Institut für Physik und Astronomie
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Mobilities and lifetimes of photogenerated charge carriers are core properties of photovoltaic materials and can both be characterized by contactless terahertz or microwave measurements. Here, the expertise from fifteen laboratories is combined to quantitatively model the current-voltage characteristics of a solar cell from such measurements. To this end, the impact of measurement conditions, alternate interpretations, and experimental inter-laboratory variations are discussed using a (Cs,FA,MA)Pb(I,Br)(3) halide perovskite thin-film as a case study. At 1 sun equivalent excitation, neither transport nor recombination is significantly affected by exciton formation or trapping. Terahertz, microwave, and photoluminescence transients for the neat material yield consistent effective lifetimes implying a resistance-free JV-curve with a potential power conversion efficiency of 24.6 %. For grainsizes above approximate to 20 nm, intra-grain charge transport is characterized by terahertz sum mobilities of approximate to 32 cm(2) V-1 s(-1). Drift-diffusion simulations indicate that these intra-grain mobilities can slightly reduce the fill factor of perovskite solar cells to 0.82, in accordance with the best-realized devices in the literature. Beyond perovskites, this work can guide a highly predictive characterization of any emerging semiconductor for photovoltaic or photoelectrochemical energy conversion. A best practice for the interpretation of terahertz and microwave measurements on photovoltaic materials is presented.
Perovskite semiconductors are an attractive option to overcome the limitations of established silicon based photovoltaic (PV) technologies due to their exceptional opto-electronic properties and their successful integration into multijunction cells. However, the performance of single- and multijunction cells is largely limited by significant nonradiative recombination at the perovskite/organic electron transport layer junctions. In this work, the cause of interfacial recombination at the perovskite/C-60 interface is revealed via a combination of photoluminescence, photoelectron spectroscopy, and first-principle numerical simulations. It is found that the most significant contribution to the total C-60-induced recombination loss occurs within the first monolayer of C-60, rather than in the bulk of C-60 or at the perovskite surface. The experiments show that the C-60 molecules act as deep trap states when in direct contact with the perovskite. It is further demonstrated that by reducing the surface coverage of C-60, the radiative efficiency of the bare perovskite layer can be retained. The findings of this work pave the way toward overcoming one of the most critical remaining performance losses in perovskite solar cells.
Inorganic perovskite solar cells show excellent thermal stability, but the reported power conversion efficiencies are still lower than for organic-inorganic perovskites. This is mainly caused by lower open-circuit voltages (V(OC)s). Herein, the reasons for the low V-OC in inorganic CsPbI2Br perovskite solar cells are investigated. Intensity-dependent photoluminescence measurements for different layer stacks reveal that n-i-p and p-i-n CsPbI2Br solar cells exhibit a strong mismatch between quasi-Fermi level splitting (QFLS) and V-OC. Specifically, the CsPbI2Br p-i-n perovskite solar cell has a QFLS-e center dot V-OC mismatch of 179 meV, compared with 11 meV for a reference cell with an organic-inorganic perovskite of similar bandgap. On the other hand, this study shows that the CsPbI2Br films with a bandgap of 1.9 eV have a very low defect density, resulting in an efficiency potential of 20.3% with a MeO-2PACz hole-transporting layer and 20.8% on compact TiO2. Using ultraviolet photoelectron spectroscopy measurements, energy level misalignment is identified as a possible reason for the QFLS-e center dot V-OC mismatch and strategies for overcoming this V-OC limitation are discussed. This work highlights the need to control the interfacial energetics in inorganic perovskite solar cells, but also gives promise for high efficiencies once this issue is resolved.
Engineering the interface between the perovskite absorber and the charge-transporting layers has become an important method for improving the charge extraction and open-circuit voltage (V-OC) of hybrid perovskite solar cells. Conjugated polymers are particularly suited to form the hole-transporting layer, but their hydrophobicity renders it difficult to solution-process the perovskite absorber on top. Herein, oxygen plasma treatment is introduced as a simple means to change the surface energy and work function of hydrophobic polymer interlayers for use as p-contacts in perovskite solar cells. We find that upon oxygen plasma treatment, the hydrophobic surfaces of different prototypical p-type polymers became sufficiently hydrophilic to enable subsequent perovskite junction processing. In addition, the oxygen plasma treatment also increased the ionization potential of the polymer such that it became closer to the valance band energy of the perovskite. It was also found that the oxygen plasma treatment could increase the electrical conductivity of the p-type polymers, facilitating more efficient charge extraction. On the basis of this concept, inverted MAPbI(3) perovskite devices with different oxygen plasma-treated polymers such as P3HT, P3OT, polyTPD, or PTAA were fabricated with power conversion efficiencies of up to 19%.
In the last decade the photovoltaic research has been preponderantly overturned by the arrival of metal halide perovskites. The introduction of this class of materials in the academic research for renewable energy literally shifted the focus of a large number of research groups and institutions. The attractiveness of halide perovskites lays particularly on their skyrocketing efficiencies and relatively simple and cheap fabrication methods. Specifically, the latter allowed for a quick development of this research in many universities and institutes around the world at the same time. The outcome has been a fast and beneficial increase in knowledge with a consequent terrific improvement of this new technology. On the other side, the enormous amount of research promoted an immense outgrowth of scientific literature, perpetually published. Halide perovskite solar cells are now effectively competing with other established photovoltaic technologies in terms of power conversion efficiencies and production costs. Despite the tremendous improvement, a thorough understanding of the energy losses in these systems is of imperative importance to unlock the full thermodynamic potential of this material. This thesis focuses on the understanding of the non-radiative recombination processes in the neat perovskite and in complete devices. Specifically, photoluminescence quantum yield (PLQY) measurements were applied to multilayer stacks and cells under different illumination conditions to accurately determine the quasi-Fermi levels splitting (QFLS) in the absorber, and compare it with the external open-circuit voltage of the device (V_OC). Combined with drift-diffusion simulations, this approach allowed us to pinpoint the sites of predominant recombination, but also to investigate the dynamics of the underlying processes. As such, the internal and external ideality factors, associated to the QFLS and V_OC respectively, are studied with the aim of understanding the type of recombination processes taking place in the multilayered architecture of the device. Our findings highlight the failure of the equality between QFLS and V_OC in the case of strong interface recombination, as well as the detrimental effect of all commonly used transport layers in terms of V_OC losses. In these regards, we show how, in most perovskite solar cells, different recombination processes can affect the internal QFLS and the external V_OC and that interface recombination dictates the V_OC losses. This line of arguments allowed to rationalize that, in our devices, the external ideality factor is completely dominated by interface recombination, and that this process can alone be responsible for values of the ideality factor between 1 and 2, typically observed in perovskite solar cells. Importantly, our studies demonstrated how strong interface recombination can lower the ideality factor towards values of 1, often misinterpreted as pure radiative second order recombination. As such, a comprehensive understanding of the recombination loss mechanisms currently limiting the device performance was achieved. In order to reach the full thermodynamic potential of the perovskite absorber, the interfaces of both the electron and hole transport layers (ETL/HTL) must be properly addressed and improved. From here, the second part of the research work is devoted on reducing the interfacial non-radiative energy losses by optimizing the structure and energetics of the relevant interface in our solar cell devices, with the aim of bringing their quasi-Fermi level splitting closer to its radiative limit. As such, the interfaces have been carefully addressed and optimized with different methodologies. First, a small amount of Sr is added into the perovskite precursor solution with the effect of effectively reducing surface and interface recombination. In this case, devices with V_OC up to 1.23 V were achieved and the energy losses were minimized to as low as 100 meV from the radiative limit of the material. Through a combination of different methods, we showed that these improvements are related to a strong n-type surface doping, which repels the holes in the perovskite from the surface and the interface with the ETL. Second, a more general device improvement was achieved by depositing a defect-passivating poly(ionic-liquid) layer on top of the perovskite absorber. The resulting devices featured a concomitant improvement of the V_OC and fill factor, up to 1.17 V and 83% respectively, reaching efficiency as high as 21.4%. Moreover, the protecting polymer layer helped to enhance the stability of the devices under prolonged maximum power point tracking measurements. Lastly, PLQY measurements are used to investigate the recombination mechanisms in halide-segregated large bandgap perovskite materials. Here, our findings showed how few iodide-rich low-energy domains act as highly efficient radiative recombination centers, capable of generating PLQY values up to 25%. Coupling these results with a detailed microscopic cathodoluminescence analysis and absorption profiles allowed to demonstrate how the emission from these low energy domains is due to the trapping of the carriers photogenerated in the Br-rich high-energy domains. Thereby, the strong implications of this phenomenon are discussed in relation to the failure of the optical reciprocity between absorption and emission and on the consequent applicability of the Shockley-Queisser theory for studying the energy losses such systems. In conclusion, the identification and quantification of the non-radiative QFLS and V_OC losses provided a base knowledge of the fundamental limitation of perovskite solar cells and served as guidance for future optimization and development of this technology. Furthermore, by providing practical examples of solar cell improvements, we corroborated the correctness of our fundamental understanding and proposed new methodologies to be further explored by new generations of scientists.
A fundamental understanding of the relationship between the bulk morphology and device performance is required for the further development of bulk heterojunction organic solar cells. Here, non-optimized (chloroform cast) and nearly optimized (solvent-annealed o-dichlorobenzene cast) P3HT:PCBM blend films treated over a range of annealing temperatures are studied via optical and photovoltaic device measurements. Parameters related to the P3HT aggregate morphology in the blend are obtained through a recently established analytical model developed by F. C. Spano for the absorption of weakly interacting H-aggregates. Thermally induced changes are related to the glass transition range of the blend. In the chloroform prepared devices, the improvement in device efficiency upon annealing within the glass transition range can be attributed to the growth of P3HT aggregates, an overall increase in the percentage of chain crystallinity, and a concurrent increase in the hole mobilities. Films treated above the glass transition range show an increase in efficiency and fill factor not only associated with the change in chain crystallinity, but also with a decrease in the energetic disorder. On the other hand, the properties of the P3HT phase in the solvent-annealed o-dichlorobenzene cast blends are almost indistinguishable from those of the corresponding pristine P3HT layer and are only weakly affected by thermal annealing. Apparently, slow drying of the blend allows the P3HT chains to crystallize into large domains with low degrees of intra- and interchain disorder. This morphology appears to be most favorable for the efficient generation and extraction of charges.
Charge transport and nongeminate recombination are investigated in two solution-processed small molecule bulk heterojunction solar cells consisting of diketopyrrolopyrrole (DPP)-based donor molecules, mono-DPP and bis-DPP, blended with [6,6]-phenyl-C71-butyric acid methyl ester (PCBM). While the bis-DPP system exhibits a high fill factor (62%) the mono-DPP system suffers from pronounced voltage dependent losses, which limit both the fill factor (46%) and short circuit current. A method to determine the average charge carrier density, recombination current, and effective carrier lifetime in operating solar cells as a function of applied bias is demonstrated. These results and light intensity measurements of the current-voltage characteristics indicate that the mono-DPP system is severely limited by nongeminate recombination losses. Further analysis reveals that the most significant factor leading to the difference in fill factor is the comparatively poor hole transport properties in the mono-DPP system (2 x 10(-5) cm(2) V-1 s(-1) versus 34 x 10(-5) cm(2) V-1 s(-1)). These results suggest that future design of donor molecules for organic photovoltaics should aim to increase charge carrier mobility thereby enabling faster sweep out of charge carriers before they are lost to nongeminate recombination.
Organische Halbleiter besitzen neue, bemerkenswerte Materialeigenschaften, die sie für die grundlegende Forschung wie auch aktuelle technologische Entwicklung (bsw. org. Leuchtdioden, org. Solarzellen) interessant werden lassen. Aufgrund der starken konformative Freiheit der konjugierten Polymerketten führt die Vielzahl der möglichen Anordnungen und die schwache intermolekulare Wechselwirkung für gewöhnlich zu geringer struktureller Ordnung im Festkörper. Die Morphologie hat gleichzeitig direkten Einfluss auf die elektronische Struktur der organischen Halbleiter, welches sich meistens in einer deutlichen Reduktion der Ladungsträgerbeweglichkeit gegenüber den anorganischen Verwandten zeigt. So stellt die Beweglichkeit der Ladungen im Halbleiter einen der limitierenden Faktoren für die Leistungsfähigkeit bzw. den Wirkungsgrad von funktionellen organischen Bauteilen dar. Im Jahr 2009 wurde ein neues auf Naphthalindiimid und Bithiophen basierendes Dornor/Akzeptor Copolymer vorgestellt [P(NDI2OD‑T2)], welches sich durch seine außergewöhnlich hohe Ladungsträgermobilität auszeichnet. In dieser Arbeit wird die Ladungsträgermobilität in P(NDI2OD‑T2) bestimmt, und der Transport durch eine geringe energetischer Unordnung charakterisiert. Obwohl dieses Material zunächst als amorph beschrieben wurde zeigt eine detaillierte Analyse der optischen Eigenschaften von P(NDI2OD‑T2), dass bereits in Lösung geordnete Vorstufen supramolekularer Strukturen (Aggregate) existieren. Quantenchemische Berechnungen belegen die beobachteten spektralen Änderungen. Mithilfe der NMR-Spektroskopie kann die Bildung der Aggregate unabhängig von optischer Spektroskopie bestätigt werden. Die Analytische Ultrazentrifugation an P(NDI2OD‑T2) Lösungen legt nahe, dass sich die Aggregation innerhalb der einzelnen Ketten unter Reduktion des hydrodynamischen Radius vollzieht. Die Ausbildung supramolekularen Strukturen nimmt auch eine signifikante Rolle bei der Filmbildung ein und verhindert gleichzeitig die Herstellung amorpher P(NDI2OD‑T2) Filme. Durch chemische Modifikation der P(NDI2OD‑T2)-Kette und verschiedener Prozessierungs-Methoden wurde eine Änderung des Kristallinitätsgrades und gleichzeitig der Orientierung der kristallinen Domänen erreicht und mittels Röntgenbeugung quantifiziert. In hochauflösenden Elektronenmikroskopie-Messungen werden die Netzebenen und deren Einbettung in die semikristallinen Strukturen direkt abgebildet. Aus der Kombination der verschiedenen Methoden erschließt sich ein Gesamtbild der Nah- und Fernordnung in P(NDI2OD‑T2). Über die Messung der Elektronenmobilität dieser Schichten wird die Anisotropie des Ladungstransports in den kristallographischen Raumrichtungen von P(NDI2OD‑T2) charakterisiert und die Bedeutung der intramolekularen Wechselwirkung für effizienten Ladungstransport herausgearbeitet. Gleichzeitig wird deutlich, wie die Verwendung von größeren und planaren funktionellen Gruppen zu höheren Ladungsträgermobilitäten führt, welche im Vergleich zu klassischen semikristallinen Polymeren weniger sensitiv auf die strukturelle Unordnung im Film sind.