Synthesis and characterization of polymers
The preparation routes for the monomers and polymers are shown in Scheme 1, and their synthetic details and analytical results are described in the experimental section of the Electronic Supporting Information (ESI). First, the reaction of 1-iodo-4-methoxybenzene with aniline-afforded N,N-bis(4-methoxyphenyl)benzenamine (1) was performed. Second, α-diketone 1,2-bis(4-(bis(4-methoxyphenyl)amino)phenyl)ethane-1,2-dione (2) was prepared via the Friedel–Crafts reaction of 1 in the presence of oxalyl chloride [23]. Third, two reactions, i.e., zinc-mediated reduction and condensation, were performed on 4,7-dibromo[c][1, 2, 5]thiadiazole derivatives (3 and 4) to synthesize dibrominated quinoxaline monomers with strong electron-withdrawing F (5) and CN substituents (6). Finally, the polymerization of a chlorinated BDT donor (7) with 5 and 6 under the Stille coupling condition yielded the target D–A-type quinoxaline-based polymers, i.e., PBCl-MTQF and PBCl-MTQCN, respectively. In this synthetic strategy, a unique 2D polymeric architecture, in which the electron-donating BDT and methoxy-TPA groups are located in the horizontal and vertical directions of the electron-accepting quinoxaline unit, respectively, was achieved. The formation of the 2D structure not only strengthened the structural uniqueness of the target polymers, but also induced broad light absorption and reduced the bandgap through the facile electron transfer process in both directions. The molecular weights of the polymers were analyzed via gel permeation chromatography using o-dichlorobenzene as the eluent. The number-average molecular weight and polydispersity index of PBCl-MTQF and PBCl-MTQCN were 20.82 kDa and 2.48, and 26.23 kDa and 2.24, respectively. These polymers exhibited good solubility in various organic solvents such as chloroform, toluene, and chlorobenzene, owing to the existence of 2-ethylhexyl and methoxy side chains on BDT and quinoxaline units, respectively.
Optical and electrochemical properties
The optical properties of the polymers were analyzed using ultraviolet–visible (UV–Vis) spectroscopy. As shown in Figures 1a and 1b, all polymers exhibited two similar absorption peaks in both the chloroform solution and film on the glass substrate. The peak in the shorter wavelength region of 300–450 nm was associated with the π–π* transitions of the conjugated backbones, whereas that at longer wavelength regions of 450–650 nm originated from the formation of an ICT state between the donor and acceptor units in the polymer chains. The molar extinction coefficients (ε) in the ICT region of PBCl-MTQF and PBCl-MTQCN in chloroform solution were 6.12 × 104 and 6.50 × 104 M−1 cm−1, respectively (Figure 1a). The maximum absorption peak of PBCl-MTQCN was red shifted by approximately 10 nm compared with that of PBCl-MTQF. The higher ε value of PBCl-MTQCN at longer wavelengths compared with that of PBCl-MTQF can be attributed to the stronger ICT formation caused by the availability of more electron-withdrawing CN units [24]. The electronic effects of the substituent can be correlated with the Hammett constant, and the values for F and CN at meta-positions were determined to be 0.34 and 0.56, respectively [25]. The two polymers exhibited good complementary light absorption spectra with an n-type Y6 acceptor in the film state (Figure 1b), which is beneficial for improving the photovoltaic properties of the devices. In addition, the optical bandgaps of PBCl-MTQF and PBCl-MTQCN calculated from the absorption edge in film state were 1.81 and 1.80 eV, respectively.
The electrochemical properties of the polymers were analyzed using cyclic voltammetry (CV) measurements with a ferrocene (Fc)/ferrocenium (Fc+) external standard. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were determined from the onset oxidation and reduction potentials, respectively, in the CV curves (Figure 1c). The calculated HOMO/LUMO energy levels of PBCl-MTQF and PBCl-MTQCN were ˗5.06/˗3.27 and ˗5.14/˗3.38 eV, respectively. The higher electron-withdrawing capability of the CN unit compared with that of the F atom in the quinoxaline acceptor can induce a significant reduction in both the HOMO and LUMO energy levels of PBCl-MTQCN compared with those of PBCl-MTQF. In addition, the electrochemical bandgaps of PBCl-MTQF and PBCl-MTQCN estimated from the difference between their HOMO and LUMO energy levels were 1.79 and 1.76 eV, respectively. The electrochemical bandgap of the polymers exhibited the same trend as the optical bandgaps. The optical and electrochemical properties of the polymers are listed in Table 1. Based on the results, it was discovered that the replacement of the F atom with the CN moiety in the quinoxaline acceptor significantly affected the optical and electrochemical properties of the corresponding D–A-type polymers.
Table 1
Optical and electrochemical properties of the polymers.
Polymers | ε (M−1 cm−1) | \({E}_{gap}^{opt}\)a (eV) | \({\lambda }_{max}^{solution}\) (nm)b | HOMO (eV)c | LUMO (eV)d | \({E}_{gap}^{elec}\) (eV) e |
PBCl-MTQF | 6.16 \(\times\) 104 | 1.81 | 366, 536 | -5.06 | -3.27 | 1.79 |
PBCl-MTQCN | 6.50 \(\times\) 104 | 1.80 | 370, 548 | -5.14 | -3.38 | 1.76 |
aEstimated from the absorption edge in the film state. bMaximum absorption wavelengths of polymers in chloroform solution. cEstimated from the oxidation onset potential. dEstimated from the reduction onset potential. eCalculated from the oxidation and reduction onset potentials in the CV curves. |
Theoretical calculation
Density functional simulations using the Gaussian 09 program at the B3LYP/6-31G** level were performed to estimate the optimized geometries and frontier molecular orbitals of the polymers [26]. To reduce complicated computational calculations, 2-ethylhexyl chains on BDT donors and long polymer backbones were simplified to the shortest methyl group and small dimer unit, respectively. In the optimized geometries, the dihedral angles between the thiophene unit and quinoxaline acceptor in the polymer backbone changed significantly from 16.34° in PBCl-MTQF to 41.16° in PBCl-MTQCN (Figure 2). The increased steric hindrance induced by the substitution of the bulkier CN moiety instead of the F atom can readily generate more twisted conformation in PBCl-MTQCN. From the viewpoint of frontier molecular orbitals, similar characteristic features were observed in the two polymers. The HOMO wave functions of all the polymers were localized on the methoxy-TPA units, whereas their LUMO wave functions were delocalized along the polymer backbones. However, the HOMO and LUMO energy levels of the polymers were altered significantly by the type of electron-withdrawing substituent on the quinoxaline acceptor. The simulated HOMO/LUMO energy levels of PBCl-MTQF and PBCl-MTQCN were ˗4.68/˗2.38 eV and ˗4.74/˗2.51 eV, respectively. Both the HOMO and LUMO energy levels of PBCl-MTQCN were more stable than those of PBCl-MTQF. As experimentally observed based on the HOMO/LUMO energy levels of the polymers using CV measurements, the theoretical HOMO/LUMO energy levels of the polymers reduced owing to the substitution of F atom with CN moiety.
Photovoltaic Properties
To investigate the effects of the CN and F substituents on the photovoltaic properties of the polymer, we introduced an inverted device configuration of ITO/SnO/polymer:Y6/MoO3/Ag (Figure 3a). Because Y6 is one of the best non-fullerene acceptors for sufficient light absorption and efficient charge transport [7], we selected Y6 as an electron acceptor for device fabrication. As shown in Figure 3b, the HOMO and LUMO levels of both polymers agreed well with those of Y6 for cascade energy level alignment. For device optimization, various D:A ratios of the active layers of the devices were tested (Figure S1 and Table S1 in the ESI). The optimum devices comprising PBCl-MTQF and PBCl-MTQCN had D:A ratios of 1:1.5 and 1:1.0, respectively, in the presence of 1,8-diiodooctane as a processing additive. The current density–voltage (J–V) characteristics and the external quantum efficiency (EQE) of the optimized devices are shown in Figures 3c and 3d, respectively. The corresponding photovoltaic parameters are presented in Table 2. It was discovered that the device based on PBCl-MTQF exhibited a higher PCE of 7.48% with a short-circuit current density (JSC) of 19.26 mA/cm2, open-circuit voltage (VOC) of 0.71 V, and fill factor (FF) of 0.54. By contrast, the device based on PBCl-MTQCN indicated lower values for their photovoltaic parameters (PCE, 3.10%; JSC: 11.46 mA/cm2, VOC, 0.67; and FF, 0.39). In addition, the EQE curves of both devices encompassed broad wavelengths ranging from 350 to 950 nm (Figure 3d). The maximum EQE value of the device based on PBCl-MTQF was 67% higher than that of the device based on PBCl-MTQCN (44%). The calculated JSC values from the EQE curves were consistent with those obtained from the J–V characteristics. These results demonstrate the significant dependence of the photovoltaic performance of D-A-type quinoxaline-based polymers on the type of electron-withdrawing substituent on the quinoxaline acceptor.
Table 2
Best photovoltaic parameters of PSCs. Values in parentheses represent average (of 10 devices) value of photovoltaic parameters for each device.
Polymer | Blend Ratio (Polymer:Y6) | JSC (mA/cm2) | JSC (mA/cm2)a | VOC (V) | FF | PCE (%) |
PBCl-MTQF | 1:1.5 | 19.26 | 19.13 | 0.71 | 0.54 | 7.48 (7.21 ± 0.20)b |
PBCl-MTQCN | 1:1 | 11.46 | 11.12 | 0.67 | 0.39 | 3.10 (2.80 ± 0.31)b |
aCalculated from EQE curves of the devices. bValues in parenthesis mean average PCE. |
Charge recombination characteristics
To further evaluate the charge transport characteristics of the active blends in single-carrier devices, J–V characteristics of the electron- and hole-only devices were analyzed with a well-known space-charge-limited-current model [27]. The structures of the devices employed were ITO/SnO/active layer/LiF/Al and ITO/PEDOT:PSS/active layer/Au for the electron- and hole-only devices, respectively. The characteristic J–V curves of the single-carrier devices are shown in Figure S2 and Table S2 in the ESI. The electron (µe) and hole (µh) mobilities of the PBCl-MTQF:Y6 device were measured to be 1.8 ⋅ 10−4 and 3.2 ⋅ 10−4 cm2 V−1 s−1, whereas those of the PBCl-MTQCN:Y6 device were 1.2 ⋅ 10−4 and 2.0 ⋅ 10−4 cm2 V−1 s−1, respectively. The decreased charge transfer ability of the PBCl-MTQCN:Y6 device might have contributed to the lower JSC values. Owing to the high µe and µh values of PBCl-MTQF:Y6, high values of JSC and FF were observed, which might have promoted charge transfer in the device performance. To compare the charge recombination behaviors of the devices comprising PBCl-MTQF and PBCl-MTQCN, we measured the dependence of JSC and VOC on light intensity. Figures 4a and 4b show the JSC and VOC dependence curves as a function of light intensity, respectively. Based on the power-law relationship, the JSC vs. light intensity (Plight) can be described as JSC ∝ Plightα, where α is the power-law factor and reflects the tendency of bimolecular recombination [28]. The α value of approximately unity in the log–log plot of JSC vs. light intensity indicates weak bimolecular recombination under short-circuit conditions [29]. As shown in Figure 4a, the PBCl-MTQF and PBCl-MTQCN devices exhibited α values of 0.97 and 0.86, respectively. These results indicate the suppression of undesirable bimolecular recombination loss in the PBCl-MTQF device, whereas dominant bimolecular charge-carrier recombination loss was observed in the PBCl-MTQCN device during charge transfer.
The relationship between the VOC of the devices and light intensity can be expressed as Voc = (nkT/q) × ln[\(\frac{{J}_{ph}}{{J}_{o}}+1\)], where n is the ideality factor, k the Boltzmann constant, T the absolute temperature, and q the elementary charge. The slope from the VOC–light intensity curve provides information regarding the trap-assisted recombination loss within the device [30, 31]. As shown in Figure 4b, the devices comprising PBCl-MTQF and PBCl-MTQCN exhibited n values of 1.08 kT/q and 1.91 kT/q, respectively. The PBCl-MTQF device exhibited a lower n value, indicating reduced trap-assisted recombination during charge transfer. By contrast, the introduction of CN groups can significantly increase the population of trap-assisted recombination, thereby decreasing the charge mobility in the device. Weak bimolecular and trap-assisted recombination losses enable higher efficiencies in devices based on PBCl-MTQF.
To further evaluate the exciton dissociation and charge extraction properties, we analyzed the correlation between the photocurrent density (Jph) and effective voltage (Veff), where Jph = JL (current density under illumination) – JD (current density in dark) and Veff = V0 (voltage at Jph = 0) - Va (applied voltage) (Figure 4c). At Veff >> 2.0 V, the saturated Jsc values of devices PBCl-MTQF and PBCl-MTQCN with Y6 were calculated to be 19.43 and 11.67 mA cm−2, respectively (Figure 4c). Under the short-circuit conditions, the dissociation probability [P(E,T)] at the D/A interfaces was calculated to be 98.2% (PBCl-MTQF) and 94.6% (PBCl-MTQCN).32 Additionally, the maximum charge collection efficiency of the devices with PBCl-MTQF and PBCl-MTQCN were 70.1% and 22.7%, respectively. The high Jsc and PCE values of the PBCl-MTQF device was due to the efficient exciton dissociation and charge collection efficiency. In general, the device comprising PBCl-MTQF exhibited better charge recombination and charge extraction properties compared with the device comprising PBCl-MTQCN.
Morphology of blended films
To analyze the surface morphology of the active layer, atomic force microscopy (AFM) measurements were performed in the tapping mode, and the resultant images are shown in Figure 5. The polymer:Y6 blend films based on different polymers showed distinct morphological differences. A homogeneous spherical morphology was observed for the blend film comprising PBCl-MTQF, whereas the film comprising PBCl-MTQCN exhibited an irregular granular morphology. Consequently, the blend film comprising PBCl-MTQF exhibited a relatively uniform film and contained bicontinuous interpenetrating networks, as compared with the film comprising PBCl-MTQCN. The larger domain size of the film comprising PBCl-MTQCN yielded a high root-mean-square (RMS) surface roughness of 5.4 nm, compared with that of the film comprising PBCl-MTQF (RMS value of 3.1 nm). The introduction of CN-groups in the polymer chain resulted in the formation of larger DA domains, which hindered efficient exciton dissociation and charge transport.
To investigate the molecular orientation and crystallinity of the neat and blended films, grazing incidence X-ray scattering (GIWAXS) measurements were performed. Their GIWAXS patterns and corresponding line-cut profiles are shown in Figure 6. The corresponding GIWAXS parameters are listed in Table S3 in the ESI. The neat PBCl-MTQF film exhibited an extremely weak π–π stacking (010) peak at 1.54 Å−1 in the out-of-plane (OOP) direction and multiple lamellar packing (h00) diffraction peaks in the in-plane (IP) direction (Figure 6a). This suggests that the PBCl-MTQF film exhibited different packing modes with moderate crystalline features, indicating a moderate face-on orientation in favor of charge transport. By contrast, the neat PBCl-MTQCN film exhibited a relatively clear π–π stacking (010) peak at 1.51 Å−1 and multiple lamellar packing (h00) peaks in the OOP and IP directions, respectively (Figure 6b), indicating the stronger crystalline properties of PBCl-MTQCN compared with that of PBCl-MTQF in the pristine polymer state. Moreover, pristine PBCl-MTQF and PBCl-MTQCN films showed different crystal coherence length (CCL) of 6.25 and 7.67 Å, respectively, suggesting the stronger crystallinity of PBCl-MTQCN. The neat film of Y6 exhibited a strong π–π stacking diffraction peak in the OOP direction at 1.72 Å−1 (d = 3.65 Å−1), and two other diffraction peaks at q = 0.27 and 0.415 Å−1 in the IP direction (Figure S3 in ESI). This suggests the coexistence of two different ordered structures in Y6.
The GIWAXS analysis of the blended films revealed that both blend films exhibited a lamellar diffraction peak (100) along the IP direction and a clear π–π stacking diffraction peak (010) in the OOP direction (Figures 6c and 6d). The GIWAXS pattern of the PBCl-MTQF:Y6 blend film showed a dominant diffraction peak for Y6 (Figure S3 in ESI). These results agreed relatively well with those of the pristine PBCl-MTQF film as compared with those of PBCl-MTQCN. Hence, a more homogeneous mixing between PBCl-MTQF and Y6 can be expected in the blend film, which is consistent with the AFM results (Figure 5a). The CCL values of the pristine films confirmed the strong internal π–π stacking in PBCl-MTQCN compared with that of PBCl-MTQF, which indicates a stronger intramolecular interaction in PBCl-MTQCN. By contrast, the blends of PBCl-MTQF:Y6 showed an enhanced crystalline phase with coherence to the pristine Y6 diffraction peaks; this yielded a more preferable face-on molecular orientation packing, which is advantageous for charge transport.