Copper Complexes as Alternative Redox Mediators in Dye-Sensitized Solar Cells

Thirty years ago, dye-sensitized solar cells (DSSCs) emerged as a method for harnessing the sun’s energy and converting it into electricity. Since then, a lot of work has been dedicated to improving their global photovoltaic efficiency and their eco-sustainability. Recently, various articles showed the great potential of copper complexes as a convenient and cheap alternative to the traditional ruthenium dyes. In addition, copper complexes demonstrate that they can act as redox mediators for DSSCs, thus being an answer to the problems related to the I₃⁻/I⁻ redox couple. The aim of this review is to report on the most recent impact made by copper complexes as alternative redox mediators. The coverage, mainly from 2016 up to now, is not exhaustive, but allows us to understand the great role played by copper complexes in the design of eco-sustainable DSSCs.     

Influence of Triarylamine and Indoline as Donor on Photovoltaic Performance of Dye-Sensitized Solar Cells Employing Cobalt Redox Shuttle

Two organic dyes XS51 and XS52 derivated from triarylamine and indoline are synthesized for dye-sensitized solar cells (DSCs) employing cobalt and iodine redox shuttles. The effects of dye structure upon the photophysical, electro-chemical characteristics and cell performance are investigated. XS51 with four hexyloxyl groups on triarylamine performs better steric hindrance and an improvement of photovoltage. XS52 provides higher short-circuit photocurrent density due to the strong electron-donating capability of indoline unit. The results from the redox electrolyte on cell performances indicate that the synthesized dyes are more suitable for tris(1,10-phenanthroline)cobalt(II/III) redox couple than I^?/I₃^? redox couple in assembling DSCs. Application of XS52 in the cobalt electrolyte yields a DSC with an overall power conversion efficiency of 6.58% under AM 1.5 (100 mW/cm²) irradiation.     

Adaptive response by an electrolyte: resilience to electron losses in a dye-sensitized porous photoanode

Photovoltage and photocurrents below theoretical limits in dye-sensitized photoelectrochemical solar energy conversion systems are usually attributed to electron loss processes such as dye–electron and electrolyte–electron recombination reactions within the porous photoanode. Whether recombination is a major loss mechanism is examined here, using a multiscale reaction–diffusion computational model to evaluate system characteristics. The dye-sensitized solar cell with an I⁻/I₃⁻ redox couple is chosen as a simple, representative model system because of the extensive information available for it. Two photoanode architectures with dye excitation frequencies spanning 1–25 s⁻¹ are examined, assuming two distinct recombination mechanisms. The simulation results show that although electrolyte–electron reactions are very efficient, they do not significantly impact photoanode performance within the system as defined. This is because the solution-phase electrolyte chemistry plays a key role in mitigating electron losses through coupled reactions that produce I⁻ within the photoanode pores, thereby cycling the electrolyte species without requiring that all electrolyte reduction reactions take place at the more distantly located cathode. This is a functionally adaptive response of the chemistry that may be partly responsible for the great success of this redox couple for dye-sensitized solar cells. The simulation results provide predictions that can be tested experimentally.

Interfacial electrolyte reactions in the pores of a photoanode consume electrons. The losses are offset by compensating solution-phase reactions that generate I⁻ locally, and promote efficient dye cycling and photocurrent generation.     

Thiophene–nitroxide radical as a novel combination of sensitizer–redox mediator for dye-sensitized solar cells

We report a novel combination of organic sensitizer and redox mediator in the electrolyte for dye-sensitized solar cells (DSSCs): a thiophene dye and nitroxide radicals. Nitroxide radicals and their oxidized counterparts of oxoammonium cations show robust reversible redox reactions, thus supporting robust DSSC operations. Moreover, their redox potentials (E _1/2) and thus open-circuit voltages (V _OC) can be tuned further by attached functional groups. Optical and electrochemical characterization reveal that these new combinations exhibit enhanced V _OC and power conversion efficiencies compared to the existing iodine mediator (I⁻/I₃⁻) due to the increased V _OC. Also, the selection of the sensitizer–redox mediator turns out to be critical in the overall cell performance. Indeed, the typical ruthenium dye loses its light absorption capability when it is operated in conjunction with the nitroxide radicals.     

Molecular Design of D‐π‐A Type II Organic Sensitizers for Dye Sensitized Solar Cells

Four new type II organic dyes with D‐π‐A structure (donor‐π‐conjugated‐acceptor) and two typical type II sensitizers based on catechol as reference dyes are synthesized and applied in dye sensitized solar cells (DSCs). The four dyes can be adsorbed on TiO₂ through hydroxyl group directly. Electron injection can occur not only through the anchoring group (hydroxyl group) but also through the electron‐withdrawing group (? CN) located close to the semiconductor surface. Experimental results show that the type II sensitizers with a D‐π‐A system obviously outperform the typical type II sensitizers providing much higher conversion efficiency due to the strong electronic push‐pull effect. Among these dyes, LS223 gives the best solar energy conversion efficiency of 3.6%, with J_sc=7.3 mA·cm^?2, V_oc=0.69 V, FF=0.71, the maximum IPCE value reaches 74.9%.     

Zinc Porphyrins with a Pyridine‐Ring‐Anchoring Group for Dye‐Sensitized Solar Cells

Anchoring groups are extremely important in controlling the performance of dye‐sensitized solar cells (DSCs). The design and characterization of sensitizers with new anchoring groups, in particular non‐carboxylic acid groups, has become a recent focus of DSC research. Herein, new donor? π? acceptor zinc? porphyrin dyes with a pyridine ring as an anchoring group have been designed and synthesized for applications in DSCs. Photophysical and electrochemical investigations demonstrated that the pyridine ring worked effectively as an anchoring group for the porphyrin sensitizers. DSCs that were based on these new porphyrins showed an overall power‐conversion efficiency of about 4.0 % under full sunlight (AM 1.5G, 100 mW cm^?2).     

Dye-sensitized solar cells based on Fe N-heterocyclic carbene photosensitizers with improved rod-like push-pull functionality

A new generation of octahedral iron(ii)–N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push–pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push–pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I⁻/I₃⁻ redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO₂. Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO₂. However, an ultrafast recombination process results in undesirable fast charge recombination from TiO₂ back to the oxidized dye, leaving only 5–10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6–8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work.

Iron-based photosensitizers for dye-sensitized solar cells with a rod-like push–pull design. Solar cell performance was limited by ultrafast (sub-ps) recombination, but yielded better performance than the homoleptic parent photosensitizer.     

Electron-rich heteroaromatic conjugated polypyridine ruthenium sensitizers for dye-sensitized solar cells

Ru(II) heteroleptic complexes as photosensitizers for dye-sensitized solar cells (DSCs) are presented. The article outlines design strategies, synthetic routes, optical and photovoltaic properties of ruthenium dyes based on polypyridines as ancillary ligands containing π-conjugated electron-rich heteroaromatic groups. The integration of donor heteroaromatic substituents, typically thiophene-based moieties, strongly improves the optical properties of the sensitizers in terms of bathochromic and hyperchromic shift compared to prototypical dyes N3 and N719. These favorable properties in turn yield DSCs with superior light harvesting abilities, higher external quantum efficiencies, improved device photocurrents, and top-ranked power conversion efficiencies. In combination with excellent stabilities under thermal stress and light soaking, this class of DSC photosensitizer has great potential for practical applications.     

Phenanthrene-Fused-Quinoxaline as a Key Building Block for Highly Efficient and Stable Sensitizers in Copper-Electrolyte-Based Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSSCs) based on Cu^II/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open-circuit voltages (V_OC, more than 1 V). However, their short-circuit photocurrent density (J_SC) has remained modest. Increasing the J_SC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO₂ film and fast regeneration by the Cu^I complex. Herein, we report two new D-A-π-A-featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene-fused-quinoxaline (PFQ), respectively, as the auxiliary electron-withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 -based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near-quantitative collection of photogenerated charge carriers.     

SnO2 Transparent Printing Pastes from Powders for Photon Conversion in SnO2-Based Dye-Sensitized Solar Cells

Tin oxide (SnO₂) is the most attractive alternative to titanium oxide (TiO₂) with the aim of identifying a more positive conduction band material for dye-sensitized solar cells (DSCs). This study puts forward a protocol based on grinding, sonication, and centrifuge to generate transparent SnO₂ pastes to minimize light reflectance losses from the metal oxide. Under optimized conditions, a highly transparent film with substantially enhanced light penetration depth through active layer SnO₂ is realized for efficient light harvesting from two different commercially available powders (18 and 35 nm nanoparticle sizes). A ruthenium sensitizer ( B11 ) and two organic sensitizers ( NL3 and MK2 ) are shown to achieve higher or comparable photocurrent densities with SnO₂ relative to standard TiO₂-based DSCs. SnO₂-based DSCs show minimum recombination losses, comparable charge collection efficiencies, and minimal photovoltage losses relative to TiO₂ DSCs. Thus, the option of a transparent metal oxide, which can facilitate high photocurrents (>16 mA cm⁻² observed) and lower recombination rates than TiO₂ is an attractive material for DSC applications.     

Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO2 reduction coupled with water oxidation

The development of systems for photocatalytic CO₂ reduction with water as a reductant and solar light as an energy source is one of the most important milestones on the way to artificial photosynthesis. Although such reduction can be performed using dye-sensitized molecular photocathodes comprising metal complexes as redox photosensitizers and catalyst units fixed on a p-type semiconductor electrode, the performance of the corresponding photoelectrochemical cells remains low, e.g., their highest incident photon-to-current conversion efficiency (IPCE) equals 1.2%. Herein, we report a novel dye-sensitized molecular photocathode for photocatalytic CO₂ reduction in water featuring a polypyrrole layer, [Ru(diimine)₃]²⁺ as a redox photosensitizer unit, and Ru(diimine)(CO)₂Cl₂ as the catalyst unit and reveal that the incorporation of the polypyrrole network significantly improves reactivity and durability relative to those of previously reported dye-sensitized molecular photocathodes. The irradiation of the novel photocathode with visible light under low applied bias stably induces the photocatalytic reduction of CO₂ to CO and HCOOH with high faradaic efficiency and selectivity (even in aqueous solution), and the highest IPCE is determined as 4.7%. The novel photocathode is coupled with n-type semiconductor photoanodes (CoO_x/BiVO₄ and RhO_x/TaON) to construct full cells that photocatalytically reduce CO₂ using water as the reductant upon visible light irradiation as the only energy input at zero bias. The artificial Z-scheme photoelectrochemical cell with the dye-sensitized molecular photocathode achieves the highest energy conversion efficiency of 8.3 × 10⁻²% under the irradiation of both electrodes with visible light, while a solar to chemical conversion efficiency of 4.2 × 10⁻²% is achieved for a tandem-type cell using a solar light simulator (AM 1.5, 100 mW cm⁻²).

A novel dye-sensitized molecular photocathode with polypyrrole networks exhibits high efficiency and durability for photocatalytic CO₂ reduction by using water as reductant and visible light as energy.     

Comparison of low crystallinity TiO2 film with nanocrystalline anatase film for dye-sensitized solar cells

Dye adsorption and microstructure of TiO₂ film are important properties when it is used as photoelectrode of dye-sensitized solar cells (DSCs). This study investigated the application of a low crystallinity TiO₂ film in DSCs. The low crystallinity TiO₂ film is composed of interconnected spherical particles with an average size of 20 nm and has homogeneous mesoporous inner structure. A DSC based on the anatase nanocrystalline mesoporous film prepared by P25 was used for comparison purpose. It is shown that although loaded with much less dye, the DSC based on the low crystallinity TiO₂ film generated I_sc (short circuit photocurrent) as much as the one based on the conventional anatase nanocrystalline film does and obtained higher V_oc (open circuit photovoltage) as well as ff (fill factor). The overall light-to-electricity efficiency (η) of the DSC based on the low crystallinity TiO₂ film reached 5.37%, while the η of the DSC based on anatase nanocrystalline film was 4.69% in this work condition. It is suggested that a low crystallinity TiO₂ mesoporous film with a proper microstructure is as efficient as the anatase nanocrystalline mesoporous film when used in DSCs.     

Phenanthrene‐Fused‐Quinoxaline as a Key Building Block for Highly Efficient and Stable Sensitizers in Copper‐Electrolyte‐Based Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) based on Cu^II/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (V_OC, more than 1 V). However, their short‐circuit photocurrent density (J_SC) has remained modest. Increasing the J_SC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO₂ film and fast regeneration by the Cu^I complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 ‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers.     

Application of Triphenylamine-Based Sensitizers with Two Carboxylic Acid Groups to Dye-Sensitized Solar Cells

Two triphenylamine-based dyes (TPAR3 and TPAR6) containing two carboxylic acid groups with different conjugated lengths were synthesized and characterized with regard to their photophysical and photoelectrochemical properties. Experimental results showed that the λ_max of TPAR6 either in methanol solution or on TiO₂ film was red-shifted and broadened by extending the π-conjugated bridge. However, the performance of TPAR3-based dye-sensitized solar cell (DSC) was superior to that of TPAR6. This reason was due to the serious self-quenching of the electronically excited state in TPAR6 molecule, resulting from its cis-trans isomerization. The effects of addition of guanidinium thiocyanate (GT) in the electrolyte on the performance of DSCs based on TPAR3 were also investigated, revealing a maximum energy conversion efficiency of 4.02% at 0.100 mol·L⁻¹ GT.     

Synthesis and Characterization of Organic Dyes with Various Electron‐Accepting Substituents for p‐Type Dye‐Sensitized Solar Cells

Four new donor‐π‐acceptor dyes differing in their acceptor group have been synthesized and employed as model systems to study the influence of the acceptor groups on the photophysical properties and in NiO‐based p‐type dye‐sensitized solar cells. UV/Vis absorption spectra showed a broad range of absorption coverage with maxima between 331 and 653 nm. Redox potentials as well as HOMO and LUMO energies of the dyes were determined from cyclic voltammetry measurements and evaluated concerning their potential use as sensitizers in p‐type dye‐sensitized solar cells (p‐DSCs). Quantum‐chemical density functional theory calculations gave further insight into the frontier orbital distributions, which are relevant for the electronic processes in p‐DSCs. In p‐DSCs using an iodide/triiodide‐based electrolyte, the polycyclic 9,10‐dicyano‐acenaphtho[1,2‐b]quinoxaline (DCANQ) acceptor‐containing dye gave the highest power conversion efficiency of 0.08 %, which is comparable to that obtained with the perylenemonoimide (PMI)‐containing dye. Interestingly, devices containing the DCANQ‐based dye achieve a higher V_OC of 163 mV compared to 158 mV for the PMI‐containing dye. The result was further confirmed by impedance spectroscopic analysis showing higher recombination resistance and thus a lower recombination rate for devices containing the DCANQ dye than for PMI dye‐based devices. However, the use of the strong electron‐accepting tricyanofurane (TCF) group played a negative role in the device performance, yielding an efficiency of only 0.01 % due to a low‐lying LUMO energy level, thus resulting in an insufficient driving force for efficient dye regeneration. The results demonstrate that a careful molecular design with a proper choice of the acceptor unit is essential for development of sensitizers for p‐DSCs.     

The effects of polymer gel electrolyte composition on performance of quasi-solid-state dye-sensitized solar cells

Polymer gel electrolytes based on poly(acrylic acid)-poly(ethylene glycol) (PAA–PEG) hybrid have been prepared and applied to developed quasi-solid-state dye-sensitized solar cells (DSCs). PAA–PEG hybrid was synthesized by polymerization reaction. Quasi-solid-state DSCs were fabricated with synthesized PAA–PEG electrolyte. The effects of alkali iodides LiI, KI, and I₂ concentrations on liquid electrolyte absorbency and ionic conductivity of PAA–PEG were investigated. The evolution of the solar cell parameters with polymer gel electrolyte compositions was revealed. DSCs based on PAA–PEG with optimized KI/I₂ concentrations showed better performances than those with optimized LiI/I₂ concentrations. The electrochemical impedance spectroscopy technique was employed to examine the electron lifetime in the TiO₂ electrode and quantify charge transfer resistances at the TiO₂/dye/electrolyte interface and the counter electrode in the solar cells based on the PAA–PEG hybrid gels. A maximum conversion efficiency of 4.96% was obtained for DSCs using KI based quasi-solid electrolyte under 100 mW cm⁻². Our work suggests that KI can be the promising alkali metal iodide for improving the performance of PAA–PEG hybrid gel DSCs.     

Dye-sensitized solar cells based on bisindolylmaleimide derivatives

Three organic dyes based on bisindolylmaleimide derivatives (I1, I2 and I3) were synthesized and investigated as sensitizers for the application in nanocrystalline TiO₂ solar cells. The indole group, maleimide group and carboxylic group functioned as electron donor, acceptor and anchoring group, respectively. Solar-to-electrical energy conversion efficiencies under simulated amplitude-modulated 1.5 irradiation (100 mW·cm⁻²) of 2.07% were obtained for solar cells based on I2 and of 1.87% and 1.50% for I3 and I1, respectively. The open circuit voltage V _oc was demonstrated to be enhanced by the introduction of dodecyl or benzyl moieties on the indole groups. The nonplanar structure of bisindolylmaleimide was proven to be effective in aggregation resistance. This work suggests that organic sensitizers with maleimide as electron acceptor are promising candidates as organic sensitizers in dye-sensitized solar cells.     

Energy and hole transfer between dyes attached to titania in cosensitized dye-sensitized solar cells

Cosensitization of broadly absorbing ruthenium metal complex dyes with highly absorptive near-infrared (NIR) organic dyes is a clear pathway to increase near-infrared light harvesting in liquid-based dye-sensitized solar cells (DSCs). In cosensitized DSCs, dyes are intimately mixed, and intermolecular charge and energy transfer processes play an important role in device performance. Here, we demonstrate that an organic NIR dye incapable of hole regeneration is able to produce photocurrent via intermolecular energy transfer with an average excitation transfer efficiency of over 25% when cosensitized with a metal complex sensitizing dye (SD). We also show that intermolecular hole transfer from the SD to NIR dye is a competitive process with dye regeneration, reducing the internal quantum efficiency and the electron lifetime of the DSC. This work demonstrates the general feasibility of using energy transfer to boost light harvesting from 700 to 800 nm and also highlights a key challenge for developing highly efficient cosensitized dye-sensitized solar cells.     

Engineering of highly efficient tetrahydroquinoline sensitizers for dye-sensitized solar cells

Four novel tetrahydroquinoline dyes by inserting isophorone and/or thiophene moieties as π bridge between the electron donating unit of substituted tetrahydroquinoline and the electron withdrawing unit of cyano carboxylic acid have been synthesized and successfully applied to dye-sensitized solar cells. Among them, DSCs sensitized by HYTIC, which shows the simplest molecular structure, exhibit improved efficiency of 7.0%. This by now is the highest efficiency for the reported tetrahydroquinoline sensitizers and comparable to the performance of N719-sensitized solar cells under the conditions employed here.     

Optically Transparent Gold Nanoparticles for DSSC Counter-Electrode: An Electrochemical Characterization

A gold nanoparticles transparent electrode was realized by chemical reduction. This work aims to compare the transparent gold nanoparticles electrode with a more commonly utilized gold-film-coated electrode in order to investigate its potential use as counter-electrode (CE) in dye-sensitized solar cells (DSSCs). A series of DSSC devices, utilizing I⁻/I³⁻ and Co(III)/(II) polypyridine redox mediators [Co(dtb)3]³⁺/²⁺; dtb = 4,4′ditert-butyl-2,2′-bipyridine)], were evaluated. The investigation focused firstly on the structural characterization of the deposited gold layers and then on the electrochemical study. The novelty of the work is the realization of a gold nanoparticles CE that reached 80% of average visible transmittance. We finally examined the performance of the transparent gold nanoparticles CE in DSSC devices. A maximum power conversion efficiency (PCE) of 4.56% was obtained with a commercial I⁻/I³⁻-based electrolyte, while a maximum 3.1% of PCE was obtained with the homemade Co-based electrolyte.