Transport in organic solar-cell materials studied by time-resolved terahertz spectroscopy

People involved: Villy Sundstrm, Carlito S. Ponseca Jr. Former members: Han-Kwang Nienhuys, Hynek Nmec This project is related to the following Fields, Subjects and Techniques: Fields: Ultrafast Chemistry, Physics and Biology Subjects: Novel Solar Cell Materials, Polymer Solar Cells Techniques: Time-resolved terahertz spectroscopy

Motivation
Blends of polymers with electron acceptors are promising materials for fabrication of inexpensive solar cells. Using time-resolved terahertz (THz) spectroscopy, we can directly probe the very early phases of the photo-initiated charge transport, and thus to contribute to the understanding of the basic photo-processes in solar cells.

Operation of organic solar cell

Scheme of basic processes occurring in organic solar cells. These include photo-generation of excitons, exciton dissociation into separated charges and transport of the separated charges to the electrodes.

Simplified picture of processes occurring in organic solar cells A photon is absorbed in the polymer, thus creating an exciton. The nascent exciton dissociates into separated charge carriers. This is facilitated by the presence of an electron acceptor, which accepts the electron while the hole remains on the polymer chains. The difference in work functions of the electrodes gives rise to an electric field which drives the separated charge carriers towards electrodes. The charge carriers are collected at the electrodes. If an electrical circuit is connected to the electrodes, an electrical current flows through it. Visit the site of the polymer solar cells project to see more details.

Studied materials

Chemical structure of polymers and of the electron acceptor used in our studies. The polymers have been synthesized in the Department of Biomolecular and Organic Electronics at Linkping University. [Appl. Phys. A 79, 31 (2004), Adv. Mat. 19, 3308 (2007)].

We investigate two types of polymers. The APFO-3 is a polyfluorene co-polymer. It has quite low band gap (1.9 eV) which allows collection of about 40 % of the incident solar spectrum energy. In conjunction with PCBM electron acceptor, it reaches power conversion efficiency of 2.6 % [Thin Solid Films 515, 3126 (2007)]. The LBPP-1 co-polymer has an even lower band gap (1.0 eV). However, its power conversion efficiency is much lower (0.38 %, [Adv. Mat. 19, 3308 (2007)]).

Information provided by THz spectroscopy

The fundamental output of time-resolved THz spectroscopy consists in transient conductivity spectra (f). From the shape of these spectra, it is possible to distinguish between the response of free and bound charge carriers. Response of free charges is characterized by non-zero real part of conductivity at the lowest frequencies. Response of localized charge carriers causes increase of the real part of conductivity with frequencies while the corresponding imaginary part is negative. The spectra in the following graph thus exhibit a response of both types of charge carriers.

Example of transient far-infrared conductivity spectra measured in an APFO-3:PCBM blend at various pump-probe delays. The weight fraction of PCBM in this example was 80 %. The points represent measured data while the curves are results of a fit to a theoretical model [Submitted to J. Phys. Chem. C].

The important information which can be extracted from the measured transient conductivity spectra is a product of quantum efficiencywith which free charge carriers are generatedand of their mobility. For example, in the above graph this product reaches 4.7 %cm2V1s1, measured 2 ps after photo-excitation. The separated charge carriers thus necessarily exhibit much higher mobility as compared to measurements in a dc electrical field [Appl. Phys. Lett. 88, 082103 (2006)].

Organic Solar Cells Photons from Flexible Plastics A plastic film that can power a radio on the beachSolar cells made of organic materials have brought this vision within reach. Konarka, a leading manufacturer of these materials, has joined forces with Siemens and is planning to introduce its first prototypes this year.

Solar cells made of organic materials can supply power for portable devices. The cells are manufactured in clean rooms (top) because dust particles can lead to short circuits in nanometerthin layers

They look like oversized photographic negatives, but they also have some of the characteristics of leaves. They can generate energy from sunlight and are made of organic materials. Welcome to the world of organic solar cells. And unlike their inorganic silicon relatives, which dominate 95 % of todays solar cell market, these plastics can be produced faster and at much lower cost, because they dont require high-purity crystals, which must be grown. This means they create opportunities for entirely new applications, such as plastic films that can power small devices. Initially, solar cells made of organic semiconductors offered very low efficienciesbarely 1 %, compared to the 14 to 17 % of conventional silicon cells. Thats because photons impinging on plastics dont immediately produce electrons; they generate excited states that must then be converted into free charge carriers. Nanotechnology paved the way for the breakthrough. A Siemens team in Erlangen incorporated fullerenesmolecules containing 60 carbon atoms and resembling tiny soccer ballsin a matrix of semiconducting polymers. Impinging light liberates electrons within the plastic, which are captured and transported to an electrode by the fullerenes. In early 2004, researchers used this technology to achieve an efficiency of 5 % for the first timea world record. "10 % efficiency has come within our reach. But were not just out to set records," explains Dr. Christoph Brabec, who headed this research at Siemens Corporate Technology. "We want to make products." After Siemens sold its solar cell activities to Shell Solar in 2002, Brabec and his team initially focused on photodetectors. But that didnt give them the opportunity to fully exploit the potential of this technology. Thats why a decision was made to involve an external partner with abundant

applications know-how in the field. Thus, since August 2004, Lowell, Massachusetts-based Konarka, has been conducting Siemens organic solar cell business. Brabec and five of his colleagues transferred to Konarka, where they already had excellent connections from previous joint projects. Konarka is the worldwide leader in organic photovoltaics. Alan J. Heeger was one of Konarkas cofounders back in 2001. In the early 1980s, he and his partners discovered conductive plastics, which earned them the Nobel Prize in 2001. "Were very pleased to have the opportunity to be working with Christoph Brabec," says Heeger. "Including my colleague Serdar Sariciftci, we now have three of the most prominent pioneers in conductive polymer research on the same team." Just Print It. Brabec and his team are now working in Linz, Austria, and Nuremberg, Germany, where Konarka has its European headquarters. "We come from the electronics and semiconductor industry," Brabec explains. "Thats why we complement the materials scientists and chemists at Konarka so well." The company plans to introduce a range of solar cells to the market and is already setting up its first production lines. Prototypes of so-called dye-sensitized cells are scheduled to be delivered by the end of 2005. Konarka researchers are also developing market-ready multilayer solar cells and cells based on composites of two organic materials (box). They are searching for the ideal combinations of plastics and layer thicknesses, and are developing materials that can optimize the conversion of a broad segment of the spectrumincluding infraredinto electricity. A major advantage of organic solar cells is that they can be produced using a simple printing process. Individual plastic layers are printed, one after the other, on a supporting material, in a process similar to that used by a printing press. However, the production process requires very clean working conditions, because dust particles can lead to short circuits in the nanometer-thin layers. The initial goal is not to replace the existing technology, such as solar panels used on rooftops. Konarka is instead focusing on the unique characteristics of the new modules. And the fact that they can be dyed and easily shaped creates a multitude of new opportunities. Solar cells sewn into garments could power portable devices, such as mobile phones or the coolest new digital music players, and colorful awnings could some day even serve as electric power sources. Other applications could range from unmanned vehicles to tents to battery chargers. And since these solar cells can be folded and stored in small spaces anytime, they can recharge batteries in notebooks or mobile phoneseven inside buildings. Thats because, unlike crystalline semiconductors, organic solar cells can efficiently convert artificial light as well as sunlight. Three key factors will determine the success of organic solar cells: price, efficiency and service life. And because theyre manufactured without complex, high-vacuum crystal growing systems, their cost will probably only amount to approximately one fifth of the cost of those based on silicon. Their efficiency is already considerable, and it will continue to increase. Service life is

still a critical factor, though, because the cells are susceptible to oxidation and can be damaged by humidity. Whats more, there is still a lack of long-term experience and of standardized test methods that can be used to measure product life of flexible cells. Konarkas near-term objective is to perfect solar cells that deliver an efficiency of 5 %, have a service life of at least three years, and that can be manufactured on a commercial scale. Realizing these goals would establish Konarkas organic solar cells in the field of consumer electronics. "You never know. In five to ten years we might be a dominant force on the power generation market. By then you might see rooftops covered with our solar panels," says Brabec with a confident grin. Bernhard Gerl
How an organic solar cell works

Conventional solar cells consist of two semiconductor layers. At the boundary surface of these layers, an electric field develops. Impinging photons liberate charge carrierselectrons and holes (i.e. ions lacking electrons) that are conducted to the cells metallic contacts. This causes current to flow in the external electric circuit. Even organic semiconductors can be excited by photons. But when these absorb light, no free electrons are initially generated. Instead, excitons are createdelectron-hole pairs that are linked by electromagnetic forces and must first be separated. This separation is achieved by two layersone that readily emits electrons (a donor) and another that readily receives them (an acceptor). If such an exciton migrates to the boundary surface between the two layers, the donor transfers an electron to the acceptor. Those charge carriers are conducted to the external electrodes, and the unit generates electric current. Instead of using several layers, composites of two organic materials can also be used (see illustration below). In such cells, donor and acceptor substances, which serve as hole and electron conductors respectively, are mixed. As a result, the entire volume of the solar cell is utilized. In the most successful solar cells, a conjugated polymer, such as poly-(3hexylthiophene), is used as a donor, and a fullerene as an acceptor.