyl-1,4-phenylenediamine) (PFB) and poly(9,9'-dioctylfluorene- co-benzothiadiazole) (F8BT) and 8 x 10 (5) V/m for slow-grown blends of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). A comparison with material properties reveals that the primary route to improved photovoltaic materials is enhanced charge delocalization.     

Influence of thermal annealing-induced molecular aggregation on film properties and photovoltaic performance of bulk heterojunction solar cells based on a squaraine dye

Squaraine (SQ) dyes have been considered as efficient photoactive materials for organic solar cells. In this work, we purposely controlled the molecular aggregation of an SQ dye, 2,4-bis[4-(N,N-dibutylamino)-2-dihydroxyphenyl] SQ (DBSQ-(OH)₂) in the DBSQ(OH)₂:[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) blend film by using the thermal annealing method, to study the influence of the molecular aggregation on film properties as well as the photovoltaic performance of DBSQ(OH)₂:PCBM-based bulk heterojunction (BHJ) solar cells. Our results demonstrate that thermal annealing may change the aggregation behavior of DBSQ(OH)₂ in the DBSQ(OH)₂:PCBM film, and thus significantly influence the surface morphology, optical and electrical properties of the blend film, as well as the photovoltaic performance of DBSQ(OH)₂:PCBM BHJ cells.     

Developing 1D Sb‐Embedded Carbon Nanorods to Improve Efficiency and Stability of Inverted Planar Perovskite Solar Cells

To overcome the zigzag pathway transport of the electron diffusion process and eliminate the surface trap states of phenyl‐C61‐butyric acid methyl ester (PCBM) nanofilms in inverted perovskite solar cells, novel 1D N‐type doped carbon nanorods (CNRs) are developed by a stibonium (Sb) auxiliary ball milling method and introduced into the PCBM film to prepare the PCBM:Sb‐CNRs hybrid transport layer. In this way, the N‐type doped Sb‐CNRs can extend the built‐in electric field between CH₃NH₃PbI₃ and PCBM to facilitate the separation of electron/hole pairs. The discontinuous band with the built‐in potential in the PCBM/Sb‐CNRs heterojunction can boost interfacial charge redistribution and promote electrons diffusion from PCBM to electrode through 1D Sb‐CNRs network. As a result, the high device efficiency of 19.26% with enhanced air stability and little hysteresis are achieved. This work demonstrates a simple strategy to improve the efficiency and stability of perovskite photovoltaic devices using low‐cost carbon nanomaterials.     

The role of solvent and morphology on miscibility of methanofullerene and poly(3-hexylthiophene)

A bicontinuous, percolating bulk heterojunction morphology is integral to organic polymer solar cells. Understanding the factors affecting the miscibility of photovoltaic polymers with a fullerene electron acceptor molecule is a key to controlling the morphology. Starting from discreet pure phases - a poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) bilayer film - the evolution of the P3HT-PCBM interface was studied with particular attention to the role of residual solvent in P3HT on PCBM interdiffusion. This investigation shows that in the bilayer geometry PCBM can rapidly diffuse into amorphous P3HT, but phase separation is maintained if the P3HT layer is cast from a very volatile solvent or if it is annealed prior to casting the PCBM overlayer to complete the bilayer geometry.     

Improved photovoltaic properties of fluorene-thiophene-based copolymers by an electron-transporting triazole unit in the main chain

An electron-transporting triazole (Tz) unit was introduced into the fluorene-thiophene-based copolymer backbone via a Suzuki coupling reaction. The resulting copolymer, poly[9,9'-dioctyl-fluorene-co-5, 5-(4', 7'-di-2-thienyl-2', 1',3'-benzothiadiazole)-co-(4-(4-butyl-phenyl)-3, 5-diphenyl-4H-1,2,4]triazole)] (PF3TBTz), was soluble in common organic solvents and can be easily used as the active layer in organic photovoltaic cells (OPVs). By the introduction of the triazole unit, the OPV performance was nearly doubled from 0.62% (PF3TB) to 1.25% (PF3TBTz) under the same conditions. The higher performance can be explained by the improved surface morphology, resulting in better charge photogeneration and higher short circuit current (J(sc)) value in PF3TBTz in comparison with PF3TB. The possibility of the use of triazole units in OPV applications are described herein.     

Dithiapyrannylidenes as efficient hole collection interfacial layers in organic solar cells

One inherent limitation to the efficiency of photovoltaic solar cells based on polymer/fullerene bulk heterojunctions (BHJs) is the accumulation of positive charges at the anodic interface. The unsymmetrical charge collection of holes and electrons dramatically decreases the short-circuit current. Interfacial layers (IFLs) such as poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) have no effect on the unbalanced electron/hole transport across the BHJ. We report here on the use of dithiapyrannylidenes (DITPY), a new class of planar quinoid compounds, as efficient hole-transporting/electron-blocking layers in organic solar cells based on poly(3-hexylthiophene)/[6,6]-phenyl-C(61)-butyric acid methyl ester (P3HT:PCBM) BHJs. Inserting a 15-nm-thick IFL of 4,4'-bis(diphenyl-2,6-thiapyrannylidene) (DITPY-Ph(4)) between the indium-tin oxide electrode and the P3HT:PCBM BHJ prevents detrimental space-charge effects and favors recombination-limited currents. Current-sensing atomic force microscopy reveals a drastic increase of the hole-carrying pathways in DITPY-Ph(4) compared to PEDOT:PSS. In ambient conditions, photovoltaic cells using DITPY-Ph(4) exhibit an 8% increase in the current density, although the conversion efficiency remains slightly lower compared to PEDOT:PSS-based devices. Finally, we present a detailed analysis of the photocurrent generation, showing that DITPY-Ph(4) IFLs induce a transition from unproductive space-charge-limited currents to recombination-limited currents.