Martin Helgesen

Advanced materials and processes for polymer solar cell devices

The rapidly expanding field of polymer and organic solar cells is reviewed in the context of materials, processes and devices that significantly deviate from the standard approach which involves rigid glass substrates, indium-tin-oxide electrodes, spincoated layers of conjugated polymer/fullerene mixtures and evaporated metal electrodes in a flat multilayer geometry. It is likely that significant advances can be found by pursuing many of these novel ideas further and the purpose of this review is to highlight these reports and hopefully spark new interest in materials and methods that may be performing less than the current state-of-the-art in their present form but that may have the potential to outperform these pending a larger investment in effort.

Photochemical stability of π-conjugated polymers for polymer solar cells: a rule of thumb

A comparative photochemical stability study of a wide range of π-conjugated polymers relevant to polymer solar cells is presented. The behavior of each material has been investigated under simulated sunlight (1 sun, 1000 W m−2, AM 1.5G) and ambient atmosphere. Degradation was monitored during ageing combining UV-visible and infrared spectroscopies. From the comparison of the collected data, the influence of the polymer chemical structure on its stability has been discussed. General rules relative to the polymer structure–stability relationship are proposed.

Scalable, ambient atmosphere roll-to-roll manufacture of encapsulated large area, flexible organic tandem solar cell modules

Inline printing and coating methods have been demonstrated to enable a high technical yield of fully roll-to-roll processed polymer tandem solar cell modules. We demonstrate generality by employing different material sets and also describe how the ink systems must be carefully co-developed in order to reach the ambitious objective of a fully printed and coated 14-layer flexible tandem solar cell stack. The roll-to-roll methodologies involved are flexographic printing, rotary screen printing, slot-die coating, X-ray scattering, electrical testing and UV-lamination. Their combination enables the manufacture of completely functional devices in exceptionally high yields. Critical to the ink and process development is a carefully chosen technology transfer to industry method where first a roll coater is employed enabling contactless stack build up, followed by a small roll-to-roll coater fitted to an X-ray machine enabling in situ studies of wet ink deposition and drying mechanisms, ultimately elucidating how a robust inline processed recombination layer is key to a high technical yield. Finally, the transfer to full roll-to-roll processing is demonstrated.

Upscaling from single cells to modules – fabrication of vacuum- and ITO-free polymer solar cells on flexible substrates with long lifetime

Fabrication of polymer solar cell (PSC) modules was done on a previously reported compact coating/printing machine and tested in a readily scalable roll process on flexible substrates without applying vacuum, ITO or spin coating. Our aim was to establish loss upon scaling from cells to small modules. We studied from single cells (1 cm2) to modules comprising four serially connected devices with a total active area of 8 cm2. Four different polymers (P3HT, PV-D4610, PDTSTTz-4 and PBDTTTz-4) were applied in the preparation of the modules and efficiencies of more than 3% were achieved which is comparable to single cell devices prepared using the same process. This proves that it is possible to scale up new materials in an ITO free device context to modules without having an efficiency drop, due to reliable and consistent processing. The main loss observed was due to the packaging using barrier materials. The photochemical stability of the materials was therefore studied using intense light along with the operational stability of the corresponding devices according to the ISOS-D-1 and ISOS-L-1 standards. For devices under constant illumination we found that barrier materials from Mitsubishi and 3M provide better operational stability over time, compared to the barrier foil obtained from Amcor, for all the polymers, which is ascribed to the cut-off at higher wavelengths thereby lowering the degree of UV light that reaches the device. When comparing the operational stability of the four polymers under constant illumination, P3HT generally retains its performance better with higher T80 values, while the polymer PV-D4610 shows the highest PCE (1.6%) after 300 hours of operation.

Photochemical stability of conjugated polymers, electron acceptors and blends for polymer solar cells resolved in terms of film thickness and absorbance

Photochemical degradation at 1 sun under AM1.5G illumination was performed on six conjugated polymers and five different electron acceptors. Additionally, the respective polymer:PC60BM and P3HT:electron acceptor blends were studied, and all degradations were resolved in terms of film thickness and absorbance. A fully automated degradation setup allowed for inclusion of in excess of 1000 degradations in this study to enable a discussion of reliability of the technique. Degradation rates were found to increase exponentially with decreasing film absorbance for all materials. The relative stabilities within each material group were found to vary for both the pure polymers and the blends. The stability ranking between the materials of the pure polymers was found to be similar to the ranking for their respective blends, implying that the photochemical stability of a pure polymer is a good measure of its associated blend stability. Different electron acceptors were found to stabilize P3HT decreasingly with decreasing donor–acceptor LUMO–LUMO gap. Destabilization of P3HT was observed in the case of the electron acceptor ICBA. Additionally, the decreased stabilization of P3HT by high LUMO electron acceptors poses a challenge to solar cell encapsulation if these materials are to be of commercial interest. The presented method is generally applicable to all types of organic materials to assess photochemical stabilities. The presented results of conjugated polymers demonstrate that this is a powerful tool for conjugated polymer stability assessment if the results are interpreted correctly.

Incorporation of ester groups into low band-gap diketopyrrolopyrrole containing polymers for solar cell applications

To increase the open circuit voltage (VOC) of polymer solar cells based on diketopyrrolopyrrole (DPP) containing polymers, the weakly electron-withdrawing thiophene-3,4-dicarboxylate unit was introduced into the polymer backbone. Two ester group functionalized DPP containing polymers, PCTDPP with a random structure and PDCTDPP with a regular structure, were designed and synthesized by the Stille coupling reaction. The resulting copolymers exhibit broad and strong absorption bands from 350 to 1000 nm with low optical band gaps below 1.40 eV. Through cyclic voltammetry measurements, it is found that regular PDCTDPPs HOMO energy level is 0.18 V lower than that of the corresponding random PCTDPP (−5.14 eV for PCTDPP and −5.32 eV for PDCTDPP). Preliminary photovoltaic properties of the copolymers blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as an electron acceptor were investigated. The PSC based on a PCTDPP:PCBM blend shows a power conversion efficiency (PCE) up to 3.52%, with a VOC of 0.66 V, a short circuit current (ISC) of 8.53 mA cm−2, and a fill factor (FF) of 0.63. For the PDCTDPP:PCBM blend, the highest VOC reaches a value of 0.84 V, and a final PCE (0.92%) is limited by the poor hole mobility of the active layer.

Rapid flash annealing of thermally reactive copolymers in a roll-to-roll process for polymer solar cells

Light induced thermocleaving of a thermally reactive copolymer based on dithienylthiazolo[5,4-d]thiazole (DTZ) and silolodithiophene (SDT) in contact with the heat sensitive substrate the heat sensitive substrate polyethyleneterphthalate (PET) was effectively demonstrated with the use of high intensity pulsed light, delivered by a commercial photonic sintering system. Thermally labile ester groups are positioned on the DTZ unit of the copolymer that can be eliminated thermally for enhanced photochemical stability and advantages in terms of processing (solubility/insolubility switching). The photonic sintering system was successfully implemented in a full roll-to-roll process on flexible PET substrates and large-area polymer solar cell modules were prepared by solution processing of five layers under ambient conditions using the photonic sintering system for thermocleaving of the active layer. The PET foil did not show any deformation after exposure to the high intensity light only leaving the insoluble thermocleaved active layer. The active layer remained planar after light exposure thereby allowing the coating of supplementary material on top.

Thermally reactive Thiazolo[5,4-d]thiazole based copolymers for high photochemical stability in polymer solar cells

New thermally reactive copolymers based on dithienylthiazolo[5,4-d]thiazole (DTZ) and silolodithiophene (SDT) have been synthesized and explored in bulk heterojunction solar cells as mixtures with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). In thin films the polymers had optical band gaps in the range of 1.64–1.80 eV. For solubility the polymers have incorporated alkyl groups on the SDT unit and thermally removable ester groups on the DTZ unit that can be eliminated around 200 °C for improved photochemical stability in thin films. The bulkiness of the alkyl chains on the SDT unit proved to be very significant in terms of photovoltaic performance of the polymer:PCBM solar cells. Polymers based on 4,4-dihexyl-4H-silolo[3,2-b:4,5-b′]dithiophene reached power conversion efficiencies (PCEs) up to 1.45% but changing the alkyl groups to more bulky ethylhexyl chains reduced the PCE to 1.17%. More noteworthy is that the photovoltaic performance improves for the polymers based on 4,4-dihexyl-4H-silolo[3,2-b:4,5-b′]dithiophene after the ester groups has been eliminated from the DTZ unit by a thermal treatment around 200 °C. To confirm that elimination of the solubilizing groups improve the long term durability of the materials the photochemical stability was estimated by a novel accelerated degradation method by which the photobleaching of the polymer was followed during degradation at 100 solar intensities. This clearly shows that the pristine polymer films are by far the most unstable under the given conditions emphasizing the unfavorable effect of solubilizing groups on the photochemical stability of conjugated polymers.

Photochemical stability and photovoltaic performance of low-band gap polymers based on dithiophene with different bridging atoms

New low-band gap polymers based on dithienylbenzothiadiazole (DBT) and dithiophene with different bridging atoms have been synthesized and explored in a comparative study on the photochemical stability and photovoltaic performance. Two differently modified DBT units were exploited, namely 5,6-bis(tetradecyloxy)-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DBT1) and 4,7-bis(4-dodecylthiophen-2-yl)benzo[c][1,2,5]thiadiazole (DBT2). In thin films the polymers had optical band gaps in the range of 1.51–1.70 eV where the DBT2 based polymers are red shifted 61–81 nm compared to the DBT1 based polymers indicating greater interchain packing when the side chains are situated on the thienyl groups compared to on the benzothiadiazole unit. The best photovoltaic devices based on blends of polymer and [6,6]-phenyl C61butyric acid methyl ester (PCBM) were prepared with polymers based on the DBT1 unit giving efficiencies up to 2.3%. The photochemical stability was measured by the amount of absorbed photons under 1 sun versus the ageing time for each polymer, which clearly shows that the two polymers containing a 4,4-bis(2-ethylhexyl)-4H-cyclopenta[1,2-b:5,4-b′]dithiophene (CPDT) unit are by far the most unstable. Substitution of the bridging carbon atom with silicon results in a significant stability improvement by a factor 5.

In-line, roll-to-roll morphology analysis of organic solar cell active layers

We present the first comparative in situ small and wide angle X-ray scattering study of two polymers that are relevant for organic photovoltaics, during coating on a flexible substrate. From the obtained measurements we identified several differences between the drying of the two polymers. The polymer optimized for roll-to-roll coating attained its final morphological packing nearly instantly after deposition, and had the shortest drying profile. We therefore conclude that fast-drying polymers which are influenced less by drying temperature or substrate inhomogeneities are better suited for roll-to-roll coating, and that fundamentally, the kinetics of drying dominate the process in the case of roll-to-roll slot-die coating.