Wenjing
Xu
a,
Xiong
Li
*b,
Sang Young
Jeong
c,
Jae Hoon
Son
c,
Zhengji
Zhou
*d,
Qiuju
Jiang
e,
Han Young
Woo
c,
Qinghe
Wu
e,
Xixiang
Zhu
a,
Xiaoling
Ma
a and
Fujun
Zhang
*a
aKey Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing Jiaotong University, 100044, Beijing, China. E-mail: fjzhang@bjtu.edu.cn
bDepartment of Physics, Beijing Technology and Business University, 100048, Beijing, China. E-mail: lixiong@btbu.edu.cn
cOrganic Optoelectronic Materials Laboratory, Department of Chemistry, College of Science, Korea University, 02841, Seoul, Republic of Korea
dKey Lab for Special Functional Materials, Ministry of Education, National and Local Joint Engineering Research Center for High-Efficiency Display and Lighting Technology, and School of Materials, Henan University, 475004, Kaifeng, Henan Province, China. E-mail: zzj@henu.edu.cn
eDepartment of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong, Shantou University, 515063, Guangdong, China
First published on 1st March 2022
Layer-by-layer polymer solar cells (LbL-PSCs) were prepared with PNTB6-Cl as the donor and Y6 as the acceptor by a sequential spin-coating method. Two solvent additives DPE and DFB were individually incorporated into PNTB6-Cl chlorobenzene solution and Y6 chloroform solution. A PCE of 17.53% was achieved for the optimal LbL-PSCs with two solvent additives, which is much larger than the PCE of 16.38% for the LbL-PSCs without solvent additives. Over 7% PCE enhancement can be realized by individually employing solvent additives in donor and acceptor layers, resulting from the simultaneously enhanced open circuit voltage (VOC) of 0.88 V, short circuit current density (JSC) of 26.63 mA cm−2 and fill factor (FF) of 74.83%. The photogenerated exciton distribution, charge transport and collection in the LbL-PSCs can be optimized by employing different solvent additives in donor and acceptor solutions. Meanwhile, the efficient energy transfer from PNTB6-Cl to Y6 can provide an additional channel for improving the exciton utilization efficiency through exciton dissociation at PNTB6-Cl/Y6 interfaces. Meanwhile, the PCEs of LbL-PSCs are better than those of bulk heterojunction PSCs with the same materials and solvent additives, indicating the great potential of LbL-PSCs for commercial application.
In this work, a series of LbL-PSCs and BHJ-PSCs were prepared by employing PNTB6-Cl as the donor and Y6 as the acceptor based on the normal structures of ITO/PEDOT:PSS/PNTB6-Cl/Y6/PNDIT-F3N/Ag and ITO/PEDOT:PSS/PNTB6-Cl:Y6/PNDIT-F3N/Ag, respectively. The solvent additives DPE with a boiling point (BP) of 259 °C and DFB with a BP of 90.4 °C were selected to optimize the molecular arrangement in BHJ and LbL active layers. The DPE was incorporated into PNTB6-Cl in chlorobenzene solution and DFB was incorporated into Y6 in chloroform solution for optimizing the donor and acceptor layers, respectively. The PNTB6-Cl chain arrangement should be optimized during the DPE slow volatilization process. The DFB with a low BP will suffer a rapid volatilization to adjust a small molecular acceptor arrangement, leading to more efficient electron transport channels, which can be confirmed from the enhanced FF of PSCs with solvent additives. The chemical structures of used materials are exhibited in Fig. 1a. The PNTB6-Cl film can be kept well while spin-coating Y6 solution on it because the polymer PNTB6-Cl is hardly dissolved in chloroform.29 The absorption spectra of LbL films without or with solvent additives were measured and are shown in Fig. 1b. The refractive index (n) and extinction coefficient (k) of LbL films were measured to investigate the effect of solvent additives on the photogenerated exciton distribution and are exhibited in Fig. 1c. The n and k of LbL films are slightly increased by incorporating appropriate solvent additives, indicating the enhanced photon harvesting ability of LbL films due to the optimized molecular arrangement. The optimal LbL-PSCs exhibit a PCE of 17.53%, benefiting from the simultaneously enhanced open circuit voltage (VOC) of 0.88 V, short circuit current density (JSC) of 26.63 mA cm−2 and fill factor (FF) of 74.83%. The PCE of the optimal LbL-PSCs is much larger than 16.38%, 16.61% and 16.65% obtained for the LbL-PSCs without and with DPE or DFB as the solvent additive, which should result from the enhanced photon harvesting and well optimized molecular arrangement in the PNTB6-Cl and Y6 layers. More than 7% PCE improvement can be achieved by employing the two solvent additive strategy, benefiting from the individually layered optimization on donor and acceptor layers. Although the PCEs of BHJ-PSCs are slightly increased from 14.46% to 14.81% by incorporating DPE and DFB solvent additives in the blended chlorobenzene solutions, they are still much lower than 17.53% for the optimized LbL-PSCs.
Structure | Active layer | J SC | Cal. J SC | V OC | FF | PCE (Ave. ± Dev.) | R S | R SH |
---|---|---|---|---|---|---|---|---|
(mA cm−2) | (mA cm−2) | (V) | (%) | (%) | [Ω cm2] | [Ω cm2] | ||
The average and deviation of PCEs were calculated from 10 individual cells. | ||||||||
BHJ | D:A | 23.29 | 22.87 | 0.85 | 72.08 | 14.46 (14.35 ± 0.12) | 2.06 | 237 |
D:A + DPE + DFB | 23.78 | 23.56 | 0.85 | 73.28 | 14.81 (14.68 ± 0.13) | 2.01 | 267 | |
LbL | D/A | 26.29 | 25.26 | 0.85 | 73.25 | 16.36 (16.23 ± 0.14) | 1.80 | 342 |
D + DPE/A | 26.53 | 25.39 | 0.85 | 73.64 | 16.61 (16.53 ± 0.17) | 1.38 | 359 | |
D/A + DFB | 26.51 | 25.31 | 0.87 | 72.16 | 16.65 (16.47 ± 0.15) | 1.81 | 340 | |
D + DPE/A + DFB | 26.63 | 25.64 | 0.88 | 74.83 | 17.53 (17.34 ± 0.19) | 1.24 | 399 |
To further investigate the underlying reason for PCE improvement of LbL-PSCs by solvent additives, the J–V curves of all LbL-PSCs were measured in the dark and one standard simulated solar light illumination under bias; the photogenerated current density (JPH) is equal to the photocurrent density (JL) minus dark current density (JD), expressed as JPH = JL–JD. The effective voltage (Veff) is defined as the voltage at JPH = 0 minus the applied bias. The JPHversus effective bias (JPH–Veff) curves of all LbL-PSCs were measured and are exhibited in Fig. 3a. The photogenerated current density of LbL-PSCs can be defined as JPH*, JPH& and JSAT under the short-circuit condition, the maximal output-power condition and the saturated state condition, respectively. The exciton dissociation efficiency (ηD) and charge collection efficiency (ηC) can be well evaluated from the ratios of JPH*/JSAT and JPH&/JSAT, respectively.33,34 The detailed values of all LbL-PSCs are listed in Table 2. The ηD and ηC of the optimal LbL-PSCs are 96.69% and 86.34%, which are larger than 95.57% and 82.32% for the LbL-PSCs without any solvent additive. The enhanced ηD and ηC can well support the PCE improvement in optimal LbL-PSCs. The JPH of LbL-PSCs can rapidly arrive at the saturated states, also indicating the more efficient charge collection in LbL active layers processed with solvent additives. The exciton dynamic process between PNTB6-Cl and Y6 was investigated according to the photoluminescence (PL) spectra of neat and layer-by-layer films without or with solvent additives, and the corresponding PL spectra are shown in Fig. 3b. It is apparent that PL emission of PNTB6-Cl can be sufficiently quenched in the PNTB6-Cl/Y6 layer, indicating efficient exciton dissociation or energy transfer from PNTB6-Cl to Y6. The apparent spectral overlap between the PL spectrum of PNTB6-Cl and the absorption spectrum of Y6 can be observed from the image of Fig. 3b, suggesting the efficient energy transfer from PNTB6-Cl to Y6 according to the FÖrster energy principle.35–38 The photogenerated excitons on PNTB6-Cl near the ITO electrode can transfer their energy to Y6; the excitons generated via energy transfer on Y6 near PNTB6-Cl/Y6 interfaces will be dissociated into free charge carriers. The efficient energy transfer from PNTB6-Cl to Y6 will provide another channel for improving the PCE of LbL-PSCs.
Active layer | J SAT (mA cm−2) | J PH* (mA cm−2) | J PH & (mA cm−2) | η D (%) | η C (%) |
---|---|---|---|---|---|
D/A | 27.52 | 26.30 | 22.65 | 95.57 | 82.32 |
D + DPE/A | 27.63 | 26.53 | 22.95 | 96.02 | 83.06 |
D/A + DFB | 27.59 | 26.51 | 22.93 | 96.09 | 83.10 |
D + DPE/A + DFB | 27.82 | 26.87 | 24.02 | 96.69 | 86.34 |
Transient photovoltage (TPV) is a convenient method to analyze the charge recombination degree in PSCs by evaluating the photocarrier lifetime (τpc) under open-circuit conditions.39–41 The TPV curves of all LbL-PSCs were measured under a white LED with a light intensity of 720 W m−2 and are shown in Fig. 3c. The τpc in the optimal LbL-PSCs is about 41.78 μs, which is much longer than 24.06 μs in LbL-PSCs without solvent additives, 24.49 μs in LbL-PSCs with the solvent additive DPE and 39.35 μs in LbL-PSCs with the solvent additive DFB. The prolonged τpc in the optimal LbL-PSCs further proves the weakest charge recombination, which should be beneficial to charge transport and collection in the corresponding LbL-PSCs. Under a short circuit condition, the transient photocurrent (TPC) of all LbL-PSCs were measured to obtain the charge extraction time (τext).42–45 The TPC curves of all LbL-PSCs are exhibited in Fig. S2 (ESI†). The τext in optimal LbL-PSCs is about 0.207 μs, which is much shorter than 0.285 μs in LbL-PSCs without solvent additives, 0.239 μs in LbL-PSCs with the solvent additive DPE and 0.220 μs in LbL-PSCs with the solvent additive DFB. The relatively short τext in the optimal LbL-PSCs reveals that the appropriate solvent additives can enhance charge transport and collection in the corresponding LbL-PSCs. It is well known that charge carrier mobility (μ) will directly influence charge transport and recombination in the active layers, which can be estimated from the photo-CELIV measurements.46–48 The photo-CELIV curves of all LbL-PSCs were measured under a white LED with light intensity of 720 W m−2 and are exhibited in Fig. 3d. The charge mobility in the LbL active layers can be estimated based on the following equation: , where d is the active layer thickness, A is the ramp rate, tmax is the time when the extracted current reaches its maximum value, j(0) represents the dark capacitive current, and Δj is the transient current peak height. The factor 1 + 0.36 Δj/j(0) in the formula is an empirical correction accounting for the redistribution of the electric field. As seen from Fig. 3d, the relatively small Δj is conducive to obtaining a large μ in the optimal LbL-PSCs. The calculated μ in the optimal LbL-PSCs is about 1.843 × 10−4 cm2 V−1 s−1, which is larger than 1.428 × 10−4 cm2 V−1 s−1 in LbL-PSCs without solvent additives, 1.584 × 10−4 cm2 V−1 s−1 in LbL-PSCs with the solvent additive DPE and 1.755 × 10−4 cm2 V−1 s−1 in LbL-PSCs with the solvent additive DFB. The enhanced μ in LbL-PSCs should be beneficial to suppress charge recombination and improve charge collection, resulting in the relatively large FF of 74.83% for the optimal LbL-PSCs. The space charge limited current (SCLC) model was further employed to investigate hole mobility (μh) and electron mobility (μe) values based on the hole-only and electron-only devices.49–51 The detailed ln(JL3/V2) versus (V/L)0.5 curves of hole-only and electron-only devices are exhibited in Fig. S3 (ESI†); the μh, μe and μh/μe in the LbL active layers without or with solvent additives are summarized in Table 3. It is apparent that the μh and μe in the LbL active layers can be slightly increased by incorporating appropriate solvent additives. The μh/μe in the LbL active layers with two solvent additives is closest to 1, indicating the more balanced hole and electron mobility as confirmed from the relatively large FF of 74.83% in the optimal LbL-PSCs.52
Active layer | TPV (μs) | TPC (μs) | μ (cm−2 V−1 s−1) | μ h (cm−2 V−1 s−1) | μ e (cm−2 V−1 s−1) | μ h/μe |
---|---|---|---|---|---|---|
D/A | 24.06 | 0.285 | 1.42 × 10−4 | 4.15 × 10−4 | 3.20 × 10−4 | 1.30 |
D + DPE/A | 24.49 | 0.239 | 1.58 × 10−4 | 5.54 × 10−4 | 4.50 × 10−4 | 1.23 |
D/A + DFB | 39.35 | 0.220 | 1.75 × 10−4 | 7.16 × 10−4 | 6.12 × 10−4 | 1.17 |
D + DPE/A + DFB | 41.78 | 0.207 | 1.84 × 10−4 | 9.13 × 10−4 | 8.52 × 10−4 | 1.07 |
To investigate the effects of solvent additives on the morphology, AFM was employed to characterize morphology of the neat and layer-by-layer films without or with solvent additives, as exhibited in Fig. S4 (ESI†). It is apparent that the root-mean-square (RMS) roughness of neat and layer-by-layer films can be slightly increased by incorporation of solvent additives, and the detailed RMS values are listed in the corresponding AFM images. The enhanced RMS of PNTB6-Cl with the DPE layer may be conducive to enlarging PNTB6-Cl/Y6 interfaces for exciton dissociation.53 The AFM images of PNTB6-Cl + DPE/Y6 + DFB and PNTB6-Cl/Y6 films are exhibited in Fig. 4a. The RMS values of LbL films are increased from 0.618 nm to 0.702 nm by incorporation of solvent additives, which may result from the molecular crystallization induced by solvent additives.54,55 GIWAXS characterization was carried out to further investigate molecular crystallization induced by solvent additives. The 2D-GIWAXS images and the corresponding out-of-plane (OOP) and in-plane (IP) profiles of PNTB6-Cl + DPE/Y6 + DFB and PNTB6-Cl/Y6 films are displayed in Fig. 4b and c. The PNTB6-Cl/Y6 films exhibit a lamellar stacking peak at 0.28 Å−1 in the IP direction and π–π stacking peak at 1.71 Å−1 in the OOP direction, implying the existence of face-on molecular orientation in LbL films without solvent additives.56–58 The OOP (010) and IP (100) diffraction peak intensity of the PNTB6-Cl + DPE/Y6 + DFB films are obviously enhanced by incorporation of solvent additives, indicating the more ordered face-on orientation in the LbL films. The improved molecular arrangement is beneficial to charge transport in the optimal LbL active layers, which can be confirmed from the relatively large μh and μe in comparison with the LbL active layers without solvent additives. The more ordered molecular arrangement in LbL active layers is conducive to charge transport and suppresses charge recombination, resulting from the enhanced performance of LbL-PSCs processed with two solvent additives.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/d2tc00024e |
This journal is © The Royal Society of Chemistry 2022 |