Dye-sensitized solar cell (DSSC) is considered as a feasible route to the clean and renewable energy conversion technique. The commercial application requires further enhancements on photovoltaic efficiency and simplification on the device fabrication. For avoiding the unpreferable trade-off between photocurrent (JSC) and photovoltage (VOC), here we report the molecular engineering and comprehensive photovoltaic characterization of three cyclopentadithiophene-bridged D-A-π-A motif sensitizers with a change in donor group. We make a careful choice on the donor and conjugation bridge for synergistically increasing JSC and VOC. Comparing with the reference dye WS-2, the photovoltaic efficiency with the single component dye of WS-51 increases by 18%, among one of the rare examples in pure metal-free organic dyes exceeding 10% in combination with traditional iodine redox couples. Moreover, WS-51 exhibits several prominent merits on potentially scale-up industrial application: i) facile synthetic route to target molecule, ii) simple dipping procedure without requirement of co-sensitization, and iii) rapid dye adsorption capability.

Indoline-based D-A-π-A organic sensitizers are promising candidates for highly efficient and long-term stable dye-sensitized solar cells (DSSCs). In order to further broaden the spectral response of the known indoline dye WS-2, we rationally engineer the molecular structure through enhancing the electron donor and extending the π-bridge, resulting in two novel indoline-based D-A-π-A organic sensitizers WS-92 and WS-95. By replacing the 4-methylphenyl group on the indoline donor of WS-2 with a more electron-rich carbazole unit, the intramolecular charge transfer (ICT) absorption band of dye WS-92 is slightly red-shifted from 550 nm (WS-2) to 554 nm (WS-92). In comparison, the incorporation of a larger π-bridge of cyclopentadithiophene (CPDT) unit in dye WS-95 not only greatly bathochromatically tunes the absorption band to 574 nm but also largely enhances the molar extinction coefficients (ε), thus dramatically improving the light-harvesting capability. Under the standard global AM 1.5 solar light condition, the photovoltaic performances of both organic dyes have been evaluated in DSSCs on the basis of the iodide/triiodide electrolyte without any coadsorbent or cosensitizer. The DSSCs based on WS-95 display better device performance with power conversion efficiency (η) of 7.69%. The additional coadsorbent in the dye bath of WS-95 does not improve the photovoltaic performance, indicative of its negligible dye aggregation, which can be rationalized by the grafted dioctyl chains on the CPDT unit. The cosensitization of WS-95 with a short absorption wavelength dye S2 enhances the IPCE and improves the η to 9.18%. Our results indicate that extending the π-spacer is more rational than enhancing the electron donor in terms of broadening the spectral response of indoline-based D-A-π-A organic sensitizers.

The option of using conjugated π-linkers is critical for rational molecular design toward an energy-level strategy for organic sensitizers. To further optimize photovoltaic performance, methyl- and octyl-substituted 4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) are introduced into D-A-π-A featured sensitizers. Along with CPDT, instead of thiophene as conjugated bridge, WS-39 and WS-43 exhibit an extended spectral response due to the excellent conjugation and coplanarity of CPDT. Specifically, we focused on the critical effect of length of the alkyl group linked to the bridging carbon atoms of CPDT on the photovoltaic performances. Octyl-substituted WS-39 shows a broader IPCE onset with an enhanced photovoltage relative to the analogue WS-5. In contrast, WS-43, with methyl substituted on the CPDT moiety, presents a relatively low quantum conversion efficiency within the whole spectral response region, along with low photocurrent density. WS-43 displays a distinctly low IPCE platform, predominately arising from the short electron diffusion length with significant electron loss during the electron transport. The relative movement of the conduction band edge (E(CB)) and charge transfer resistance as well as lifetime of injected electrons are studied in detail. Under standard AM 1.5 conditions, WS-39-based solar cells show a promising photovoltaic efficiency of 9.07% (J(SC) = 16.61 mA cm(-2), V(OC) = 770 mV, FF = 0.71). The octyl chains attached on CPDT can provide dual protection and exhibit a high propensity to prevent binding of the iodide-triiodide redox couple, producing an efficient shielding effect to retard the charge recombination and resulting in improvement of V(OC). Our research paves the way to explore more efficient sensitizers through ingenious molecular engineering.

To optimize light harvesting capabilities, one or two indoline units are introduced as additional donors into the traditional D−π–A model and constructed D–D−π–A sensitizers, CQ2 and CQ3. Absorption spectra and cyclic voltammetry are performed to evaluate the influence of different donor configurations on photophysical and electrochemical properties as well as photovoltaic performances. Incorporating the strong electron-donating indoline unit as an additional donor in CQ2 and CQ3 brings several characteristics, such as improving the visible light-harvesting capability and strengthening the intramolecular charge transfer (ICT) process, as well as positively shifting the HOMO energy level. Moreover, CQ3 is more dependent upon coadsorbents. Upon coadsorption with 5 mM CDCA, an obvious increment of more than 160% in J sc is achieved for CQ3, from 4.26 (without CDCA) to 11.15 mA cm–2 (5 mM CDCA). From photovoltaic performances, dye CQ2 with one additional indoline unit is preferable. Among the three dyes, CQ2 containing one indoline unit shows the highest conversion efficiency of 6.38%, with the photovoltaic parameters of J sc = 11.33 mA cm–2, V oc = 792 mV, and ff = 0.71 under 100 mW cm–2 simulated AM 1.5 G solar irradiation. It is indicative that the incorporation of the additional donor indoline on the framework of the triphenylamine core of CQ1 is beneficial to the optimization of photovoltaic performances. However, the incorporated multidonor units as additional donors in D-D−π–A type sensitizers can bring deteriorating intermolecular interactions between crowded donor units.

Cosensitization based on two or multiple dyes as "dye cocktails" can hit the target on compensating and broadening light-harvesting region. Two indoline D-A-p-A motif sensitizers (WS-2 and WS-39) that possess similar light response area but distinctly reversed feature in photovoltaic performance are selected as the specific cosensitization couple. That is, WS-2 shows quite high photocurrent but low photovoltage, and WS-39 gives relatively low photocurrent but quite high photovoltage. Due to the obvious "barrel effect", both dyes show medium PCE around 8.50%. In contrast with the previous cosensitization strategy mostly focused on the compensation of light response region, herein we perform different cosensitization sequence, for taking insight into the balance of photocurrent and photovoltage, and achieving the synergistic improvement in power conversion efficiency (PCE). Electronic impedance spectra (EIS) indicate that exploiting dye WS-39 with high V OC value as the primary sensitizer can repress the charge recombination more effectively, resulting in superior V OC rather than using dye WS-2 with high J SC as the primary sensitizer. As a consequence, a high PCE value of 9.48% is obtained with the delicate cosensitization using WS-39 as primary dye and WS-2 as accessory dye, which is higher than the corresponding devices sensitized by each individual dye (around 8.48e8.67%). It provides an effective optimizing strategy of cosensitization how to combine the individual dye advantages for developing highly efficient solar cells.

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