| 1. |
- Jacobsson, T. Jesper, et al.
(author)
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A theoretical analysis of optical absorption limits and performance of tandem devices and series interconnected architectures for solar hydrogen production
- 2015
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In: Solar Energy Materials and Solar Cells. - : Elsevier BV. - 0927-0248 .- 1879-3398. ; 138, s. 86-95
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Journal article (peer-reviewed)abstract
- Photo-driven catalytic (PDC) water splitting, using either photoelectrochemical cells (PEC-cells), PV-electrolyzers, or some hybrid system in-between, has attracted a lot of attention. In single-cell device architectures for solar hydrogen production, based on single band gap photoabsorbers, there is a fundamental efficiency problem originating from the energy distribution of the solar spectrum and the thermodynamic and kinetic requirements for splitting water. The minimum band gap for a single-junction device in order to withhold unbiased overall water splitting is considered to be at least 2.0 eV. This is far from the 1.35 eV which is the optimal band gap of a semiconductor for maximum power conversion of light in the solar spectrum. This discrepancy has been termed as the solar spectrum mismatch problem (the SSM-problem). The standard solution to this problem is to construct tandem devices, whereas an alternative is to interconnect several one band gap cells in series, side by side. Both approaches enable the use of low energy photons in the solar spectrum while still providing a sufficiently high photopotential for driving the full reaction, without seriously compromising with the area efficiency. In this paper, the tandem and serial architectures for handling the SSM-problem are analyzed and compared. The analysis is focused towards differences in the limits of optical absorption, the optimal number of optical. absorbers, and their corresponding band gaps. Taking losses due to charge carrier separation and catalysis into account, the maximum STH-efficiency for a series interconnected solar splitting device was found to be 24.6%, compared to 32.0% for an optimum tandem device at 1 Sun (air mass 1.5, 1000 W m(-2)). This can be compared with the maximum efficiency of 18.0% for an ideal single band gap photoabsorber in single junction device. The analysis shows that the maximum STH efficiency limits for series interconnected architectures for unassisted solar water splitting are not particularly far behind the more commonly studied tandem devices. They could then be an interesting alternative given the simplicity and versatility of series interconnected device architectures. The analysis also compares how tandem devices and series interconnected devices can differ in terms of charge carrier separation, charge carrier transport, catalysis, overall efficiency, device architecture, and expected cost.
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| 2. |
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| 3. |
- Jacobsson, T. Jesper, et al.
(author)
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Determination of Thermal Expansion Coefficients and Locating the Temperature-Induced Phase Transition in Methylammonium Lead Perovskites Using X-ray Diffraction
- 2015
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In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 54:22, s. 10678-10685
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Journal article (peer-reviewed)abstract
- Lead halogen perovskites, and particularly methylammonium lead iodine, CH3NH3PbI3, have recently attracted considerable interest as alternative solar cell materials, and record solar cell efficiencies have now surpassed 20%. Concerns have, however, been raised about the thermal stability of methylammonium lead iodine, and a phase transformation from a tetragonal to a cubic phase has been reported at elevated temperature. Here, this phase transition has been investigated in detail using temperature-dependent X-ray diffraction measurements. The phase transformation is pinpointed to 54 degrees C, which is well within the normal operating range of a typical solar cell. The cell parameters were extracted as a function of the temperature, from which the thermal expansion coefficient was calculated. The latter was found to be rather high (alpha(v) = 1.57 X 10(-4) K-1) for both the tetragonal and cubic phases. This is 6 times higher than the thermal expansion coefficient for soda lime glass and CIGS and 11 times larger than that of CdTe. This could potentially be of importance for the mechanical stability of perovskite solar cells in the temperature cycling experienced under normal day night operation. The experimental knowledge of the thermal expansion coefficients and precise determination of the cell parameters can potentially also be valuable while conducting density functional theory simulations on these systems in order to deliver more accurate band structure calculations.
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| 4. |
- Jacobsson, T. Jesper, et al.
(author)
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Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells
- 2016
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In: Energy & Environmental Science. - : Royal Society of Chemistry (RSC). - 1754-5692 .- 1754-5706. ; 9:5, s. 1706-1724
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Journal article (peer-reviewed)abstract
- Lead halide perovskites have attracted considerable interest as photoabsorbers in PV-applications over the last few years. The most studied perovskite material achieving high photovoltaic performance has been methyl ammonium lead iodide, CH3NH3PbI3. Recently the highest solar cell efficiencies have, however, been achieved with mixed perovskites where iodide and methyl ammonium partially have been replaced by bromide and formamidinium. In this work, the mixed perovskites were explored in a systematic way by manufacturing devices where both iodide and methyl ammonium were gradually replaced by bromide and formamidinium. The absorption and the emission behavior as well as the crystallographic properties were explored for the perovskites in this compositional space. The band gaps as well as the crystallographic structures were extracted. Small changes in the composition of the perovskite were found to have a large impact on the properties of the materials and the device performance. In the investigated compositional space, cell efficiencies, for example, vary from a few percent up to 20.7%. From the perspective of applications, exchanging iodide with bromide is especially interesting as it allows tuning of the band gap from 1.5 to 2.3 eV. This is highly beneficial for tandem applications, and an empirical expression for the band gap as a function of composition was determined. Exchanging a small amount of iodide with bromide is found to be highly beneficial, whereas a larger amount of bromide in the perovskite was found to cause intense sub band gap photoemission with detrimental results for the device performance. This could be caused by the formation of a small amount of an iodide rich phase with a lower band gap, even though such a phase was not observed in diffraction experiments. This shows that stabilizing the mixed perovskites will be an important task in order to get the bromide rich perovskites, which has a higher band gap, to reach the same high performance obtained with the best compositions.
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| 5. |
- Jacobsson, T. Jesper, et al.
(author)
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Goldschmidt's Rules and Strontium Replacement in Lead Halogen Perovskite Solar Cells : Theory and Preliminary Experiments on CH3NH3SrI3
- 2015
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In: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 119:46, s. 25673-25683
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Journal article (peer-reviewed)abstract
- During the past few years, organic lead halogen perovskites have emerged as a class of highly promising solar cell materials, with certified solar cell efficiencies now surpassing 20%. Concerns have, however, been raised about the possible environmental and legalization problems associated with a new solar cell technology based on a water-soluble lead compound. Replacing lead in the perovskite structure: with a less toxic element, without degrading the favorable photo physical properties, would therefore be of interest. In this paper, the possibility of replacing lead with other metal ions is explored by following the replacement rules of Goldschmidt together with additional quantum mechanical considerations. This analysis provides a conceptual toolbox toward replacing lead, as well as additional insights into the photo physics of the metal halogen perovskites. This approach is exemplified by focusing on strontium in particular, which is nontoxic and relatively inexpensive. The ionic radius of Sr2+ and Pb2+ are almost identical, suggesting an exchange could be made without affecting the crystal structure. Couple cluster calculations on the metal ions and their halogen salts give the bonding patterns to be sufficiently similar and density functional theory (DFT) revealed the strontium perovskite, CH3NH3SrI3, to be a stable phase, despite the difference in electronegativity between lead and strontium. This is further supported by the existence of binary PM, and SrI2 compounds and the beneficial formation energy of the strontium perovskite. The electronic properties of both CH3NH3SrI3 and CH3NH3PbI3 were simulated and compared, revealing a higher degree of ionic interaction in the metal halogen bound in the strontium perovskite. This is a consequence of the lower electronegativity of strontium, which, together with the lack of d-orbitals in the Valence of Sr2+, results, in a higher band gap. The band gap for the strontium perovskite was estimated to 3.6 eV, which unfortunately is too high for an efficient photo absorber. Initial investigations on experimental synthesis of the strontium perovskite, using wet chemical methods, revealed it to be harder to produce than the lead perovskite This is explained as a:consequence of different bonding patterns in the metal iodine salts, which obstruct the methylammonium intercalation pathway utilized for forming the perovskite. Vapor phase methods are instead suggested as more promising synthesis routes.
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| 6. |
- Jacobsson, T. Jesper, et al.
(author)
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Room Temperature as a Goldilocks Environment for CH3NH3PbI3 Perovskite Solar Cells : The Importance of Temperature on Device Performance
- 2016
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In: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:21, s. 11382-11393
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Journal article (peer-reviewed)abstract
- Terrestrial applications of solar cells during day-night cycling as well as operation in winter and summer involve substantial temperature variations, which influence the photophysics as well as the charge separation and transport properties in the various materials employed in a device. In this study, the optical absorption of methylammonium lead iodide (MAPbI(3)) and the device performance of MAPbI(3) solar cells have been investigated in an extended temperature range between -190 and 80 degrees C. The optical properties were found to change by only a small amount in that temperature range. The device performance did, however, show more dramatic changes and decreased in a reversible manner for temperatures both higher and lower than room temperature. For temperatures up to 80 degrees C and down to -80 degrees C, the drop in performance was up to 25% compared to the room temperature value. Given thermal stability and reversible device performance, this is probably not a showstopper for terrestrial applications of perovskite solar cells but should be considered when evaluating the total energy yield under outdoor operations. At temperatures of 100 degrees C and below, which are relevant for outer atmosphere and space applications, the performance decreases rather dramatically and approaches zero at even lower temperature. Irreversible changes set in for temperatures above 50 degrees C. In addition, the hysteresis decreases at reduced temperatures. As the effects for the absorption properties are minor, the decrease in performance can be attributed to a temperature induced limitation in the transport and extraction of the photogenerated charge carriers which is seen as a strong increase of the series resistance at reduced temperature. The drop of the photovoltage for temperatures below -100 degrees C might be related to reduced charge carrier separation in the perovskite due to excitonic effects and a lower dielectric constant.
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| 7. |
- Jacobsson, T. Jesper, et al.
(author)
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Unreacted PbI2 as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells
- 2016
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In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 138:32, s. 10331-10343
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Journal article (peer-reviewed)abstract
- Lead halide perovskites have over the past few years attracted considerable interest as photo absorbers in PV applications with record efficiencies now reaching 22%. It has recently been found that not only the composition but also the precise stoichiometry is important for the device performance. Recent reports have, for example, demonstrated small amount of PbI2 in the perovskite films to be beneficial for the overall performance of both the standard perovskite, CH3NH3PbI3, as well as for the mixed perovskites (CH3NH3)(x)-(CH(NH2)(2))((1x))PbBryI(3y). In this work a broad range of characterization techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photo electron spectroscopy (PES), transient absorption spectroscopy (TAS), UVvis, electroluminescence (EL), photoluminescence (PL), and confocal PL mapping have been used to further understand the importance of remnant PbI2 in perovskite solar cells. Our best devices were over 18% efficient, and had in line with previous results a small amount of excess PbI2. For the PbI2-deficient samples, the photocurrent dropped, which could be attributed to accumulation of organic species at the grain boundaries, low charge carrier mobility, and decreased electron injection into the TiO2. The PbI2-deficient compositions did, however, also have advantages. The record V-oc was as high as 1.20 V and was found in PbI2-deficient samples. This was correlated with high crystal quality, longer charge carrier lifetimes, and high PL yields and was rationalized as a consequence of the dynamics of the perovskite formation. We further found the ion migration to be obstructed in the PbI2-deficient samples, which decreased the JV hysteresis and increased the photostability. PbI2-deficient synthesis conditions can thus be used to deposit perovskites with excellent crystal quality but with the downside of grain boundaries enriched in organic species, which act as a barrier toward current transport. Exploring ways to tune the synthesis conditions to give the high crystal quality obtained under PbI2-poor condition while maintaining the favorable grain boundary characteristics obtained under PbI2-rich conditions would thus be a strategy toward more efficiency devices.
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| 8. |
- Jogi, Indrek, et al.
(author)
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Phase Formation Behavior in Ultrathin Iron Oxide
- 2015
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In: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 31:45, s. 12372-12381
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Journal article (peer-reviewed)abstract
- Nanostructured iron oxides, and especially hematite, are interesting for a wide range of applications ranging from gas sensors to renewable solar hydrogen production. A promising method for deposition of low-dimensional films is atomic layer deposition (ALD). Although a potent technique, ALD of ultrathin films is critically sensitive to the substrate and temperature conditions where initial formation of islands and crystallites influences the properties of the films. In this work, deposition at the border of the ALD window forming a hybrid ALD/pulsed CVD (pCVD) deposition is utilized to obtain a deposition less sensitive to the substrate. A thorough analysis of iron oxide phases formation on two different substrates, Si(100) and SiO2, was performed. Films between 3 and SO rim were deposited and analyzed with diffraction techniques, high-resolution Raman spectroscopy, and optical spectroscopy. Below 10 nm nominal film thickness, island formation and phase dependent particle crystallization impose constraints for deposition of phase pure iron oxides on non-lattice-matching substrates. Films between 10 and 20 nm thickness on SiO2 could effectively be recrystallized into hematite whereas for the corresponding films on Si(100), no recrystallization occurred. For films thicker than 20 nm, phase pure hematite can be formed directly with ALD/pCVD with very low influence of the substrate on either Si or SiO2. For more lattice matched substrates such as SnO2:F, Raman spectroscopy indicated formation of the hematite phase already for films with 3 rim nominal thickness and clearly for 6 nm films. Analysis of the optical properties corroborated the analysis and showed a quantum confined blue-shift of the absorption edge for the thinnest films.
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| 9. |
- Otnes, Gaute, et al.
(author)
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Strategies to obtain pattern fidelity in nanowire growth from large-area surfaces patterned using nanoimprint lithography
- 2016
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In: Nano Research. - : Springer Science and Business Media LLC. - 1998-0124 .- 1998-0000. ; 9:10, s. 2852-2861
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Journal article (peer-reviewed)abstract
- Position controlled nanowire growth is important for nanowire-based optoelectronic components which rely on light emission or light absorption. For solar energy harvesting applications, dense arrays of nanowires are needed; however, a major obstacle to obtaining dense nanowire arrays is seed particle displacement and coalescing during the annealing stage prior to nanowire growth. Here, we explore three different strategies to improve pattern preservation of large-area catalyst particle arrays defined by nanoimprint lithography for nanowire growth. First, we see that heat treating the growth substrate prior to nanoimprint lithography improves pattern preservation. Second, we explore the possibility of improving pattern preservation by fixing the seed particles in place prior to annealing by modifying the growth procedure. And third, we show that a SiNx growth mask can fully prevent seed particle displacement. We show how these strategies allow us to greatly improve the pattern fidelity of grown InP nanowire arrays with dimensions suitable for solar cell applications, ultimately achieving 100% pattern preservation over the sampled area. The generic nature of these strategies is supported through the synthesis of GaAs and GaP nanowires. [Figure not available: see fulltext.]
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| 10. |
- Pazoki, Meysam, et al.
(author)
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Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites : Replacement of lead with alkaline-earth metals
- 2016
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In: PHYSICAL REVIEW B. - 2469-9950. ; 93:14
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Journal article (peer-reviewed)abstract
- Organic and inorganic lead halogen perovskites, and in particular, CH3NH3PbI3, have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, CH3NH3CaI3, CH3NH3SrI3, and CH3NH3BaI3, as well as the reference compound, CH3NH3PbI3, are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACaI(3), MASrI(3), and MABaI(3) were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, CH3NH3PbI3, where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large difference of the electron and hole effective masses make them good candidates for n-type selective layers in hot carrier injection solar cell devices together with some light absorber candidates. The fact that they have similar lattice constants as the lead perovskite and suitable positions of the valence band edges open up the possibility to use them also as thin epitaxial p-type hole selective contacts in combination with the lead halogen perovskite materials. This can lead to both charge selectivity as well as to superior crystal growth of lead perovskite with less contact stress, which is interesting for further investigations.
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| 11. |
- Pazoki, Meysam, et al.
(author)
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Photoinduced Stark Effects and Mechanism of Ion Displacement in Perovskite Solar Cell Materials
- 2017
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In: ACS Nano. - : AMER CHEMICAL SOC. - 1936-0851 .- 1936-086X. ; 11:3, s. 2823-2834
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Journal article (peer-reviewed)abstract
- Organometallic halide perovskites (OMHPs) have recently emerged as a promising class of materials in photovoltaic technology. Here, we present an in-depth investigation of the physics in these systems by measuring the photoinduced absorption (PIA) in OMHPs as a function of materials composition, excitation wavelength, and modulation frequency. We report a photoinduced Stark effect that depends on the excitation wavelength and on the dipole strength of the monovalent cations in the A position of the ABX(3) perovskite. The results presented are corroborated by density functional theory calculations and provide fundamental information about the photoinduced local electric field change under blue and red excitation as well as insights into the mechanism of light induced ion displacement in OMHPs. For optimized perovskite solar cell devices beyond 19% efficiency, we show that excess thermalization energy of blue photons plays a role in overcoming the activation energy for ion diffusion.
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| 12. |
- Pazoki, Meysam, et al.
(author)
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Photon Energy-Dependent Hysteresis Effects in Lead Halide Perovskite Materials
- 2017
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In: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 121:47, s. 26180-26187
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Journal article (peer-reviewed)abstract
- Lead halide perovskites have a range of spectacular properties and interesting phenomena and are a serious candidate for the next generation of photovoltaics with high efficiencies and low fabrication costs. An interesting phenomenon is the anomalous hysteresis often seen in current-voltage scans, which complicates accurate performance measurements but has also been explored to obtain a more comprehensive understanding of the device physics. Herein, we demonstrate a wavelength and illumination intensity dependency of the hysteresis in state-of-the-art perovskite solar cells with 18% power conversion efficiency (PCE), which gives new insights into ion migration. The perovskite devices show lower hysteresis under illumination with near band edge (red) wavelengths compared to more energetic (blue) excitation. This can be rationalized with thermalization-assisted ion movement or thermalization-assisted vacancy generation. These explanations are supported by the dependency of the photovoltage decay with illumination time and excitation wavelength, as well as by impedance spectroscopy. The suggested mechanism is that high-energy photons create hot charge carriers that either through thermalization can create additional vacancies or by release of more energetic phonons play a role in overcoming the activation energy for ion movement. The excitation wavelength dependency of the hysteresis presented here gives valuable insights into the photophysics of the lead halide perovskite solar cells.
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| 13. |
- Philippe, Bertrand, Dr. 1986-, et al.
(author)
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Valence Level Character in a Mixed Perovskite Material and Determination of the Valence Band Maximum from Photoelectron Spectroscopy : Variation with Photon Energy
- 2017
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In: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 121:48, s. 26655-26666
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Journal article (peer-reviewed)abstract
- A better understanding of the electronic structure of perovskite materials used in photovoltaic devices is essential for their development and optimization. In this investigation, synchrotron-based photoelectron spectroscopy (PES) was used to experimentally delineate the character and energy position of the valence band structures of a mixed perovskite. The valence band was measured using PES with photon energies ranging from ultraviolet photoelectron spectroscopy (21.2 eV) to hard X-rays (up to 4000 eV), and by taking the variation of the photoionization cross sections into account, we could experimentally determine the inorganic and organic contributions. The experiments were compared to theoretical calculations to further distinguish the role of the different anions in the electronic structure. This work also includes a thorough study of the valence band maximum and its position in relation to the Fermi level, which is crucial for the design and optimization of complete solar cells and their functional properties.
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| 14. |
- Svanström, Sebastian, et al.
(author)
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Effect of halide ratio and Cs+ addition on the photochemical stability of lead halide perovskites
- 2018
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In: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 6:44, s. 22134-22144
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Journal article (peer-reviewed)abstract
- Lead halide perovskite solar cells with multi-cation/mixed halide materials now give power conversion efficiencies of more than 20%. The stability of these mixed materials has been significantly improved through the addition of Cs+ compared to the original methylammonium lead iodide. However, it remains one of the most significant challenges for commercialisation. In this study, we use photoelectron spectroscopy (PES) in combination with visible laser illumination to study the photo-stability of perovskite films with different compositions. These include Br : I ratios of 50 : 50 and 17 : 83 and compositions with and without Cs+. For the samples without Cs and the 50 : 50 samples, we found that the surface was enriched in Br and depleted in I during illumination and that some of the perovskite decomposed into Pb-0, organic halide salts, and iodine. After illumination, both of these reactions were partially reversible. Furthermore, the surfaces of the films were enriched in organic halide salts indicating that the cations were not degraded into volatile products. With the addition of Cs+ to the samples, photo-induced changes were significantly suppressed for a 50 : 50 bromide to iodide ratio and completely suppressed for perovskites with a 17 : 83 ratio at light intensities exceeding 1 sun equivalent.
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| 15. |
- Wallentin, Jesper, et al.
(author)
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Bending and Twisting Lattice Tilt in Strained Core-Shell Nanowires Revealed by Nanofocused X-ray Diffraction
- 2017
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In: Nano Letters. - : American Chemical Society (ACS). - 1530-6984 .- 1530-6992. ; 17:7, s. 4143-4150
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Journal article (peer-reviewed)abstract
- We have investigated strained GaAs-GaInP core-shell nanowires using transmission electron microscopy and nanofocused scanning X-ray diffraction. Nominally identical growth conditions for each sample were achieved by using nanoimprint lithography to create wafer-scale arrays of Au seed particles. However, we observe large individual differences, with neighboring nanowires showing either straight, bent, or twisted morphology. Using scanning X-ray diffraction, we reconstructed and quantified the bending and twisting of the nanowires in three dimensions. In one nanowire, we find that the shell lattice is tilted with respect to the core lattice, with an angle that increases from 2° at the base to 5° at the top. Furthermore, the azimuthal orientation of the tilt changes by 30° along the nanowire axis. Our results demonstrate how strained core-shell nanowire growth can lead to a rich interplay of composition, lattice mismatch, bending and lattice tilt, with additional degrees of complexity compared with thin films.
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