P3HT/TiO2 bulk-heterojunction solar cell sensitized by a perylene derivative

In this work, a new type of dye-sensitized bulk-heterojunction hybrid solar cells has been developed. The heterojunction films were prepared to contain poly(3-hexylthiophene) (P3HT), N,N′-diphenyl glyoxaline-3,4,9,10-perylene tetracarboxylic acid diacidamide (PDI) and TiO₂. In the architecture, TiO₂ and P3HT were designed to act as the electron acceptor and donor. PDI was used as sensitizer to enhance the photon absorption. Results showed that by incorporation of PDI in the P3HT/TiO₂ composite, the light absorption, exciton separation and photocurrent under white light were dramatically enhanced. Solar decay analyses showed that devices contained TiO₂ required 12 h to obtain maximum current density and the addition of PDI did not affect the solar decay behavior and stability of device composed of P3HT/TiO₂. The devices of P3HT, P3HT/TiO₂, P3HT/TiO₂/PDI could work for 5, 42, 45 h under continuous white light illumination (100 mW/m²) under the ambient condition.     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

Hybrid inverted bulk heterojunction solar cells with nanoimprinted TiO2 nanopores

Photovoltaic devices with highly ordered nanoporous titanium dioxide (titania; TiO₂) were fabricated to improve the photovoltaic performances by increasing TiO₂ interface area. The nanoimprinting lithography technique with polymethyl methacrylate (PMMA) mold was used to form titania nanopores. The solar cell with poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) active layer on nanoporous titania showed higher power conversion efficiency (PCE) of 1.49% than on flat titania of 1.18%. The improved efficiency using nanoporous titania is interpreted with the enhanced-charge separation and collection by increasing the interface area between TiO₂ and active layer.     

Fabrication of CuInSe2 films and solar cells by the sequential evaporation of In2Se3 and Cu2Se binary compounds

Cu₂Se/In_xSe(x≈1) double layers were prepared by sequentially evaporating In₂Se₃ and Cu₂Se binary compounds at room temperature on glass or Mo-coated glass substrates and CuInSe₂ films were formed by annealing them in a Se atmosphere at 550°C in the same vacuum chamber. The In_xSe thickness was fixed at 1 μm and the Cu₂Se thickness was varied from 0.2 to 0.5 μm. The CuInSe₂ films were single phase and the compositions were Cu-rich when the Cu₂Se thickness was above 0.35 μm. And then, a thin CuIn₃Se₅ layer was formed on the top of the CuInSe₂ film by co-evaporating In₂Se₃ and Se at 550°C. When the thickness of CuIn₃Se₅ layer was about 150 nm, the CuInSe₂ cell showed the active area efficiency of 5.4% with V_oc=286 mV, J_sc=36 mA/cm² and FF=0.52. As the CuIn₃Se₅ thickness increased further, the efficiency decreased.     

CuGaSe2 solar cells prepared by MOVPE

Metal organic vapor-phase epitaxy (MOVPE) is used to prepare epitaxial reference films and solar cells based on CuGaSe₂. Room temperature Hall measurements are performed on epitaxial CuGaSe₂. Conductivities up to 0.7 (Ω cm)⁻¹ were obtained. Highest mobilities of 270 cm²/Vs are observed for near stoichiometric slightly Ga-rich films. Net charge carrier concentration is higher in the Cu-rich grown films than in the Ga-rich films. Solar cells with epitaxial absorber are prepared that reach efficiencies of 3.3%. First polycrystalline solar cells are grown on Mo/glass at reduced substrate temperatures. Under AM1.5 illumination open-circuit voltages up to 740 mV and efficiencies of 2.0% are obtained.     

Al2O3-coated nanoporous TiO2 electrode for solid-state dye-sensitized solar cell

This paper reports the preparation of a core-shell nanoporous electrode consisting of an inner TiO₂ porous matrix and a thin overlayer of Al₂O₃, and its application for solid-state dye-sensitized solar cell using p-CuI as hole conductor. Al₂O₃ overlayer was coated onto TiO₂ porous film by the surface sol–gel process. The role of Al₂O₃ layer thickness on the cell performance was investigated. The solar cells fabricated from Al₂O₃-coated electrodes showed superior performance to the bare TiO₂ electrode. Under illumination of AM 1.5 simulated sunlight (89 mW/cm²), a ca. 0.19 nm Al₂O₃ overlayer increased the photo-to-electric conversion efficiency from 1.94% to 2.59%.     

Electrodeposition of TiO2/SiO2 nanocomposite for dye-sensitized solar cell

For the working electrode of dye-sensitized solar cell (DSC), TiO₂/SiO₂ nanocomposite materials were electrodeposited on transparent fluorine doped tin oxide-coated glass by cathodic electrodeposition at room temperature. The electrode and DSC fabricated with TiO₂/SiO₂ nanocomposite were characterized with photocurrent density, X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM) and a photovoltaic performance test. On the electrodeposition, the addition of an appropriate amount of SiO₂ in the bath containing TiO₂ slurry was essential to achieve the superior crystallinity, photocurrent density and photovoltaic performance of the resulting TiO₂/SiO₂ electrode, which was significantly superior to a bare TiO₂ electrode. This enhanced performance of optimized TiO₂/SiO₂ electrode was ascribed to the role of SiO₂ as an energy barrier, increasing the physical separation of injected electrons and oxidized dyes/redox couple, and thereby retarding the recombination reactions in the resulting DSC.     

Surface ligand effects in MEH-PPV/TiO2 hybrid solar cells

TiO₂ nanorods (NRs) were synthesized by hydrolysis of titanium tetraisopropoxide (TTIP) using oleic acid (99%) as surfactant at low temperatures (80-100 °C) and are modified with different ligands: oleic acid (OLA), n-octyl-phosphonic acid (OPA) and thiophenol (TP) in order to investigate the effect of surface ligand on the excition dissociation and the charge transport in hybrid MEH-PPV/TiO₂ photovoltaic (PV) cells. The morphology and crystalline form of as-prepared TiO₂ NRs are examined by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray diffraction (XRD) and Raman spectrometer (RS). The FTIR analysis confirms all the ligands coordinated with the Ti center of TiO₂ NRs. The optical properties of the modified TiO₂ NRs are characterized by UV-vis absorption spectra and photoluminescence (PL) spectra. Thiophenol modified TiO₂ NRs quench the PL of MEH-PPV more effectively than OLA-TiO₂ NRs and OPA-TiO₂ NRs. The power conversion efficiency of hybrid PV cells from thiophenol modified TiO₂ NRs and MEH-PPV is the highest among the investigated TiO₂ NRs.     

Dye-sensitized nanocrystalline TiO2 solar cells based on novel coumarin dyes

We have developed dye-sensitized nanocrystalline TiO₂ solar cells (DSSCs) based on novel coumarin-dye photosensitizers. The absorption spectra of these novel dyes are red-shifted remarkably in the visible region relative to the spectrum of C343, a conventional coumarin dye. Introduction of a methine unit (–CH=CH–) connecting the cyano (–CN) and carboxyl (–COOH) groups into the coumarin framework expanded the π-conjugation in the dye and thus resulted in a wide absorption in the visible region. These novel dyes performed as efficient photosensitizers for DSSCs. A DSSC based on 2-cyano-5-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-penta-2,4-dienoic acid (NKX-2311), produced a 6.0% solar energy-to-electricity conversion efficiency (η), the highest performance among DSSCs based on organic-dye photosensitizers, under AM 1.5 irradiation (100 mW cm^–2) with a short-circuit current density (J_sc) of 14.0 mA cm^–2, an open-circuit voltage (V_oc) of 0.60 V, and a fill factor of 0.71. Our results suggests that the structure of NKX-2311 whose carboxyl group is directly connected to the –CH=CH– unit, is advantageous for effective electron injection from the dye into the conduction band of TiO₂. In addition, the cyano group, owing to its strong electron-withdrawing ability, might play an important role in electron injection in addition to a red shift in the absorption region. On a long-term stability test under continuous irradiation with white light (80 mW cm^–2), stable performance was attained with a solar cell based on the NKX-2311 dye with a turnover number of 2.6×10⁷ per one molecule.     

Unique TiO2 paste for high efficiency dye-sensitized solar cells

A novel titanium oxide paste based on Pechini sol-gel method and nanocrystalline titanium oxide powder have been successfully developed. Titanium oxide layers possess high inner surface area assuring high dye loading and well-connected nanocrystalline grains assuring good electron transport within the layer. The dye-sensitized layers have been used to assemble dye-sensitized solar cells with acetonitrile- and ionic liquid-based electrolyte. Overall conversion efficiencies of dye-sensitized solar cells (DSSCs) determined under standard test conditions (100 mW/cm², 25 °C and AM 1.5 G) are 10.2% for acetonitrile and 7.3% for ionic liquid-based electrolyte.     

Bulk p-CuInSe2 photo-electrochemical solar cells

Dense CuInSe₂ of high quality, prepared by the fusion technique in evacuated quartz ampoule from stoichiometric melt, crystallizes in the chalcopyrite structure. Compositional analysis carried out by secondary ion mass spectrometry (SIMS) and energy dispersive spectroscopy (EDS) indicates a uniform distribution of elements through the depth and a composition close to the stoichiometry. The diffuse reflectance spectrum gives a band gap at 0.94 eV. The electrical conductivity follows an Arrhenius-type law with activation energy of 23 meV in conformity with polarons hopping. Above 320 °C, CuInSe₂ undergoes an irreversible oxidation. The thermal variation of the thermopower indicates p-type behavior attributed to copper deficiency and a hole mobility μ_300 K of 0.133 cm² V⁻¹ s⁻¹, thermally activated. In KCl media, the compound exhibits an excellent chemical stability with a corrosion rate of 8 μmol cm⁻² month⁻¹. The photo-electrochemical properties, investigated for the first time on the ingots, confirm the p-type conductivity. From the capacitance measurements, the flat band potential (V_fb=−0.62V_SCE) and the holes density (N_A=4×10¹⁷ cm⁻³) were determined. The valence band, located at 4.43 eV below vacuum, is made up of mainly Se orbital with little admixture of Cu character. The change of the electrolyte causes a variation in the potential V_fb (dV_fb/dpH=−0.058 V pH⁻¹) indicating strong OH⁻ adsorption. The fill factor in S²⁻ media was found to be 0.54; such result was corroborated by semi-logarithmic plots.     

Efficient hybrid carboxylated polythiophene/nanocrystalline TiO2 heterojunction solar cells

Efficient hybrid solar cells fabricated from TiO₂, novel carboxylated polythiophene poly (3-thiophenemalonic acid) P3TMA as sensitizer as well as hole conductor and poly (3-hexylthiophene) (P3HT) as hole transporter was described. UV-Vis absorption and morphology of the active layer were investigated. Device J/V characterizations with different P3HT layer thickness were measured and discussed. Efficiency improvements were observed in thinner P3HT layer thickness and with poly[3,4-(ethylenedioxy)-thiophene]:poly(styrene sulfonate) (PEDOT:PSS) as charge collection layer, and such device showed a short-circuit current density of 1.32 mA/cm², an open-circuit voltage of 0.44 V, a fill factor of 0.43, and a energy conversion efficiency of 0.25% at A.M. 1.5 solar illumination (100 mW/cm²).     

Columnar rutile TiO2 based dye-sensitized solar cells by radio-frequency magnetron sputtering

Columnar-structured rutile TiO₂ film with a thickness of 1.4 μm is prepared using the radio-frequency (RF) magnetron sputtering technique, for application in dye-sensitized solar cells (DSSCs). Pure rutile TiO₂ films are fabricated by controlling the substrate temperature during sputtering and using a substrate with a rough surface morphology. Successive substrate heating to 623 K induces the growth of a rutile TiO₂ film that has a specific direction in the (1 1 0) plane, which results in a decrease in the average grain size. This causes in an increase of dye uptake and thereby contributes to enhancement of the photocurrent in the DSSC.     

UV light protection through TiO2 blocking layers for inverted organic solar cells

Fully organic solar cells (OSCs) based on polymers and fullerenes have attracted remarkable interest during the last decade and high power conversion efficiencies (PCEs) beyond 8% have been realized. However, air stability of these cells remains poor. The conventional geometry of OSCs utilizes strongly oxidizing metal top contacts like Al or Ca. These metals are easily oxidized in air resulting in rapid decrease of PCE if cells are not perfectly encapsulated. Using a thin electron-selective hole-blocking bottom layer like TiO₂ enables fabrication of solar cells in a so-called inverted geometry. In this geometry, noble metals like Ag or Au can be used as top contacts, which are less sensitive to ambient oxygen. Thus, air-stability of these inverted solar cells is significantly improved. In this study we investigate inverted polythiophene-methanofullerene solar cells. We find significant influence of the TiO₂ layer thickness on light absorption and illumination stability of the solar cells, as well as the trap filling by photoinduced carriers. Even though TiO₂ layers as thick as 500 nm seem not to be detrimental for charge transport, light intensity losses limit the device performance. In turn, illumination stability is better for thicker TiO₂ layers, which can serve as UV filters and protect the photoactive materials from degradation, when compared to thin TiO₂ layers. Considering these different effects we state that a thickness of 100 nm is the optimization of the TiO₂ layer.     

CuInS2/In2S3 thin film solar cell using spray pyrolysis technique having 9.5% efficiency

Copper indium sulfide (CuInS₂)/In₂S₃ solar cells were fabricated using spray pyrolysis method and high short circuit current density and moderate open circuit voltage were obtained by adjusting the condition of deposition and thickness of both the layers. Consequently, a relatively high efficiency of 9.5% (active area) was obtained without any anti-reflection coating. The cell structure was ITO/CuInS₂/In₂S₃/Ag. We avoided the usual cyanide etching and CdS buffer layer, both toxic, for the fabrication of the cell.     

Performance of dye-sensitized solar cell based on nanocrystals TiO2 film prepared with mixed template method

Highly efficient dye-sensitized solar cells were produced using high-crystalline TiO₂ nanoparticles as a thin-film semiconductor prepared with a mixed template of copolymer F127 (poly(ethylene oxide)₁₀₆-poly(propylene oxide)₇₀-poly(ethylene oxide)₁₀₆) and surfactant CTAB (cetyltrimethylammonium bromide) which allows access to larger surface area, smaller size and higher crystallinity TiO₂ particles. The light-to-electricity conversion of the TiO₂ film composed of nanocrystals with the size of 35 nm, which carry out perfect electrical contiguity between film and conducting glass and between every TiO₂ coating, was over 6% with a film of 5.5 μm thickness. Over 8% conversion efficiency has been obtained with a double-layer film composed by the TiO₂ layer and the scattering layer.     

CVD of CuGaSe2 for thin film solar cells with various transport agents

Chemical vapor deposition (CVD) in an open tube system was employed to deposit single-phase CuGaSe₂ thin films on plain and Mo-coated glass substrates. The use of HCl and ternary CuGaSe₂ source material resulted in non-stoichiometric volatilization of the source material. The use of binary source materials – Cu₂Se and Ga₂Se₃ – in combination with I₂ and HCl as the respective transport agents yielded single-phase CuGaSe₂ thin films while the source materials were volatilized stoichiometrically. Mo/CuGaSe₂/CdS/ZnO devices were fabricated from these samples exhibiting an open-circuit voltages up to V_oc=853 mV.     

Improvement in dye-sensitized solar cells employing TiO2 electrodes coated with Al2O3 by reactive direct current magnetron sputtering

A novel surface modification method was carried out by reactive dc magnetron sputtering to fabricate TiO₂ electrodes coated with Al₂O₃ for improving the performance of dye-sensitized solar cells (DSSCs). The Al₂O₃-coated TiO₂ electrodes had been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV–vis spectrophotometer, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The study results revealed that the modification to TiO₂ increases dye absorption amount, reduces trap sites on TiO₂, and suppresses interfacial recombination. The impact of sputtering time on photoelectric performance of DSSCs was investigated. Sputtering Al₂O₃ for 4 min on 5-μm thick TiO₂ greatly improves all cell parameters, resulting in enhancing the conversion efficiency from 3.93% to 5.91%. Further increasing sputtering time decreases conversion efficiency.     

Nanoporous SnO2 electrodes for dye-sensitized solar cells: improved cell performance by the synthesis of 18 nm SnO2 colloids

This paper reports on the synthesis of SnO₂ 18 nm diameter colloidal suspension for the fabrication of nanoporous electrodes. The new suspension allows the fabrication of thick and homogeneous electrodes by simple one layer spreading; in contrast to the successive spin coating of the commonly used commercial suspension that results in a thin inhomogeneous electrode. When used in dye-sensitized solar cells, the new electrodes increase the light-to-energy conversion efficiency by a factor of 2.1 in comparison with standard commercial suspension based electrodes. The improvement is mostly the result of an increase of the photocurrent. This increase is attributed to the better electrolyte migration, and presumably also to an increase of the photoinjected electron diffusion rate in the electrode.     

Slow interfacial charge recombination in solid-state dye-sensitized solar cell using Al2O3-coated nanoporous TiO2 films

Al₂O₃-coated TiO₂ porous films were used to fabricate solid-state dye-sensitized solar cells using CuI as hole conductor. Investigation with transient photovoltage measurements showed that the Al₂O₃ interlayer slowed down the interfacial recombination of electrons in TiO₂ with holes in CuI by forming a potential barrier at the TiO₂/CuI interface. As a consequence, the cell made from Al₂O₃-coated TiO₂ film showed superior cell performance than the cell made from TiO₂ film only, especially under relative high intensity of simulated sunlight.