| 1. |
- Abdi-Jalebi, Mojtaba, et al.
(författare)
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Dedoping of Lead Halide Perovskites Incorporating Monovalent Cations
- 2018
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 12:7, s. 7301-7311
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Tidskriftsartikel (refereegranskat)abstract
- We report significant improvements in the optoelectronic properties of lead halide perovskites with the addition of monovalent ions with ionic radii close to Pb2+. We investigate the chemical distribution and electronic structure of solution processed CH3NH3PbI3 perovskite structures containing Na+, Cu+, and Ag+, which are lower valence metal ions than Pb2+ but have similar ionic radii. Synchrotron X-ray diffraction reveals a pronounced shift in the main perovskite peaks for the monovalent cation-based films, suggesting incorporation of these cations into the perovskite lattice as well as a preferential crystal growth in Ag+ containing perovskite structures. Furthermore, the synchrotron X-ray photoelectron measurements show a significant change in the valence band position for Cu- and Ag-doped films, although the perovskite bandgap remains the same, indicating a shift in the Fermi level position toward the middle of the bandgap. Such a shift infers that incorporation of these monovalent cations dedope the n-type perovskite films when formed without added cations. This dedoping effect leads to cleaner bandgaps as reflected by the lower energetic disorder in the monovalent cation-doped perovskite thin films as compared to pristine films. We also find that in contrast to Ag+ and Cu+, Na+ locates mainly at the grain boundaries and surfaces. Our theoretical calculations confirm the observed shifts in X-ray diffraction peaks and Fermi level as well as absence of intrabandgap states upon energetically favorable doping of perovskite lattice by the monovalent cations. We also model a significant change in the local structure, chemical bonding of metal-halide, and the electronic structure in the doped perovskites. In summary, our work highlights the local chemistry and influence of monovalent cation dopants on crystallization and the electronic structure in the doped perovskite thin films.
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| 2. |
- Abdi-Jalebi, Mojtaba, et al.
(författare)
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Maximizing and stabilizing luminescence from halide perovskites with potassium passivation
- 2018
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Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 555, s. 497-501
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Tidskriftsartikel (refereegranskat)abstract
- Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability2 (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach the efficiency limits in tandem solar cells, coloured-light-emitting diodes and other optoelectronic applications.
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| 3. |
- Alarcon, Hugo, et al.
(författare)
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Modification of nanostructured TiO2 electrodes by electrochemical Al3+ insertion : Effects on dye-sensitized solar cell performance
- 2007
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 111:35, s. 13267-13274
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Tidskriftsartikel (refereegranskat)abstract
- Nanostructured TiO2 films were modified by insertion with aluminum ions using an electrochemical process. After heat treatment these films were found suitable as electrodes in dye-sensitized solar cells. By means of a catechol adsorption test, as well as photoelectron spectroscopy (PES), it was demonstrated that the density of Ti atoms at the metal oxide/electrolyte interface is reduced after Al modification. There is, however, not a complete coverage of aluminum oxide onto the TiO2, but the results rather suggest either the formation of a mixed Al-Ti oxide surface layer or formation of a partial aluminum oxide coating. No new phase could, however, be detected. In solar cells incorporating Al-modified TiO2 electrodes, both electron lifetimes and electron transport times were increased. At high concentrations of inserted aluminum ions, the quantum efficiency for electron injection was significantly decreased. Results are discussed at the hand of different models: A multiple trapping model, which can explain slower kinetics by the creation of additional traps during Al insertion, and a surface layer model, which can explain the reduced recombination rate, as well as the reduced injection efficiency, by the formation of a blocking layer.
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| 4. |
- Andaji-Garmaroudi, Z., et al.
(författare)
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Elucidating and Mitigating Degradation Processes in Perovskite Light-Emitting Diodes
- 2020
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Ingår i: Advanced Energy Materials. - : Wiley-VCH Verlag. - 1614-6832 .- 1614-6840. ; 10:48
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Tidskriftsartikel (refereegranskat)abstract
- Halide perovskites have attracted substantial interest for their potential as disruptive display and lighting technologies. However, perovskite light-emitting diodes (PeLEDs) are still hindered by poor operational stability. A fundamental understanding of the degradation processes is lacking but will be key to mitigating these pathways. Here, a combination of in operando and ex situ measurements to monitor the performance degradation of (Cs0.06FA0.79MA0.15)Pb(I0.85Br0.15)3 PeLEDs over time is used. Through device, nanoscale cross-sectional chemical mapping, and optical spectroscopy measurements, it is revealed that the degraded performance arises from an irreversible accumulation of bromide content at one interface, which leads to barriers to injection of charge carriers and thus increased nonradiative recombination. This ionic segregation is impeded by passivating the perovskite films with potassium halides, which immobilizes the excess halide species. The passivated PeLEDs show enhanced external quantum efficiency (EQE) from 0.5% to 4.5% and, importantly, show significantly enhanced stability, with minimal performance roll-off even at high current densities (>200 mA cm−2). The decay half-life for the devices under continuous operation at peak EQE increases from <1 to ≈15 h through passivation, and ≈200 h under pulsed operation. The results provide generalized insight into degradation pathways in PeLEDs and highlight routes to overcome these challenges.
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| 5. |
- Anselmo, Ana Sofia, 1980-
(författare)
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The morphology of polyfluorene : fullerene blend films for photovoltaic applications
- 2011
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Polymer photovoltaic systems whose photoactive layer is a blend of a semiconducting polymer with a fullerene derivative in a bulk heterojunction configuration are amongst the most successful organic photovoltaic devices nowadays. The three-dimensional organization in these layers (the morphology) plays a crucial role in the performance of the devices. Detailed characterization of this organization at the nanoscale would provide valuable information for improving future material and architectural design and for device optimization.In this thesis, the results of morphology studies of blends of several polyfluorene copolymers (APFOs) blended with a fullerene derivative are presented. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy was combined with dynamic Secondary Ion Mass Spectrometry (dSIMS) for surface and in-depth characterization of the blend films. NEXAFS was performed using two different electron detection methods, partial (PEY) and total (TEY) electron yield, which provide information from different depth regimes. Quantitative compositional information was obtained by fitting the spectra of the blend films with a linear combination of the spectra of films of the pure components. In blends of APFO3 with PCBM in two different blend ratios (1:1 and 1:4 of polymer:fullerene) NEXAFS data show the existence of compositional gradients in the vertical direction for both blend ratios, with clear polymer enrichment of the free surface. A series of APFOs with systematic changes in the side-chains was studied and it was shown that those small modifications can affect polymer:fullerene interaction and induce vertical phase separation. Polymer-enrichment of the free surface was clearly identified, in accordance with surface energy minimization mechanisms, and a compositional gradient was revealed already in the first few nanometers of the surface of the blend films. dSIMS showed that this vertical phase separation propagates throughout the film. It was possible to determine that as the polar character of the polymer increases, and thus the polymer:fullerene miscibility is improved, the tendency for vertical phase separation becomes stronger.
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| 6. |
- Avendano, Esteban, et al.
(författare)
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Coloration Mechanism in Proton-Intercalated Electrochromic Hydrated NiOy and Ni1-xVxOy Thin Films
- 2009
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 156:8, s. p132-p138
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Tidskriftsartikel (refereegranskat)abstract
- Electrochromic (EC) films of nickel oxide, with and without vanadium, were prepared by reactive dc magnetron sputtering. They were characterized by electrochemical and optical measurements and studied by X-ray photoelectron spectroscopy (PES) using synchrotron radiation. The films were analyzed under as-deposited conditions and after bleaching/coloration by insertion/extraction of protons from a basic solution and ensuing charge stabilization. Optical measurements were consistent with a coloration process due to charge-transfer transitions from Ni2+ to Ni3+ states. The PES measurements showed a higher concentration of Ni3+ in the colored films. Moreover, two peaks were present in the O 1s spectra of the bleached film and pointed to contributions of Ni(OH)(2) and NiO. The changes in the O 1s spectra upon coloration treatment indicate the presence of Ni2O3 in the colored film and necessitated an extension of the conventional model for the mechanism of EC coloration. The model involves not only proton extraction from nickel hydroxide to form nickel oxyhydroxide but also participation of NiO in the coloration process to form Ni2O3.
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| 7. |
- Bertrand, Philippe, et al.
(författare)
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Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES
- 2017
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Konferensbidrag (övrigt vetenskapligt/konstnärligt)abstract
- In this presentation, we will present a recent example on electrode/electrolyte interfaces of materials for energy storage devices using hard X-rays photoelectron spectroscopy (HAXPES). A nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). [1] While electrode/electrolyte study has been performed widely on Li-ion battery, not so much attention as been addressed to the Na-ion technology so far. We will focus in this presentation to NaxCo2/3Mn2/9Ni1/9O2, a novel intercalation material that could be be used as cathode in Na-ion batteries. [2] During a typical charge/discharge cycle (i.e. extraction/insertion of Na+ ions), the oxidation state of the various transition metals in the compound changes in a reversible way. A step by step analysis of the first electrochemical cycle was carried out by HAXPES providing unique information on the oxidation state of Ni, Co and Mn as well as a very interesting insight into the passivation layer present at the surface of the electrode, which results from the degradation of the electrolyte components upon reaction. This investigation shows the role of the SPI and the complexity of the redox reactions. [3] [1] B. Philippe, M. Hahlin, K. Edström, T. Gustafsson, H. Siegbahn, H. Rensmo, J. Electrochem. Soc, 2016, 163, A178-A191[2] S. Doubaji, M. Valvo, I. Saadoune, M. Dahbi, K.Edström, J. Power Sources, 2014, 266, 275-281[3] S. Doubaji, B. Philippe, I. Saadoune, M. Gorgoi, T. Gustafsson, A. Solhy, M. Valvo, H. Rensmo, K. Edström, ChemSusChem, 2016, 9, 97-108
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| 8. |
- Cappel, Ute B., et al.
(författare)
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Characterization of the Interface Properties and Processes in Solid State Dye-Sensitized Solar Cells Employing a Perylene Sensitizer
- 2011
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 115:10, s. 4345-4358
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Tidskriftsartikel (refereegranskat)abstract
- We recently reported on a perylene sensitizer, ID176, which performs much better in solid state dye-sensitized solar cells than in those using liquid electrolytes with iodide/tri-iodide as the redox couple (J. Phys. Chem. C2009, 113, 14595-14597). Here, we present a characterization of the sensitizer and of the TiO2/dye interface by UV-visible absorption and fluorescence spectroscopy, spectroelectrochemistry, photoelectron spectroscopy, electroabsorption spectroscopy, photoinduced absorption spectroscopy, and femtosecond transient absorption measurements. We report that the absorption spectrum of the sensitizer is red-shifted by addition of lithium ions to the surface due to a downward shift of the excited state level of the sensitizer, which is of the same order of magnitude as the downward shift of the titanium dioxide conduction band edge. Results from photoelectron spectroscopy and electrochemistry suggest that the excited state is largely located below the conduction band edge of TiO2 but that there are states in the band gap of TiO2 which might be available for photoinduced electron injection. The sensitizer was able to efficiently inject into TiO2, when a lithium salt was present on the surface, while injection was much less effective in the absence of lithium ions or in the presence of solvent. In the presence of the hole conductor 2,2-,7,7-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9-spirobifluorene (spiro-MeOTAD) and LiTFSI, charge separation was monitored by the emergence of a Stark shift of the dye in transient absorption spectra, and both injection and regeneration appear to be completed within 1 ps. Regeneration by spiro-MeOTAD is therefore several orders of magnitude faster than regeneration by iodide, and ID176 can even be photoreduced by spiro-MeOTAD.
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| 9. |
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| 10. |
- Cappel, Ute B., et al.
(författare)
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Electronic Structure Characterization of Cross-Linked Sulfur Polymers
- 2018
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Ingår i: ChemPhysChem. - : WILEY-V C H VERLAG GMBH. - 1439-4235 .- 1439-7641. ; 19:9, s. 1041-1047
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Tidskriftsartikel (refereegranskat)abstract
- Cross-linked polymers of elemental sulfur are of potential interest for electronic applications as they enable facile thin-film processing of an abundant and inexpensive starting material. Here, we characterize the electronic structure of a cross-linked sulfur/diisopropenyl benzene (DIB) polymer by a combination of soft and hard X-ray photoelectron spectroscopy (SOXPES and HAXPES). Two different approaches for enhancing the conductivity of the polymer are compared: the addition of selenium in the polymer synthesis and the addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) during film preparation. For the former, we observe the incorporation of Se into the polymer structure resulting in a changed valence-band structure. For the latter, a Fermi level shift in agreement with p-type doping of the polymer is observed and also the formation of a surface layer consisting mostly of TFSI anions.
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