Light-induced electron spin resonance study of galvinoxyl-doped P3HT/PCBM bulk heterojunctions

We report the effects of doping of P3HT/PCBM layers with spin 1/2 radicals of galvinoxyl (Gx) based on light-induced electron spin resonance (LESR), photoluminescence-detected magnetic resonance (PLDMR), and post-annealing experiments.LESR showed both a P3HT⁺ and PCBM⁻ signal for undoped P3HT/PCBM; however, as Gx doping increased (above ∼1 wt%), only the P3HT⁺ signal was evident in the LESR spectra, with no PCBM⁻ signal.The PLDMR exhibited a strong narrow signal at g = 2.002 that originates from nongeminate polaron pairs; no triplet PLDMR signal has been observed throughout the whole range of Gx concentrations (x = 0, 0.1, 1, 2, 4, 12 wt%). Adding Gx to ∼3 wt% led to a decrease of the PL-enhancement.There was big difference between the slow-dried P3HT/PCBM samples and the post-annealed samples. For the slow-dried samples, efficiency monotonously decreased with Gx additives. When post-annealed, however, an enhancement in η was observed at ∼2 wt% for P3HT/PCBM(1:2) samples.The LESR spectra for post-annealed samples revealed disappearance of Gx spin signals, and thus no spin interactions with PCBM⁻ spins. It is unlikely that the increase of efficiency after Gx doping of P3HT/PCBM solar cell is due to an increase of triplet states.     

Optical,Electrical, and Magnetic Studies of Organic Solar Cells Based on Low Bandgap Copolymer with Spin ½ Radical Additives

The charge photogeneration and recombination processes in organic photovoltaic solar cells based on blend of the low bandgap copolymer, PTB7 (fluorinated poly‐thienothiophene‐benzodithiophene) with C60‐PCBM using optical, electrical, and magnetic measurements in thin films and devices is studied. A variety of steady state optical and magneto‐optical techniques were employed, such as photoinduced absorption (PA), magneto‐PA, doping‐induced absorption, and PA‐detected magnetic resonance (PADMR); as well as picosecond time‐resolved PA. The charge polarons and triplet exciton dynamics in films of pristine PTB7, PTB7/fullerene donor–acceptor (D–A) blend is followed. It is found that a major loss mechanism that limits the power conversion efficiency (PCE) of PTB7‐based solar cell devices is the “back reaction” that leads to triplet exciton formation in the polymer donor from the photogenerated charge‐transfer excitons at the D–A interfaces. A method of suppressing this “back reaction” by adding spin½ radicals Galvinoxyl to the D–A blend is presented; this enhances the cell PCE by ≈30%. The same method is not effective for cells based on PTB7/C70‐PCBM blend, where high PCE is reached even without Galvinoxyl radical additives.     

Correlation Between Structural and Optical Properties of Composite Polymer/Fullerene Films for Organic Solar Cells

We investigate thin poly(3‐hexylthiophene‐2,5‐diyl)/[6,6]‐phenyl C₆₁ butyric acid methyl ester (P3HT/PCBM) films, which are widely used as active layers in plastic solar cells. Their structural properties are studied by grazing‐incidence X‐ray diffraction (XRD). The size and the orientation of crystalline P3HT nanodomains within the films are determined. PCBM crystallites are not detected in thin films by XRD. Upon annealing, the P3HT crystallinity increases, leading to an increase in the optical absorption and spectral photocurrent in the low‐photon‐energy region. As a consequence, the efficiency of P3HT/PCBM solar cells is significantly increased. A direct relation between efficiency and P3HT crystallinity is demonstrated.     

Effect of Alkyl Side‐Chain Length on Photovoltaic Properties of Poly(3‐alkylthiophene)/PCBM Bulk Heterojunctions

The morphological, bipolar charge‐carrier transport, and photovoltaic characteristics of poly(3‐alkylthiophene) (P3AT):[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blends are studied as a function of alkyl side‐chain length m, where m equals the number of alkyl carbon atoms. The P3ATs studied are poly(3‐butylthiophene) (P3BT, m = 4), poly(3‐pentylthiophene) (P3PT, m = 5), and poly(3‐hexylthiophene) (P3HT, m = 6). Solar cells with these blends deliver similar order of photo‐current yield (exceeding 10 mA cm^?2) irrespective of side‐chain length. Power conversion efficiencies of 3.2, 4.3, and 4.6% are within reach using solar cells with active layers of P3BT:PCBM (1:0.8), P3PT:PCBM (1:1), and P3HT:PCBM (1:1), respectively. A difference in fill factor values is found to be the main source of efficiency difference. Morphological studies reveal an increase in the degree of phase separation with increasing alkyl chain length. Moreover, while P3PT:PCBM and P3HT:PCBM films have similar hole mobility, measured by hole‐only diodes, the hole mobility in P3BT:PCBM lowers by nearly a factor of four. Bipolar measurements made by field‐effect transistor showed a decrease in the hole mobility and an increase in the electron mobility with increasing alkyl chain length. Balanced charge transport is only achieved in the P3HT:PCBM blend. This, together with better processing properties, explains the superior properties of P3HT as a solar cell material. P3PT is proved to be a potentially competitive material. The optoelectronic and charge transport properties observed in the different P3AT:PCBM bulk heterojunction (BHJ) blends provide useful information for understanding the physics of BHJ films and the working principles of the corresponding solar cells.     

Comparative study of spectral and morphological properties of blends of P3HT with PCBM and ICBA

We report a comparative study on spectral and morphological properties of two blend systems for polymer solar cells: the donor material poly(3-hexylthiophene) (P3HT) in combination with the acceptor material of either [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) or indene-C₆₀ bisadduct (ICBA) that was reported to enhance efficiencies of polymer solar cells. Optical microscopy and grazing incidence X-ray scattering reveal the stronger tendency of PCBM to from larger and more ordered domains/grains than ICBA either in pure or blend films. Compared to PCBM, the presence of ICBA also substantially perturbs the organization and longer-range ordering of P3HT in increasing the ICBA ratio in blends. With larger and more ordered phase-separated domains, the P3HT/PCBM blend films exhibit significant optical scattering at higher PCBM ratios. Yet, such optical scattering is not significant for P3HT/ICBA blends (even with high ICBA ratios). Overall, results here suggest the reported higher efficiencies of P3HT/ICBA solar cells (vs. P3HT/PCBM cells) cannot be attributed to larger and/or more ordered phase-separated donor–acceptor domains and other characteristics play more important roles in this case.     

Photovoltaic Processes of Singlet and Triplet Excited States in Organic Solar Cells

This article reports the respective photovoltaic processes of singlet and triplet photoexcited states in dissociation and charge reactions based on the studies of magnetic‐field effects of photocurrents. The magnetic‐field effects of photocurrents reveal that weak donor‐acceptor interactions lead to a two‐step photovoltaic process: dissociation in polaron‐pair states evolved from singlet excitonic states and exciton‐charge reactions occurred in triplet excitonic states in the generation of the photocurrent. However, strong donor‐acceptor interactions yield a one‐step photovoltaic process: direct dissociation of both singlet and triplet excitons in bulk‐heterojunction organic solar cells. In addition, the magnetic‐field effects of photocurrents indicate that the dissociated electrons and holes form charge‐transfer complexes with singlet and triplet spin configurations at donor‐acceptor intermolecular interfaces. As a result, the magnetic‐field effects of photocurrents can deliver a critical understanding of singlet and triplet photovoltaic processes to design advanced solar‐energy materials and devices.     

The Origin of the High Voltage in DPM12/P3HT Organic Solar Cells

Organic solar cells made using a blend of DPM12 and P3HT are studied. The results show that higher V_oc can be obtained when using DPM12 in comparison to the usual mono‐substituted PCBM electron acceptor. Moreover, better device performances are also registered when the cells are irradiated with sun‐simulated light of 10–50 mW cm^?2 intensity. Electrochemical and time‐resolved spectroscopic measurements are compared for both devices and a 100‐mV shift in the density of states (DOS) is observed for DPM12/P3HT devices with respect to PCBM/P3HT solar cells and slow polaron‐recombination dynamics are found for the DPM12/P3HT devices. These observations can be directly correlated with the observed increase in V_oc, which is in contrast with previous results that correlated the higher V_oc with different ideality factors obtained using dark‐diode measurements. The origin for the shift in the DOS can be correlated to the crystallinity of the blend that is influenced by the properties of the included fullerene.     

Enhanced Thermal Stability and Efficiency of Polymer Bulk‐Heterojunction Solar Cells by Low‐Temperature Drying of the Active Layer

This study addresses two key issues, stability and efficiency, of polymer solar cells based on blended poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) by demonstrating a film‐forming process that involves low‐temperature drying (?5 °C) and subsequent annealing of the active layer. The low‐temperature process achieves 4.70% power conversion efficiency (PCE) and ～1250 h storage half‐life at 65 °C, which are significant improvements over the 3.39% PCE and ～143 h half‐life of the regular room‐temperature process. The improvements are attributed to the enhanced nucleation of P3HT crystallites as well as the minimized separation of the P3HT and PCBM phases at the low drying temperature, which upon post‐drying annealing results in a morphology consisting of small PCBM‐rich domains interspersed within a densely interconnected P3HT crystal network. This morphology provides ample bulk‐heterojunction area for charge generation while allowing for facile charge transport; moreover, the P3HT crystal network serves as an immobile frame at heating temperatures less than the melting point (T_m) of P3HT, thus preventing PCBM/P3HT phase separation and the corresponding device degradation.     

Correlation between ultrafast transient photomodulation spectroscopy and organic photovoltaic solar cell efficiency based on RR-P3HT/PCBM blends

Ultrafast transient spectroscopy was applied to various films of regio-regular polythiophene (RR-P3HT, donor-D) and C₆₀ derivative (PCBM, acceptor-A) blends, in conjunction with organic photovoltaic (OPV) solar cell fabrication and evaluation based on the same blends, for investigating the existence of a correlation between the device efficiency and the transient photophysics characteristics. For our transient spectroscopy measurements we used the ps pump–probe transient photomodulation (PM) technique having a unique probe spectral range in the mid-IR (0.25–1.05 eV). We found that the transient PM spectra contain photoinduced absorption bands of excitons in the donor polymer, charge transfer excitons (CTE) at the D–A interfaces, and free polarons. We compared the relative density of photogenerated CTE in D–A blends having various D–A weight ratio with the photocurrent density of fabricated solar cells based on the same blends. We found that the dissociation of CTE into free charges correlates well with the optoelectronic measurements of the corresponding solar cell. The more efficient CTE dissociation occurs in films having the optimum D–A weight ratio (which is 1.2:1 for the P3HT/PCBM system) that shows the highest OPV power conversion efficiency; this is due to the lowest CTE binding energy for this blend that results from the most suitable D- and A- grain sizes. We also show that the exciton lifetime is the shortest for the optimum blend, and this helps boosting the device efficiency by reducing energy loss.     

Non‐destructive lateral mapping of the thickness of the photoactive layer in polymer‐based solar cells

Non‐destructive lateral mapping of the thickness of the photoactive layer in poly(3‐hexyl‐thiophene) : 1‐(3‐methoxy‐carbonyl)propyl‐1‐phenyl‐(6,6)C₆₁ (P3HT : PCBM) solar cells is demonstrated. The method employs a spatially resolved (XY) recording of ultraviolet‐visible spectra in reflection geometry at normal incidence, using a dense raster defined by a circular probe spot of 800‐µm diameter. The evaluation of the thickness of the photoactive layer at each raster point employs an algorithm‐driven comparison of the measured absorption spectrum with spectral features, as compiled from the corresponding simulated spectrum. For the robustness of the applied algorithm toward noise in the recorded absorption data to be increased, a new minimum finder algorithm is described and implemented. The thickness evaluation relies on the correct assignment of extrema in the experimental absorption spectra to the corresponding extrema in the simulated absorption spectra, and a new algorithm for this is also implemented and described. For a level of confidence for the method to be established, first thickness mapping is performed for a set of reference samples consisting of P3HT : PCBM spin‐coated on indium tin oxide‐coated float glass substrates. After this, two application examples for solar cells processed either by spin coating or slot die coating of the P3HT : PCBM layer follow. The spin‐coated solar cells have glass as the substrate with the P3HT : PCBM spun at different spinning speeds. The slot die‐coated solar cells were processed on polyethylene terephthalate foil in a roll‐to‐roll experiment involving a continuously changing P3HT : PCBM concentration along the printing direction. Copyright © 2011 John Wiley & Sons, Ltd.     

Abrupt Morphology Change upon Thermal Annealing in Poly(3‐Hexylthiophene)/Soluble Fullerene Blend Films for Polymer Solar Cells

The in situ morphology change upon thermal annealing in bulk heterojunction blend films of regioregular poly(3‐hexylthiophene) (P3HT) and 1‐(3‐methoxycarbonyl)‐propyl‐1‐phenyl‐(6,6)C₆₁ (PCBM) is measured by a grazing incidence X‐ray diffraction (GIXD) method using a synchrotron radiation source. The results show that the film morphology—including the size and population of P3HT crystallites—abruptly changes at 140 °C between 5 and 30 min and is then stable up to 120 min. This trend is almost in good agreement with the performance change of polymer solar cells fabricated under the same conditions. The certain morphology change after 5 min annealing at 140 °C is assigned to the on‐going thermal transition of P3HT molecules in the presence of PCBM transition. Field‐emission scanning electron microscopy measurements show that the crack‐like surface of blend films becomes smaller after a very short annealing time, but does not change further with increasing annealing time. These findings indicate that the stability of P3HT:PCBM solar cells cannot be secured by short‐time annealing owing to the unsettled morphology, even though the resulting efficiency is high.     

Effect of coupling between excitons and gold nanoparticle surface plasmons on emission behavior of phosphorescent organic light-emitting diodes

Enhanced efficiency and reduced efficiency roll-off in phosphorescent organic light-emitting diodes (PhOLEDs) are realized by interposing a solution-processed gold nanoparticle (GNP)-based interlayer between the anode and the hole-injection layer. Transient photoluminescence measurements elucidate that a reduced lifetime of the triplet excitons was observed for samples having a GNP-interlayer as compared to a control sample without the GNP-interlayer. The decrease in the triplet exciton lifetime, caused by the coupling between the triplet excitons and the localized surface plasmons (LSPs) excited by the GNPs, enables reducing the triplet–triplet and triplet–polaron annihilation processes, thereby a reduced efficiency roll-off in PhOLEDs. The presence of a GNP-interlayer also acts as an optical out-coupling layer contributing to the efficiency enhancement and was demonstrated by the theoretical simulation.     

P3HT/PCBM Bulk Heterojunction Solar Cells: Impact of Blend Composition and 3D Morphology on Device Performance

The performance of polymer solar cells (PSC) strongly depends on the 3D morphological organization of the donor and acceptor compounds within the bulk heterojunction active layer. The technique of electron tomography is a powerful tool for studying 3D morphology of the layers composed of poly(3‐hexylthiophene) (P3HT) and a fullerene derivative ([6,6]‐phenyl‐C61‐butyric acid methyl ester; PCBM), especially to quantify the amount and distribution of fibrillar P3HT nanocrystals throughout the volume of the active layer. In this study, electron tomography is used to characterize P3HT/PCBM layers with different blend compositions, both before and after thermal annealing. The power conversion efficiency of the corresponding PSCs is strongly dependent on the overall crystallinity of P3HT and the way P3HT crystals are distributed throughout the thickness of the active layer.     

Time‐Dependent Morphology Evolution by Annealing Processes on Polymer:Fullerene Blend Solar Cells

Changes in the nanoscale morphologies of the blend films of poly (3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), for high‐performance bulk‐heterojunction (BHJ) solar cells, are compared and investigated for two annealing treatments with different morphology evolution time scales, having special consideration for the diffusion and aggregation of PCBM molecules. An annealing condition with relatively fast diffusion and aggregation of the PCBM molecules during P3HT crystallization results in poor BHJ morphology because of prevention of the formation of the more elongated P3HT crystals. However, an annealing condition, accelerating PCBM diffusion after the formation of a well‐ordered morphology, results in a relatively stable morphology with less destruction of crystalline P3HT. Based on these results, an effective strategy for determining an optimized annealing treatment is suggested that considers the effect of relative kinetics on the crystallization of the components for a blend film with a new BHJ materials pair, upon which BHJ solar cells are based.     

Annealing‐Free High Efficiency and Large Area Polymer Solar Cells Fabricated by a Roller Painting Process

Polymer solar cells are fabricated by a novel solution coating process, roller painting. The roller‐painted film – composed of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) – has a smoother surface than a spin‐coated film. Since the roller painting is accompanied by shear and normal stresses and is also a slow drying process, the process effectively induces crystallization of P3HT and PCBM. Both crystalline P3HT and PCBM in the roller‐painted active layer contribute to enhanced and balanced charge‐carrier mobility. Consequently, the roller‐painting process results in a higher power conversion efficiency (PCE) of 4.6%, as compared to that for spin coating (3.9%). Furthermore, annealing‐free polymer solar cells (PSCs) with high PCE are fabricated by the roller painting process with the addition of a small amount of octanedi‐1,8‐thiol. Since the addition of octanedi‐1,8‐thiol induces phase separation between P3HT and PCBM and the roller‐painting process induces crystallization of P3HT and PCBM, a PCE of roller‐painted PSCs of up to 3.8% is achieved without post‐annealing. A PCE of over 2.7% can also be achieved with 5 cm² of active area without post‐annealing.     

Triplet Exciton and Polaron Dynamics in Phosphorescent Dye Blended Polymer Photovoltaic Devices

The triplet exciton and polaron dynamics in phosphorescent dye (PtOEP) blended polymer (MEH‐PPV) photovoltaic devices are investigated by quasi‐steady‐state photo‐induced absorption (PIA) spectroscopy. According to the low‐temperature PIA and photoluminescence (PL) results, the increase in strength of the triplet‐triplet (T₁‐T_n) absorption of MEH‐PPV in the blend system originates from the triplet‐triplet energy transfer from PtOEP to MEH‐PPV. The PtOEP blended MEH‐PPV/C₆₀ bilayer photovoltaic device shows a roughly 30%–40% enhancement in photocurrent and power‐conversion efficiency compared to the device without PtOEP. However, in contrast to the bilayer device results, the bulk heterojunction photovoltaic devices do not show a noticeable change in photocurrent and power‐conversion efficiency in the presence of PtOEP. The PIA intensity, originating from the polaron state, is only slightly higher (within the experimental error), indicating that carrier generation in the bulk heterojunction is not enhanced in the presence of PtOEP. The rate and probability of the exciton dissociation between PtOEP and PCBM is much faster and higher than that of the triplet‐triplet energy transfer between PtOEP and MEH‐PPV.     

Evaluating Carrier Accumulation in Degraded Bulk Heterojunction Organic Solar Cells by a Thermally Stimulated Current Technique

Here, the initial photo‐degradation of encapsulated P3HT:PCBM bulk heterojunction organic solar cells is investigated. The degraded device is recovered by thermal annealing treatment. Thermally stimulated current measurements reveal that the cause of photo‐degradation is carrier accumulation and that the degraded organic solar cell has two broad trap levels, of 0.71 and 0.81 eV. These traps are independent of the thickness of the photoactive layers, the mixing ratio of the photoactive materials and the cathode materials. In addition, it is confirmed that there is a close relationship between the degree of degradation and the amount of accumulated charge carriers.     

Effect of Carbon Chain Length in the Substituent of PCBM‐like Molecules on Their Photovoltaic Properties

A series of [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM)‐like fullerene derivatives with the butyl chain in PCBM changing from 3 to 7 carbon atoms, respectively (F1–F5), are designed and synthesized to investigate the relationship between photovoltaic properties and the molecular structure of fullerene derivative acceptors. F2 with a butyl chain is PCBM itself for comparison. Electrochemical, optical, electron mobility, morphology, and photovoltaic properties of the molecules are characterized, and the effect of the alkyl chain length on their properties is investigated. Although there is little difference in the absorption spectra and LUMO energy levels of F1–F5, an interesting effect of the alkyl chain length on the photovoltaic properties is observed. For the polymer solar cells (PSCs) based on P3HT as donor and F1–F5, respectively, as acceptors, the photovoltaic behavior of the P3HT/F1 and P3HT/F4 systems are similar to or a little better than that of the P3HT/PCBM device with power conversion efficiencies (PCEs) above 3.5%, while the performances of P3HT/F3 and P3HT/F5‐based solar cells are poorer, with PCE values below 3.0%. The phenomenon is explained by the effect of the alkyl chain length on the absorption spectra, fluorescence quenching degree, electron mobility, and morphology of the P3HT/F1–F5 (1:1, w/w) blend films.     

Performance Analysis of Printed Bulk Heterojunction Solar Cells

In this paper we report on printed bulk heterojunction solar cells from poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) with power efficiencies of over 4 %. Devices have been produced by doctor blading, which is a reel‐to‐reel compatible large‐area coating technique. Devices exhibit a short‐circuit current of over 11.5 mA cm^–2, a fill factor of 58 %, and an open‐circuit voltage of 615 mV, resulting in an AM1.5 power efficiency of over 4.0 % at 25 °C and under 100 mW cm^–2. The mismatch factor of the solar simulator is cross‐calibrated by determining the spectral quantum efficiency of organic devices as well as of a calibrated Si device, and by the combination of outdoor tests; these efficiencies are precise within less than 3 % relative variation. Although the devices are regarded as fairly optimized, analysis in terms of a one‐diode equivalent circuit reveals residual losses and loss mechanisms. Most interestingly, the analysis points out the different properties of spin‐coated versus bladed devices. Based on this analysis, the future efficiency potential of P3HT–PCBM solar cells is analyzed.     

Comparison of the Operation of Polymer/Fullerene,Polymer/Polymer,and Polymer/Nanocrystal Solar Cells: A Transient Photocurrent and Photovoltage Study

We utilize transient techniques to directly compare the operation of polymer/fullerene, polymer/nanocrystal, and polymer/polymer bulk heterojunction solar cells. For all devices, poly(3‐hexylthiophene) (P3HT) is used as the electron donating polymer, in combination with either the fullerene derivative phenyl‐C₆₁‐butyric acid methyl ester (PCBM) in polymer/fullerene cells, CdSe nanoparticles in polymer/nanocrystal cells, or the polyfluorene copolymer poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthien‐5‐yl)‐2,1,3‐benzothiadiazole]‐2,2‐diyl) (F8TBT) in polymer/polymer cells. Transient photocurrent and photovoltage measurements are used to probe the dynamics of charge‐separated carriers, with vastly different dynamic behavior observed for polymer/fullerene, polymer/polymer, and polymer/nanocrystal devices on the microsecond to millisecond timescale. Furthermore, by employing transient photocurrent analysis with different applied voltages we are also able to probe the dynamics behavior of these cells from short circuit to open circuit. P3HT/F8TBT and P3HT/CdSe devices are characterized by poor charge extraction of the long‐lived carriers attributed to charge trapping. P3HT/PCBM devices, in contrast, show relatively trap‐free operation with the variation in the photocurrent decay kinetics with applied bias at low intensity, consistent with the drift of free charges under a uniform electric field. Under solar conditions at the maximum power point, we see direct evidence of bimolecular recombination in the P3HT/PCBM device competing with charge extraction. Transient photovoltage measurements reveal that, at open circuit, photogenerated charges have similar lifetimes in all device types, and hence, the extraction of these long‐lived charges is a limiting process in polymer/nanocrystal and polymer/polymer devices.