Semiconducting polymer-incorporated nanocrystalline TiO2 particles for photovoltaic applications

In this work, we study hybrid solar cells based on blends of the semiconducting polymer poly(3-octylthiophene-2,5-diyl)(P3OT) and [6,6]-phenyl C₆₁ butyric acid methyl (PCBM) coated titanium dioxide (TiO₂) nanocrystal film. The Fourier transform infrared spectra (FTIR), UV–vis absorption spectra and PL quenching researches show that the films had a stronger absorption in visible light range. The influence of the PCBM:P3OT ratio were researched and the optimized ratio of PCBM to P3OT (1:1.5) exhibit a short circuit current of 4.42 mA cm⁻², an open circuit voltage of 0.81 V, a fill factor of 0.73 and a light-to-electric conversion efficiency of 2.61% under a simulated solar light irradiation of 100 mW cm⁻².     

Investigation of bulk hybrid heterojunction solar cells based on Cu(In,Ga)Se2 nanocrystals

This work presents the systematic studies of bulk hybrid heterojunction solar cells based on Cu(In, Ga)Se₂ (CIGS) nanocrystals (NCs) embedded in poly(3-hexylthiophene) matrix. The CIGS NCs of approximately 17 nm in diameter were homogeneously blended with P3HT layer to form an active layer of a photovoltaic device. The blend ratios of CIGS NCs to P3HT, solvent effects on thin film morphologies, interface between P3HT/CIGS NCs and post-production annealing of devices were investigated, and the best performance of photovoltaic devices was measured under AM 1.5 simulated solar illumination (100 mW/cm²).     

Influence of molecular weight of PEG on the property of polymer gel electrolyte and performance of quasi-solid-state dye-sensitized solar cells

A new kind of polymer gel electrolyte based on poly(acrylic acid)-poly(ethylene glycol) (PAA-PEG) hybrid was synthesized. The factor of molecular weight of PEG in the hybrid plays an important role in determining the liquid electrolyte absorbency of the hybrid and ionic conductivity of the polymer gel electrolyte, sequentially affects the photovoltaic performance of quasi-solid-state dye-sensitized solar cells. Using the hybrid with PEG molecular weight of 20,000, a polymer gel electrolyte with liquid electrolyte absorbency of 6.9 g g⁻¹ and ionic conductivity of 5.35 mS cm⁻¹ was obtained. Based on the polymer gel electrolyte, a quasi-solid-state dye-sensitized solar cell with conversion efficiency of 5.25% was achieved under irradiation of AM 1.5, 100 mW cm⁻².     

Stability study of carbon-based counter electrodes in dye-sensitized solar cells

This study describes a systematic investigation of the stability of a carbon/TiO₂ counter electrode for use in dye-sensitized solar cells (DSSCs). In this system, nanoparticle additives were introduced by adding Ti-hydrogel. The additives then bound carbon particles and enhanced the adhesion of carbon materials to the conductive substrate. After introducing the Ti-hydrogel into the carbon paste, the carbon/Ti-hydrogel composited counter electrode (HC-CE) showed a better conductivity and stability compared with that of the carbon counter electrode (C-CE), while the catalytic activity was not influenced. The device based on the HC-CE showed superior power conversion efficiency (6.3%) and long-term stability over the device based on the C-CE (5.8%).     

Influences of poly(ether urethane) introduction on poly(ethylene oxide) based polymer electrolyte for solvent-free dye-sensitized solar cells

A poly(ether urethane) (PEUR)/poly(ethylene oxide) (PEO)/SiO₂ based nanocomposite polymer is prepared and employed in the construction of high efficiency all-solid-state dye-sensitized nanocrystalline solar cells. The introduction of low-molecular weight PEUR prepolymer into PEO electrolyte has greatly enhance the electrolyte performance by both improving the interfacial contact properties of electrode/electrolyte and decreasing the PEO crystallization, which were confirmed by XRD and SEM characteristics. The effects of polymer composition, nano SiO₂ content on the ionic conductivity and I₃⁻ ions diffusion of polymer-blend electrolyte are investigated. The optimized composition yields an energy conversion efficiency of 3.71% under irradiation by white light (100 mW cm⁻²).     

Effect of Cr-doping on the physicochemical properties of blue TiO2 and its application in dye-sensitized solar cells via low-temperature fabrication process

Cr-doped blue TiO₂ (Cr-BTiO₂) nanoparticles were fabricated at room temperature using lithium-ethylenediamine (Li-EDA) as reducing agent. The addition of Li-EDA promotes the selective reduction of the rutile phase of TiO₂ into the amorphous phase keeping anatase phase unaltered. Hence, the phase-selective reduction of TiO₂ leads to the formation of blue TiO₂ nanoparticles. Synthesized samples were characterized by equipment fitted with modern technology. The shifting of (101) peak to a lower angle (2θ) in Cr-BTiO₂ in X-ray diffraction (XRD) pattern suggests the successful doping of chromium into TiO₂ lattices. In Raman spectra, the shifting of the active Eg peak of Cr-BTiO₂ nanoparticles to higher wavenumber also suggests the successful substitution of Ti by Cr. The blue TiO₂ and Cr-BTiO₂ show increased absorption of light in the visible region compared to TiO₂ (P25). The modified TiO₂ samples have improved electron-hole separation tendency as predicted by the photoluminescence spectra (PL). Also, doping of Cr- into TiO₂ lattice results the formation of oxygen vacancy as detected by X-ray photoelectron spectroscopy (XPS). Among all samples, Cr-BTiO₂ demonstrated improvement in J_sc and overall incident photon to current conversion efficiency. Therefore, the synthetic effect is thus responsible for the enhancement in efficiency of Cr-BTiO₂ towards the dye-sensitized solar cell (DSSC) by 2.5 and 1.5 times higher than the P25 and blue TiO₂, respectively.     

The use of poly(vinylpyridine-co-acrylonitrile) in polymer electrolytes for quasi-solid dye-sensitized solar cells

Poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) was used to form polymer electrolytes for dye-sensitized solar cells (DSSCs). The effects of P(VP-co-AN) on the photovoltaic performances of DSSCs have been investigated with nonaqueous electrolytes containing alkali-iodide and iodine. It was found that the effect of P(VP-co-AN) on V_oc closely related to its amount in the electrolyte. Lower amount of P(VP-co-AN) was benefit for the construction of a solar cell containing P(VP-co-AN) with higher energy conversion efficiency. Chemically crosslinking solidification with backbone polymer P(VP-co-AN) amount of 3% fabricated quasi-solid DSSCs with 10% increased conversion efficiencies with relative to that of the initial liquid DSSCs.     

Studies on isomeric effects of 2- and 4-Mercapto pyridine as dopants in polymer electrolyte in dye-sensitized solar cells

In this present work, isomers like 2- and 4-Mercapto pyridine were used as dopants (additives) in Poly (ethylene oxide) based polymer electrolyte and their effects in dye-sensitized solar cells (DSC) have been investigated. Due to the coordinating and plasticizing effects of Mercapto pyridine, enhanced ionic conductivity and reduced crystallinity of PEO polymer electrolyte accompanied by a better penetration of the same into the dye coated nanocrystalline TiO₂ in order to have better performances were achieved. The 2-Mercapto pyridine doped PEO (E) shows comparatively better performance than 4-Mercapto pyridine doped one (F), is due to the fact that the π-electron donicity of 2-Mercapto pyridine is greater. These results suggests that the electron donating capacity of 2-Mercapto pyridine and 4-Mercapto pyridine would influence the interaction of nanocrystalline TiO₂ electrode and I⁻/I₃⁻ redox couple leading to radical changes in the cell performance.     

A series of LiI/acetamide phase transition electrolytes and their applications in dye-sensitized solar cells

A new series of electrolytes composed of LiI and acetamide have been investigated in dye-sensitized solar cells (DSSCs). These electrolytes melt at about 50 °C and their ionic conductivities vary drastically below and above the melting points (T_m). They tend to form large crystals at low temperature, leading to poor penetration and contact within porous TiO₂ anode film. This shortage is improved by introducing nano-SiO₂ particles into the electrolyte. A total conversion efficiencies (η) of 0.3% at 35 °C and 4.2% at 75 °C are achieved respectively under AM 1.5 simulated solar light illumination when a LiI/acetamide (1:16) electrolyte with 8 wt% nano-SiO₂ is used. It is expected that the DSSC using phase transition electrolyte could show high efficiency for operation at high temperature and high stability for storage at low temperature.     

The application of P(MMA-co-MAA)/PEG polyblend gel electrolyte in quasi-solid state dye-sensitized solar cell at higher temperature

A poly(methyl methacrylate-co-methacrylate acid)/poly(ethylene glycol) [P(MMA-co-MAA)/PEG] polyblend with viscoelasticity was synthesized by a copolymerizing reaction between methyl methacrylate (MMA) and methacrylate acid (MAA) using azobisisobutyronitrile (AIBN) as initiator in poly(ethylene glycol) (PEG) methanol solution. Then, a polyblend gel electrolyte was prepared by adding KI and I₂ to P(MMA-co-MAA)/PEG system. The influence of compositions of the polyblend gel electrolyte on the ionic conductivity and the effect of temperature on photoelectronic performance of quasi-solid state dye-sensitized solar cell (QS-DSSC) were discussed. It was found that the polyblend gel electrolyte was a good candidate as high-temperature electrolyte for QS-DSSCs. Under an optimized condition, the highest conductivity of the polyblend gel electrolyte was 2.70 mS/cm² at 30 °C. Based on the polyblend gel electrolyte, a light-to-electricity conversion efficiency of 4.85% for QS-DSSC was achieved under AM 1.5 simulated solar light illumination at 60 °C.     

TiO2 micro-flowers composed of nanotubes and their application to dye-sensitized solar cells

TiO₂ micro-flowers were made to bloom on Ti foil by the anodic oxidation of Ti-protruding dots with a cylindrical shape. Arrays of the Ti-protruding dots were prepared by photolithography, which consisted of coating the photoresists, attaching a patterned mask, illuminating with UV light, etching the Ti surface by reactive ion etching (RIE), and stripping the photoresist on the Ti foil. The procedure for the blooming of the TiO₂ micro-flowers was analyzed by field emission scanning electron microscopy (FESEM) as the anodizing time was increased. Photoelectrodes of dye-sensitized solar cells (DSCs) were fabricated using TiO₂ micro-flowers. Bare TiO₂ nanotube arrays were used for reference samples. The short-circuit current (J_sc) and the power conversion efficiency of the DSCs based on the TiO₂ micro-flowers were 4.340 mA/cm² and 1.517%, respectively. These values of DSCs based on TiO₂ micro-flowers were higher than those of bare samples. The TiO₂ micro-flowers had a larger surface area for dye adsorption compared to bare TiO₂ nanotube arrays, resulting in improved J_sc characteristics. The structure of the TiO₂ micro-flowers allowed it to adsorb dyes very effectively, also demonstrating the potential to achieve higher power conversion efficiency levels for DSCs compared to a bare TiO₂ nanotube array structure and the conventional TiO₂ nanoparticle structure.     

Plastic-polymer composite electrolytes for solid state dye-sensitized solar cells

Three types of alkyl-substituted poly(N-alkyl-1-vinyl-imidazolium) iodides were synthesized and plasticized using succinonitrile as a solid plasticizer to develop a series of novel solvent-free plastic-polymer composite electrolytes. All these electrolytes appeared as a soft solid at room temperature and became sticky gel state at high temperature of 100 °C. Among the as-prepared plastic-polymer electrolytes, the SCN-PMVII (succinonitrile-poly(1-vinyl-3-methylimidazolium) iodide) electrolytes with a SCN content of 40-60 wt.% showed a room temperature conductivity of 1.0-1.6 mS cm⁻¹and a photoconversion efficiency of >4.1%, which are comparable to those observed from liquid organic carbonate electrolyte and the DSSCs using the liquid electrolyte at the same experimental conditions. Also, the DSSCs assembled with the SCN-PMVII electrolytes maintained their photoconversion efficiency very steadily during aging test of 50 days despite of being placed at 40 °C under 1 sun illumination or stored at 60 °C in an oven. Since these plastic-polymer electrolytes are solvent-free, highly conductive and electrochemically compatible, it is possible to use this type electrolyte for development of practical DSSCs.     

Influence of 2,6 (N-pyrazolyl)isonicotinic acid on the photovoltaic properties of a dye-sensitized solar cell fabricated using poly(vinylidene fluoride) blended with poly(ethylene oxide) polymer electrolyte

A novel method of introducing a synthesized organic nitrogenous compound 2,6 (N-pyrazolyl)isonicotinic acid (BNIN) and its effect on the conduction behavior of poly(vinylidene fluoride) (PVdF)–poly(ethylene oxide) (PEO) polymer-blend electrolyte with potassium iodide (KI) and iodine (I₂) and the corresponding performance of the dye-sensitized solar cells (DSSCs) were studied. A systematic investigation of the blends using FTIR provides evidence of interaction of BNIN with the polymer. Differential scanning calorimetry (DSC) study proves the miscibility of these polymers. Due to the coordinating and plasticizing effects of BNIN, the ionic conductivity of polymer blend electrolytes is enhanced. The efficiency of DSSC using BNIN doped polymer blend electrolyte was 7.3% under an illumination of 60 mW cm⁻² were observed for the best performance of a solar cell in this work.     

The preparation of poly(glycidyl acrylate)-polypyrrole gel-electrolyte and its application in dye-sensitized solar cells

A microporous hybrid of poly(glycidyl acrylate)-polypyrrole (PGA-PPy) was synthesized by a two-step solution polymerization. Using this hybrid as polymer host, a gel-electrolyte with high conductivity of 12.83 mS cm⁻¹ was prepared. The researches by scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and cyclic voltammetry (CV) show that the microporous structure and functional groups for PGA allows the higher absorbency and good ionic salt tolerance for the electrolyte, the introduction of PPy causes a lower charge-transfer resistance and higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction for the electrolyte. Based on the electrolyte, a dye-sensitized solar cell with a light-to-electrical energy conversion efficiency of 5.03% is achieved, under illumination with a simulated solar light of 100 mW cm⁻² (AM 1.5).     

Synthesis of a new class of cyclometallated ruthenium(II) complexes and their application in dye-sensitized solar cells

We synthesized a new class of cyclometallated ruthenium(II) complexes, Ru(tctpy)(C^N)(NCS) (1, 2), where C^N is a bidentate cyclometallating ligand such as 2-phenylpyridinato or 2-(4-(2-phenylethynyl)phenyl)pyridinato. Although these complexes exist as stereoisomers, the microwave synthetic technique yielded only one isomer. These compounds act as light sensitizers and have excellent light-harvesting properties, especially in the near-IR region. Therefore, they can be used in dye-sensitized solar cells (DSCs). A DSC sensitized with 2 shows a 10% incident photon-to-current conversion efficiency at 900 nm.     

Polymer electrolytes from PEO and novel quaternary ammonium iodides for dye-sensitized solar cells

Polymer electrolytes were prepared by blending high molecular weight poly(ethylene oxide) (PEO) and a series of novel quaternary ammonium iodides, the polysiloxanes with oligo(oxyethylene) side chains and quaternary ammonium groups. X-ray diffraction (XRD) measurements ensured relatively low crystallinity when the quaternary ammonium iodides were incorporated into the PEO host. The ionic conductivity of these complexes was improved with the addition of plasticizers. The improvement in the ionic conductivity was determined by the polarity, viscosity and amounts of plasticizers. A plasticized electrolyte containing the novel quaternary ammonium iodide was successfully used in fabricating a quasi-solid-state dye-sensitized solar cell for the first time. The fill factor and energy conversion efficiency of the cell were calculated to be 0.68 and 1.39%, respectively.     

新型聚合物太阳能电池电子受体材料的制备及热稳定性

该文合成了一种类PCBM([6,6]-苯基-C61-丁酸甲酯)富勒烯衍生物[6,6]-苯基-C61-丁酸异丙酯(PCBIP)。利用UV-Vis、FTIR、1HNMR、13CNMR、MS和元素分析对产物进行了表征。理论计算其LUMO和HOMO能级比PCBM高0.029 eV。通过差热和热重分析对PCBIP的热稳定性进了探讨,结果表明,PCBIP热稳定性良好,在空气中200℃未见分解。可作为受体材料应用于聚合物太阳能电池。     

Effect of TiO2 rutile nanorods on the photoelectrodes of dye-sensitized solar cells

In order to enhance the electron transport on the photoelectrodes of dye-sensitized solar cells, one-dimensional rutile nanorods were prepared using electrospun TiO₂ nanofibers. The grain size of the nanorods increased with increasing temperature. Electrochemical impedance spectroscopy measurements revealed reduced interface resistance of the cells with the one-dimensional rutile nanorods due to the improved electron transport and the enhanced electrolyte penetration. Intensity-modulated photocurrent/photovoltage spectroscopy showed that the one-dimensional rutile nanorods provided the electrons with a moving pathway and suppressed the recombination of photogenerated electrons. However, an excessive quantity of rutile nanorods created an obstacle to the electrons moving in the TiO₂ thin film. The photoelectrode with 7 wt.% rutile nanorods optimized the performance of the dye-sensitized solar cells.     

Synthesis of Zn-doped TiO2 microspheres with enhanced photovoltaic performance and application for dye-sensitized solar cells

Zn-doped TiO₂ microspheres have been synthesized by introducing a trace amount of zinc nitrate hexahydrate to the reaction system. Scanning electron microscope (SEM), field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) have been utilized to characterize the samples. Both surface photovoltage spectroscopy (SPS) technique based on lock-in amplifier and transient photovoltage (TPV) measurement reveal that the slight doping of Zn can promote the separation of photo-generated charges as well as restrain the recombination due to the strong interface built-in electric field and the decreasing of surface trap states. The photovoltaic parameters of dye-sensitized solar cells (DSSCs) based on Zn-doped TiO₂ are significantly better, compared to that of a cell based on undoped TiO₂. The relation between the performance of DSSCs and their photovoltaic properties is also discussed.     

The use of 2,6-bis (N-pyrazolyl) pyridine as an efficient dopant in conjugation with poly(ethylene oxide) for nanocrystalline dye-sensitized solar cells

Poly(ethylene oxide) (PEO)/2,6-bis (N-pyrazolyl) pyridine (BNPP) polymer electrolyte based photoelectrochemical cells have been fabricated with [cis-dithiocyanato-N, N-bis (2,2′ bipyridyl-4, 4′ dicarboxylic acid)ruthenium(II)] dihydrate (N3 dye) dye complex as the sensitizer and nanoporous TiO₂ film as photo anode. The introduction of 2,6-bis (N-pyrazolyl) pyridine into the poly (ethylene oxide) matrix reduces the crystallinity of the polymer and enhances the mobility of I⁻/I₃⁻ redox couple resulting in an improved performance with a higher conversion efficiency of 8.8% in terms of light energy to electric energy when compared to that of the corresponding dye-sensitized nanocrystalline TiO₂ solar cell.