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The development of p–n tandem dye-sensitized solar cells (t-DSCs) offers the potential for substantial open-circuit voltages, holding great promise for a wide range of applications, particularly in the fields of photovoltaics and photoelectrochemical devices. Most reported t-DSCs are liquid-based, and suffer from unsatisfactory stability due to the leakage of liquid electrolytes and photovoltage that is limited to the energy difference of the two utilized semiconductors. In this study, we present the first realization of a solid-state p–n tandem dye-sensitized solar cell that incorporates both p-type and n-type solid-state dye-sensitized solar cells (ssDSCs) by using a transparent indium-doped tin oxide (ITO) back contact for both sides. Notably, this tandem system shows a remarkable open-circuit voltage of 1.4 V, surpassing the constraints of its liquid-based counterparts. Although the performance variations between p-ssDSCs and n-ssDSCs hint at challenges related to charge recombination and the efficiency of p-ssDSCs, this study underscores the significant potential inherent in solid-state tandem configurations.

Symmetry-breaking charge separation in molecular materials has attracted increasing attention for optoelectronics based on single-material active layers. To this end, Fe(III) complexes with particularly electron-donating N-heterocyclic carbene ligands offer interesting properties with a (LMCT)-L-2 excited state capable of oxidizing or reducing the complex in its ground state. In this Communication, we show that the corresponding symmetry-breaking charge separation occurs in amorphous films of pristine [Fe(III)L-2]PF6 (L = [phenyl(tris(3-methylimidazol-2-ylidene))borate](-)). Excitation of the solid material with visible light leads to ultrafast electron transfer quenching of the (LMCT)-L-2 excited state, generating Fe(II) and Fe(IV) products with high efficiency. Sub-picosecond charge separation followed by recombination in about 1 ns could be monitored by transient absorption spectroscopy. Photoconductivity measurements of films deposited on microelectrode arrays demonstrated that photogenerated charge carriers can be collected at external contacts.

Mixed tin/lead (Sn/Pb) perovskites have the potential to achieve higher performances in single junction solar cells compared to Pb-based compounds. The best Sn/Pb based devices are fabricated in a p-i-n structure, and PEDOT:PSS is frequently utilized as the hole transport layer, even if there are many doubts on a possible detrimental role of this conductive polymer. Here, we propose the use of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) and [2-(3, 6-dibromo-9H-carbazol-9-yl) ethyl] phosphonic acid (Br-2PACz) as substitutes for PEDOT:PSS. By using Cs(0.25)FA(0.75)Sn(0.5)Pb(0.5)I(3) as the active layer, we obtained record efficiencies as high as 19.51% on Br-2PACz, while 18.44% and 16.33% efficiencies were obtained using 2PACz and PEDOT:PSS, respectively. In addition, the implemented monolayers enhance both the shelf lifetime of the device as well as the operational stability. Finally, the Br-2PACz-based devices maintained 80% of their initial efficiency under continuous illumination for 230 h, and after being stored in a N-2 atmosphere for 4224 h (176 days).

Lead-free double perovskites, A(2)M(+)M(' 3+)X(6), are considered as promising alternatives to lead-halide perovskites, in optoelectronics applications. Although iodide (I) and bromide (Br) mixing is a versatile tool for bandgap tuning in lead perovskites, similar mixed I/Br double perovskite films have not been reported in double perovskites, which may be due to the large activation energy for ion migration. In this work, mixed Br/I double perovskites were realized utilizing an anion exchange method starting from Cs2AgBiBr6 solid thin-films with large grain-size. The optical and structural properties were studied experimentally and theoretically. Importantly, the halide exchange mechanism was investigated. Hydroiodic acid was the key factor to facilitate the halide exchange reaction, through a dissolution-recrystallization process. In addition, the common organic iodide salts could successfully perform halide-exchange while retaining high mixed-halide phase stability and strong light absorption capability.

In this work, four-terminal (4T) tandem solar cells were fabricated by using a methylammonium lead iodide (MAPbI3) perovskite solar cell (PSC) as the front-cell and a lead sulfide (PbS) colloidal quantum dot solar cell (CQDSC) as the back-cell. Different modifications of the tandem interlayer, at the interface between the sub-cells, were tested in order to improve the infrared transparency of the perovskite sub-cell and consequently increase the utilization of infrared (IR) light by the tandem system. This included the incorporation of a semi-transparent thin gold electrode (Au) on the MAPbI3 solar cell, followed by adding a molybdenum(VI) oxide (MoO3) layer or a surlyn layer. These interlayer modifications resulted in an increase of the IR transmittance to the back cell and improved the optical stability, compared to that in the reference devices. This investigation shows the importance of the interlayer, connecting the PSC with a strong absorption in the visible region and the CQDSC with a strong infrared absorption to obtain efficient next-generation tandem photovoltaics (PVs).

In this work, high-performance four-terminal solution-processed tandem solar cells were fabricated by using dye-sensitized solar cells (DSSCs) as top-cells and lead sulfide (PbS) colloidal quantum dot solar cells (CQDSCs) as bottom-cells. For dye-sensitized top-cells, three different dye combinations were used while the titanium dioxide (TiO2) scattering layer was removed to maximize the transmission. For the PbS bottom-cells, quantum dots with different sizes were compared. Over 12% power conversion efficiency has been achieved by using the XL dye mixture and 890 nm PbS QDs, which shows a significant efficiency enhancement when compared to single DSSC or CQDSC subcells.

Silver bismuth iodide (Ag-Bi-I) light absorbers are interesting candidates as lead-free and low-toxic metal-halide materials for solar cell applications. In this work, the partial exchange of bismuth, Bi, with antimony, Sb, is investigated in samples prepared from a solution targeting stoichiometry AgBi2I7. Samples with a gradually increased exchange of Bi by Sb are prepared and light absorption measurements show that the absorption edge is gradually blue-shifted with increasing the amount of Sb. This trend in the shift in combination with the X-ray diffraction and X-ray photoelectron spectroscopy measurements, suggest that new materials with a mixture of Sb and Bi are formed. The density functional theory based electronic structure calculations reproduce the trend observed in the experiments when including spin-orbit coupling, which indicates the importance of relativistic effects in these materials. X-ray photoelectron spectroscopy is used to characterize the materials, and confirms the exchange of Bi to Sb in the samples. When Sb is included in the material, the grain size changes between 50 and 200 nm and the solar cell performance also changes. An optimal power conversion efficiency with excellent reproducibility and stability is obtained for a solar cell with the ratio of Sb/Bi equal to 3.

Scalable methods for deposition of lead halide perovskite thin films are required to enable commercialization of the highly promising perovskite photovoltaics. Here, we have developed a slot-die coating process under ambient conditions for methylammonium lead iodide (MAPbI(3)) perovskite on heated substrates (about 90 degrees C on the substrate surface). Dense, highly crystalline perovskite films with large grains (100-200 mu m) were obtained by careful adjustment of the deposition parameters, using solutions that are similar but more dilute than those used in typical spin-coating procedures. Without any further after treatments, such as antisolvent treatment or vapor annealing, we achieved power conversion efficiencies up of 14.5% for devices with the following structure: conducting tin oxide glass (FTO)/TiO2/MAPbI(3)/spiro-MeOTAD/Au. The performance was limited by the significant roughness of the deposited films, resulting from the hot-casting method, and the relatively high deposition temperature, which led to a defect-rich surface due to loss of MAI.

Bismuth halide perovskites have recently been considered a potential alternative to lead halide analogues due to their low toxicity and high stability. However, the layered flake structure and wide band gap limit their applications in perovskite solar cells (PSCs). We herein show that large-grained all-inorganic bismuth-based perovskites with a narrow band gap can be obtained from a Lewis acid-base adduct reaction under ambient conditions. Thiourea (CH4N2S) is utilized as a Lewis base to interact with BiI3, confirmed with infrared (IR) spectra. The strong coordination between thiourea and the Bi3+ center could slow down the perovskite crystallization and promote the preferred orientation of the perovskite crystals with a hexagonal phase. The morphology of the perovskite films varies dramatically with an increase of molar ratio of BiI3 and thiourea in the precursor. The perovskites derived from a BiI3/thiourea ratio of 1:2 display extrathick grains, higher surface coverage, extended light absorption, higher crystallinity, and similar air stability compared to the pristine sample. The power conversion efficiency (PCE) of the thiourea-induced bismuth perovskite solar cells is significantly enhanced due to the higher surface coverage and the broader absorption of the perovskite film.

Interface modification in perovskite solar cells is a key factor for achieving high power conversion efficiency by suppressing electron-hole recombination and accelerating charge carrier extraction. Here, we use a series of phenyl ammonium derivatives, phenyl ammonium iodide (PAI), benzyl ammonium iodide (BAI), and phenyl ethyl ammonium iodide (PEAI), to modify the interface between methylammonium lead triiodide (MAPbI3) perovskite and Spiro-OMeTAD as a hole transport layer in solar cell devices. The structural and optical properties of the perovskite films are studied and the results reveal the formation of two-dimensional perovskite interfacial layers on the surface of the MAPbI3 film modified with PEAI and BAI whereas the MAPbI3 layer modified with PAI gives an interface layer with slightly different properties compared to the two-dimensional perovskite. Impedance spectroscopy shows that the charge transport resistance of the interface engineered solar cells decreases when compared to pristine MAPbI3. In addition, slower open-circuit voltage decay and longer carrier lifetime are also observed for the modified cells which in total lead to the improvement of the photovoltaic performance. The investigation therefore gives insight in the effect of interface modifications, and especially how different sizes of the molecular interface modifier results in different interface formation and characteristics.

Recent progress in colloidal quantum dot (CQD)-based solar cells indicates that low-toxicity materials such as AgBiS2 nanocrystals (NCs) show potential in replacing toxic PbS and CdS CQDs in solar cell applications. In this study, an investigation on the importance of the composition and sensitivity toward synthesis conditions was performed by adjusting concentrations and ratios of Ag and Bi precursors-first, by varying the ratio of Ag toward Bi precursors and, second, by varying the concentration of Ag with a constant ratio toward Bi precursors in the solution. Furthermore, elemental XPS studies and TEM imaging together with solar cell analysis indicated a strong correlation between the concentration of Ag precursor and the NC properties and, moreover, the solar cell properties based on these NCs. In short, a large amount of Ag precursor resulted in smaller Ag-rich NCs, which resulted in solar cells with high photovoltage but low photocurrent density, while a lower amount of Ag precursor resulted in larger NCs and solar cells with a lower photovoltage. The Ag:Bi:S ratio of 0.72:0.9:1 resulted in almost stoichiometric NCs but with a slight excess of Ag, which in turn resulted in solar cells with the highest performance. This work therefore gives insight into how the elemental composition and size of the NCs can be tuned by the precursor ratios and how this, in turn, affects the performance of the solar cell devices.

In this work, silver-bismuth-halide thin films, exhibiting low toxicity and good stability, were explored systemically by gradually substituting iodide, I, with bromide, Br, in the AgBi2I7 system. It was found that the optical bandgap can be tuned by varying the I/Br ratio. Moreover, the film quality was improved when introducing a small amount of Br. The solar cell was demonstrated to be more stable at ambient conditions and most efficient when incorporating 10% Br, as a result of decreased recombination originating from the increased grain size. Thus, replacing a small amount of I with Br was beneficial for photovoltaic performance.

Fe-air or Ni-Fe cells can offer low-cost and large-scale sustainable energy storage. At present, they are limited by low coulombic efficiency, low active material use, and poor rate capability. To overcome these challenges, two types of nanostructured doped iron materials were investigated: (1) copper and tin doped iron (CuSn); and (2) tin doped iron (Sn). Single-wall carbon nanotube (SWCNT) was added to the electrode and LiOH to the electrolyte. In the 2 wt. % Cu + 2 wt. % Sn sample, the addition of SWCNT increased the discharge capacity from 430 to 475 mAh g-1, and charge efficiency increased from 83% to 93.5%. With the addition of both SWCNT and LiOH, the charge efficiency and discharge capacity improved to 91% and 603 mAh g-1, respectively. Meanwhile, the 4 wt. % Sn substituted sample performance is not on par with the 2 wt. % Cu + 2 wt. % Sn sample. The dopant elements (Cu and Sn) and additives (SWCNT and LiOH) have a major impact on the electrode performance. To understand the relation between hydrogen evolution and charge current density, we have used in operando charging measurements combined with mass spectrometry to quantify the evolved hydrogen. The electrodes that were subjected to prolonged overcharge upon hydrogen evolution failed rapidly. This insight could help in the development of better charging schemes for the iron electrodes.

Metal halide compounds with photovoltaic properties prepared from solution have received increased attention for utilization in solar cells. In this work, low-toxicity cesium bismuth iodides are synthesized from solution, and their photovoltaic and, optical properties as well as electronic and crystal structures are investigated. The X-ray diffraction patterns reveal that a CsI/BiI3 precursor ratio of 1.5:1 can convert pure rhombohedral BiI3 to pure hexagonal Cs3Bi2I9, but any ratio intermediate of this stoichiometry and pure BiI3 yields a mixture containing the two crystalline phases Cs3Bi2I9 and BiI3, with their relative fraction depending on the CsI/BiI3 ratio. Solar cells from the series of compounds are characterized, showing the highest efficiency for the compounds with a mixture of the two structures. The energies of the valence band edge were estimated using hard and soft X-ray photoelectron spectroscopy for more bulk and surface electronic properties, respectively. On the basis of these measurements, together with UV-vis-near-IR spectrophotometry, measuring the band gap, and Kelvin probe measurements for estimating the work function, an approximate energy diagram has been compiled clarifying the relationship between the positions of the valence and conduction band edges and the Fermi level.

This article reports the two-step synthesis of NiFeOx nanomaterials and their characterization and bifunctional electrocatalytic activity measurements in alkaline electrolyte for metal-air batteries. The samples were mostly in layered double hydroxide at the initial temperature, but upon heat treatment, they were converted to NiFe2O4 phases. The electrochemical behaviour of the different samples was studied by linear sweep voltammetry and cyclic voltammetry on the glassy carbon electrode. The OER catalyst activity was observed for low mass loadings (0.125 mg cm(-2)), whereas high catalyst loading exhibited the best performance on the ORR side. The sample heat-treated at 250 degrees C delivered the highest bi-functional oxygen evolution and reduction reaction activity (OER/ORR) thanks to its thin-holey nanosheet-like structure with higher nickel oxidation state at 250 degrees C. This work further helps to develop low-cost electrocatalyst development for metal-air batteries.

Solution-processed colloidal quantum dot (CQD) solar cells harvesting the infrared part of the solar spectrum are especially interesting for future use in semitransparent windows or multilayer solar cells. To improve the device power conversion efficiency (PCE) and stability of the solar cells, surface passivation of the quantum dots is vital in the research of CQD solar cells. Herein, inorganic CsPbI3 perovskite (CsPbI3-P) coating on PbS CQDs with a low-temperature, solution-processed approach is reported. The PbS CQD solar cell with CsPbI3-P coating gives a high PCE of 10.5% and exhibits remarkable stability both under long-term constant illumination and storage under ambient conditions. Detailed characterization and analysis reveal improved passivation of the PbS CQDs with the CsPbI3-P coating, and the results suggest that the lattice coherence between CsPbI3-P and PbS results in epitaxial induced growth of the CsPbI3-P coating. The improved passivation significantly diminishes the sub-bandgap trap-state assisted recombination, leading to improved charge collection and therefore higher photovoltaic performance. This work therefore provides important insight to improve the CQD passivation by coating with an inorganic perovskite ligand for photovoltaics or other optoelectronic applications.

In this study, a core-shell NiO-dye-TiO2 mesoporous film was fabricated for the first time, utilizing atomic layer deposition technique and a newly designed triphenylamine dye. The structure of the film was confirmed by SEM, TEM, and EDX. Excitation of the dye led to efficient and fast charge separation, by hole injection into NiO, followed by an unprecedentedly fast dye regeneration (t1/2 [less-than-or-equal] 500 fs) by electron transfer to TiO2. The resulting charge separated state showed a pronounced transient absorption spectrum caused by the Stark effect, and no significant decay was found within 1.9 ns. This indicates that charge recombination between NiO and TiO2 is much slower than that between the NiO and the reduced dye in the absence of the TiO2 layer (t1/2 [approximate] 100 ps)., Correction in: PHYSICAL CHEMISTRY CHEMICAL PHYSICS, Volume: 20, Issue: 46, Pages: 29566-29566, DOI: 10.1039/c8cp91912g

Isopropanol solution based methylammonium lead triiodide (MAPbI3) is studied during the crystallization process. The crystal growth starts in an unstable suspension far from equilibrium by forming different dendritic patterns and terminates with aggregation of stable cubic crystalline grains into fractal clusters. Using transmission electron microscopy (TEM), the time evolution of a newly mixed suspension was studied over a period of two weeks at room temperature and a sequence of the morphological changes was observed. The crystallization process started with single dendritic growth exhibiting branches at 90 degrees angles to one another. After 4 hours, a multi-dendritic growth pattern and a transformation into small crystalline quantum dots were observed. After a week, clusters of crystal grains were formed into a fractal pattern and these patterns appear to be stable also during the second week. Electron and x-ray diffraction revealed the crystallinity of the quantum dots and the clusters of micrometer-sized crystals. Scanning transmission electron microscope (STEM) together with energy dispersive X-ray spectroscopy (EDS) showed that newly formed large grains, from a one hour old solution, displayed a core-shell structure with higher percentage of Pb atoms as compared to iodine at the surface. In the inner core of the grains the percentage of iodine was slightly higher. The electron diffraction (ED) scan over the newly formed grains revealed a polycrystalline surface whereas the inner part had a single crystal pattern. The same solution, now one-week-old, contained grains with only single crystal patterns in the ED scan and showed no core-shell character or polycrystalline surface. The measured percentage of iodine atoms compared to lead was 2:1 throughout the cross section, which is a quantitative value within the measurement. It can be concluded from these measurements that the suspension approaches higher crystallinity of the perovskite grains in an irreversib

A hot-injection synthesis method was used to synthesize low-toxicity Ag2S colloidal quantum dots (CQDs) with strong and broad light absorption as an ultra-thin photo-absorber in CQD heterojunction solar cells. By using iodide and sulfur linkers it was possible to accomplish efficient charge carrier extraction, resulting in a high photocurrent due to the broad absorption spectrum. Transient photovoltage decay measurements were used to obtain information about trap states in the CQDs and the effect on the lifetime of the photoinduced carriers. The devices show very promising stability under constant long-term illumination and they are stable under ambient storage conditions with low losses to the performance over a period of over two months. These results show that Ag2S CQDs have high potential within solar cell applications, and point the direction for further improvements.

The photovoltaic characteristics of CsBi3I10-based solar cells with three dopant-free hole-conducting polymers are investigated. The effect on charge generation and charge recombination in the solar cells using the different polymers is studied and the results indicate that the choice of polymer strongly affects the device properties. Interestingly, for the solar cell with poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] (TQ1), the photon-to-current conversion spectrum is highly improved in the red wavelength region, suggesting that the polymer also contributes to the photocurrent generation in this case. This report provides a new direction for further optimization of Bi-halide solar cells by using dopant-free hole-transporting polymers and shows that the energy levels and the interaction between the Bi-halide and the conducting polymers are very important for solar cell performance.

Bismuth halide compounds as a non-toxic alternative are increasingly investigated because of their potential in optoelectronic devices and their rich structural chemistry. Hard X-ray spectroscopy was applied to the ternary bismuth halide Cs3Bi2I9 and its related precursors BiI3 and CsI to understand its electronic structure at an atomic level. We specifically investigated the core levels and valence band using X-ray photoemission spectroscopy (PES), high-resolution X-ray absorption (HERFD-XAS), and resonant inelastic X-ray scattering (RIXS) to get insight into the chemistry and the band edge properties of the two bismuth compounds. Using these element specific X-ray techniques, our experimental electronic structures show that the primary differences between the two bismuth samples are the position of the iodine states in the valence and conduction bands and the degree of hybridization with bismuth lone pair (6s(2)) states. The crystal structure of the two layered quasi-perovskite compounds plays a minor role in modifying the overall electronic structure, with variations in bismuth lone pair states and iodine band edge states. Density Functional Theory (DFT) calculations are used to compare with experimental data. The results demonstrate the effectiveness of hard X-ray spectroscopies to identify element specific bulk electronic structures and their use in optoelectronic devices.

Fe-air or Ni-Fe cells can offer low-cost and large-scale sustainable energy storage. At present, they are limited by low coulombic efficiency, low active material use, and poor rate capability. To overcome these challenges, two types of nanostructured doped iron materials were investigated: (1) copper and tin doped iron (CuSn); and (2) tin doped iron (Sn). Single-wall carbon nanotube (SWCNT) was added to the electrode and LiOH to the electrolyte. In the 2 wt. % Cu + 2 wt. % Sn sample, the addition of SWCNT increased the discharge capacity from 430 to 475 mAh g(-1), and charge efficiency increased from 83% to 93.5%. With the addition of both SWCNT and LiOH, the charge efficiency and discharge capacity improved to 91% and 603 mAh g(-1), respectively. Meanwhile, the 4 wt. % Sn substituted sample performance is not on par with the 2 wt. % Cu + 2 wt. % Sn sample. The dopant elements (Cu and Sn) and additives (SWCNT and LiOH) have a major impact on the electrode performance. To understand the relation between hydrogen evolution and charge current density, we have used in operando charging measurements combined with mass spectrometry to quantify the evolved hydrogen. The electrodes that were subjected to prolonged overcharge upon hydrogen evolution failed rapidly. This insight could help in the development of better charging schemes for the iron electrodes.