Thermal-induced changes on the properties of spin-coated P3HT:C60 thin films for solar cell applications

The thermal transition behaviour, optical and structural properties of spin-coated P3HT:C₆₀ blended films with different C₆₀ ratios were investigated using differential scanning calorimetry (DSC), thermo-gravimetric analysis (TGA), ultraviolet-visible (UV-vis) spectroscopy, photoluminescence (PL), Fourier transform infrared absorption (FT-IR) spectroscopy and Raman spectroscopy. DSC analysis showed that the P3HT:C₆₀ blends have quite different thermal characteristics. The absorption spectra of the annealed P3HT:C₆₀ (1:1 wt%) films becomes enhanced and red shifted. This feature is evident in the photoluminescence measurements where the formation of polymer crystallites upon annealing is observed. Raman spectroscopy showed a substantial ordering in the polymer film during annealing. It was found that the performance of a P3HT:C₆₀ (1:1 wt%) device was dramatically improved by annealing.     

Analysis of electrical parameters in heterojunctions based on poly 3-octylthiophene and cadmium sulfide thin films

Planar hybrid heterojunctions were built with poly 3-octylthiophene (P3OT) and chemical bath-deposited cadmium sulfide (CdS) thin films on a conductive glass substrate. The organic material, P3OT, acts as a light absorber and the inorganic one, CdS, as the electron acceptor. Two types of CdS films had been used: one is as-deposited and the other doped with HgCl₂. Heterojunctions were formed by casting a chemically synthesized P3OT solution onto CdS films. The P3OT film thickness was also varied for heterojunction studies. Current vs. potential (I–V) characterizations under dark and illumination conditions were performed for the P3OT/CdS heterojunctions under 88 mW/cm² irradiance level, which show photovoltaic effect with different open circuit voltage (V_OC) levels, being as high as 1 V for some devices. A parametric analysis of I–V curves details the effect of CdS resistivity and P3OT film thickness on series and shunt resistance of the heterojunctions.     

Synthesis of derivatives of polythiophene and their application in an electrochromic device

Poly(3-methylthiophene) (P3MT) and poly(3-octylthiophene) (P3OT) are conducting polymers with interesting optoelectronic properties and a wide variety of optoelectronic applications. In this work, 3-octylthiophene was synthesized through a Grignard reactive and was analyzed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR). The morphology of electrosynthesized P3OT and P3MT thin films was analyzed by atomic force microscopy and different film morphologies were found for different electrodeposition technique and the solution temperature. Optical absorbance spectra of the two types of films confirm the bipolaron band structure and a starting π–π^* interband transition around 2 eV. Electrochromic performance of the polymers with both liquid and polymeric electrolytes showed a high switch potential for P3OT that for P3MT films. The kinetic optical response of a P3MT electrochromic device shows a good color contrast and a capacitive current characteristic under a square electrical potential.     

Metal contact properties of poly3-octylthiophene thin films

Chemically synthesized undoped poly3-octylthiophene (P3OT) was deposited as thin films on conducting glass substrates by drop casting. Doping state of P3OT was obtained by adding FeCl₃ into the original P3OT solution. A qualitative explanation of the electrical contact behavior of the P3OT films was given by a band diagram made from optical absorbance spectra and electrochemical current–voltage curves of the polymeric films. Gold contacts on both undoped and doped P3OT films give an ohmic contact. Silver/P3OT contact shows a rectifying behavior; the forward current is 500 times the reverse current at 0.5 V. Aluminum also forms rectifying contact with the two types of P3OT films, although the experimental rectification ratio is lower than that of the silver. The I–V curves of rectifying contacts were analyzed with Schottky equation and different diode parameters were obtained.     

Panchromatic response composed of hybrid visible-light absorbing polymers and near-IR absorbing dyes for nanocrystalline TiO2-based solid-state solar cells

In pursuit of panchromatic sensitizers for mesoporous TiO₂-based solid-state solar cells, a near-IR absorbing zinc phthalocyanine dye (coded TT1) was firstly adsorbed over relatively thin (∼1 μm) TiO₂ mesoporous films and then a visible-light absorbing polymer [regioregular poly(3-hexylthiophene), P3HT] was incorporated into the mesopores as both a second sensitizer and a solid hole conductor. After optimizing some experimental parameters, these hybrid solid-state cells exhibited a clear panchromatic response, and an overall conversion efficiency of around 1% at full sun intensity.     

Nanostructured Ti-doped hematite (α-Fe2O3) photoanodes for efficient photoelectrochemical water oxidation

We present a form of hematite (α-Fe₂O₃) nanostructured architecture suitable for photoelectrochemical water oxidation that is easily synthesized by a pulsed laser deposition (PLD) method. The architecture is a column-like porous nanostructure consisting of nanoparticles 30–50 nm in size with open channels of pores between the columns. This nanostructured film is generated by controlling the kinetic energy of the ablated species during the pulsed laser deposition process. In a comparison with the nanostructured film, hematite thin film was also synthesized by PLD. All of the developed films were successfully doped with 1.0 at% of titanium. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and UV–visible spectroscopy were used to characterize the films. To fabricate the photoelectrochemical (PEC) cell, Ti-doped hematite films were used as the working electrode, Ag/AgCl as the reference electrode, platinum wire as the counter electrode and an aqueous solution of 1 M NaOH as the electrolyte. The photovoltaic characteristics of all cells were investigated under AM 1.5G sunlight illumination of 100 mW/cm². The photocurrent density was enhanced by approximately 220% using nanostructured film at 0.7 V versus Ag/AgCl compared to hematite thin film, and the highest photocurrent density of 2.1 mA/cm² at 0.7 V/Ag/AgCl was obtained from the 1.0 at% Ti-doped hematite nanostructured film. The enhanced photocurrent density is attributed to its effective charge collection due to its unique column-like architecture with a large surface area.     

Poly(3-hexylthiophene)/C60 heterojunction solar cells: Implication of morphology on performance and ambipolar charge collection

The performance of heterojunction organic solar cells is critically dependent on the morphology of the donor and acceptor components in the active film. We report results of photovoltaic devices consisting of bilayers and bulk heterojunctions using poly(3-hexylthiophene) (P3HT) and Buckminsterfullerene C₆₀. White light power efficiencies of η2.2% (bulk heterojunction) and 2.6% (bilayer) were measured after a thermal annealing step on completed devices. Optical and structural investigations on non-annealed bilayer thin films indicated a distinct porosity of the spin-coated polymer, which allows C₆₀ to penetrate the P3HT layer and to touch the anode. This resulted for these bilayer solar cells in the experimental observation that electrons were collected predominantly at the cathode after photo-excitation of P3HT, but predominantly at the anode after C₆₀ excitation. A morphological model to explain the ambipolar charge collection phenomenon is proposed.     

Triphenylamine-substituted methanofullerene derivatives for enhanced open-circuit voltages and efficiencies in polymer solar cells

A new class of triphenylamine substituted methanofullerene derivatives, bis(4'-(diphenylamino)biphenyl-4-yl)methanofullerene (1) and the bisadduct (2), were synthesized. The incident photon to current efficiency (IPCE) studies revealed that the diphenylamino components have contribution to the photocurrent that expands the light harvesting window around 400 nm. When being blended with poly (3-hexylthiophene) (P3HT) to fabricate the solar cell, the device of P3HT:1 (1:0.7) shows high open circuit voltage (V_oc) of 0.69 V under the illumination of AM 1.5, 100 mW/cm² with high power conversion efficiency (PCE) of 3.16%, which is about 0.1 V higher than that of the corresponding [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) devices. This indicates that the arylamine substituents on 1 have played some special roles on the high V_oc performance. Similar effects are also observed for 2. The device of P3HT:2 (1:1) shows even higher V_oc of 0.87 V with the PCE of 1.83%. These results indicate that 1 and 2 are alternative high performance acceptors.     

A novel high-performance gel polymer electrolyte membrane basing on electrospinning technique for lithium rechargeable batteries

Nonwoven films of composites of thermoplastic polyurethane (TPU) with different proportion of poly(vinylidene fluoride) (PVdF) (80, 50 and 20%, w/w) are prepared by electrospinning 9 wt% polymer solution at room temperature. Then the gel polymer electrolytes (GPEs) are prepared by soaking the electrospun TPU-PVdF blending membranes in 1 M LiClO₄/ethylene carbonate (EC)/propylene carbonate (PC) for 1 h. The gel polymer electrolyte (GPE) shows a maximum ionic conductivity of 3.2 × 10⁻³ S cm⁻¹ at room temperature and electrochemical stability up to 5.0 V versus Li⁺/Li for the 50:50 blend ratio of TPU:PVdF system. At the first cycle, it shows a first charge-discharge capacity of 168.9 mAh g⁻¹ when the gel polymer electrolyte (GPE) is evaluated in a Li/PE/lithium iron phosphate (LiFePO₄) cell at 0.1 C-rate at 25 °C. TPU-PVdF (50:50, w/w) based gel polymer electrolyte is observed much more suitable than the composite films with other ratios for high-performance lithium rechargeable batteries.     

Photovoltaic devices based on electrochemical-chemical deposited CdS and poly3-octylthiophene thin films

Cadmium sulfide (CdS) is a well-known wide bandgap semiconductor for solar cell applications. In this work we report an electrochemical/chemical method to prepare CdS thin films on gold (Au)-coated glass substrates. 10 nm thick of titanium (Ti) film was first sputtered on glass surface to improve the adhesion between the subsequent sputtered Au film and the glass surface. Cadmium films were then electrochemically deposited on Au surface in an acidic solution with negative potential, and the obtained glass/Ti/Au/Cd samples were annealed in H₂S atmosphere to convert Cd into CdS. XRD pattern of H₂S-annealed Cd samples shows a hexagonal wurtzite phase in CdS with (0 0 2) as the preferential crystalline plane. Photovoltaic properties were clearly shown in hybrid heterojunctions of CdS and poly3-octylthiophene (P3OT) with Au as the top and the back metal contacts.     

Fabricating red-blue-switching dual polymer electrochromic devices using room temperature ionic liquid

In this work, room temperature ionic liquid (RTIL)—1-butyl-3-methyl-imidazolium hexafluorophosphate ([BMIM]PF₆)—was employed to fabricate dual polymer electrochromic devices (DPECDs). [BMIM]PF₆ was used as the electrolyte both in the electrochemical synthesis of conducting polymers (CPs) and in the fabrication of DPECDs. The electrochemically deposited poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3-methylthiophene) (PMeT) were employed to serve as two complementary coloring electrochromic thin films. Through combining these two electrochromic layers, the assembled DPECDs were found to switch between deep red and deep blue, which are two primary colors for a display. By employing RTIL as electrolyte, the devices retained 65% of their optical contrast and electroactivity after 5×10³ deep double potential steps, showing enhanced stability and durability. The DPECDs also exhibited stable electrochromic performance, with a maximum optical contrast of 26% at 665 nm, and achieved a high coloring efficiency of 460 cm² C^-1.     

Influence of photo-induced degradation on the optoelectronic properties of regioregular poly(3-hexylthiophene)

Recently, head-to-tail regioregular poly(3-hexylthiophene) (P3HT) has been widely used as an active material in fabricating polymer optoelectronic devices. This study employs UV-vis absorption, photoluminescence (PL), X-ray diffraction (XRD) and the space-charge limited current (SCLC) model to elucidate the effect of light illumination on the optic and optoelectronic properties of P3HT. The degraded performance of P3HT, such as low absorbance, PL emission, and charge-carrier mobility is caused mostly by a reduction in the degree of conjugated structure and the lower crystallinity.     

Poly(3-methylthiophene)/MnO2 composite electrodes as electrochemical capacitors

Composite electrodes prepared by electrodeposition of manganese oxide on titanium substrates modified with poly(3-methylthiophene) (PMeT) were investigated and compared with Ti/MnO₂ electrodes. The polymer films were prepared by galvanostatic deposition at 2 mA cm⁻² with different deposition charges (250 and 1500 mC cm⁻²). The electrodes were characterized by cyclic voltammetry in 1 mol L⁻¹ Na₂SO₄ and by scanning electron microscopy. The results show a very significant improvement in the specific capacitance of the oxide due the presence of the polymer coating. For Ti/MnO₂ the specific capacitance was of 122 F g⁻¹, while Ti/PMeT₂₅₀/MnO₂ and Ti/PMeT₁₅₀₀/MnO₂ displayed values of 218 and 66 F g⁻¹, respectively. If only oxide mass is considered, the capacitances of the composite electrode increases to 381 and 153 F g⁻¹, respectively. The micrographs of samples show that the polymer coating leads to very significant changes in the morphology of the oxide deposit, which in consequence, generate the improvement observed in the charge storage property.     

Comparison of the electrochemical oxidation of borohydride and dimethylamine borane on platinum electrodes: Implication for direct fuel cells

The electrochemical behaviour of dimethylamine borane and borohydride on platinum electrodes was investigated by cyclic voltammetry and polarization curves in discharges processes. Several overlapping peaks appear in the domain of hydrogen oxidation, i.e., in the potential range of −1.25 V to −0.50 V versus Ag/AgCl, mainly with the borohydride. This behaviour is associated with the hydrolysis of BH₄⁻ or (CH₃)₂NHBH₃. As a consequence of secondary reactions the borohydride and dimethylamine borane oxidation in 3 M NaOH solution shows, respectively, a four- to six-electron process and a four- to five-electron process in direct fuel cells. The direct oxidation of the borohydride exhibits a peak at about −0.07 V versus Ag/AgCl, while the dimethylamine borane peak is at about −0.03 V versus Ag/AgCl. For the 0.04 M concentration the borohydride displays a power density of 31 W m⁻² which is 16% higher than that of the dimethylamine borane.     

Inorganic-organic polymer electrolytes based on poly(vinyl alcohol) and borane/poly(ethylene glycol) monomethyl ether for Li-ion batteries

In this study, poly(vinyl alcohol) (PVA) was modified with poly(ethylene glycol) monomethyl ether (PEGME) using borane-tetrahydrofuran (BH₃/THF) complex. Molecular weights of both PVA and PEGME were varied prior to reaction. Boron containing comb-branched copolymers were produced and abbreviated as PVA1PEGMEX and PVA2PEGMEX. Then polymer electrolytes were successfully prepared by doping of the host matrix with CF₃SO₃Li at several stoichiomeric ratios with respect to EO to Li. The materials were characterized via nuclear magnetic resonance (¹H NMR and ¹¹B NMR), Fourier transform infrared spectroscopy (FT-IR), Thermogravimetry (TG) and differential scanning calorimeter (DSC). The ionic conductivity of these novel polymer electrolytes were studied by dielectric-impedance spectroscopy. Li-ion conductivity of these polymer electrolytes depends on the length of the side units as well as the doping ratio. Such electrolytes possess satisfactory ambient temperature ionic conductivity (>10⁻⁴ S cm⁻¹). Cyclic voltammetry results illustrated that the electrochemical stability domain extends over 4 V.     

Novel hybrid polymer photovoltaics made by generating silver nanoparticles in polymer:fullerene bulk-heterojunction structures

Here, we developed the high efficient poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C₆₁-butyric acid butyl ester (PCBB):Ag nanoparticle hybrid photovoltaic cells by generating the silver nanoparticles in the bulk-heterojunction structures of P3HT:PCBB prior to the spin-coating process. Hybrid bulk-heterojunction solar cells with an ITO/(G)-PEDOT/P3HT:PCBB:Ag/Al was fabricated, which shows open-circuit voltage, short-circuit current density, and power conversion efficiency of 0.639 V, 12.29 mA/cm², and 4.30% under AM1.5 irradiation (100 mW/cm²), respectively.     

Effects of a perfluorinated compound as an additive on the power conversion efficiencies of polymer solar cells

A perfluorinated compound, 4-amino-2-(trifluoromethyl)benzonitrile (ATMB), was applied as an additive to polymer solar cells (PSCs) with P3HT [poly(3-hexylthiophene)]:PCBM [[6,6]-phenyl-C₆₁-butyric acid methyl ester] blend films. The addition of 6 wt% ATMB to a P3HT:PCBM layer led to an increased power conversion efficiency of 5.03% due to the enhanced short circuit current and fill factor when compared with that of the reference cell without an additive. On the other hand, the devices with 4-aminobenzonitrile as an additive, not containing fluorine atoms in the molecule, displayed lower PCEs than that of the reference cell. The UV-visible absorption spectra, X-ray measurements and carrier mobility studies revealed that ATMB facilitated ordering of the P3HT chains, resulting in higher absorbance, larger crystal size of P3HT and enhanced hole mobility. XPS depth profiling measurements also showed that the additive molecules were predominantly positioned in the range of 25 nm under the surface of the P3HT:PCBM film, leading to improved fill factor.     

Photocatalytic water oxidation at bismuth vanadate thin film electrodes grown by direct liquid injection chemical vapor deposition method

Photoelectrochemical cells (PECs) are devices that can harvest and convert solar energy to produce consumable fuel, e.g. by splitting water into oxygen and hydrogen. Photocatalytic semiconductor materials play a major role in PECs, and their overall efficiency is usually limited by short carrier diffusion length because of structural defects, poor light absorptivity, and sluggish kinetics of photoelectrochemical reactions at the semiconductor electrode. Synthesis of high quality defect-free semiconductor materials using high temperature deposition techniques generally yield films with good adhesion to substrates while improving charge carrier transport and hence the overall efficiency of a PEC. A direct liquid injection chemical vapor deposition (DLI-CVD) technique has been utilized to synthesize monoclinic clinobisvanite phase bismuth vanadate (BiVO₄) films for photocatalytic water oxidation. The technique yields dense high quality epitaxial and polycrystalline BiVO₄ films on Yttria stabilized zirconia (YSZ) and Fluorine doped tin oxide (FTO) substrates, respectively, at growth temperature in the range of 500–550 °C. The photoelectrochemical characteristics of the films grown on FTO have been studied and a photocurrent value of 2.1 mA/cm² at 1.23 V vs Normal hydrogen electrode (NHE) (0.5 V vs. Ag/AgCl), with onset potential values as low as 0.23 V vs. NHE (?0.5 V vs. Ag/AgCl), are obtained despite the low porosity of the films. The PEC performance is further improved by synthesizing BiVO₄ directly on top of a tungsten oxide interlayer and modifying its surface with FeOOH co-catalyst.     

The influence of UV radiation and ozone exposure on the electronic properties of poly-3-octyl-thiophene thin films

The modification of the conductivity as well as the nanoscale morphology and electrostatic properties of poly-3-octyl-thiophene (P3OT) thin films have been studied as these films are irradiated by ultraviolet light (UV). Films of about 100 nm thickness were prepared by spin-coating a P3OT solution in toluene on glass substrates. The samples were characterized by electronic transport measurements and non-contact scanning force microscopy (NC-SFM) for every cycle of UV radiation. Nanoscale topographic and electrostatic characterization using NC-SFM were performed on the same location using a specially designed sample holder. A two stage degradation process has been observed, the first one presents a chemical modification of the polymer (decoloration of sample) and free carrier mobility reduction, the second one is characterized by a strong structural modification, thickness reduction, oxygen doping and further mobility reduction. The comparison of these results on P3OT with other studies performed on P3HT will allow for a detailed analysis of the role of side-chains in the degradation mechanism upon UV irradiation.     

Hyperbranched-linear poly(ether sulfone) blend films for proton exchange membranes

Hyperbranched poly(ether sulfone) polymers having sulfonyl chloride end-groups is blended at up to 30 w% with linear poly(ether ether ether sulfone)s and a two-phase system is generated via spinodal decomposition upon drying from a DMAc solution. Conversion of the end-groups from sulfonyl chloride to sulfonic acid is accomplished using 16 M H₂SO₄ that is also believed to introduce additional sulfonic acid groups at the interface of the linear polymer. The blend films before and after conversion to sulfonic acid have similar tensile strengths as films composed of solely linear polymer (yield stress >40 MPa and Young's modulus >3 GPa m). These films are designed to test the viability of hyperbranched polymers as fuel cell membranes. Proton conductivities of up to 0.03 S cm⁻¹ are observed at 80 °C and 90% R.H indicating a good potential for use of hyperbranched polymers as a proton conduction material.