Charge carrier mobility,bimolecular recombination and trapping in polycarbazole copolymer:fullerene (PCDTBT:PCBM) bulk heterojunction solar cells

Organic photovoltaic devices based on the donor:acceptor blend of poly[N-9″-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) have received considerable attention in recent years due to their high power conversion efficiencies and the ability to achieve close to 100% internal quantum efficiency. However, the highest efficiencies were all attained using active layers of less than 100 nm, which is not ideal for either maximised potential performance or commercial viability. Furthermore, more recent reports have documented significant charge carrier trapping in these devices. In this paper two charge extraction techniques (photo-CELIV and time-of-flight) have been used to investigate the mobility and recombination behaviour in a series of PCDTBT:PCBM devices. The results not only confirm significant charge carrier trapping in this system, but also reveal close to Langevin-type bimolecular recombination. The Langevin recombination causes a short charge carrier lifetime that results in a short drift length. The combination of these two characteristics (trapping and fast bimolecular recombination) has a detrimental effect on the charge extraction efficiency when active layers greater than ∼100 nm are used. This accounts for the pronounced decrease in fill factor with increasing active layer thickness that is typically observed in PCDTBT:PCBM devices.     

Synthesis and characterizations of poly(3,6-thienophenanthrene) and poly(2,7-thienophenanthrene) and their applications in polymer light-emitting devices and solar cells

Here we report the synthesis of two novel phenylene-based polymers-poly(3,6-thienophenanthrene) (PTP36) and poly(2,7-thienophenanthrene) (PTP27) via base-free Suzuki–Miyaura reaction. The structure and electroluminescent properties of the meta-linked PTP36 and para-linked PTP27 are fully characterized. The obtained polymers were found to be liquid-crystalline, with broad band gap of 2.72 eV and 2.49 eV, respectively, which are much smaller than those of corresponding polyphenanthrenes. On the basis of PTP36 and PTP27, copolymers of 2,7-thienophenanthrene and 3,6-thienophenanthrene with 5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)benzothiadiazole (DBT), namely PTP36-DBT and PTP27-DBT were prepared and be investigated as a potential donor material for polymer solar cells. The preliminary data show that the maximal power conversion efficiencies (PCEs) of the PTP27-DBT- and PTP36-DBT-based polymer solar cells are 3.5% and 0.9%, respectively.     

Charge transport in poly(p-phenylene vinylene) at low temperature and high electric field

Charge transport in poly(2-methoxy, 5-(2′-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV)-based hole-only diodes is investigated at high electric fields and low temperatures using a novel diode architecture. Charge carrier densities that are in the range of those in a field-effect transistor are achieved, bridging the gap in the mobility versus charge carrier density plot between polymer-based light-emitting diodes and field-effect transistors. The extended field range that is accessed allows us to discuss the applicability of current theoretical models of charge transport, using numerical simulations. Finally, within a simple approximation, we extract the hopping length for holes in MEH-PPV directly from the experimental data at high fields, and we derive a value of 1.0 ± 0.1 nm.     

Theoretical studies of poly(para-phenylene vinylene) (PPV) and poly(para-phenylene) (PPP)

The electroluminescence from PPV and the blue light emission from PPP constitute exciting subjects of study. The band gap of these semiconducting polymers can be engineered in a wide range from red to ultraviolet by structural changes made on them. In the present work, we present a theoretical approach based on semiempirical and ab initio total energy and force calculations of PPV and PPP. We perform a conformational analysis in order to investigate the connection between their structural, optical and electronic properties. We use the large cell approach, in connection with the semiempirical quantum method Extended Hückel (BICON-CEDiT code) and the density functional theory (DFT) within the full-potential linearized augmented-plane-wave method (FPLAPW) as implemented in the computational code WIEN2k. Our results are compared to other calculations and to optical absorption measurements.     

The effect of residual palladium catalyst on the performance and stability of PCDTBT:PC70BM organic solar cells

Palladium (Pd) is commonly used as a catalyst in the polymerisation of conjugated polymers such as poly[N-9′-heptadecanyl-2,7-carbozole-alt-5,5-(4′,7′-di-2-thenyl-2′,1′,3′-benzothiadiazole)] (PCDTBT). Here we explore the effect of residual catalyst on the performance of organic photovoltaic devices (OPVs) based on a PCDTBT:fullerene thin-film blend. We find that as the relative concentration of Pd increases, the power conversion efficiency of the PV is reduced, dropping from 4.55% to 2.42% as the Pd concentration was increased to 2570 ppm (relative to that of the PCDTBT). This reduction in efficiency resulted primarily from a reduction in PV fill factor and shunt-resistance, indicating the presence of current-shunts within the device. Using optical microscopy, laser beam induced current mapping and scanning electron microscopy, we are able to demonstrate that such current shunts are associated with micron-sized aggregates of Pd-containing nanoparticles. We show that the presence of high concentrations of Pd within a PCDTBT OPV contribute to a larger drop in efficiency during the initial ‘burn-in’ period.     

Laser-induced crystallization and conformation control of poly(3-hexylthiophene) for improving the performance of organic solar cells

Femto-second laser irradiation on P3HT:PCBM solutions have been demonstrated to have a significant impact on the conformational structures and photovoltaic performance of the resultant thin films. The crystallinity and edge-on/face-on conformations of P3HT and the aggregation of PCBM can be manipulated by controlling the wavelength (400–800 nm) and illumination duration (1–3 h) of the lasers. Grazing incidence wide- and small-angle X-ray scattering (GIWAXS and GISAXS) have been simultaneously utilized to characterize the nanostructures of the P3HT:PCBM blend films spin-cast from pristine and laser-irradiated solutions. The results show that the crystallinity, π-π* stacking and face-on conformations of P3HT can be enhanced as a result of the laser irradiation at 500 nm for 3 h. Furthermore, the diffusion and aggregation of PCBM molecules are suppressed by the photo-induced dimerization, as evidenced by the Raman spectra of the films cast from laser-irradiated PCBM solutions. The time-resolved fluorescence decay profiles show the charge transfer efficiency is improved, which may correlate to the supramolecular ordering of the polythiophene chains and the optimized phase separation in P3HT:PCBM composite. In the P3HT:PCBM active layer of the organic solar cells, more efficient charge transport and fine interpenetrating networks can be achieved due to the improved conformational microstructures. Consequently, the short-circuit current densities and power conversion efficiencies can be enhanced in organic solar cells based on the laser-irradiation processed P3HT:PCBM solutions.     

Bacterial adhesion to toroidal nano-structures from poly(styrene)-block-poly(tert-butyl acrylate) diblock copolymer thin films

Nano-structured thin films with protruding PtBA nanodomain structures were obtained from the deposition, spin-coating, self-assembly and annealing of the diblock copolymer poly(styrene)-block-poly(tert-butyl acrylate) (PS-b-PtBA). The topography has been documented by atomic force microscopy. The sacrificial removal of the PtBA block from these thin film structures after UV irradiation yielded surfaces with 5/7 segmented polystyrene (PS) toroids of 100–150 nm diameter. These polymeric materials (as well as the corresponding homopolymeric materials derived from PS and PtBA) were incubated with Staphylococcus aureus cells. Live and dead cell numbers were determined in replicate trials by fluorescence microscopy after the cells were stained for viability. S. aureus formed colonies of 5–200 cells on the nanodomain and toroid-containing surfaces as assessed by AFM, but only attached sparsely as single cells onto a planar PtBA surface. Cell viability and adhesion was found to be influenced by a combined effect of the surface hydrophilicity and topography. The results demonstrate a synthetic route to produce polymeric surfaces with nano-toroids which are capable of modifying bacterial adhesion.     

Self-assembled monolayers mediated charge injection for high performance bottom-contact poly(3,3′′′-didodecylquaterthiophene) thin-film transistors

Device performance of bottom-contact poly(3,3′′′-didodecylquaterthiophene) (PQT-12) thin-film transistors (TFTs) was significantly improved via surface-modification of Au source–drain (S–D) electrodes with 1-decanethiol and 1H,1H,2H,2H-perfluorodecanethiol self-assembled monolayers (SAMs). By improving the PQT-12 morphology and modulating the Schottky barrier at electrode/PQT-12 contacts, the thiol SAMs chemisorbed onto Au surfaces can improve the charge carrier injection at electrode/PQT-12 contacts and result in dramatic enhancements in device mobilities. Device mobilities up to 0.09 and 0.19 cm² V⁻¹ s⁻¹ were obtained in high performance bottom-contact PQT-12 TFTs with 1-decanethiol and 1H,1H,2H,2H-perfluorodecanethiol SAMs surface-modified Au S–D electrodes, compared with 0.015 cm² V⁻¹ s⁻¹ in PQT-12 TFTs with bare Au electrodes. This work may provide a simple path to the fabrication of high performance, low-cost, and solution-processable bottom-contact OTFTs using fine lithography technology.     

Influence of side chain symmetry on the performance of poly(2,5-dialkoxy-p-phenylenevinylene): fullerene blend solar cells

We report on studies of poly-(2,5-dihexyloxy-p-phenylenevinylene) (PDHeOPV), a symmetric side-chain polymer, as a potential new donor material for polymer:fullerene blend solar cells. We study the surface morphology of blend films of PDHeOPV with PCBM, the transport properties of the blend films, and the performance of photovoltaic devices made from such blend films, all as a function of PCBM content. In each case, results are compared with those obtained using the asymmetric side chain polymer, poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV), in order to investigate the influence of polymer side chain symmetry on solar cell performance. AFM images show that large PCBM aggregates appear at lower PCBM content (50 wt.% PCBM) for PDHeOPV:PCBM than for MDMO-PPV:PCBM (67 wt.% PCBM) blend films. Time-of-Flight (ToF) mobility measurements show that charge mobilities depend more weakly on PCBM content in PDHeOPV:PCBM than in MDMO:PPV:PCBM, with the result that at high PCBM content the mobilities in PDHeOPV:PCBM are significantly lower than in MDMO:PPV:PCBM blend films, despite the higher mobilities in pristine PDHeOPV compared to pristine MDMO-PPV. Photovoltaic devices show significantly lower power conversion efficiency (～0.93%) for PDHeOPV:PCBM (80 wt.% PCBM) blend films than for MDMO-PPV:PCBM (2.2% at 80 wt.% PCBM) blends. This is attributed to the relatively poor transport properties of the PDHeOPV:PCBM blend, which limit the optimum thickness of the photoactive layer in PDHeOPV:PCBM blend devices. The behaviour is tentatively attributed to a higher tendency for the symmetric side-chain polymer chains to aggregate, resulting in poorer interaction with the fullerene and poorer network formation for charge transport.     

Synthesis and photo-electrochemical properties of novel thienopyrazine and quinoxaline derivatives,and their dye-sensitized solar cell performance

Light absorption from visible to NIR region is required to increase the photocurrent and to enhance the photo-energy conversion efficiencies in dye-sensitized solar cells (DSSCs). We have now developed novel thienopyrazine dye TP1 which has absorption up to 700 nm. Quinoxaline dye QX2 with absorption at shorter wavelengths than TP1 has been synthesized for comparisons. The power conversion efficiencies of DSSCs with TP1 and QX2 showed 4.4% and 3.2%, respectively. The absorption edge in IPCE of TP1 reached 800 nm and the open circuit voltage (Voc) of QX2 was high (0.77 V). To improve the device performances, QX2 was used as a co-adsorbent dye with TP1. In the mixed sensitizer based DSSC, a high power conversion efficiency of 6.2% was achieved due to the effective light harvesting and steric effect of QX2.     

The performance of alloyed (CdS0.33Se0.67) quantum dots-sensitized TiO2 solar cell

The performance of alloyed CdS_0.33Se_0.67 quantum dots-sensitized solar cells (QDSSCs) is studied. Fluorine doped Tin Oxide (FTO) substrates were coated with 20nm-diameter TiO₂ nanoparticles (NPs). Presynthesized CdS_0.33Se_0.67 quantum dots (QDs) (radius 3.1 nm) were deposited onto TiO₂ nanoparticles (NPs) using direct adsorption (DA) method, by dipping for different times at ambient conditions. The FTO counter electrodes were coated with platinum, while the electrolyte containing I ^?/I ₃ ^? redox species was sand-wiched between the two electrodes. The characteristic parameters of the assembled QDSSCs were measured at different dipping times, under AM 1.5 sun illuminations. The maximum values of short circuit current density (J _sc) and conversion efficiency (η) are 1.115 mA/cm² and 0.25% respectively, corresponding 6h dipping time. Furthermore, the J _sc increases linearly with increasing the intensities of the sun light which indicates the linear response of the assembled cells.     

Ester-functionalized poly(3-alkylthiophene) copolymers: Synthesis,physicochemical characterization and performance in bulk heterojunction organic solar cells

The introduction of functional moieties in the donor polymer (side chains) offers a potential pathway toward selective modification of the nanomorphology of conjugated polymer:fullerene active layer blends applied in bulk heterojunction organic photovoltaics, pursuing morphology control and solar cell stability. For this purpose, two types of poly(3-alkylthiophene) random copolymers, incorporating different amounts (10/30/50%) of ester-functionalized side chains, were efficiently synthesized using the Rieke method. The solar cell performance of the functionalized copolymers was evaluated and compared to the pristine P3HT:PCBM system. It was observed that the physicochemical and opto-electronic characteristics of the polythiophene donor material can be modified to a certain extent via copolymerization without (too much) jeopardizing the OPV efficiency, as far as the functionalized side chains are introduced in a moderate ratio (<30%) and that preference is given to side chains with a small molar volume. A range of complementary techniques – UV–Vis spectroscopy, (modulated temperature) differential scanning calorimetry, transmission electron microscopy and X-ray diffraction analysis – indicated that variations in polymer crystallinity, while maintaining a high level of regioregularity, are probably the main factor responsible for the observed differences.     

P(VDF-TrFE)/Ag复合薄膜的铁电以及介电性能研究

利用旋涂法制备并采用氢气退火处理得到P(VDF-TrFE)/Ag复合薄膜,在XRD图像上可以观察到在2θ=38.1°的Ag(111)相的衍射峰,同样在SEM图像上观察到银纳米粒子的存在.在薄膜的红外透射光谱上可以观察到β相特征峰的蓝移,这可归结为银纳米粒子与偶极子的相互作用.银纳米粒子的掺杂增强了薄膜的铁电和介电性能.与传统退火方式处理的纯P(VDF-TrFE)薄膜相比,纳米银掺杂比例为10％的P(VDF-TrFE)/Ag复合薄膜的铁电剩余极化强度和介电常数分别提高了32.5％和13.3％.介电损耗不随纳米银掺杂比例的增加而变化的现象不符合渗流理论.     

P(VDF-TrFE)/Ag复合薄膜的铁电以及介电性能研究

利用旋涂法制备并采用氢气退火处理得到P(VDF-TrFE)/Ag复合薄膜,在XRD图像上可以观察在2θ=38.1?的Ag(111)相得衍射峰,同样在SEM图像上观察到银纳米粒子的存在。在薄膜的红外透射光谱上可以观察到β相特征峰的蓝移可归结为银纳米粒子与偶极子的相互作用。银纳米粒子的掺杂增强了薄膜的铁电和介电性能。介电损耗随着掺杂比例的增加而降低的趋势不符合渗流理论。     

Improvement of photovoltaic performance of inverted hybrid solar cells by adding single-wall carbon nanotubes in poly(3-hexylthiophene)

Solution prepared hybrid solar cells show promising low cost technology for electricity generation from sun light, although their power conversion efficiency has to be improved. One of the approaches is to increase the absorbance or charge carrier mobility of organic semiconductors. In this work, pristine single walled carbon nanotubes (SWCNT) were added into poly(3-hexylthiophene) (P3HT) solution to form P3HT:SWCNT composite films with different weight percent (wt%) of SWCNT. It is observed that optical absorbance spectra as well as the morphology of the composite films were modified by the addition of SWCNTs. This phenomenon could be explained by the π-π interaction between the conjugated polymer and carbon nanotubes. Most importantly, the electrical conductivities of the composite films increased with the SWCNT wt%. When these films were used as hole conductor layers in inverted planar hybrid solar cell, with CdS thin films as electron acceptor layers, the fill factor (FF) and open-circuit voltage (Voc) of the corresponding cells were decreased with the increase of the wt% of SWCNT. However, the short-circuit current density (Jsc) and the power conversion efficiency (PCE) showed a maximum value at about 0.4 wt% of SWCNT in P3HT. The transient photovoltage measurements (TPV) revealed that the presence of SWNCT promoted the charge recombination process at P3HT/CdS interface, and as a result, reduced the Voc. The photovoltaic performance of the hybrid solar cells could be optimized by choosing an adequate weight percentage of SWCNT in P3HT to balance the charge carrier transport and charge recombination processes at the donor-acceptor interface.     

Comparison of device performance and measured transport parameters in widely‐varying Cu(In,Ga) (Se,S) solar cells

We report the results of an extensive study employing numerous methods to characterize carrier transport within copper indium gallium sulfoselenide (CIGSS) photovoltaic devices, whose absorber layers were fabricated by diverse process methods in multiple laboratories. This collection of samples exhibits a wide variation of morphologies, compositions, and solar power conversion efficiencies. An extensive characterization of transport properties is reported here—including those derived from capacitance–voltage, admittance spectroscopy, deep level transient spectroscopy, time‐resolved photoluminescence, Auger emission profiling, Hall effect, and drive level capacitance profiling. Data from each technique were examined for correlation with device performance, and those providing indicators of related properties were compared to determine which techniques and interpretations provide credible values for transport properties. Although these transport properties are not sufficient to predict all aspects of current‐voltage characteristics, we have identified specific physical and transport characterization methods that can be combined using a model‐based analysis algorithm to provide a quantitative prediction of voltage loss within the absorber. The approach has potential as a tool to optimize and understand device performance irrespective of the specific process used to fabricate the CIGSS absorber layer. Copyright © 2005 John Wiley & Sons, Ltd.     

All-conjugated diblock copolymer of poly(3-hexylthiophene)-block-poly(3-phenoxymethylthiophene) for field-effect transistor and photovoltaic applications

The electronic properties, morphology and optoelectronic device characteristics of conjugated diblock copolythiophene, poly(3-hexylthiophene)-block -poly(3-phenoxymethylthiophene) (P3HT-b-P3PT), are firstly reported. The polymer properties and structures were explored through different solvent mixtures of chloroform (CHCl₃), dichlorobenzene (DCB), and CHCl₃:DCB (1:1 ratio). The absorption maximum (λ_max) of P3HT-b-P3PT prepared from DCB was around 554 nm with a shoulder peak indicative for the highly crystalline structure around 604 nm while that from CHCl₃ was 516 nm without the clear shoulder peak. The field-effect hole mobility of P3HT-b-P3PT increased from ～6.0 × 10^?3, ～8.0 × 10^?3 to ～2.0 × 10^?2 cm² V^?1 s^?1 as the DCB content in the solvent mixture enhanced. The AFM images suggested that the highly volatile CHCl₃ processing solvent led to the amorphous structure, on the other hand, less volatile DCB resulted in the largely crystalline structure of the P3HT-b-P3PT. Such difference on the polymer structure and hole mobility led to the varied power conversion efficiency (PCE) of the photovoltaic cells fabricated from the blend of P3HT-b-P3PT/[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) (1:1, w/w): 1.88 (CHCl₃), 2.13 (CHCl₃:DCB (1:1)), and 2.60% (DCB). The PCBM blend ratio also significantly affected the surface structure and the solar cell performance. The PCE of polymer/PCBM could be improved to 2.80% while the ratio of polymer to PCBM went to 1:0.7. The present study suggested that the surface structures and optoelectronic device characteristics of conjugated diblock copolymers could be easily manipulated by the processing solvent, the block segment characteristic, and blend composition.     

Influence of the Cu(In,Ga)Se2 thickness and Ga grading on solar cell performance

Thin‐film solar cells with Cu(In,Ga)Se₂ (CIGS) absorber layers ranging from 1.8 to 0.15 μm in thickness were fabricated by co‐evaporation, with both homogeneous and Ga/(Ga + In) graded composition. The absorption of the CIGS layers was determined and compared with corresponding QE measurements in order to obtain the optical related losses. The material characterization included XRD as well as cross‐sectional SEM analysis. Devices with CIGS layers of all thicknesses were fabricated, and down to 0.8–1 μm they showed a maintained high performance (η ∼ 15%). When the CIGS layer was further reduced in thickness the loss in performance increased. The main loss was observed for the short‐circuit current, although the loss was not only due to a reduced absorbance. The open‐circuit voltage was essentially not affected by the reduction of the CIGS thickness, while the fill factor showed a slight decrease. The fill factor loss was eliminated by introducing a Ga/(Ga+In) graded CIGS, which also resulted in an increased open‐circuit voltage of 20–30 mV for all CIGS thicknesses. Device results of 16.1% efficiency at 1.8 μm CIGS thickness, 15.0% at 1.0 μm and 12.1% at 0.6 μm (total area without anti‐reflective coating) were achieved. Copyright © 2002 John Wiley & Sons, Ltd.