The Relation Between Open‐Circuit Voltage and the Onset of Photocurrent Generation by Charge‐Transfer Absorption in Polymer : Fullerene Bulk Heterojunction Solar Cells

Photocurrent generation by charge‐transfer (CT) absorption is detected in a range of conjugated polymer–[6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) based solar cells. The low intensity CT absorption bands are observed using a highly sensitive measurement of the external quantum efficiency (EQE) spectrum by means of Fourier‐transform photocurrent spectroscopy (FTPS). The presence of these CT bands implies the formation of weak ground‐state charge‐transfer complexes in the studied polymer–fullerene blends. The effective band gap (E_g) of the material blends used in these photovoltaic devices is determined from the energetic onset of the photocurrent generated by CT absorption. It is shown that for all devices, under various preparation conditions, the open‐circuit voltage (V_oc) scales linearly with E_g. The redshift of the CT band upon thermal annealing of regioregular poly(3‐hexylthiophene):PCBM and thermal aging of poly(phenylenevinylene)(PPV):PCBM photovoltaic devices correlates with the observed drop in open‐circuit voltage of high‐temperature treated versus untreated devices. Increasing the weight fraction of PCBM also results in a redshift of E_g, proportional with the observed changes in V_oc for different PPV:PCBM ratios. As E_g corresponds with the effective bandgap of the material blends, a measurement of the EQE spectrum by FTPS allows us to measure this energy directly on photovoltaic devices, and makes it a valuable technique in the study of organic bulk heterojunction solar cells.     

Beyond PCBM: Understanding the Photovoltaic Performance of Blends of Indene‐C60 Multiadducts with Poly(3‐hexylthiophene)

The effect of functionalization of the C₆₀ cage with multiple indene groups in relation to the dynamics of photogenerated species in blends with poly(3‐hexylthiophene) (P3HT) and the performance of P3HT:indene‐C₆₀ photovoltaic devices is reported. Despite the systematic decrease of the electron affinity of the acceptor with the number of additions, exciton dissociation is efficient in blends of P3HT with all three indene‐C₆₀ derivatives. By replacing the prototypical acceptor [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) with mono‐indene‐C₆₀ (ICMA) or a sample of a mixture of bis‐indene‐C₆₀ regioisomers (ICBA) the power conversion efficiency is enhanced, predominantly due to an increase in the open‐circuit voltage that originates from the lower electron affinity of the indene‐C₆₀ acceptor. The use of an acceptor sample that represents a mixture of tris‐indene‐C₆₀ (ICTA) regioisomers results in a reduction of the short‐circuit current density, fill factor, and open‐circuit voltage of the photovoltaic device. The electron mobility in ICTA domains is ca. a factor 10 lower than in ICMA and ICBA. Density functional theory calculations of the LUMO energies in ICTA isomers demonstrate that energetic disorder caused by the presence of regioisomers is unlikely to be responsible for the low electron mobility in ICTA. The observed deterioration in device performance is attributed to the formation of small ICTA clusters “coated” in insulating indene units that reduce electronic coupling between the molecules and cause the low electron mobility in ICTA domains. These findings indicate that while multiple additions to a fullerene cage provide a facile methodology for controlling the energy levels, they may have limited success in improving OPV device performance.     

Nanoscale Morphology of Conjugated Polymer/Fullerene‐Based Bulk‐ Heterojunction Solar Cells

The relation between the nanoscale morphology and associated device properties in conjugated polymer/fullerene bulk‐heterojunction “plastic solar cells” is investigated. We perform complementary measurements on solid‐state blends of poly[2‐methoxy‐5‐(3,7‐dimethyloctyloxy)]‐1,4‐phenylenevinylene (MDMO‐PPV) and the soluble fullerene C₆₀ derivative 1‐(3‐methoxycarbonyl) propyl‐1‐phenyl [6,6]C₆₁ (PCBM), spin‐cast from either toluene or chlorobenzene solutions. The characterization of the nanomorphology is carried out via scanning electron microscopy (SEM) and atomic force microscopy (AFM), while solar‐cell devices were characterized by means of current–voltage (I–V) and spectral photocurrent measurements. In addition, the morphology is manipulated via annealing, to increase the extent of phase separation in the thin‐film blends and to identify the distribution of materials. Photoluminescence measurements confirm the demixing of the materials under thermal treatment. Furthermore the photoluminescence of PCBM clusters with sizes of up to a few hundred nanometers indicates a photocurrent loss in films of the coarser phase‐separated blends cast from toluene. For toluene‐cast films the scale of phase separation depends strongly on the ratio of MDMO‐PPV to PCBM, as well as on the total concentration of the casting solution. Finally we observe small beads of 20–30 nm diameter, attributed to MDMO‐PPV, in blend films cast from both toluene and chlorobenzene.     

Cyclobutadiene–C60 Adducts: N‐Type Materials for Organic Photovoltaic Cells with High VOC

New tetraalkylcyclobutadiene–C₆₀ adducts are developed via Diels–Alder cycloaddition of C₆₀ with in situ generated cyclobutadienes. The cofacial π‐orbital interactions between the fullerene orbitals and the cyclobutene are shown to decrease the electron affinity and thereby increase the lowest unoccupied molecular orbital (LUMO) energy level of C₆₀ significantly (ca. 100 and 300 meV for mono‐ and bisadducts, respectively). These variations in LUMO levels of fullerene can be used to generate higher open‐circuit voltages (V_OC) in bulk heterojunction polymer solar cells. The tetramethylcyclobutadiene–C₆₀ monoadduct displays an open‐circuit voltage (0.61 V) and a power conversion efficiency (2.49%) comparable to the widely used P3HT/PCBM (poly(3‐hexylthiophene/([6,6]‐phenyl‐C61‐butyric acid methyl ester) composite (0.58 V and 2.57%, respectively). The role of the cofacial π‐orbital interactions between C₆₀ and the attached cyclobutene group was probed chemically by epoxidation of the cyclobutene moiety and theoretically through density functional theory calculations. The electrochemical, photophysical, and thermal properties of the newly synthesized fullerene derivatives support the proposed effect of functionalization on electron affinities and photovoltaic performance.     

Influence of Solvent Mixing on the Morphology and Performance of Solar Cells Based on Polyfluorene Copolymer/Fullerene Blends

The influence of the solvent on the morphology and performance of polymer solar cells is investigated in devices based on blends of the polyfluorene copolymer, poly(2,7‐(9,9‐dioctyl‐fluorene)‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)), and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester. The blends are spin‐coated from chloroform or from chloroform mixed with small amounts of xylene, toluene, or chlorobenzene. The devices are characterized under monochromatic light and solar illumination AM1.5 (AM: air mass). An enhancement of the photocurrent density is observed in diodes made from chloroform mixed with chlorobenzene, and reduced photocurrent density is observed in diodes made from chloroform mixed with xylene or toluene, compared to diodes made from neat chloroform. The open‐circuit voltages are almost the same in all diodes. The surfaces of the active layers are imaged using atomic force microscopy. Height images indicate that a finer and more uniform distribution of domains corresponds to the diodes with enhanced photocurrent that are made from chloroform mixed with chlorobenzene, while a structure with larger domains is associated with the lower photocurrents in the diodes made from chloroform mixed with xylene or toluene. The influence of the morphology on the excited‐state dynamics and charge generation is investigated using time‐resolved spectroscopy. Fast formation of bound charge pairs followed by their conversion into free charge carriers is resolved, and excitation‐intensity‐dependent non‐geminate recombination of free charges is observed. A significant enhancement in free‐charge‐carrier generation is observed on introducing chlorobenzene into chloroform. Imaging photocurrent generation from the solar cells with a light‐pulse technique shows an inhomogeneous photocurrent distribution, which is related to the undulations in the thickness of the active layer. Thicker parts of the diodes yield higher photocurrent values.     

In‐Situ Compositional and Structural Analysis of Plastic Solar Cells

Bulk‐heterojunction photovoltaic cells consisting of a photoactive layer of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene] (MDMO‐PPV) and a C₆₀ derivative, (1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐methanofullerene), (PCBM), sandwiched between an indium tin oxide (ITO) anode covered with poly(ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), and an aluminum cathode have been analyzed using transmission electron microscopy (TEM) and cryogenic Rutherford backscattering spectrometry (RBS) to assess the structural and elemental composition of these devices. TEM of cross sections of fully processed photovoltaic cells, prepared using a focused ion beam, provide a clear view of the individual layers and their interfaces. RBS shows that during preparation diffusion of indium into the PEDOT:PSS occurs while the diffusion of aluminum into the polymer layers is negligible. An iodinated C₆₀ derivative (I‐PCBM) was used to determine the concentration profile of this derivative in the vertical direction of a 100 nm active layer.     

A New Donor–Acceptor–Donor Polyfluorene Copolymer with Balanced Electron and Hole Mobility

A new alternating polyfluorene copolymer poly[2,7‐(9,9‐dioctylfluoren)‐alt‐5,5‐(5′,8′‐di‐2‐thienyl‐(2′,3′‐bis‐(3′′‐octyloxyphenyl)‐quinoxaline))] (APFO‐15), which has electron donor–acceptor–donor units in between the fluorene units, is synthesized and characterized. This polymer has a strong absorption and emission in the visible range of the solar spectrum. Its electroluminescence and photoluminescence emissions extend from about 560 to 900 nm. Moreover, solar cells with efficiencies in excess of 3.5 % have been realized from blends of APFO‐15 and an electron acceptor molecule, a methanofullerene [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM). It has also been observed that electron and hole transport is balanced both in the pure polymer phase and in polymer/PCBM bulk heterojunction films, which makes this material quite attractive for applications in opto‐electronic devices.     

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.     

Photoconductivity of C60 as an Origin of Bias‐Dependent Photocurrent in Organic Photovoltaics

The bulk‐ionized photoconductivity of C₆₀ is reported as an origin of the bias‐dependent linear change of the photocurrent in copper phthalocyanine (CuPc)/C₆₀ planar heterojunction solar cells, based on the observation of the variation of the bias‐dependent photocurrent on excitation wavelengths and the thickness‐dependent photocurrent of the C₆₀ layer. A theoretical model, which is a combination of the Braun‐Onsager model for the dissociation of excitons at the donor/acceptor interface and the Onsager model for the bulk ionization of excitons in the C₆₀ layer, describes the bias‐dependent photocurrent in the devices very well. The bulk‐ionized photoconductivity of C₆₀ must generally contribute to the photocurrent in organic photovoltaics, since fullerene and fullerene derivatives are widely used in these devices.     

Photoinduced Hole Transfer Becomes Suppressed with Diminished Driving Force in Polymer‐Fullerene Solar Cells While Electron Transfer Remains Active

Device performance and photoinduced charge transfer are studied in donor/acceptor blends of the oxidation‐resistant conjugated polymer poly[(4,8‐bis(2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐2,6‐diyl‐alt‐(2,5‐bis(3‐dodecylthiophen‐2‐yl)benzo[1,2‐d;4,5‐d′]bisthiazole)] (PBTHDDT) with the following fullerene acceptors: [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM); [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM); and the indene‐C₆₀ bis‐adduct IC₆₀BA). Power conversion efficiency improves from 1.52% in IC₆₀BA‐based solar cells to 3.75% in PC₇₁BM‐based devices. Photoinduced absorption (PIA) of the PBTHDDT:fullerene blends suggests that exciting the donor polymer leads to long‐lived positive polarons on the polymer and negative polarons on the fullerene in all three polymer fullerene blends. Selective excitation of the fullerene in PC₇₁BM or PC₆₁BM blends also generates long‐lived polarons. In contrast, no discernible PIA features are observed when selectively exciting the fullerene in a PBTHDDT/IC₆₀BA blend. A relatively small driving force of ca. 70 meV appears to sustain charge separation via photoinduced hole transfer from photoexcited PC₆₁BM to the polymer. The decreased driving force for photoinduced hole transfer in the IC₆₀BA blend effectively turns off hole transfer from IC₆₀BA excitons to the host polymer, even while electron transfer from the polymer to the IC₆₀BA remains active. Suppressed hole transfer from fullerene excitons is a potentially important consideration for materials design and device engineering of organic solar cells.     

Compositional Dependence of the Performance of Poly(p‐phenylene vinylene):Methanofullerene Bulk‐Heterojunction Solar Cells

The dependence of the performance of OC₁C₁₀‐PPV:PCBM (poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐p‐phenylene vinylene):methanofullerene [6,6]‐phenyl C₆₁‐butyric acid methyl ester)‐based bulk heterojunction solar cells on their composition has been investigated. With regard to charge transport, we demonstrate that the electron mobility gradually increases on increasing the PCBM weight ratio, up to 80 wt.‐%, and subsequently saturates to its bulk value. Surprisingly, the hole mobility in the PPV phase shows an identical behavior and saturates beyond 67 wt.‐% PCBM, a value which is more than two orders of magnitude higher than that of the pure polymer. The experimental electron and hole mobilities were used to study the photocurrent generation of OC₁C₁₀‐PPV:PCBM bulk‐heterojunction (BHJ) solar cells. From numerical calculations, it is shown that for PCBM concentrations exceeding 80 wt.‐% reduced light absorption is responsible for the loss of device performance. From 80 to 67 wt.‐%, the decrease in power conversion efficiency is mainly due to a decreased separation efficiency of bound electron–hole (e–h) pairs. Below 67 wt.‐%, the performance loss is governed by a combination of a reduced generation rate of e–h pairs and a strong decrease in hole transport.     

Loading Fullerene into a Conjugated Polymer Without Chemical Modification

Conjugated polymers doped with fullerenes show excellent photoconversion efficiencies. However, due to the poor solubility of pure C₆₀ in common organic solvents, it was thought that some chemical modifications to C₆₀ were required in order to load conjugated polymers with comparable weights of fullerene. Here, we report a novel way to load large amounts of unmodified C₆₀ fullerene into the conjugated polymer poly(2‐methoxy‐5‐(2′‐ethylhexoxy)‐1,4‐phenylenevinylene), MEH‐PPV. The principle of our approach is to separate the film‐deposition stage from the material‐solidification stage. That is, materials are quickly solidified from dilute solution into colloidal particles, which are large enough to be collected by electrophoretic deposition. Deposition from a mixture of separate suspensions of MEH‐PPV and C₆₀ fullerene resulted in films consisting of isolated particles. In contrast, by using a suspension made of a dilute solution of MEH‐PPV and C₆₀, which was so dilute that traditional techniques such as spin‐coating were not applicable, an MEH‐PPV film doped with 20 mol‐% C₆₀, corresponding to an almost 1:1 ratio by weight of molecularly dispersed C₆₀, was easily obtained. To the best of our knowledge, this is the first report on the successful loading of an equivalent weight ratio of unmodified C₆₀ molecules into MEH‐PPV.     

Formation of a Ground‐State Charge‐Transfer Complex in Polyfluorene//[6,6]‐Phenyl‐C61 Butyric Acid Methyl Ester (PCBM) Blend Films and Its Role in the Function of Polymer/PCBM Solar Cells

Evidence is presented for the formation of a weak ground‐state charge‐transfer complex in the blend films of poly[9,9‐dioctylfluorene‐co‐N‐(4‐methoxyphenyl)diphenylamine] polymer (TFMO) and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM), using photothermal deflection spectroscopy (PDS) and photoluminescence (PL) spectroscopy. Comparison of this polymer blend with other polyfluorene polymer/PCBM blends shows that the appearance of this ground‐state charge‐transfer complex is correlated to the ionization potential of the polymer, but not to the optical gap of the polymer or the surface morphology of the blend film. Moreover, the polymer/PCBM blend films in which this charge‐transfer complex is observed also exhibit efficient photocurrent generation in photovoltaic devices, suggesting that the charge‐transfer complex may be involved in charge separation. Possible mechanisms for this charge‐transfer state formation are discussed as well as the significance of this finding to the understanding and optimization of polymer blend solar cells.     

High Molecular Weights,Polydispersities, and Annealing Temperatures in the Optimization of Bulk‐Heterojunction Photovoltaic Cells Based on Poly(3‐hexylthiophene) or Poly(3‐butylthiophene)

A series of poly(3‐hexylthiophene)s (P3HTs) and poly(3‐butylthiophene)s (P3BTs) with predetermined molecular weights and varying polydispersities are prepared using a simplified Grignard metathesis chain‐growth polymerization. Techniques were elaborated to prepare extremely high molecular weight P3HT (number‐average molecular weight of around 280 000 g mol^–1) with a low polydispersity (< 1.1) without resorting to fractionation. Optimization of the annealing of a series of solar cells based on blends of poly(3‐alkylthiophene)s (P3ATs) and [6,6]‐phenyl C₆₁ butyric acid methyl ester indicates that the polydispersities, molecular weights, and degrees of conjugation of the P3ATs all have an important impact not only on cell characteristics but also on the most effective annealing temperature required. The results indicate that each cell requires annealing treatments specific to the type of polymer and its molecular weight distribution.     

Design of Multilayered Nanostructures and Donor–Acceptor Interfaces in Solution‐Processed Thin‐Film Organic Solar Cells

Multilayered polymer thin‐film solar cells have been fabricated by wet processes such as spin‐coating and layer‐by‐layer deposition. Hole‐ and electron‐transporting layers were prepared by spin‐coating with poly(3,4‐ethylenedioxythiophene) oxidized with poly(4‐styrenesulfonate) (PEDOT:PSS) and fullerene (C₆₀), respectively. The light‐harvesting layer of poly‐(p‐phenylenevinylene) (PPV) was fabricated by layer‐by‐layer deposition of the PPV precursor cation and poly(sodium 4‐styrenesulfonate) (PSS). The layer‐by‐layer technique enables us to control the layer thickness with nanometer precision and select the interfacial material at the donor–acceptor heterojunction. Optimizing the layered nanostructures, we obtained the best‐performance device with a triple‐layered structure of PEDOT:PSS|PPV|C₆₀, where the thickness of the PPV layer was 11 nm, comparable to the diffusion length of the PPV singlet exciton. The external quantum efficiency spectrum was maximum (ca. 20%) around the absorption peak of PPV and the internal quantum efficiency was estimated to be as high as ca. 50% from a saturated photocurrent at a reverse bias of ?3 V. The power conversion efficiency of the triple‐layer solar cell was 0.26% under AM1.5G simulated solar illumination with 100 mW cm^?2 in air.     

Thieno[3,2‐b]thiophene‐diketopyrrolopyrrole Containing Polymers for Inverted Solar Cells Devices with High Short Circuit Currents

The synthesis and characterization four diketopyrrolopyrrole containing conjugated polymers for use in organic photovoltaics is presented. Excellent energy level control is demonstrated through heteroatomic substitution whilst maintaining similar solid state properties as shown by X‐ray diffraction and atomic force microscopy. Inverted solar cells were fabricated with the best devices having short circuit currents exceeding 16 mA cm^?2 and efficiencies of over 5% irrespective of whether [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₀BM) or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₀BM) is used. Transient absorption spectroscopy on the bulk heterojunction blends shows efficient charge photo‐generation, with the variations in short circuit current correlated to the energetic offset between polymer and fullerene.     

Origin of the Open Circuit Voltage of Plastic Solar Cells

A series of highly soluble fullerene derivatives with varying acceptor strengths (i.e., first reduction potentials) was synthesized and used as electron acceptors in plastic solar cells. These fullerene derivatives, methanofullerene [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM), a new azafulleroid, and a ketolactam quasifullerene, show a variation of almost 200 mV in their first reduction potential. The open circuit voltage of the corresponding devices was found to correlate directly with the acceptor strength of the fullerenes, whereas it was rather insensitive to variations of the work function of the negative electrode. These observations are discussed within the concept of Fermi level pinning between fullerenes and metals via surface charges.     

Solvation‐Induced Morphology Effects on the Performance of Polymer‐Based Photovoltaic Devices

Polymer‐based photovoltaic devices have been fabricated by blending the conjugated polymer, poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV) with the buckminsterfullerene, C₆₀. The photo‐induced current and the open‐circuit voltage show a strong dependence on the polymer processing conditions. It was found that the photovoltaic devices fabricated with tetrahydrofuran or chloroform (non‐aromatic solvents) have smaller photocurrents under same reverse bias as well as higher open circuit voltages than the devices fabricated with xylene, dichlorobenzene, or chlorobenzene (aromatic solvents). The device performance dependence on the processing solvent is attributed to the different solvation‐induced polymer morphology.     

Effects of Photo‐oxidation on the Performance of Poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene]:[6,6]‐Phenyl C61‐Butyric Acid Methyl Ester Solar Cells

A study of the photo‐oxidation of films of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV) blended with [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM), and solar cells based thereon, is presented. Solar‐cell performance is degraded primarily through loss in short‐circuit current density, J_SC. The effect of the same photodegradation treatment on the optical‐absorption, charge‐recombination, and charge‐transport properties of the active layer is studied. It is concluded that the loss in J_SC is primarily due to a reduction in charge‐carrier mobility, owing to the creation of more deep traps in the polymer during photo‐oxidation. Recombination is slowed down by the degradation and cannot therefore explain the loss in photocurrent. Optical absorption is reduced by photo‐bleaching, but the size of this effect alone is insufficient to explain the loss in device photocurrent.     

Synthesis and Characterization of a Low Bandgap Conjugated Polymer for Bulk Heterojunction Photovoltaic Cells

Low optical bandgap conjugated polymers may improve the efficiency of organic photovoltaic devices by increasing the absorption in the visible and near infrared region of the solar spectrum. Here we demonstrate that condensation polymerization of 2,5‐bis(5‐trimethylstannyl‐2‐thienyl)‐N‐dodecylpyrrole and 4,7‐dibromo‐2,1,3‐benzothiadiazole in the presence of Pd(PPh₃)₂Cl₂ as a catalyst affords a novel conjugated oligomeric material (PTPTB), which exhibits a low optical bandgap as a result of the alternation of electron‐rich and electron‐deficient units along the chain. By varying the molar ratio of the monomers in the reaction and fractionation of the reaction product, two different molecular weight fractions (PTPTB‐I and PTPTB‐II, see Experimental section) were isolated, containing 5–17 and 13–33 aromatic units respectively, as inferred from matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry (MALDI‐TOF‐MS). Thin films of PTPTB‐I and PTPTB‐II exhibit an optical bandgap of 1.60 and 1.46 eV, respectively. Photoinduced absorption (PIA) and photoluminescence spectroscopy of blends of PTPTB‐I and a methanofullerene (1‐(3‐methoxycarbonyl)‐propyl‐1‐phenyl‐[6,6]C₆₁, PCBM) gave direct spectral evidence of the photoinduced electron‐transfer reaction from PTPTB‐I as a donor to the fullerene derivative as an acceptor. Thin PTPTB‐I:PCBM composite films were sandwiched between indium tin oxide/poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (ITO/PEDOT:PSS) and Al electrodes to prepare working photovoltaic devices, which show an open circuit voltage of 0.67 V under white‐light illumination. The spectral dependence of the device shows an onset of the photocurrent at 1.65 eV (750 nm).