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AgBiS2 nanocrystals have been shown to be a promising material for solar cell applications due to their high absorption coefficient, solution-processability and stability. However, detailed and systematic insight into how different surface passivation agents affect the overall material properties and corresponding device performance is still limited. Herein, a study about AgBiS2 nanocrystals treated with five different halide-based compounds – TBAI, TMAI, TBABr, TMABr and TMACl – is presented, with the nanocrystals themselves being synthesised via a newly adapted route under atmospheric conditions. For the differently passivated samples, variation in the ligand uptake, as well as shifts in the position of the valence and conduction bands could be observed. Incorporating these ligand-treated thin films into solar cell devices allowed for further investigation of their overall performance as well as into their respective charge carrier dynamics. Markedly longer charge carrier lifetimes were observed for the bromide- and chloride-passivated samples through transient photovoltage and photocurrent measurements as well as impedance spectroscopy. The effect of the surface modification on the charge carrier transport behaviour, on the other hand, was found to be less pronounced. Overall, this work demonstrates the importance of better understanding how different ligands affect nanocrystal properties, showcasing how it influences a wide variety of parameters controlling final device performance. [ABSTRACT FROM AUTHOR]

Bromide-based perovskites have large bandgaps, making them attractive for tandem solar cells developed to overcome the Shockley–Queisser limit. A perovskite solar cell architecture employs transporting layers to improve charge extraction and transport. Due to the wide variety of materials and preparation methods, it is critical to devise fast screening methods to rank transporting layers. Herein, we evaluate perovskite fluorescence quenching followed by time- and energy-resolved photoluminescence (TER-PL) and analyse the intensity dependence as a potential method to qualify charge-transporting layers rapidly. The capability of the technique was evaluated with TiO2/FAPbBr3 and SnO2/FAPbBr3, the most commonly used electron transporting layers, which were prepared using standard protocols to make best-performing devices. The results revealed that TiO2 is the most effective quencher due to the higher density of states in the conduction band, consistent with Marcus-Gerischer's theory. However, record-performance devices use SnO2 as the electron transport layer. This shows that the relationship between photoluminescence quenching and device performance is not bidirectional. Therefore, additional measurements like conductivity are also needed to provide reliable feedback for device performance. [ABSTRACT FROM AUTHOR]

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 Cs0.25FA0.75Sn0.5Pb0.5I3 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 N2 atmosphere for 4224 h (176 days). [ABSTRACT FROM AUTHOR]

In this work, the photovoltaic performance and stability of perovskite solar cells (PSCs) based on a dopant-free hole transport layer (HTL) are efficiently improved by inserting a two-dimensional (2D) interfacial layer. The benzyl ammonium lead iodide (BA2PbI4) 2D perovskite is used as an interfacial layer between the 3D CH3NH3PbI3 perovskite and two moisture-resistant dopant-free HTLs including poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] (TQ1) and poly(3-hexylthiophene) (P3HT). TQ1 with a facile synthesis procedure has a higher moisture resistivity compared to P3HT which can improve the stability of PSCs. The 2D BA2PbI4 perovskite with a less-volatile bulkier organic cation efficiently passivates the defects at the perovskite/HTL interface, leading to 11.95% and 15.04% efficiency for the modified TQ1 and P3HT based cells, respectively. For a better understanding, the structural, optical, and electrical properties of PSCs comprising P3HT and TQ1 HTLs with and without interface modification are studied. The interface modified PSCs show slower open-circuit voltage decay and longer carrier lifetimes compared to unmodified cells. In addition, impedance spectroscopy reveals lower charge transport resistance and higher recombination resistance for the modified devices, which could be associated with the modification of the interface between the 3D CH3NH3PbI3 perovskite and HTL caused by the 2D interfacial layer. Also after aging under ambient conditions for about 800 hours, the modified PCSs retain more than 80% of their initial PCEs. These results give us the hope of achieving simpler, cheaper, and more stable PSCs with dopant-free HTLs through 2D interfacial layers, which have great potential for commercialization. [ABSTRACT FROM AUTHOR]

The interfacial properties between a perovskite layer and carbon electrode are critical for the photovoltaic performance of carbon electrode-based perovskite solar cells (PSCs). Herein, a methylammonium lead mixed halide (MAPbIxBr3−x) perovskite layer is in situ grown on the top of a methylammonium lead iodide (MAPbI3) perovskite layer forming a MAPbI3/MAPbIxBr3−x perovskite stacking structure (PSS) to improve the interfacial properties at the perovskite/carbon electrode interface. The charge carrier dynamics in both the perovskite and the PSC device induced by the MAPbIxBr3−x perovskite stacking layer are studied using extensive characterization. The charge interfacial recombination at the perovskite/carbon electrode interface is significantly diminished using the PSS within the PSC, resulting in largely improved charge extraction and therefore high photovoltaic performance. The PSS-based PSC shows a power conversion efficiency of up to 16.2% (increased by 43% compared with that of a conventional MAPbI3-based PSC), which is among the highest efficiencies of carbon electrode-based hole conductor free PSCs. Meanwhile, the PSS-based PSC also exhibits good stability under both continuous illumination and storage under dark conditions. This work may provide a new avenue to fine tune the interfacial properties of carbon electrode-based PSCs for further improving their photovoltaic performance. [ABSTRACT FROM AUTHOR]

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 (6s2) 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. [ABSTRACT FROM AUTHOR]

Efficient charge carrier extraction from a colloidal quantum dot (CQD) solid is crucial for high performance of CQD solar cells (CQDSCs). Herein, highly ordered wrinkled MgZnO (MZO) thin films are demonstrated to improve the charge carrier extraction of PbS CQDSCs. The highly ordered wrinkled MZO thin films are prepared using a low-temperature combustion method. The photovoltaic performances of CQDSCs with a combustion-processed MZO (CP-MZO) thin film as an electron transport material (ETM) are compared to those of CQDSCs with a conventional sol–gel processed MZO (SGP-MZO) thin film as an ETM. We performed photoluminescence quenching measurements of the colloidal quantum dot (CQD) solid and charge carrier dynamic analysis of full solar cell devices. The results show that the highly ordered wrinkled CP-MZO thin film significantly increases the charge carrier extraction from the CQD solid and therefore diminishes the charge interfacial recombination at the CQD/ETM junction, leading to a 15.5% increase in power conversion efficiency. The improved efficiency in the CP-MZO based CQDSC is also attributed to the compact and pin-hole free CP-MZO thin film. [ABSTRACT FROM AUTHOR]

Interfacial charge recombination occurring at the interface between a colloidal quantum dot (CQD) solid and the electron collecting layer (ECL) in CQD solar cells significantly affects the charge carrier collection, therefore limiting the device photovoltaic performance. In this work CQD solar cells with an improved performance are reported by employing MgZnO as a buffer layer (BL) with tunable electronic energy levels in the solar cells to reduce interfacial charge recombination and hence improve the solar cell photovoltaic performance. The effect of the BL on the solar cell performance is experimentally investigated and compared to theoretical calculations. Incorporation of a BL with favorable electronic energy levels forming a suitable band alignment with the CQD layer in solar cells diminishes the interfacial charge recombination and an increased photovoltage can be obtained. A CQD solar cell with a BL shows a power conversion efficiency of up to 9.3%, compared to that of 8.2% for a solar cell without any BLs. The unsealed solar cells are also rather stable under ambient conditions both in the dark and under continuous illumination. This work suggests that a MgZnO BL with energy level tunability provides a potential strategy to improve the interfacial properties of CQD photovoltaic devices. [ABSTRACT FROM AUTHOR]

Mixed-ion (FAPbI3)1−x(MAPbBr3)x perovskite solar cells have achieved power conversion efficiencies surpassing 20%. However, in order to obtain these high efficiencies the preparation is performed in a controlled inert atmosphere. Here, we report a procedure for manufacturing highly efficient solar cells with a mixed-ion perovskite in ambient atmosphere. By including a heating step at moderate temperatures of the mesoporous titanium dioxide substrates, and spin-coating the perovskite solution on the warm substrates in ambient air, a red intermediate phase is obtained. Annealing the red phase at 100 °C results in a uniform and crystalline perovskite film, whose thickness is dependent on the substrate temperature prior to spin-coating. The temperature was optimized between 20 and 100 °C and it was observed that 50 °C substrate temperature yielded the best solar cell performances. The average efficiency of the best device was 17.6%, accounting for current–voltage (I–V) measurement hysteresis, with 18.8% performance in the backward scan direction and 16.4% in the forward scan direction. Our results show that it is possible to manufacture high-efficiency mixed-ion perovskite solar cells under ambient conditions, which is relevant for large-scale and low-cost device manufacturing processing. [ABSTRACT FROM AUTHOR]

Means to measure the temporal evolution following a photo-excitation in conjugated polymers are a key for the understanding and optimization of their function in applications such as organic solar cells. In this paper we study the electronic structure dynamics by direct pump–probe measurements of the excited electrons in such materials. Specifically, we carried out a time-resolved photoelectron spectroscopy (TRPES) study of the polymer PCPDTBT by combining an extreme ultraviolet (XUV) high harmonic generation source with a time-of-flight spectrometer. After excitation to either the 1st excited state or to a higher excited state, we follow how the electronic structure develops and relaxes on the electron binding energy scale. Specifically, we follow a less than 50 fs relaxation of the higher exited state and a 10 times slower relaxation of the 1st excited state. We corroborate the results using DFT calculations. Our study demonstrates the power of TRPES for studying photo-excited electron energetics and dynamics of solar cell materials. [ABSTRACT FROM AUTHOR]

Degradation of the materials in dye-sensitized solar cells at elevated temperatures is critical for use in real applications. Both during fabrication of the solar cell and under real working conditions the solar cells will be exposed to heat. In this work, mesoporous TiO2 electrodes sensitized with the dyes D35 and K77 were subject to heat-treatment and the effects of this were thereafter investigated by photoelectron spectroscopy. For D35 it was found that heat-treatment changes the binding configuration inducing an increased interaction between the sulfur of the linker unit and the TiO2 surface. The interaction resulting from the change in binding configuration also affects the position of the HOMO level, where a shift of +0.2 eV is observed when heated to 200 °C. For K77, parts of the thiocyanate units are detached and the nitrogen atom leaves the electrode whereas sulfur remains on the surface in various forms of sulfurous oxides. The total dye coverage of K77 gets reduced by heat-treatment. The HOMO level gets progressively less pronounced due to a loss of HOMO level electrons as a consequence of the lower dye coverage when heat-treated, which leads to a lower excitation rate and lower efficiency. The results are discussed in the context of performance for dye-sensitized solar cells. [ABSTRACT FROM AUTHOR]

The formation of CH3NH3PbI3 (MAPbI3) from its precursors is probably the most significant step in the control of the quality of this semiconductor perovskite material, which is highly promising for photovoltaic applications. Here we investigated the transformation of spin coated PbI2 films to MAPbI3 using a reaction with MAI in vapor phase, referred to as vapor assisted solution process (VASP). The presence of a mesoporous TiO2 scaffold on the substrate was found to speed up reaction and led to complete conversion of PbI2, while reaction on glass substrates was slower, with some PbI2 remaining even after prolonged reaction time. Based on data from UV-visible spectroscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy, the formation of an X-ray amorphous intermediate phase is proposed, which is identified by an increasing absorption from 650 to 500 nm in the absorption spectrum. This feature disappears upon long reaction times for films on planar substrates, but persists for films on mesoporous TiO2. Poor solar cell performance of planar VASP prepared devices was ascribed to PbI2 remaining in the film, forming a barrier between the perovskite layer and the compact TiO2/FTO contact. Good performance, with efficiencies up to 13.3%, was obtained for VASP prepared devices on mesoporous TiO2. [ABSTRACT FROM AUTHOR]

The effects of alkoxy chain length in triarylamine based donor–acceptor organic dyes are investigated with respect to the electronic and molecular surface structures on the performance of solar cells and the electron lifetime. The dyes were investigated when adsorbed on TiO2 in a configuration that can be used for dye-sensitized solar cells (DSCs). Specifically, the two dyes D35 and D45 were compared using photoelectron spectroscopy (PES) and density functional theory (DFT) calculations. The differences in solar cell characteristics when longer alkoxy chains are introduced in the dye donor unit are attributed to geometrical changes in dye packing while only minor differences were observed in the electronic structure. A higher dye load was observed for D45 on TiO2. However, D35 based solar cells result in higher photocurrent although the dye load is lower. This is explained by different geometrical structures of the dyes on the surface. [ABSTRACT FROM AUTHOR]

The interfaces between different materials in the heterojunction colloidal quantum dot (QD) solar cell play an important role for charge carrier separation, recombination and collection. Here, an organic–inorganic hybrid p–i–n architecture for the heterojunction PbS QD solid solar cell is constructed to increase the charge extraction and reduce charge recombination. Heavily doped poly(3-hexylthiophene-2,5-diyl) (P3HT) is applied as hole transport interlayer between the QD film and metal contact electrode. The results show that the P3HT interlayer diminishes the charge carrier recombination at the QD film/metal contact electrode interface leading to increased open-circuit voltage and increased electron life time. Furthermore, after incorporation of P3HT interlayer an additional p–i heterojunction might form at P3HT/QD film interface resulting in increased depletion region, which promotes charge carrier extraction under working conditions. Two other organic p-type interlayers are also investigated, however, the results indicate that a barrier for charge extraction is formed for these devices, which is explained by the difference in energy levels. The solar cell with the P3HT interlayer exhibits a power conversion efficiency of 5.1% at 1 sun of illumination and ambient atmosphere, which is ∼20% higher compared to the solar cell without any hole transport interlayer. [ABSTRACT FROM AUTHOR]

A solid-state environmentally friendly Ag2S quantum dot-sensitized solar cell (QDSSC) is demonstrated. The photovoltaic device is fabricated by applying ZnO@Ag2S core–shell nanowire arrays (NWAs) as light absorbers and electron conductors, and poly-3-hexylthiophene (P3HT) as a solid-state hole conductor. Ag2S quantum dots (QDs) were directly grown on the ZnO nanowires by the successive ionic layer adsorption and reaction (SILAR) method to obtain the core–shell nanostructure. The number of SILAR cycles for QD formation and the length of the core–shell NWs significantly affect the photocurrent. The device with a core–shell NWAs photoanode shows a power conversion efficiency increase by 32% compared with the device based on a typical nanoparticle-based photoanode with Ag2S QDs. The enhanced performance is attributed to enhanced collection of the photogenerated electrons utilizing the ZnO nanowire as an efficient pathway for transporting the photogenerated electrons from the QD to the contact. [ABSTRACT FROM AUTHOR]

Semiconductor sensitized solar cell interfaces have been studied with photoelectron spectroscopy to understand the interfacial electronic structures. In particular, the experimental energy level alignment has been determined for complete TiO2/metal sulfide/polymer interfaces. For the metal sulfides CdS, Sb2S3 and Bi2S3 deposited from single source metal xanthate precursors, it was shown that both driving forces for electron injection into TiO2 and hole transfer to the polymer decrease for narrower bandgaps. The energy level alignment results were used in the discussion of the function of solar cells with the same metal sulfides as light absorbers. For example Sb2S3 showed the most favourable energy level alignment with 0.3 eV driving force for electron injection and 0.4 eV driving force for hole transfer and also the most efficient solar cells due to high photocurrent generation. The energy level alignment of the TiO2/Bi2S3 interface on the other hand showed no driving force for electron injection to TiO2, and the performance of the corresponding solar cell was very low. [ABSTRACT FROM AUTHOR]

A low-cost and easily-synthesized organic hole transport material (HTM) X3 bearing triphenylamine units and an organic dye was utilized for solid state dye sensitized solar cells (ssDSCs), which have achieved the power conversion efficiencies of 5.8% and 7.1% under 1 sun and 0.46 sun, respectively, outperforming the ssDSC based on Spiro-OMeTAD 5.4% (1 sun) and 6.4% (0.46 sun). [ABSTRACT FROM AUTHOR]

The energy loss in dye-sensitized solar cells calculated from the energy difference between the lowest electronic transition of the dye and the obtained open-circuit voltage is often 1 eV or even more. To minimize this loss, it is important to accurately determine the energy alignment at the TiO2/dye/redox-mediator interface. In this study, we compared the results from electrochemistry and photoelectron spectroscopy for determining the energy alignment of three rylene dyes, two of which absorb relatively far in the red. The trends observed with the methods were different, as in the former, the energy alignment is measured relative to an external reference and includes contributions from solvent reorganization energies, while in the latter, it is measured relative to the energetics of the TiO2and is lacking such contributions. The influence of the dyes' dipole moments on the energetics of the TiO2was also measured and explained some of the differences in trends. Finally, we compared the injection efficiencies of the two red-absorbing dyes and found that the differences in injection efficiencies can be better explained using the energy alignment determined from photoelectron spectroscopy. This shows that the method for measuring the energetics of a DSC should be chosen according to what process one intends to study. [ABSTRACT FROM AUTHOR]

The frontier electronic structures of a series of organic dye molecules containing a triphenylamine moiety, a thiophene moiety and a cyanoacrylic acid moiety have been investigated by photoelectron spectroscopy (PES), X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and resonant photoelectron spectroscopy (RPES). The experimental results were compared to electronic structure calculations on the molecules, which are used to confirm and enrich the assignment of the spectra. The approach allows us to experimentally measure and interpret the basic valence energy level structure in the dye, including the highest occupied energy level and how it depends on the interaction between the different units. Based on N 1s X-ray absorption and emission spectra we also obtain insight into the structure of the excited states, the molecular orbital composition and dynamics. Together the results provide an experimentally determined energy level map useful in the design of these types of materials. Included are also results indicating femtosecond charge redistribution at the dye/TiO2interface. [ABSTRACT FROM AUTHOR]

The electronic and molecular properties of three organic dye molecules with the general structure donor–linker–anchor have been investigated using core level photoelectron spectroscopy (PES). The molecules contain a diphenylaniline donor unit, a thiophene linker unit, and cyanoacrylic acid or rhodanine-3-acetic acid anchor units. They have been investigated both in the form of a multilayer and adsorbed onto nanoporous TiO2and the experimental results were also compared with DFT calculations. The changes at the dye-sensitized TiO2surface due to the modification of either the donor unit or the anchor unit was investigated and the results showed important differences in coverage as well as in electronic and molecular surface properties. By measuring the core level binding energies, the sub-molecular properties were characterized and the result showed that the adsorption to the TiO2influences the energy levels of the sub-molecular units differently. [ABSTRACT FROM AUTHOR]

Three new sensitizers for photoelectrochemical solar cells were synthesized consisting of a triphenylamine donor, a rhodanine-3-acetic acid acceptor and a polyene connection. The conjugation length was systematically increased, which resulted in two effects: first, it led to a red-shift of the optical absorption of the dyes, resulting in an improved spectral overlap with the solar spectrum. Secondly, the oxidation potential decreased systematically. The excited state levels were, however, calculated to be nearly stationary. The experimental trends were in excellent agreement with density functional theory (DFT) computations. The photovoltaic performance of this set of dyes as sensitizers in mesoporous TiO2solar cells was investigated using electrolytes containing the iodide/triiodide redox couple. The dye with the best absorption characteristics showed the poorest solar cell efficiency, due to losses by recombination of electrons in TiO2with triiodide. Addition of 4-tertbutylpyridine to the electrolyte led to a strongly reduced photocurrent for all dyes due to a reduced electron injection efficiency, caused by a 0.15 V negative shift of the TiO2conduction band potential. [ABSTRACT FROM AUTHOR]

In this work, the photovoltaic performance and stability of perovskite solar cells (PSCs) based on a dopant-free hole transport layer (HTL) are efficiently improved by inserting a two-dimensional (2D) interfacial layer. The benzyl ammonium lead iodide (BA 2 PbI 4 ) 2D perovskite is used as an interfacial layer between the 3D CH 3 NH 3 PbI 3 perovskite and two moisture-resistant dopant-free HTLs including poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] (TQ1) and poly(3-hexylthiophene) (P3HT). TQ1 with a facile synthesis procedure has a higher moisture resistivity compared to P3HT which can improve the stability of PSCs. The 2D BA 2 PbI 4 perovskite with a less-volatile bulkier organic cation efficiently passivates the defects at the perovskite/HTL interface, leading to 11.95% and 15.04% efficiency for the modified TQ1 and P3HT based cells, respectively. For a better understanding, the structural, optical, and electrical properties of PSCs comprising P3HT and TQ1 HTLs with and without interface modification are studied. The interface modified PSCs show slower open-circuit voltage decay and longer carrier lifetimes compared to unmodified cells. In addition, impedance spectroscopy reveals lower charge transport resistance and higher recombination resistance for the modified devices, which could be associated with the modification of the interface between the 3D CH 3 NH 3 PbI 3 perovskite and HTL caused by the 2D interfacial layer. Also after aging under ambient conditions for about 800 hours, the modified PCSs retain more than 80% of their initial PCEs. These results give us the hope of achieving simpler, cheaper, and more stable PSCs with dopant-free HTLs through 2D interfacial layers, which have great potential for commercialization.

A solid-state environmentally friendly Ag2S quantum dot-sensitized solar cell (QDSSC) is demonstrated. The photovoltaic device is fabricated by applying ZnO@Ag2S core-shell nanowire arrays (NWAs) as light absorbers and electron conductors, and poly-3-hexylthiophene (P3HT) as a solid-state hole conductor. Ag2S quantum dots (QDs) were directly grown on the ZnO nanowires by the successive ionic layer adsorption and reaction (SILAR) method to obtain the core-shell nanostructure. The number of SILAR cycles for QD formation and the length of the core-shell NWs significantly affect the photocurrent. The device with a core-shell NWAs photoanode shows a power conversion efficiency increase by 32% compared with the device based on a typical nanoparticle-based photoanode with Ag2S QDs. The enhanced performance is attributed to enhanced collection of the photogenerated electrons utilizing the ZnO nanowire as an efficient pathway for transporting the photogenerated electrons from the QD to the contact.

Semiconductor sensitized solar cell interfaces have been studied with photoelectron spectroscopy to understand the interfacial electronic structures. In particular, the experimental energy level alignment has been determined for complete TiO2/metal sulfide/polymer interfaces. For the metal sulfides CdS, Sb2S3 and Bi2S3 deposited from single source metal xanthate precursors, it was shown that both driving forces for electron injection into TiO2 and hole transfer to the polymer decrease for narrower bandgaps. The energy level alignment results were used in the discussion of the function of solar cells with the same metal sulfides as light absorbers. For example Sb2S3 showed the most favourable energy level alignment with 0.3 eV driving force for electron injection and 0.4 eV driving force for hole transfer and also the most efficient solar cells due to high photocurrent generation. The energy level alignment of the TiO2/Bi2S3 interface on the other hand showed no driving force for electron injection to TiO2, and the performance of the corresponding solar cell was very low.

Two hole conductor materials, spiro-OMeTAD and P3HT, were compared in solid-state dye-sensitized solar cells. Two organic dyes containing one anchor unit (D35) or two anchor units (M3) were used in the comparison. Absorbed photon to current conversion efficiency close to unity was obtained for the devices with spiro-OMeTAD. Energy conversion efficiencies of 4.7% and 4.9% were measured for the devices with spiro-OMeTAD and the dyes D35 and M3, respectively. For the devices using the P3HT hole conductor the results were rather different comparing the two dye molecules, with energy conversion efficiencies of 3.2% and 0.5% for D35 and M3, respectively. Photo-induced absorption measurements suggest that the regeneration of the dyes, and the polymer infiltration, is not complete using P3HT, while spiro-OMeTAD regenerates the dyes efficiently. However, the TiO(2)/D35/P3HT system shows rather high energy conversion efficiency and electrochemical oxidation of the dyes on TiO(2) indicates that D35 have a more efficient dye to dye hole conduction than M3, which thereby might explain the higher performance. The dye hole conduction may therefore be of significant importance for optimizing the energy conversion in such hybrid TiO(2)/dye/polymer systems.

The electronic and molecular properties of three organic dye molecules with the general structure donor-linker-anchor have been investigated using core level photoelectron spectroscopy (PES). The molecules contain a diphenylaniline donor unit, a thiophene linker unit, and cyanoacrylic acid or rhodanine-3-acetic acid anchor units. They have been investigated both in the form of a multilayer and adsorbed onto nanoporous TiO(2) and the experimental results were also compared with DFT calculations. The changes at the dye-sensitized TiO(2) surface due to the modification of either the donor unit or the anchor unit was investigated and the results showed important differences in coverage as well as in electronic and molecular surface properties. By measuring the core level binding energies, the sub-molecular properties were characterized and the result showed that the adsorption to the TiO(2) influences the energy levels of the sub-molecular units differently.

Three new sensitizers for photoelectrochemical solar cells were synthesized consisting of a triphenylamine donor, a rhodanine-3-acetic acid acceptor and a polyene connection. The conjugation length was systematically increased, which resulted in two effects: first, it led to a red-shift of the optical absorption of the dyes, resulting in an improved spectral overlap with the solar spectrum. Secondly, the oxidation potential decreased systematically. The excited state levels were, however, calculated to be nearly stationary. The experimental trends were in excellent agreement with density functional theory (DFT) computations. The photovoltaic performance of this set of dyes as sensitizers in mesoporous TiO2 solar cells was investigated using electrolytes containing the iodide/triiodide redox couple. The dye with the best absorption characteristics showed the poorest solar cell efficiency, due to losses by recombination of electrons in TiO2 with triiodide. Addition of 4-tert butylpyridine to the electrolyte led to a strongly reduced photocurrent for all dyes due to a reduced electron injection efficiency, caused by a 0.15 V negative shift of the TiO2 conduction band potential.