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Letter
Dual Functional Molecular Imprinted Polymers-Modified Organometal Lead Halide Perovskite: Synthesis and Application for Photoelectrochemical Sensing of Salicylic Acid Xiaoyu Yang, Yuan Gao, Zhengping Ji, Li-Bang Zhu, Chen Yang, Ying Zhao, Yun Shu, Dangqin Jin, Qin Xu, and Wei-Wei Zhao Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.9b01739 • Publication Date (Web): 17 Jul 2019 Downloaded from pubs.acs.org on July 17, 2019
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Analytical Chemistry
Dual Functional Molecular Imprinted Polymers-Modified Organometal Lead Halide Perovskite: Synthesis and Application for Photoelectrochemical Sensing of Salicylic Acid Xiaoyu Yang,1,2,3 Yuan Gao,2,3 Zhengping Ji,1 Li-Bang Zhu,2 Chen Yang,1 Ying Zhao,1 Yun Shu,1 Dangqin Jin,1 Qin Xu,1,* and Wei-Wei Zhao2,* 1School
of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China 3These authors contributed equally to this work. *To whom correspondence should be addressed. *E-mail:
[email protected] or
[email protected] *E-mail:
[email protected] 2State
ABSTRACT: This work reports the synthesis of dual functional molecularly imprinted polymers (MIPs)-modified organometal lead halide perovskite (CH3NH3PbI3) and its application for photoelectrochemical (PEC) bioanalysis of salicylic acid (SA). Specifically, the CH3NH3PbI3 was encapsulated into the MIPs via a simple thermal polymerization process on the indium tin oxide (ITO) glass, and the as-obtained MIPs/CH3NH3PbI3/ITO electrode was characterized by various techniques, which revealed that the MIPs could not only stabilize CH3NH3PbI3 but also improve the electron-hole separation efficiency of CH3NH3PbI3 under light illumination. In the detection of model analyte SA, the PEC sensor, with numerous amounts of recognition sites to SA, exhibited desirable performance in terms of good sensitivity, selectivity, stability, and feasibility for real sample analysis. This work not only featured the use of MIPs/CH3NH3PbI3 for PEC detection of SA, but also provided a new horizon for the design and implementation of functional polymers/perovskite materials in the field of PEC sensors and biosensors.
INTRODUCTION Herein we report the synthesis of dual functional molecularly imprinted polymers (MIPs)-modified organometal lead halide perovskite (CH3NH3PbI3) and its application toward photoelectrochemical (PEC) bioanalysis of salicylic acid (SA). Currently, the study on functional semiconductors represents an attractive frontier in state-of-the-art PEC bioanalysis.1-3 Among various candidates, CH3NH3PbI3 is of special interest because of its high absorption coefficient for visible light, high charge-carrier mobility, small excitation binding energy and long-range exciton diffusion lengths. It has extensively applications in optoelectronic devices, solar cells, lasers and light-emitting diode due to its excellent optical and electrical properties.4,5 However, such a potential has seldom been constructed PEC sensors except the work reported by Pang et al,6,7 probably due to the inferior stability of CH3NH3PbI3 in humid environments and the inconvenience of its surface functionalization with recognition probes. It is desirable to seek an advanced strategy to overcome these two issues simultaneously. Molecularly imprinted polymer is a synthetic antibody prepared by polymerizing functional and crosslinking monomers around target molecules. Because of its good stability, robustness, and easy preparation, MIPs have been employed as recognition elements in manifold analytical areas including constructing PEC sensors.8-10 Given the stability of perovskite materials has been demonstrated to be enhanced by addition of a polymer into the precursor solutions or formation of an ultra-thin interface polymer layer,11 we hypothesize that the proper encapsulation of CH3NH3PbI3 into the MIPs matrix would ideally break the above mentioned
bottlenecks. Unfortunately, to date no effort has been devoted to shed light on such possibility. With these motivations, this work has firstly designed, fabricated, characterized, and applied the dual functional MIPs-modified CH3NH3PbI3 toward PEC bioanalysis of SA, which to our knowledge has not been reported (see the Supporting Information for Experimental Section). Specifically, as shown in Scheme 1, the MIPs precursors were prepared via a thermally initiated free radical polymerization with SA as the template, methacrylic acid (MAA) as the monomers, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and azobisisobutyronitile (AIBN) as the initiator, respectively. The MIPs/CH3NH3PbI3 was prepared by using MIPs precursor solution as polymer additives during film deposition of CH3NH3PbI3 on the indium tin oxide (ITO) glass. This process controlled the crystal growth and morphology, reduced the defect density of the film. After removal of the template, the specific imprinting sites for SA will be remained on the MIPs/CH3NH3PbI3 film. In the PEC detection, SA occupied the imprinting sites through shape and hydrogen bond recognition. These steric hindrances blocked the electron transfer between the electrode and O2, intimately affecting the photocurrent responding. This work features the synthesis of dual functional MIPs-modified CH3NH3PbI3 for PEC bioanalysis and is envisioned to ignite more interest in the exploration of advanced MIPs- and perovskite-based PEC bioanalysis. Scheme 1. Fabrication of (A) CH3NH3PbI3 Precursor Solution, (B) MIPs Precursor Solution, (C) MIPs-Modified
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CH3NH3PbI3 PEC Sensor for SA Detection, and (D) Photocurrent Generation Mechanism
RESULTS AND DISCUSSION To proof the concept, MIPs/CH3NH3PbI3 (with SA)/ITO and control samples without MIPs or SA were initially prepared and then characterized by scanning electron microscopy (SEM) and X-ray powder diffraction spectroscopy (XRD). As shown in Figure S1A, the ITO glass possessed a rather smooth surface. On the surface of ITO, we then prepared CH3NH3PbI3, non-imprinted polymers (NIPs)/CH3NH3PbI3 and MIPs/CH3NH3PbI3 (with SA), respectively. As shown in Figure 1A, deep grain boundaries (GBs) between neighboring particles with different sizes were found for the pristine CH3NH3PbI3 films (with no MIP inside). These GBs contain a large amount of dangling bonds which usually lead to non-radiative recombination of electron and holes that reduce the photovoltaic performance of CH3NH3PbI3. Such non-encapsulated film is instable.12 Figure 1A inset showed that the synthesized CH3NH3PbI3 opted rod like structure because the internal complex or adduct formation of PbI2 with the methylamine group in DMF preferred one direction arrangement of the resulted perovskite.13 For NIPs/CH3NH3PbI3/ITO, as shown in the Figure 1B and inset, the grain size of the formed perovskite increased and a thin NIP film was found to cover the surface. The presence of NIPs didn’t change the growth orientation of CH3NH3PbI3. With the further addition of SA, as shown in the Figure 1C and inset, a thin film was also formed on the surface of CH3NH3PbI3 but with a little decrease of the grain size. As compared to CH3NH3PbI3/ITO, NIPs/CH3NH3PbI3 or MIPs/CH3NH3PbI3 (with SA) showed shallow GBs along with a reduced roughness in the film, which would reduce the trapstate density and improve the carrier lifetime.12 This morphological changes were ascribed to the varied nucleation and crystallization processes of CH3NH3PbI3 in the presence of the polymer precursor. Specifically, MAA could boost the nucleation and slow down the crystal growth of perovskite through the intermediate adduct formation between MAA and PbI2.14 The abundance of nuclei formed and dispersed uniformly on ITO then grew into larger grains with few defects and ultimately coalesced into a dense poly-crystal film under thermal treatment. The polymers could also act as a surface encapsulation layer to improve the stability of perovskite. The CH3NH3PbI3 particles formed in the presence of NIPs were larger than that formed in the presence of MIPs. This may be due to the presence of SA in the MIPs precursor. The interactions between SA, MAA, and lead ions would
influence the intermediate adduct formation between methyl MAA and Pb2+. In this case, the grain size of the formed MIPs/CH3NH3PbI3 (with SA) decreased. Especially, comparison of Figure 1A inset and Figure 1C inset would find that the individual MIPs/CH3NH3PbI3 (with SA) rods were separated with each other. Such a structure has large specific surface area and thus with enhanced absorption sites, the asformed porosity would also improve the accessibility of the electrolyte to the electrode surface. Incidentally, for clarity, the magnified SEM images of Figure 1B and 1C were included in the Supporting Information. The XRD patterns of the ITO (curve a), MIPs/ITO (with SA) (curve b), CH3NH3PbI3/ITO (curve c), and MIPs/CH3NH3PbI3 (with SA)/ITO (curve d) samples were recorded and shown in Figure 1D. Detailed discussion about the XRD patterns was included in the Supporting Information. Apparently, except a little decrease of the peak intensity at 40.53° for MIPs/CH3NH3PbI3 (with SA)/ITO, there was no difference between CH3NH3PbI3/ITO and MIPs/CH3NH3PbI3 (with SA)/ITO. These results indicated that the presence of MIPs didn’t change the structure of the obtained CH3NH3PbI3 but influenced its growth direction a little which has been verified by SEM. The photoluminescence (PL) and intensitymodulated photovoltage spectroscopies (IMVS) were used to characterize the migration and separation of the photo-induced electron-hole pairs and study the effect of polymers on the performance of perovskites.15 Figure 1E showed the steadystate PL spectra of CH3NH3PbI3 and MIPs/CH3NH3PbI3 (with SA) films. Under a laser excitation wavelength at 470 nm, an emission peak centered at 766 nm was observed for CH3NH3PbI3 (curve a), as reported by Lee et al..16 Emission peak from the MIPs/CH3NH3PbI3 (with SA) demonstrated a red-shifting of 4 ± 1 nm (curve b), which may be due to the residual aggregation of CH3NH3PbI3 in the presence of MIPs. Besides, the PL emission of MIPs/CH3NH3PbI3 (with SA) was more intense. This meant that the non-radiative recombination was reduced in the polymer containing sample.17 MIP is a polymer with –COOH and atoms with high electronegativity such as O. They could form the coordination interaction with Pb and hydrogen bonds with CH3NH2+. These interactions ensure the homogeneity of the precursor distribution in the solution, enhance the interaction between grains, passivate the GBs, and reduced the defect density in the perovskite film. All of these factors suppressed the electron-hole recombination, which in turn improved the electron-hole separation efficiency of CH3NH3PbI3 under light illumination.17 Figure 1F shows the typical Nyquist plots of IMVS response curves for the CH3NH3PbI3 (curve a) and MIPs/CH3NH3PbI3 (with SA) (curve b). As illustrate, both IMVS plots displayed a semicircle i. The equation tr = 1/2fr was used to determine the recombination time where fr is the characteristic frequency at the minimum of the IMVS imaginary component.18 The recombination time of the CH3NH3PbI3 film was 172.45 ms, but it increased to 201.32 ms in the presence of MIPs. The longer photo-excited electron lifetime of MIPs/CH3NH3PbI3 (with SA) film further indicated that the recombination of electrons and hole in CH3NH3PbI3 film was suppressed in the presence of MIPs. This result was similar to the other polymers modified perovskites.19 The long life time of charge carriers assured efficient excitation, dissociation and transport of electrons and holes before their decay to the ground state or react with target molecular.20
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Figure 1. SEM images of (A) CH3NH3PbI3/ITO, (B) NIPs/CH3NH3PbI3/ITO, (C) MIPs/CH3NH3PbI3 (with SA)/ITO. (D) XRD spectra of the ITO (curve a), MIPs (with SA)/ITO (curve b), CH3NH3PbI3/ITO (curve c) and MIPs/CH3NH3PbI3 (with SA)/ITO (curve d). (E) Steady-state PL spectra of CH3NH3PbI3 (curve a) and MIPs/CH3NH3PbI3 (with SA) (curve b). (F) IMVS of CH3NH3PbI3 (with SA)/ITO (curve a) and MIPs/CH3NH3PbI3 (with SA)/ITO (curve b).
To reveal the light-harvesting properties, the PEC behaviors of MIPs/ITO, CH3NH3PbI3/ITO, NIPs/CH3NH3PbI3/ITO and MIPs/CH3NH3PbI3/ITO were then studied by I−t tests upon intermittent light irradiation. Figure 2A shows that CH3NH3PbI3/ITO (curve a), MIPs/CH3NH3PbI3/ITO (curve b) and NIPs/CH3NH3PbI3/ITO (curve c) had significant responses upon light illumination at zero bias potential. The photocurrents of MIPs/CH3NH3PbI3/ITO and NIPs/CH3NH3PbI3/ITO were further checked in an EA solution in the absence of SA (the detection solution) after they recognized 1.0 nM SA for 3 min in the incubation solution. The photocurrent on NIPs/CH3NH3PbI3 (curve d) changed slightly, but the response of MIPs/CH3NH3PbI3 decreased about 1.4 μA (curve e). The photocurrent change on MIPs/CH3NH3PbI3 was approximately 14-fold of that on NIPs/CH3NH3PbI3. This remarkable photocurrent reduction indicated the good sensitivity and specific molecular recognition capability of MIPs/CH3NH3PbI3 for SA. The recognition sites on the surface of MIPs/CH3NH3PbI3/ITO could selectively adsorb SA and thus hindered the electron transfer. In control, the responsiveness of MIPs was also tested, and almost no photocurrent was generated under the light illumination on MIPs/ITO (curve f), indicating that CH3NH3PbI3 was served as a light-responsive material. The detailed photoelectrochemical sensing mechanism was supplied in the supporting information (Scheme S1). After a serial of the experimental optimization as shown in Figure S3, the developed MIPs/CH3NH3PbI3 sensor was used to detect different concentrations of SA. Figure 2B shows that the photocurrent decreased to the concentration of SA. A linear relationship between the photocurrent changes (ΔI) and the logarithm of SA concentration from 7.0 × 10−13 to 1.0 × 10−8 M was acquired (Figure 2B inset). The limit of detection (LOD) and the limit of quantitation (LOQ) of the proposed PEC sensor were was 1.95 × 10-13 M and 6.51 × 10-13 M, respectively. Table S1 listed the performances of some reported work for the detection of SA. Compared with them, the LOD of this PEC sensor was comparable or better. Some chemicals including benzoic acid (BA), sulfosalicylic acid (SSA), 2,5-dihydroxybenzoic acid (2,5-DHBA) were selected to investigate the selectivity of the PEC sensor. The influences of these compounds were investigated by analyzing a standard solution of 1.0 nM SA to which 10.0 nM interfering species was added. Figure 2C shows the interferents did not cause any
observable interference to the response to SA. The results indicated that the interferences coexisting in the sample matrix didn’t affect the determination of SA. The shape-specific imprinted cavities and distributed functional groups in the MIPs film could help to distinguish SA from other species through the cavity size, the electrostatic interactions and hydrogen bonds between SA and the binding sites. Incidentally, the response of NIPs/CH3NH3PbI3 to SA has also been studied. As shown in Figure S3A and S3B, the NIPs/CH3NH3PbI3/ITO exhibited very poor sensitivity and selectivity to SA, indicating the good imprinting efficiency of MIPs/CH3NH3PbI3. The intra-assay RSD of MIPs/CH3NH3PbI3 for determining of SA with five replicate measurements was 4.14 %, while the inter-assay RSD for measuring 0.1 nM SA with five same PEC sensors made under the same conditions independently was 5.33 %. It means that the proposed PEC sensor has an acceptable reproducibility. Figure 2D shows the stability of the PEC sensor under continuous detection. After 30 consecutive recycle experiments, there was no obvious decrease of the photocurrent, indicating the good stability of the PEC sensor.
Figure 2. (A) Photocurrent responses of CH3NH3PbI3/ITO (curve a), MIPs/CH3NH3PbI3/ITO (curve b) and NIPs/CH3NH3PbI3/ITO (curve c) after removal SA, NIPs/CH3NH3PbI3/ITO (curve d) and MIPs/CH3NH3PbI3/ITO (curve e) after the incubation of 10-9 M SA, MIPs/ITO (curve f). (B) Photocurrent of the MIPs/CH3NH3PbI3/ITO PEC to variable concentrations of SA. Inset: Linear calibration curves for MIPs/CH3NH3PbI3/ITO (C) Selectivity of MIPs/CH3NH3PbI3/ITO to SA and the interferences. The concentration of SA was 1.0 nM and the interferences were 10.0 nM. (D) Stability of MIPs/CH3NH3PbI3. The detection solution was EA containing 0.05 M TBAPF6.
The aspirin tablets were then used as the real sample to test the feasibility of the as-prepared PEC sensor for SA detection. The SA amount in aspirin tablet determined by the PEC method was 39.23 mg, and that determined by fluorescence method was 37.71 mg. The data obtained by the two methods have been analyzed by F-test and t-test. The calculated F value and t value were 2.49 and 1.09, respectively. The two values were less than the theoretical F value (F6,6, 0.05=4.28) and t value (t0.05, 10= 2.23). No significant differences in both F-test and t- test were observed for the two methods, suggesting the feasibility of the PEC sensor for real sample analysis. Furthermore, the spike-and-recovery experiments were also performed to study the practicality of the present method. The results listed in Table S2 confirmed the practicability of the method for real sample analysis.
CONCLUSIONS In summary, on the basis of CH3NH3PbI3 strengthened by functional MIPs, this work proposed a sensitive PEC strategy for the detection of SA. Due to unique characteristics existed
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in the composite of MIPs/CH3NH3PbI3, the MIPs as a protecting layer could improve the stability of CH3NH3PbI3 and also to improve the electron-hole separation efficiency of CH3NH3PbI3 under light illumination. Exemplified by SA as a model target, desirable performances in terms of good sensitivity, selectivity and stability were demonstrated in the PEC detection application. The feasibility of the as-prepared PEC sensor for real sample was also manifested. Due to the simple and cost-effective fabrication process, as well as the quick and easy detection process, this kind of PEC sensor holds great promise for the applications in the field of MIPsbased detection. Given the large families of MIPs and perovskite materials, we further envision the innovative synergy of these materials and their application for advanced PEC sensing and biosensing.
ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.analchem…. Experimental section, XRD discussions, original SEM images, PEC mechanism scheme and discussion, experimental optimizations, linear calibration curve and selectivity of NIPs/CH3NH3PbI3@ITO, comparison of analytical performances, and the recovery test (PDF)
AUTHOR INFORMATION Corresponding Author *Q.X.: E-mail:
[email protected]. *W.W.Z.: E-mail:
[email protected].
ORCID Qin Xu: 0000-0001-9311-213X Wei-Wei Zhao: 0000-0002-8179-4775
Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We gratefully thank National Natural Science Foundation of China (21675140, 21675080, 21575124 and 21705141), the Natural Science Foundation of Jiangsu Province (Grant BK20170073 and BK20150453), the 14th Six talent peaks project in Jiangsu Province (SWYY-085), Higher Education Outstanding Scientific and Technological Innovation Team of Jiangsu Province (2017-6), Young academic leaders of Jiangsu Province (2018), the project funded by the PAPD and TAPP.
REFERENCES (1) Zhu, Y. H.; Yan, K.; Xu, Z. W.; Wu, J. N.; Zhang, J. D. Cathodic "signal-on" photoelectrochemicalaptasensor for chloramphenicol detection using hierarchical porous flower-like BiBiOI@C composite. Biosens. Bioelectron.2019, 131, 79-87. (2) Li, L.; Zheng, X. X.; Huang, Y. Z.; Zhang, L. N.; Cui, K.; Zhang, Y.; Yu, J. H. Addressable TiO2 nanotubes functionalized paper-based cyto-sensor with photocontrollable switch for highlyefficient evaluating surface protein expressions of cancer cells. Anal. Chem. 2018, 90, 13882-13890. (3) Fan, D. W.; Liu, X.; Bao, C. Z.; Feng, J. H.; Wang, H.; Ma, H. M.; Wu, D.; Wei, Q. A novel sandwich-type photoelectrochemicalimmunosensor based on Ru(bpy)32+ and Ce-CdS co-sensitized hierarchical ZnO matrix and dual-inhibited polystyrene@CuS-Ab2 composites. Biosens. Bioelectron.2019, 129, 124-131. (4) Geng, C.; Xu, S.; Zhong, H. Z.; Rogach, A. L.; Bi, W. G. Aqueous synthesis of methylammonium lead halide perovskite nanocrystals. Angew. Chem. Int. Edit.2018, 57, 9650-9654. (5) Tan, X.; Zhang, B.; Zou, G. Z. Electrochemistry and electrochemiluminescence of organometal halide perovskite
nanocrystals in aqueous medium. J. Am. Chem. Soc 2017, 139, 87728776. (6) Pang, X. H.; Qi, J. N.; Zhang, Y.; Ren, Y. Y.; Su, M. H.; Jia, B. X.; Wang, Y. G.; Wei, Q.; Du, B. Ultrasensitive photoelectrochemical aptasensing of miR-155 using efficient and stable CH3NH3PbI3 quantum dots sensitized ZnO nanosheets as light harvester. Biosens. Bioelectron. 2016, 85, 142-150. (7) Pang, X. H.; Zhang, Y.; Pan, J. H.; Zhao, Y. X.; Chen, Y.; Ren, X.; Ma, H. M.; Wei, Q.; Du, B. A photoelectrochemical biosensor for fibroblast-like synoviocyte cell using visible light-activated NCQDs sensitized-ZnO/CH3NH3PbI3. Biosens. Bioelectron. 2016, 77, 330338. (8) Gao, P.; Wang, H.; Li, P. W.; Gao, W. K.; Zhang, Y.; Chen, J. L.; Jia, N. Q. In-site synthesis molecular imprinting Nb2O5-based photoelectrochemical sensor for bisphenol A detection. Biosens. Bioelectron.2018, 121, 104-110. (9) Yang, X. M.; Li, X.; Zhang, L. Z.; Gong, J. M. Electrospun template directed molecularly imprinted nanofibers incorporated with BiOInanoflake arrays as photoactive electrode for photoelectrochemical detection of triphenyl phosphate. Biosens. Bioelectron.2017, 92, 61-67. (10) Shi, H. J.; Wang, Y. L.; Zhao, J. Z.; Huang, X. R.; Zhao, G. H. Cathodic photoelectrochemical detection of PCB101 in environmental samples with high sensitivity and selectivity. J Hazard. Mater.2018, 342, 131-138. (11) Zhao, Y. C.; Wei, J.; Li, H.; Yan, Y.; Zhou, W. K.; Yu, D. P.; Zhao, Q. A polymer scaffold for self-healing perovskite solar cells. Nat. Commun.2016, 7, 10228-10236 (12) Chu, Z. D.; Yang, M. J.; Schulz, P.; Wu, D.; Ma, X.; Seifert, E.; Sun, L. Y.; Li, X. Q.; Zhu, K.; Lai, K. J. Impact of grain boundaries on efficiency and stability of organic-inorganic trihalide perovskites. Nat. Commun.2017, 8, 2230-2238 (13) Horváth, E.; Spina, M.; Szekrényes, Z.; Kamarás, K.; Gaal, R.; Gachet, D.; Forró, L. Nanowires of methylammonium lead iodide (CH3NH3PbI3) prepared by low temperature solution-mediated crystallization. Nano Lett.2014, 14, 6761-6766. (14) Peng, J.; Khan, J. I.; Liu, W. Z.; Ugur, E.; Duong, T.; Wu, Y. L.; Shen, H. P.; Wang, K.; Dang, H.; Aydin, E.; Yang, X. B.; Wan, Y. M.; Weber, K. J.; Catchpole, K. R.; Laquai, F.; De Wolf, S.; White, T. P. A Universal double-side passivation for high open-circuit voltage in perovskite solar cells: role of carbonyl groups in poly (methyl methacrylate). Adv. Energy Mater.2018, 8, 1801208-1801216. (15) Zhao, Y. X.; Nardes, A. M.; Zhu, K. Solid-state mesostructured perovskite CH3NH3PbI3 solar cells: charge transport, recombination, and diffusion length. J. Phys. Chem. Lett.2014, 5, 490494. (16) Lee, Y. H.; Luo, J. S.; Son, M. K.; Gao, P.; Cho, K. T.; Seo, J. Y.; Zakeeruddin, S. M.; Grätzel, M.; Nazeeruddin, M. K. Enhanced charge collection with passivation layers in perovskite solar cells. Adv. Mater.2016, 28, 3966-3972. (17) Fakharuddin, A.; Seybold, M.; Agresti, A.; Pescetelli, S.; Matteocci, F.; Haider, M. I.; Birkhold, S. T.; Hu, H.; Giridharagopal, R.; Sultan, M.; Mora-Sero, I.; Di Carlo, A.; Schmidt-Mende, L. Perovskite-polymer blends influencing microstructures, nonradiative recombination pathways, and photovoltaic performance of perovskite solar cells. ACS Appl. Mater. Interfaces 2018, 10, 42542−42551. (18) Guillén, E.; Ramos, F. J.; Anta, J. A.; Ahmad, S. Elucidating transport-recombination mechanisms in perovskite solar cells by small-perturbation techniques. J. Phys. Chem. C 2014, 118, 2291322922. (19) Lee, T. W.; Kim, M. G.; Kim, S. Y.; Park, S. H.; Kwon, O.; Noh, T.; Oh, T. S. Hole-transporting interlayers for improving the device lifetime in the polymer light-emitting diodes. Appl. Phys. Lett. 2006, 89, 123505-123508. (20) Yamada, Y.; Nakamura, T.; Endo, M.; Wakamiya, A.; Kanemitsu, Y. Photocarrier recombination dynamics in perovskite CH3NH3PbI3 for solar cell applications. J. Am. Chem. Soc.2014, 136, 11610-11613.
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