Studies of Charge Transport and Energy Level in Solar Cells Based on Polymer/Fullerene Bulk Heterojunction

π-Conjugated polymers have attracted considerable attention since they are potential candidates for various opto-electronic devices such as solar cells, light emitting iodes, photodiodes, and transistors. Electronic de vices based on conjugated polymers can be easily processed at low temperature using inexpensive technologies. This leads to cost reduction, a key-deriving factor for choosing conjugated polymers for various types of applications. In particular, polymer based solar cells are of special interest due to the fact that they can play a major role in generating clean and cheap energy in the future. The investigations described in thesis are aimed mainly at understanding charge transport and the role of energy le vels in solar cells based on polymer/acceptor bulk heterojunction (BHJ) active films. Best polymer based solar cells, with efficiency 4 to 5%, rely on polymer/fullerene BHJ active films. These solar cells are in an immature state to be used for energy conversion purposes. In order to enhance their performance, it is quite important to understand the efficiency-limiting factors. Solid films of conjugated polymers compose conjugation segments that are randomly distributed in space and energy. Such distributio n gives rise to the localization of charge carriers and hence broadening of electron density of states. Consequently, electronic wave functions have quite poor overlap resulting into absence of continuous band transport. Charge transport in polymers and organic materials, in general, takes place by hopping among the localized states. This makes a bottleneck to the performance of polymer-based solar cells. In this context, the knowledge of charge transport in the solar cell materials is quite important to develop materials and device architectures that boost the efficiency of such solar cells. Most of the transport studies are based on polyfluorene copolymers and fullerene electron acceptor molecules. Fullerenes are blended with polymers to enhance the dissociation of excited state into free carriers and transport free electrons to the respective electrode. The interaction within the polymer-fullerene complex, therefore, plays a major role in the generation and transport of both electrons and holes. In this thesis, we present and discuss the effect of various polymer/fullerene compositions on hole percolation paths. We mainly focus on hole transport since its mobility is quite small as compared to electron mobility in the fullerenes, leading to creation of spa ce charges within the bulk of the solar cell composite. Changing a polymer band gap may necessitate an appropriate acceptor type in order to fulfill the need for sufficient driving force for dissociation of photogenerated electron-hole pairs. We have observed that different acceptor types give rise to completely different hole mobility in BHJ films. The change of hole transport as a function of acceptor type and concentration is mainly attributed to morphological changes. The effect of the acceptors in connection to hole transport is also discussed. The later is supported by studies of bipolar transport in pure electron acceptor layers. Moreover, the link between charge carrier mobility and photovoltaic parameters has also been studied and presented in this thesis. The efficiency of polymer/fullerene-based solar cells is also significantly limited by its open-circuit voltage (Voc), a parameter that does not obey the metal-insulator-metal principle due to its complicated characteristics. In this thesis, we address the effect of varying polymer oxidation potential on Voc of the polymer/fullerene BHJ based solar cells. Systematic investigations have been performed on solar cells that comprise several polythiophene polymers blended with a fullerene derivative electron acceptor molecule. The Voc of such solar cells was found to have a strong correlation with the oxidation potential of the polymers. The upper limit to Voc of the aforementioned solar cells is thermodynamically limited by the net internal electric filed generated by the difference in energy levels of the two materials in the blend. The cost of polymer-based solar cells can be reduced to a great extent through realization of all-plastic and flexible solar cells. This demands the replacement of the metallic components (electrodes) by highly conducting polymer films. While hole conductor polymers are available, low work function polymer electron conductors are rare. In this thesis, prototype solar cells that utilizes a highly conducting polymer, which has a work function of ~ 4.3 eV, as a cathode are demonstrated. Development of this material may eventually lead to fabrication of large area, flexible and cheap solar cells. The transparent nature of the polymer cathode may also facilitate fabrication of multi-layer and tandem solar cells. In the last chapter of this thesis, we demonstrate generation of red and near infrared polarized light by employing thermally converted thin films of polyfluorene copolymers in light emitting diodes. This study, in particular, aims at fabricating polarized infrared light emitting devices.On the day of the defence day the status of article III was In press and article VI was Manuscript.</p

Role of Near Substrate and Bulk Polymer Morphology on Out-of-Plane Space-Charge Limited Hole Mobility

Charge transport is a central issue in all types of organic electronic devices. In organic films, charge transport is crucially limited by film microstructure and the nature of the substrate/organic interface interactions. In this report, we discuss the influence of active layer thickness on space-charge limited hole transport in pristine polymer and polymer/fullerene bulk heterojunction thin films (∼15–300 nm) in a diode structure. According to the results, the out-of-plane hole mobility in pristine polymers is sensitive to the degree of polymer chain aggregation. Blending the polymers with a fullerene molecule does not change the trend of hole mobility if the polymer tends to make an amorphous structure. However, employing an aggregating polymer in a bulk heterojunction blend gives rise to a marked difference in charge carrier transport behavior compared to the pristine polymer and this difference is sensitive to active layer thickness. In aggregating polymer films, the thickness-dependent interchain interaction was found to have direct impact on hole mobility. The thickness-dependent mobility trend was found to correspond well with the trend of fill factors of corresponding bulk heterojunction solar cells. This investigation has a vital implication for material design and the development of efficient organic electronic devices, including solar cells and light-emitting diodes

Red and near infrared polarized light emissions from polyfluorene copolymer based light emitting diodes

The authors report polarized red, electroluminescence peak at 705 nm and near IR, electroluminescence peak at 950 nm, light emission from light emitting diodes based on two polyfluorene copolymers. The copolymers are synthesized from a fluorene monomer combined with donor-acceptor-donor comonomers and designed to have a low band gap and form birefringent liq. cryst. phases. Emission occurs from aligned thin films of polymer layers. The emissive layers are aligned by spin coating on a layer of rubbed conducting polymer poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) and thermally converted into glassy nematic liq. cryst. state. [on SciFinder (R)

Relating the open-circuit voltage to interface molecular properties of donor:acceptor bulk heterojunction solar cells

The open-circuit voltage (V-oc) of polymer:fullerene bulk heterojunction solar cells is determined by the interfacial charge-transfer (CT) states between polymer and fullerene. Fourier-transform photocurrent spectroscopy and electroluminescence spectra of several polymer:fullerene blends are used to extract the relevant interfacial molecular parameters. An analytical expression linking these properties to V-oc is deduced and shown to be valid for photovoltaic devices comprising three commonly used conjugated polymers blended with the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). V-oc is proportional to the energy of the CT states E-CT. The energetic loss q Delta V between E-CT and qV(oc) vanishes when approaching 0 K. It depends linearly on T and logarithmically on illumination intensity. Furthermore q Delta V can be reduced by decreasing the electronic coupling between polymer and fullerene or by reducing the nonradiative recombination rate. For the investigated devices we find a loss q Delta V of similar to 0.6 eV at room temperature and under solar illumination conditions, of which similar to 0.25 eV is due to radiative recombination via the CT state and similar to 0.35 eV is due to nonradiative recombination.Original Publication:Koen Vandewal, Kristofer Tvingstedt, Abay Gadisa, Olle Inganäs and Jean V Manca, Relating the open-circuit voltage to interface molecular properties of donor:acceptor bulk heterojunction solar cells, 2010, PHYSICAL REVIEW B, (81), 12, 125204.http://dx.doi.org/10.1103/PhysRevB.81.125204Copyright: American Physical Societyhttp://www.aps.org

New low band gap alternating polyfluorene copolymer-based photovoltaic cells

New low band gap alternating polyfluorene copolymers were synthesized for use in plastic solar cells and their optical, electrochem., and photovoltaic characteristics were detd. These polymers incorporated fluorene units alternating with groups including electron-withdrawing (A) and electron-donating (D) groups in donor-acceptor-donor (DAD) sequence to achieve the lowering of band gaps. The HOMO-LUMO values were estd. from electrochem. studies. By varying the donor and acceptor strength and position of the solubilizing substituents, similar HOMO values were obtained. These values were also found to correlate well with the open circuit voltage (VOC) values detd. from photovoltaic data of the polymers blended with the acceptor PCBM. Despite similar HOMO values, the absorption spectra of the polymers differ significantly. This prompted the prepn. of photovoltaic devices consisting of blends of two polymers with complementary absorptions in combination with PCBM to harvest more photons in the polymer solar cells. [on SciFinder (R)

Improvements of fill factor in solar cells based on blends of polyfluorene copolymers as electron donors

The photovoltaic characteristics of solar cells based on alternating polyfluorene copolymers, poly(2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4\u27,7\u27-di-2-thienyl-2\u27,1\u27,3\u27-benzothiadiazole)) (APFO-3), and poly(2,7-(9,9-didodecyl-fluorene)-alt-5,5-(4\u27,7\u27-di-2-thienyl-2\u27,1\u27,3\u27-benzothiadiazole)) (APFO-4), blended with an electron acceptor fullerene mol. [6,6]-phenyl-C61-butyric acid Me ester (PCBM), have been investigated and compared. The two copolymers have the same arom. backbone structure but differ by the length of their alkyl side chain. The overall photovoltaic performance of the solar cells is comparable irresp. of the copolymer used in the active layer. However, the fill factor (FF) values of the devices are strongly affected by the copolymer type. Higher FF values were realized in solar cells with APFO-4 (with longer alkyl side chain)/PCBM bulk heterojunction active layer. On the other hand, devices with blends of APFO-3/APFO-4/PCBM were found to render fill factor values that are intermediate between the values obtained in solar cells with APFO-3/PCBM and APFO-4/PCBM active film. Upon using APFO-3/APFO-4 blends as electron donors, the cell efficiency can be enhanced by about 16% as compared to cells with either APFO-3 or APFO-4. The transport of holes in each polymer obeys the model of hopping transport in disordered media. However, the degree of energetic barrier against hopping was found to be larger in APFO-3. The tuning of the photovoltaic parameters will be discussed based on studies of hole transport in the pure polymer films, and morphol. of blend layers. The effect of bipolar transport in PCBM will also be discussed. [on SciFinder (R)

New low band gap alternating polyfluorene copolymer-based photovoltaic cells

New low band gap alternating polyfluorene copolymers were synthesized for use in plastic solar cells and their optical, electrochem., and photovoltaic characteristics were detd. These polymers incorporated fluorene units alternating with groups including electron-withdrawing (A) and electron-donating (D) groups in donor-acceptor-donor (DAD) sequence to achieve the lowering of band gaps. The HOMO-LUMO values were estd. from electrochem. studies. By varying the donor and acceptor strength and position of the solubilizing substituents, similar HOMO values were obtained. These values were also found to correlate well with the open circuit voltage (VOC) values detd. from photovoltaic data of the polymers blended with the acceptor PCBM. Despite similar HOMO values, the absorption spectra of the polymers differ significantly. This prompted the prepn. of photovoltaic devices consisting of blends of two polymers with complementary absorptions in combination with PCBM to harvest more photons in the polymer solar cells. [on SciFinder (R)

Role of Thin n‑Type Metal-Oxide Interlayers in Inverted Organic Solar Cells

We have investigated the photovoltaic properties of inverted solar cells comprising a bulk heterojunction film of poly­(3-hexylthiophene) and phenyl-C₆₁-butyric acid methyl ester, sandwiched between an indium–tin-oxide/Al-doped zinc oxide (ZnO-Al) front, and tungsten oxide/aluminum back electrodes. The inverted solar cells convert photons to electrons at an external quantum efficiency (EQE) exceeding 70%. This is a 10–15% increase over EQEs of conventional solar cells. The increase in EQE is not fully explained by the difference in the optical transparency of electrodes, interference effects due to an optical spacer effect of the metal-oxide electrode buffer layers, or variation in charge generation profile. We propose that a large additional splitting of excited states at the ZnO–Al/polymer interface leads to the considerably large photocurrent yield in inverted cells. Our finding provides new insights into the benefits of n-type metal-oxide interlayers in bulk heterojunction solar cells, namely the splitting of excited states and conduction of free electrons simultaneously

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\u27,8\u27-di-2-thienyl-(2\u27,3\u27-bis-(3\u27\u27-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 photolumin escence 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 mol., a mathanofullerene [6,6]-phenyl-C61-butyric acid Me ester (PCBM). It has also been obsd. 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. [on SciFinder (R)

Effects of nano-patterned versus simple flat active layers in upright organic photovoltaic devices

A scalable procedure for nano-patterning the bulk heterojunction layer in organic photovoltaic (OPV) devices is reported. Nano-patterning is shown to increase light absorption in poly(3-hexylthiophene) : [6,6]-phenyl-C61-butyric acid methyl ester (P3HT : PCBM) devices (ITO\WO3\P3HT : PCBM\Ca\Al). Nano-patterning also modifies electric fields in OPV devices, thus affecting charge harvesting. Nano-patterned OPV devices with a power conversion efficiency of 4% are presented. Comparable efficiencies are also obtained by optimization of thicknesses in a flat-layer device. Trade-offs between absorption enhancement and charge harvesting deterioration induced by nano-patterning are discussed as well as possible optimization strategies