Silane Capped Zno Nanoparticles For Use As The Electron Transport Layer in Inverted Organic Solar Cells

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Article
Silane Capped ZnO Nanoparticles for Use as the
Electron Transport Layer in Inverted Organic Solar Cells
Junfeng Wei, Guoqi Ji, Chujun Zhang, Lingpeng Yan, Qun Luo,
Cheng Wang, Qi Chen, Junliang Yang, Liwei Chen, and Chang-Qi Ma
ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.8b01178 • Publication Date (Web): 08 Jun 2018
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Page 1 of 41 ACS Nano
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Silane Capped ZnO Nanoparticles for Use as the
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Electron Transport Layer in Inverted Organic Solar
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Cells
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†§ † ‡ † *, †
17 Junfeng Wei, Guoqi Ji, Chujun Zhang Lingpeng Yan Qun Luo, Cheng Wang, ξ Qi Chen, ξ
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Junliang Yang,* Liwei Chen, ξ Chang-Qi Ma
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Printable Electronics Research Center (SINANO), Suzhou Institute of Nano-Tech and
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27 Nano-Bionics, Chinese Academy of Sciences, Collaborative Innovation Center of
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29 Suzhou Nano Science and Technology, Suzhou, 215123, P. R. China
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Hunan Key Laboratory for Super Microstructure and Ultrafast Process, School of
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34 Physics and Electronics, Central South University,
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36 Changsha 410083, Hunan, P. R. China
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39 University of Chinese, Academy of Sciences, Beijing, 100049, P. R. China
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41 ξ
i-lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences,
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44 Suzhou, 215123, P. R. China
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46 E-mail: qluo2011@sinano.ac.cn; junliang.yang@csu.edu.cn; cqma2011@sinano.ac.cn
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ACS Nano Page 2 of 41
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3 ABSTRACT:
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7 Zinc oxide (ZnO) nanoparticles are widely used as the electron- transport layers (ETLs)
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materials in the organic solar cells, and are considered to be the candidate with the most potential
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12 for ETLs in roll-to-roll (R2R) printed photovoltaics. However, the tendency of the nanoparticles
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14 to aggregate reduces the stability of the metal oxides inks and creates many surface defects,
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16 which is a major barrier to its printing application. With the aim of improving the stability of
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19 metal oxide nanoparticles dispersions and suppressing the formation of surface defects, we
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21 prepared 3-aminopropyltrimethoxysilane (APTMS)-capped ZnO (ZnO@APTMS) nanoparticles
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23 through surface ligand exchange. The ZnO@APTMS nanoparticles exhibited excellent
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dispersibility in ethanol, an environmentally friendly solvent, and remained stable in air for at
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28 least one year without any aggregation. The capping of the ZnO nanoparticles with APTMS also
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30 reduced the number of surface adsorbed oxygen defects, improved the charge transfer efficiency,
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and suppressed the light-soaking effect. The thickness of the ZnO@APTMS ETL could reach
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35 100 nm without an obvious decrease in the performance. Large-area APTMS-modified ZnO
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37 films were successfully fabricated through roll-to-roll micro-gravure printing and exhibited good
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39 performance in flexible organic solar cells. This work demonstrated the distinct advantages of
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42 this ZnO@APTMS ETL as a potential buffer layer for printed organic electronics.
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Keywords: organic solar cells; ZnO nanoparticles; printable buffer layer; silane capping agent;
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48 long-term stability
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3 Organic solar cells have attracted extensive attention in the field of renewable energy due to
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6 their advantages of low cost, light weight, flexibility, colorful, and roll-to-roll printing
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8 compatibility.1-3 Considerable efforts have been made to improve the power conversion
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10 efficiency by designing new donor and acceptor materials, controlling the phase separation
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morphology, optimizing the interface, etc. The highest performance achieved recently by ternary
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15 and tandem organic solar cells is over 14% for both,4,5 showing large potential of the organic
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17 solar cells for commercial and industrial application. Organic solar cells include the conventional
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and inverted structures, and among the two types, the inverted organic solar cells using an ITO
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22 electrode as the cathode and Ag or Al metal as the anode have been proven to be more stable
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24 than devices with the conventional structure.6
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26 In the inverted organic solar cells, zinc oxide (ZnO) has been widely used as the electron
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29 transport layer (ETL) because it is cost effective, easily fabricated, and environmentally friendly.
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31 Furthermore, the ZnO electron buffer layer has been proven to be the most promising ETL for
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33 the roll-to-roll (R2R) printed photovoltaics to date.9 ZnO ETLs have been primarily prepared
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through a simple sol-gel method via spin-coating a ZnO sol precursor solution on a substrate,
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38 followed by annealing at approximately 200-350 oC for 30 min.10,11 The high-temperature
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40 annealing step of this process might be a big drawback in term of the fabrication of large area
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flexible photovoltaics due to the poor heat resistance of the typical plastic substrates. In
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45 comparison, the ZnO layer formed from ZnO nanoparticle formulations is a good choice as an
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47 ETL because of its low-temperature processability (<100 oC), and low sensitivity to the process
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49 condition,12 thereby making this material highly compatible with flexible printed photovoltaics.
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52 However, ZnO nanoparticles often suffer extensive interface recombination in inverted organic
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54 solar cells because of the surface defects such as, various dangling bonds,13 and negatively
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3 charged oxygen adsorbed on the surface.14,15 A typical example of this limitation is the well-
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6 known “light-soaking” effect that occurs when ZnO is used in the inverted organic solar cells, in
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8 which UV or white light exposure is required to enhance the performance. Many efforts have
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10 been devoted to solving or eliminating this problem through the use of the chemical doped metal
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oxides, which typically include ZnO doped with Al3+,16 Li+,17 Mg2+,18 Ga2+,19 Sn4+,20 and Cs2+.21
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15 Meanwhile, several surface modification methods, including self-assembled monolayer (SAM)
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17 modification,16 surface small molecular or polymer modification,11,22,23 and organic-inorganic
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composite 24-28 also have been utilized to passivate the surface defects, enhance charge transport,
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22 and improve the device performance.
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24 Another major issue associated with ZnO nanoparticles is their strong tendency to form large-
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26 scale aggregation through polycondensation of surface hydroxyl groups.29-31 This extensive
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29 aggregation leads to the formation of an unfavorable interface between the buffer layer and the
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31 photoactive layer,32,33 and results in poor device performance and performance uniformity,
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33 especially for printed photovoltaics. Thus, the thermodynamic instability of the ZnO ink is a
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major barrier for the large-area industrial and commercialization application of this material as a
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38 buffer layer in organic photoelectronic devices. With the aim to suppressing aggregation, several
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40 alternative approaches have been developed, such as modification with polyyinylpyrrolidone
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(PVP)22 surfactant, n-propylamine,34 2-aminoethanol,35 coupling agents29,36 and co-solvent
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45 engineering.37,38 Among them, modification with silane coupling agents involving a chemical
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47 reaction between the surface hydroxyl groups of the metal oxides and the alkoxy groups of the
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49 coupling agent is a popular approach in the field of bio-materials for improving the
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52 dispersibility,29,39 the hydrophily,29, 40 and modulating the luminescence properties.41 Meanwhile,
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54 silane coupling agents are well-known self-assembled molecular (SAM) layer materials for
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3 modifying the metal oxides,42,43 particularly for regulating the surface energy.43 Nevertheless, the
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6 application of silane coupling agent-modified ZnO nanoparticles in organic solar cells has not
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8 been developed until now. These silane modified ZnO nanoparticles might have several
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10 significant advantages for the use in the organic solar cells: the surface potential would be
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regulated through surface ligand exchange of the hydroxyl groups by alkoxy unites, which would
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15 isolate the nanoparticles from each other and enhance the ink stability. The terminal functional
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17 groups, such as the ammonia moiety of 3-aminopropyltrimethoxysilane (APTMS), would ensure
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good solubility of the modified ZnO nanoparticles in water or alcohol, and enable further
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22 modification of the surface through chemical grafting.36,44
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24 In this work, with the aim of passivating the surface defects, enhancing the photoelectronic
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26 properties and improving the long-term stability of ZnO nanoparticles, we developed a 3-
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29 aminorpropyltriethoxysilane-capped ZnO nanoparticle (ZnO@APTMS) buffer layer. The
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31 introduction of APTMS has successfully suppressed the aggregation of the ZnO nanoparticles
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33 and thus resulted in good dispersibility in ethanol with excellent long-term stability for more than
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12 months. The use the ZnO@APTMS nanoparticles as the ETL for organic solar cells
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38 effectively suppressed the light-soaking effect of the inverted organic solar cells through
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40 passivation of surface adsorbed oxygen defects. The reduction of surface defects also resulted in
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a minimal dependence of the performance on the film thickness, enabling an adjustable thickness
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45 of 100 nm. Since the modified ZnO nanoparticles can be dispersed in environmentally friendly
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47 solvents for long periods, and ensure a high device performance and lower sensitivity of the
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49 performance to the film thickness, this modified ZnO is extremely attractive for R2R printed
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3 RESULTS AND DISCUSSION
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The ZnO@APTMS nanoparticles were synthesized through surface ligand exchange of the
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9 hydrogen group with triethoxysilane groups using the method reported by Moussodia et al.44
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11 with some modifications (Scheme 1, the detailed synthetic procedures are provided in the
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13 experimental section).
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31 Scheme 1. Synthetic process of the ZnO@ATPMS nanoparticles.
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34 The formation of ZnO@APTMS nanoparticles was proven by the X-ray diffraction (XRD)
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patterns shown in Figure 1 (a), the Fourier transform infrared spectroscopy (FT-IR) provided in
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39 Figure 1 (b), and the X-ray photoelectron spectroscopy (XPS) data illustrated in Figure 1 (c) and
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41 (d). First, several typical diffraction peaks with 2theta at 31o, 35 o, 47o, 56o, 62o, and 67o which
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43 are ascribed to hexagonal ZnO, were observed in the XRD patterns of both the pristine ZnO and
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46 the ZnO@APTMS nanoparticles.
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48 As shown by the FT-IR spectra, both the ZnO and ZnO@APTMS nanoparticles contained a
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50 wide absorption peak in the range of 3000-3500 cm-1, which was ascribed to the stretching
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modes of the surface -OH groups. The two intense peaks observed at 1585 and 1400 cm-1 in
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3 indicating that the residual acetate groups were not completely removed after washing.45 Another
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6 obvious peak observed at 468 cm-1 for the two samples was attributed to the stretching vibrations
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8 of the Zn-O bonds.46 In addition to the abovementioned peaks, the FT-IR spectra of the
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10 ZnO@APTMS nanoparticles showed several additional absorptions at 3248 and 3133 cm-1,
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which could be ascribed to the asymmetric and symmetric vibrational modes of the protonated
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15 ammonium groups. The peaks at 2929 and 2860 cm-1 for the ZnO@APTMS belong to the
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17 asymmetric and symmetric stretching modes of the C-H groups in the propyl chain of APTMS.
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In addition, the peak at 1071 cm-1 could be attributed to the vibrational modes of the Si-O-Si
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22 groups formed by self-condensation of the organosilanes,44 while the peak at 1006 cm-1
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24 corresponded to Si-O-Zn.47 The observation of Si-O-Zn bounds indicated the formation of
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26 covalent bonds between ZnO and APTMS on the surface of the nanoparticles due to the
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29 successful capping ZnO nanoparticles by silane.29,48
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31 Further, the N 1s XPS spectra results revealed the presence of free -NH2 and hydrogen-bonded
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33 -NH2 groups in the ZnO@APTMS films, whose peaks were located at 399.6 and 403.3 eV,
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respectively.49 Besides, the contribution of the free -NH2 groups at 399.6 eV was much higher
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38 than that of the peak from hydrogen bonded -NH2 at 403.3 eV, indicating that the APTMS
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40 molecules mostly bound to the ZnO nanoparticles through the methoxy group and the -NH2
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group remained free outsides.49 Therefore, we speculated that the bonding between ZnO and
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45 APTMS occurs via the mode illustrated in Figure 3 (b). In addition, the obvious XPS signals
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47 from the Si 2p core level supported APTMS capping of the ZnO nanoparticles. Overall, based on
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49 the comprehensive results of the XRD patterns, FT-IR and XPS spectra, APTMS can be
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52 definitively concluded to have capped the ZnO nanoparticles.
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3 Then, the transmission electron microscopy (TEM) and the dynamic light scattering (DLS)
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6 measurements were performed to study the morphological differences between the ZnO and
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8 ZnO@APTMS nanoparticles. To exclude ZnO aggregation, the ZnO and ZnO@APTMS
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10 nanoparticles were freshly synthesized. As shown by Figure 1 (e) and (f), both the fresh ZnO and
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the ZnO@APTMS nanoparticles were well-dispersed in ethanol with average diameters approx.
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15 5.1 and 7.3 nm, respectively. The slight increase in the diameter of the ZnO@APTMS relative to
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APTMS.
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Figure 1. (a)XRD patterns and, (b) FT-IR spectra of the pristine ZnO and ZnO@APTMS
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47 nanoparticles. (c-d) N 1s and Si 2p core level XPS spectra and (e-f) TEM images of the pristine
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49 ZnO and ZnO@APTMS nanoparticles.
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52 The photoelectrical properties of the ZnO@APTMS nanoparticles were studied by the
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55 absorption spectra, the photoluminescence (PL) and the ultraviolet photoelectron spectrometer
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3 (UPS) spectra. As illustrated by the absorption spectra of the ZnO and ZnO@APTMS films
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6 shown in Figure 2 (a), a typical absorption band with an absorbance cut-off around 360 nm was
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8 observed for the pristine ZnO and ZnO@APTMS films. Under excitation at 350 nm, both the
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10 pure ZnO and ZnO@APTMS nanoparticles exhibited a weak emission peak at 360 nm and a
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strong, broad green emission peak centered at 530 nm: these two emission peaks were attributed
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15 to the band-edge emission50 and the oxygen vacancy-related defect photoluminescence,
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17 respectively.51 Interestingly, the ZnO@APTMS nanoparticles exhibited a 30 nm blue-shift in the
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emission peaks and higher photoluminescence intensity relative to those of the pure ZnO
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22 nanoparticles, particularly the green emission intensity (Figure 2(b)). Since the ZnO@APTMS
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24 film has nearly the same absorption index (Figure 2(a)), this promoted photoluminescence
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26 intensity indicated that luminescence quenching in the pristine ZnO nanoparticles was greatly
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29 suppressed through APTMS capping.
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31 The electrical properties of the interface buffer layer are known to be critical for governing the
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33 performance of organic solar cells. First, the device open voltage (VOC) is ideally determined by
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the energy level difference between the highest occupied molecular (EHOMO) of the donor and the
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38 lowest occupied molecular orbital (ELUMO) of the acceptor and strongly influenced by the work
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40 functions of the two electrodes. Second, the fill factor (FF) of devices is mainly determined by
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the series resistance and shunt resistance,52 where the series resistance is determined by the
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45 resistance of each layer and as well as the interlayer contact resistance. On this basis, the
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47 conductivity properties, including the electron mobility and the surface work function of the
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49 buffer layer, will greatly impact the performance. Therefore, the electron mobilities and surface
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52 work functions of the ZnO and ZnO@APTMS films were compared in this work. First, the
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54 electron-transporting property of the ZnO and the ZnO@APTMS films was studied through
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3 space-charge-limited current (SCLC) measurements using an electron-only device with a
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6 structure of ITO/Al/ZnO (ZnO @ APTMS)/Al. As shown by Figure 2 (c), these two J-V curves
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8 were fit well by the SCLC mode with a typical ohmic contact region and a SCLC region, and the
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10 trapped space charge region was absent due to the trap-free space charge-limited current
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behavior of these electrons only devices.53 Thus, the corresponding electron mobilities of the
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15 ZnO and ZnO@APTMS films could be calculated from the SCLC region according to the Mott-
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17 Gurney SCLC equation: 54
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9 Vଶ
20 J= ε୰ ε଴ μୣ ଷ
21 8 d
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23 where ε୰ , ε଴ , μୣ and d are the relative dielectric constant of the materials, the vacuum dielectric
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25 constant, the electron mobility and the film thickness, respectively. Based on this equation, the
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27 electron motilities of the ZnO and ZnO@APTMS films were estimated to approximately 5.88 ×
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30 10-4 and 5.78 × 10-4 cm2V-1S-1, respectively, similar to the common value of the ZnO films
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32 determined by the SCLC method.55,56 This result meant that APTMS capping has caused
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34 negligible influence on the charge transport properties of ZnO nanoparticles, which would allow
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good charge collection at cathode. However, it is worthy to note that the SCLC region was
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39 obtained at a high bias voltage, where traps of the film were fully filled by injected current. As
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41 seen from Figure 2(c), lower current density was observed for the pristine ZnO film based
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43 electron-only device than the ZnO@ATPMS one, which implied higher trap density in the
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46 pristine ZnO films than the ZnO@APTMS film. Dynamic light scattering (DLS) results (Figure
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48 S4 in supporting information) showed large agglomeration of ZnO nanoparticles at higher
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50 concentration (to achieve large layer thickness), which is supposed to be the reason for the higher
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53 trap density for the ZnO film. Besides the electron mobility, the influence of the APTMS
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55 capping on the work function was investigated using UPS. According to the UPS spectra as
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3 exhibited in Figure 2 (d), the work functions of the ZnO and the ZnO@APTMS films were
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6 estimated to be about 4.02 and 3.87 eV, respectively. The reduced work function of the
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8 ZnO@APTMS film relative to the pristine ZnO layer might be ascribed to the electron donor
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10 ability of silicon. Similar reduced work function of metal oxides films have been previously
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found in other cases, such as the silane self-assembled molecular layer (SAM) modified ZnO42
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15 and ITO films.57
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Figure 2. (a) Absorption and, (b) photoluminescence spectra of the ZnO and ZnO@APTMS
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48 films (excited at 350 nm), (c) J-V characterization of the electron - only devices with a structures
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50 of ITO/Al/ZnO (ZnO@APTMS)/Al and, (d) UPS spectra of the pristine ZnO and ZnO@APTMS
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52 films.
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3 Before moving forward to the device application, we also studied the surface properties of the
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6 APTMS-modified ZnO nanoparticles both in solution and in the form of a film. The zeta
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8 potential of the nanoparticles inks and surface energy of the ZnO and ZnO@APTMS films were
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10 studied, and the results are shown in Figure S1. Both the surface potential of the nanoparticles
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and the surface energy of the films changed through capping the ZnO nanoparticles with
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15 APTMS. Specifically, the pristine ZnO nanoparticles with negatively charged –OH groups on the
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17 surface showed a zeta potential of +20 mV. While for the ZnO@APTMS nanoparticles, the
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surface charge shifted towards positive values due to the grafting of APTMS aminopropyl units
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22 on the surface, leading to a zeta potential of -17 mV. As exhibited by the images of a
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24 water/diiodomethane droplet on the top of the ZnO and ZnO@APTMS surfaces, the contact
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26 angles of water on the top of ZnO and ZnO@APTMS films were approx. 32o and 83o,
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29 respectively. And the contact angle of diiodomethane on the top the ZnO and ZnO@APTMS
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31 films were 36 o and 13 o, respectively. These observations demonstrated that the ZnO@APTMS
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33 film was much more hydrophobic than the pristine ZnO film. This result was reasonable since
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the ZnO@APTMS nanoparticles were functionalized with hydrophobic alkyl groups and
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38 hydrophilic amine moieties in a ratio of 3:1. The surface energies of the ZnO and ZnO@APTMS
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40 films could be calculated from these contact angles using the Owns model58 (see the support
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information for detailed calculation procedures). As a result shown in Table S1, surface energies
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45 of 70.4 and 50.8 mN m-1 were determined for the ZnO and ZnO@APTMS films, respectively.59
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47 To evaluate the usage of the ZnO@APTMS nanoparticles for the application in organic
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49 photovoltaics, inverted organic solar cells with a structure of ITO/ZnO (ZnO@APTMS)
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52 /polymer: fullerene/MoO3/Al were fabricated, where ZnO@APTMS was used as the electron
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54 buffer layer. The pristine ZnO ETL was also used for comparison. Herein, PTB7-Th:PC71BM
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3 and PfffBT4T-2OD:PC61BM were selected as the photoactive layers for solar cell fabrication.
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6 The device structure and the chemical structures of PTB7-Th, PfffBT4T-2OD, PC61BM, and
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8 PC71BM are shown in Figure 3. The J-V curves and external quantum efficiency (EQE) spectra
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10 of the PTB7-Th:PC71BM and PfffBT4T-2OD:PC61BM solar cells using the pristine ZnO and
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ZnO@APTMS ETLs are shown in Figure 4, and the corresponding performance parameters are
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15 listed in Table 1. It was interesting to find that the J-V characteristics of both the PTB7-
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17 Th:PC71BM and PffBT4T-2OD:PC61BM devices using the pristine ZnO ETLs exhibited a typical
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“S”-shaped curve and the “light soaking” effect. After UV light soaking for 5 minutes, these
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22 undesired kinked J-V curves disappeared. Correspondingly, the power conversion efficiency
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24 (PCE) of the PTB7-Th:PC71BM and PffBT4T-2OD:PC61BM devices significantly improved
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26 from 4.39% to 8.73% and from 4.24% to 7.73%, respectively. This performance improvement
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29 obviously originated from a significant increase in FF and a slight improvement in VOC,
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31 revealing that the enhanced interface charge transport strongly contributed to this performance
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33 promotion. In contrast to the ZnO devices, both the PTB7-Th:PC71BM and PffBT4T-
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2OD:PC61BM devices with the ZnO@APTMS ETLs showed “light-soaking” free J-V
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38 characteristics with a reasonable performances of 9.07% and 7.97%, respectively. The dark J-V
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40 characteristics strongly supported the elimination of the “S”-shaped curve with the use of
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ZnO@APTMS ETL. As a typical example, the dark J-V curves of the PTB7-Th:PC71BM devices
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45 with ZnO and ZnO@APTMS ETLs are illustrated in Figure 4(d) for comparison. These curves
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47 were analyzed using the classic one-diode model,60,61 and the key parameters, i. e., reverse
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49 saturation current density in the dark (J0), diode ideal factor (n), series resistance (Rs), and shunt
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52 resistance (Rsh), could be calculated by simulating the J-V curves. As exhibited by Figure S2, the
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54 simulated dark J-V curves fitted well with the measured curves; thus, the diode properties could
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3 be reasonably compared using these calculated parameters. Table S2 shows that the pristine
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6 device with a pure ZnO ETL showed much poorer diode properties with a higher reverse
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8 saturation current (J0) and diode ideal factor (n) than the device after the light soaking treatment.
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10 A decreased Rs and an increased Rsh were also observed when the pristine ZnO ETL based
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device was light-soaked for 5 min, which consequently led to a better FF. However, the pristine
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15 device using the ZnO@APTMS ETL presented improved J0, n, Rs, and Rsh relative to the ZnO
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17 device even without any light-soaking treatment. In addition to these improved parameters, the
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ZnO@APTMS ETL-based device also showed a superior rectification ratio relative to both the
20
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22 ZnO ETL- based pristine device and the ZnO ETL-based light-soaked device. However, the final
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24 optimized device performance of the ZnO@APTMS ETL- based PTB7-Th:PC71BM and
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26 PffBT4T-2OD:PC61BM devices was not highly improved relative to that of the ZnO ETL- based
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29 device, which might be limited by the comparable electron mobility of the ZnO@APTMS ETL.
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31 The light-soaking issue has been frequently observed in the inverted organic solar cells with n-
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33 type metal oxide as the electron transport layers, which was almost ascribed to the low electron
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36
collection efficiencies of metal oxides62 and charge recombination in the interface of metal
37
38 oxides and organic.63 In the case of ZnO-based devices, the conductivity and electron mobility
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40 are significantly impacted by the surface state and surface defects. The pristine ZnO
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42
nanoparticles surface was mostly functionalized with hydroxyl and carboxylate groups,64 which
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45 could adsorb oxygen molecules from the air. These adsorbed oxygen molecules would create a
46
47 potential barrier and a depletion region,65 and reduce the surface conductivity of the ZnO films.50
48
49 Under illumination by UV or white light, the surface adsorbed oxygen species would desorb
50
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52 from the nanoparticle surface, leading to enhanced charge transport efficiency and consequently
53
54 a subsequent improvement in the device performance.50, 66
Based on this premise, effective
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15
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3 isolation of the surface from adsorbed oxygen molecules could be reasonably proposed as a
4
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6 practical method for solving the light-soaking issue. In the ZnO@APTMS nanoparticles, most of
7
8 the hydroxyl groups were removed through surface ligand exchange and formed alkoxy bonds as
9
10 expected, and therefore, the number of surface-adsorbed oxygen would also be decreased too (as
11
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13
shown in Figure 3(b)). And the method of defect passivation of ZnO surfaces with ethylene
14
15 dithiol (EDT) was similar to this case.64 Thus, the observation of light-soaking free J-V
16
17 characteristics for the ZnO@APTMS ETL involved devices suggested the successful
18
19
suppression of oxygen adsorption to the surface of ZnO through ligand exchange of the hydroxyl
20
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22 groups by the alkoxy bonds. Herein, we successfully solved the typical light-soaking issue
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24 through a simple and direct surface ligand exchange of ZnO nanoparticles, which is unlike the
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26 conventional ion doping approaches.62, 67-69
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34 Figure 3. (a) Schematic illustration of the device architecture of the inverted solar cells. (b)
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36 Schematic diagram of the ZnO and ZnO@APTMS nanoparticles. (c) Molecular structures of
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38 PTB7-Th, PffBT4T-2OD, PC71BM, and PC61BM.
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30 Figure 4. (a, b) J-V curves of the PTB7-Th:PC71BM and PffBT4T-2OD:PC61BM inverted
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33 organic solar cells with the pristine ZnO and ZnO@APTMS ETLs. (c) EQE spectra of the PTB7-
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35 Th:PC71BM and PffBT4T-2OD:PC61BM solar cells. (d) Dark J-V curves of the PTB7-
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37 Th:PC71BM solar cells with the pristine ZnO and ZnO@APTMS ETLs.
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3 Table 1. Device performance of the inverted organic solar cells using the pristine ZnO and
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6 ZnO@APTMS films as electron transport layers.
7
8
9 Polymer: Voc Jsc FF PCE Ave. PCE±
10 Fullerene
ETL UV
11 (V) (mA/cm2) (%) (%) std. dev.(%)a
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13 ZnO w/o 0.75 15.82 0.37 4.39 4.0±0.41
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15 PTB7-Th: ZnO with 0.80 16.53 0.66 8.73 8.66±0.11
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17 PC71BM ZnO@APTMS w/o 0.80 16.67 0.68 9.07 9.03±0.06
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19 ZnO@APTMS with 0.80 16.61 0.68 9.04 9.01±0.11
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21 ZnO w/o 0.72 15.50 0.38 4.24 4.20±0.31
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23 PffBT4T-2OD: ZnO with 0.73 15.49 0.68 7.73 7.66±0.15
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25 PC61BM ZnO@APTMS w/o 0.74 15.56 0.69 7.97 7.91±0.13
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27 ZnO@APTMS with 0.74 15.53 0.69 7.93 7.90±0.15
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a
29 The standard deviation was calculated over 8 individual devices.
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33 Besides the suppression of the light-soaking effect by using this ZnO@APTMS electron
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35 transport layer, the modified ZnO buffer layer also showed advantages of lower thickness
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38 dependence relative to that of the pristine ZnO film. As illustrated in Table 2, the device
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40 performance with pristine ZnO and ZnO@APTMS ETLs of different thicknesses was compared.
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42 ZnO and ZnO@APTMS ETLs with different thicknesses (30, 60, and 100 nm) were prepared by
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45
regulating the concentration of the nanoparticles. The film thickness was determined by profiler,
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47 and a standard error about 5 nm was taken into consideration. For the pure ZnO ETL- based
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49 inverted polymer solar cells, the device performance gradually decreased from 8.70% to 5.58%
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51
as the ZnO thickness increasing from 30 to 100 nm. This can be ascribed to the higher trap
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54 density within the ZnO film at larger layer thickness (vide supra), as well as the inferior
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56 interfacial contact between the ZnO ETL and the organic active layer caused by agglomeration
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1
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3 of the ZnO nanoparticles at high concentrations (Figure S3). In the case of ZnO@APTMS, the
4
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6 device performance remained nearly kept unchanged up to a thickness of 60 nm and then slightly
7
8 decreased to 7.83% with further increase in the thickness to 100 nm. Nevertheless, note that this
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10 decline in the performance of the 100 nm-ZnO@ APTMS ETL-based device was mainly
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13
ascribed to its lower short-circuit current density (JSC), which could be ascribed to the optical
14
15 spacer effect (Figure S4), while the device fill factor (FF) still remained above 65%. Therefore,
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17 this result suggested the ZnO@APTMS nanoparticles could ensure a reasonable device
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19
performance, even when the film thickness is increased to 100 nm.
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22 Table 2. Device performance of the inverted PTB7-Th:PC71BM solar cells with different
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24 thicknesses of ZnO and ZnO@APTMS electron transport layers.
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26
27 ETL Thickness Voc Jsc FF PCE Ave. PCE ±
28
29 (nm) (V) (mA/cm2) (%) (%) std. dev. (%) a
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31 30 0.80 16.53 0.66 8.73 8.66±0.11
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33 ZnO 60 0.81 14.66 0.62 7.36 7.21±0.22
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35 100 0.81 12.98 0.55 5.58 4.87±0.37
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37 30 0.81 16.67 0.68 9.07 9.03±0.06
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39 ZnO@APTMS 60 0.80 16.20 0.66 8.55 8.51±0.07
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41 100 0.80 15.06 0.65 7.83 7.80±0.11
42
43 a
The standard deviation was calculated over 8 individual devices.
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47
Furthermore, the long term stability of the unencapsulated organic solar cells based on the
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50 ZnO and ZnO@APTMS ETLs were monitored under different water and oxygen conditions at
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52 room temperature about 25±3 °C. Herein the long-term decay testing were carried out under the
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54 following four conditions: (a) in the N2 filled glovebox without water and oxygen, (b) in the
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1
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3 ambient atmosphere with relative humidity around 60%, (c) in the N2 filled box with a relative
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6 humidity around 60%, (d) in the O2 filled box with relative humidity around 10%. As shown by
7
8 Figure 5(a), it was obvious the evolution of PCE of the PTB7-Th:PC71BM solar cells that stored
9
10 in the glove box with water and oxygen lower than 10 ppm did not show significant degradation
11
12
13
during the whole testing process. Both the ZnO and ZnO@APTMS ETL- based devices kept
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15 PCEs higher than 90% of the initial PCE after 30 days storage. It meant that both the ZnO and
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17 ZnO@APTMS ETLs- based devices were rather stable under the water and oxygen free
18
19
condition. While for the degradation of the devices in the ambient atmosphere with relative
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22 humidity around 60%, the ZnO ETL- based device degraded much faster than the ZnO@APTMS
23
24 ETL based devices. In specific, the ZnO based device decayed to only 20% PCE of the initial
25
26 value after 30 days storage, while the ZnO@APTMS could maintain about 80% PCE of the
27
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29 initial PCE. From the inset of Figure 5(b), we can find that both the two kinds of devices
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31 exhibited an obvious fast decay process within the first 24 hours. The ZnO@APTMS ETL-based
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33 devices remained 80% of the initial PCE, but the ZnO ETL-based cells quickly dropped to 40%
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35
36
PCE of the initial value. Since other layers were the same in these two devices, the water and
37
38 oxygen caused degradation of the ZnO ETL- based device could be ascribed to sensitivity of the
39
40 pristine ZnO to water and oxygen. To further understand the underlying mechanism of the water
41
42
and oxygen caused ZnO degradation, we compared the degradation process of ZnO and
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45 ZnO@APTMS ETL- based devices under low humidity high oxygen, and high humidity lower
46
47 oxygen conditions. As shown by Figure 5 (c) and (d), the ZnO ETL- based device decayed much
48
49 faster than the ZnO@APTMS ETL-based device either under the low humidity high oxygen
50
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52 condition or under the high humidity low oxygen condition. Whatever, the O2 induced
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54 degradation of the ZnO ETL- based device was much faster, even faster than the degradation in
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1
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3 the ambient atmosphere with the humidity of 60%. Since herein the concentration of O2 for the
4
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6 high oxygen low humidity condition is approximately 100%, which is much higher than the
7
8 oxygen concentration of the ambient condition, the faster degradation speed of devices in pure
9
10 O2 atmosphere indicated the degradation of ZnO ETL- based device is oxygen-dominated
11
12
13
process. On the basis of the above results, we could draw a conclusion that both water and
14
15 oxygen induced the interface degradation in the ZnO ETL- based solar cells devices, but oxygen
16
17 played a more important role than water. The interface degradation of the ZnO ETL-based
18
19
device could be proved by the fast decay of the device FF when stored under the high oxygen
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22 condition or in the ambient atmosphere (as shown in the support information as Figure S5-S7).
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24 For the device with the ZnO@APTMS ETL, the better stability than pure ZnO ETL device was
25
26 due to the suppressing the formation of adsorbed oxygen after capped with APTMS in the
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29 ambient atmosphere. As a consequence, the ZnO@APTMS ETL-based device exhibited
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31 significantly enhanced long-term stability in the ambient atmosphere.
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30 Figure 5. PCE decays of the PTB7-Th:PC71BM solar cells as a function of the storage time with
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32 ZnO and ZnO@APTMS ETLs under different conditions. (a) in the N2 filled glovebox without
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35 water and oxygen, (b) in the ambient atmosphere with relative humidity around 60%, (c) in the
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37 N2 filled box with humidity around 60%, (d) in the O2 filled box with humidity around 10%.
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40 In the roll-to-roll printed photovoltaics, the stability of the electronic ink is crucial for ensuring
41
42 the printing reproducibility. Figure 6 (a) shows the evolution in the average diameter of the
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45 pristine ZnO and the ZnO@APTMS nanoparticles during long-term storage at the ambient
46
47 atmosphere. The same batches of ZnO and ZnO@APTMS inks were collected and stored in the
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49 open air, and the DLS spectra of these inks were recorded periodically to determine the diameter.
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52
The fresh ZnO and ZnO@APTMS nanoparticles had a similar average diameter of less than 10
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54 nm. However, during prolonged storage for 4 months, the average diameters of the pristine ZnO
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56 grew dramatically from approx. 5 nm to approx. 250 nm. In contrast, the diameter of the
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23
1
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3 ZnO@APTMS nanoparticles increased only slightly from 7 to 10 nm during about 12 months of
4
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6 storage in the air, showing a significant improvement in the long-term stability. Pristine ZnO
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8 nanoparticles are usually capped with hydroxyl groups and therefore tend to rapidly agglomerate
9
10 via the polycondensation of neighboring nanoparticles,32,38,70 whereas for the ZnO@APTMS
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13
nanoparticles, the inter-particle interaction between neighboring nanoparticles is inhibited
14
15 because of the larger electrostatic double layer, which also results in a larger inter-particle (vide
16
17 infra). Therefore, APTMS capping of the ZnO nanoparticles allowed the long-time dispersion
18
19
stability of the electronic inks, which would subsequently improve the device reproducibility.
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22 Then, we studied the performance of devices formed from ZnO and ZnO@ APTMS ETLs that
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24 were stored for different time, and the PTB7-Th:PC71BM inverted solar cell was discussed as an
25
26 example. The device performance is shown in Figure 6 (b) and Table S3. It has been known that
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29 changes in the ZnO film morphology, even slight roughness variations would significantly
30
31 influence the device performance due to unfavorable interface contact.32,37,38,71 Therefore, the
32
33 roughness of the ZnO films would increase rapidly with the rapid increase in the ZnO diameter
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36
and consequently led to a performance decrease from 8.73% to 4.87%. In contrast, the devices
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38 with a ZnO@APTMS ETL always showed a high performance about 8.2%, even the devices
39
40 were prepared from the inks stored in air for approximately 12 months. Besides the optimized
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device performance, the standard performance variation of the ZnO@APTMS ETL- based
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45 device that calculated over 8 individual devices was much smaller than that of the ZnO ETL-
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47 based devices, indicated an improved reproducibility of the ZnO@APTMS ETL employed
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49 devices.
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Figure 6. (a) Evolution in the average diameter of the ZnO and ZnO@ APTMS nanoparticles
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23 during long term storage in air. (b) Device performance of the PTB7-Th:PC71BM solar cells
24
25 using ZnO or ZnO@APTMS nanoparticles that were stored in air for different time.
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28 Finally, the ZnO@APTMS films were fabricated through roll-to-roll micro-gravure
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31
printing. The fabrication process could be found in our previous report.72 Because the inverted
32
33 solar cells has slight dependence on the thickness of the ZnO@APTMS buffer layer, here a 90
34
35 nm-thick layer was printed and used as the electron buffer layer of the inverted solar cells. As
36
37
shown by the AFM image illustrated in Figure S8, we can find that the roughness of the spin-
38
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40 coated and the R2R printed ZnO@APTMS films were 3.6, and 2.5 nm respectively. With the
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42 ZnO@APTMS buffer layer, the performance of the flexible organic cells reached to 6.83%, with
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44 a VOC, JSC, FF of 0.76 V, 15.78 mA/cm2, and 57%, respectively. For comparison, the flexible
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47 device with a 90 nm-thick spin-coated ZnO@APTMS ETL showed a performance about 6.98%,
48
49 with a VOC, JSC, and FF of 0.75 V, 15.51 mA/cm2, and 60%, respectively. This result indicated
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51 that the use of the R2R printed ZnO@APTMS ETL allowed comparable performance, indicating
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its attractive potential in R2R printed organic photovoltaics.
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21 Figure 7. J-V curves of the flexible PTB7-Th:PC71BM solar cells with the spin-coated and R2R
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23 printed ZnO@APTMS ETLs.
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26
27
28 CONCLUSION
29
30
31 In summary, in this work, we developed a ZnO@APTMS nanoparticle ink for use in inverted
32
33 solar cells as a candidate of electron transport layer for roll-to-roll printing organic photovoltaics.
34
35 The successful capping of APTMS on the ZnO nanoparticles was proven by FT-IR, XPS,
36
37
photoluminescence, and UPS. The capping of ZnO nanoparticles by APTMS lowered number of
38
39
40 the surface adsorbed oxygen defects and thus improved the charge transport efficiency,
41
42 suppressed the light-soaking effect in the inverted solar cell devices, and lowered the dependence
43
44 of the device performance on the film thickness. The ZnO@APTMS nanoparticles also exhibited
45
46
47 excellent dispensability in ethanol, an environmentally friendly solvent, and remained stable in
48
49 air for at least one year without any aggregation or, decline in the device performance. These
50
51 properties demonstrated the tremendous potential for application of the ZnO@APTMS
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54
nanoparticle as an electron buffer layer in roll-to-roll printed organic electronics.
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26
1
2
3 METHODS
4
5
6 Materials:Poly[(ethylhexyl)-thiophenyl]-benzodithiophene-(ethylhexy)-thienothiophene]
7
8 (PTB7-Th) and poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-di(2-octyldodecyl)-
9
10 2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T-2OD) were purchased from Solarmer
11
12
13
Energy, Inc. (Beijing). [6,6]-Phenyl-C71-butyric acid methyl ester (PC71BM) was provided by
14
15 American Dye Source Inc. 3-Aminorpropyltriethoxysilane (APTMS) was purchased from J&K
16
17 Scientific Ltd.
18
19
20 The Synthesis of APTMS-capped ZnO nanoparticles: The APTMS capped ZnO
21
22
23
(ZnO@APTMS) nanoparticles were synthesized through three steps: first, ZnO nanoparticles
24
25 were synthesized through reaction between KOH and Zn(OAc)2 according to the route reported
26
27 by the reference.12 Then, the obtained ZnO precipitates were washed twice and modified with
28
29
oleic acid by adding 0.5 vol% oleic acid under continuous stirring of ZnO in toluene with a
30
31
32 concentration of 10 mg/ mL. Finally, the oleic acid modified ZnO nanoparticles were reacted
33
34 with APTMS toluene solution at 85 °C for 15 min. After cooling down to room temperature, the
35
36 white APTMS-capped ZnO sediments were collected through washing with toluene and
37
38
39 centrifugation, and finally dispersed in ethanol to form the final inks.
40
41 Characterization of the ZnO nanocrystals and ZnO films: The transmission electron
42
43 microscopy (TEM) images of the ZnO and ZnO@APTMS were recorded by the EEI Tecani G2
44
45
46
F20 S-Twin 200 kV microscope. Fourier transform infrared spectra (FT-IR) of the ZnO and
47
48 ZnO@APTMS nanoparticles were recorded by Nicolet 6700 FT-IR Spectrometer. Ultraviolet
49
50 photoelectron Spectroscopy (UPS) and X-ray photoelectron Spectroscopy (XPS) were performed
51
52
on a Kratos AXIS Ultra DLD ultrahigh vacuum (UHV) surface analysis system. The diameter
53
54
55 and Zeta potential of the ZnO and silane-capped ZnO inks were determined by dynamic light
56
57
58
59
27
1
2
3 scattering (DLS) with the Malvern granulometer (Zetasizer Nano). The films thickness was
4
5
6 characterized using a profiler (VEECO, DEKTAK 150). The absorption spectra were tested by
7
8 the Lamada 750 UV/Vis/NIR spectrophotometer (PerkinElmer).
9
10 Preparation of inverted organic solar cells and characterization: Inverted organic solar
11
12
13
cells with a structure of ITO/ZnO (ZnO@APTMS)/active layer/MoO3/Al were fabricated on ITO
14
15 -coated glasses, which were cleaned by ultrasonic cleaning in deionized water, acetone, and
16
17 isopropanol for 15 min each step. After ultraviolet ozone treatment for 30 min, the ZnO or
18
19
ZnO@APTMS electron transport layers were deposited on the ITO substrate by spin-coating at
20
21
22 2500rpm for 60 s. Then both the ZnO and ZnO@APTMS films were annealed at 120 °C for 10
23
24 min in the N2-filled glove box. Then, the active layers (PTB7-Th:PC71BM and PffBT4T-
25
26 2OD:PC61BM) were spin coated from a mixed solution of the polymer donor and fullerene
27
28
29 acceptor. For the PTB7-Th:PC71BM devices, the precursor solution composed of PTB7-Th and
30
31 PC61BM were dissolved in CB with concentrations of 7.5 and 9 mg/mL, respectively; the
32
33 solution also contained 3 vol% DIO as an additive and was stirred at 50 °C for 3h. Then the
34
35
36
mixture solution was spin-coated on the top of the ZnO or ZnO@APTMS layer at 1000 rpm for
37
38 60 s. For the PffBT4T-2OD:PC61BM devices, the precursor solution composed of PffBT4T-2OD
39
40 and PC61BM were dissolved in CB with concentration of 9 and 10.8 mg/mL, respectively; the
41
42
solution also contained 3 vol% DIO as additive and was stirred at 110 °C for at least 3 h. Before
43
44
45 spin coating, both the active layer solution and the substrate were heated on a hot plate at 110 °C
46
47 and followed by spin-coating at 800 rpm for 60 s. And then spin-coated films were annealed at
48
49 80 °C for 5 min before being transferred to the vacuum chamber. Finally, 10 nm MoO3 and 100
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51
52 nm Al were thermal-deposited successively at a vacuum level below 1 x 10-5 Pa. The effective
53
54 area of the devices was 0.09 cm2.
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28
1
2
3 The roll-to-roll printed large ZnO films were fabricated using a self-developed R2R muli-
4
5
6 function printer72 at web speed of 0.3 m/min and printing roller speed of 3.6 on the top of
7
8 flexible PET/ITO substrate.
9
10 The current density-voltage (J-V) measurements were carried out in a nitrogen glove box with
11
12
13
a Keithley 2400 source meter under a Newport solar simulator (100 mW/cm2). External quantum
14
15 efficiencies (EQE) were measured under simulated one sun operation conditions with light from
16
17 a 150 W tungsten halogen lamp (Osram 64610) as the probe light, a monochromator (Zolix,
18
19
Omni-λ300) for selecting the wavelength, and an I-V converter for recording the response. A
20
21
22 calibrated Si cell was used as a reference. The test device was kept behind a quartz window in a
23
24 nitrogen-filled container.
25
26 The devices for long-term stability test were stored in dark under four different conditions and
27
28
29 J-V sweeps were performed after a period of storage in these conditions without further treatment.
30
31 For the water and oxygen free condition, a N2- filled glove box with a water and oxygen content
32
33 of lower than 10 ppm was used. For the condition of ambient atmosphere with a relative
34
35
36
humidity around 60%, an air-filled sealed container with a relative humidity around 60% was
37
38 used. For the condition of low oxygen and high moisture, a N2-filled sealed container with
39
40 humidity around 60% was used. For the condition of high oxygen and low moisture, a closed
41
42
metal chamber was vacuum treated for several minutes till achieving a lower vacuum lever lower
43
44
45 than 100 Pa, and then filled it with pure O2.
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29
1
2
3 ASSOCIATED CONTENT
4
5
6 Supporting Information
7
8
9 The Supporting Information is available free of charge via the Internet at http://pub.acs.org
10
11
12 Details of zeta potential and calculation of surface energy; simulated dark J-V curves; EQE
13
14 spectra of devices with different thickness of ETL; particle size distribution of high
15
16
17
concentration of ZnO and ZnO@APTMS inks; the evolution of VOC, JSC, FF and PCE of the
18
19 PTB7-Th:PC71BM devices during long-term storage in different conditions; device performance
20
21 fabricated from inks storage in air for different months; AFM images of the roll-to-roll printed
22
23
and spin-coated ZnO@APTMS films.
24
25
26
27
28
29
AUTHOR INFORMATION
30
31 Corresponding Authors
32
33 *E-mail: qluo2011@sinano.ac.cn
34
35
*E-mail: junliang.yang@csu.edu.cn
36
37
38 *E-mail: cqma2011@sinano.ac.cn
39
40
41
42
43
44
45 ACKNOWLEDGMENTS
46
47
48 This work is financially supported by the National Natural Science Foundation of China
49
50 (51773224), the Suzhou Science and Technology Project (SYG201735), Ministry of Science and
51
52 Technology of China (No 2016 YFA0200700), the Strategic Priority Research Program of the
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Silane Capped Zno Nanoparticles For Use As The Electron Transport Layer in Inverted Organic Solar Cells

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