Metallophthalocyanine-Based Molecular Dipole Layer As A Universal and Versatile Approach To Realize Efficient and Stable Perovskite Solar Cells

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Energy, Environmental, and Catalysis Applications

Metallophthalocyanine-based Molecular Dipole Layer as a Universal and
Versatile Approach to Realize Efficient and Stable Perovskite Solar Cells
Fangchao Li, Jianyu Yuan, Xufeng Ling, Lizhen Huang,
Nopporn Rujisamphan, Youyong Li, Lifeng Chi, and Wanli Ma
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b15870 • Publication Date (Web): 13 Nov 2018
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Page 1 of 28 ACS Applied Materials & Interfaces
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Metallophthalocyanine-based Molecular Dipole
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Layer as a Universal and Versatile Approach to
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Realize Efficient and Stable Perovskite Solar Cells
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Fangchao Li,† Jianyu Yuan,†,* Xufeng Ling,† Lizhen Huang,† Nopporn Rujisamphan,‡ Youyong
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23 Li,† Lifeng Chi,† Wanli Ma†,*
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26 †Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-
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Based Functional Materials & Devices, Soochow University, 199 Ren-Ai Road, Suzhou
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31 Industrial Park, Suzhou, Jiangsu 215123, P. R. China
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34 ‡King Mongkut’s University of Technology Thonburi (KMUTT) 126 Pracha Uthit Rd., Bang
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36 Mod, Thung Khru, Bangkok 10140, Thailand
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Corresponding Author: jyyuan@suda.edu.cn (J. Y.); wlma@suda.edu.cn(W. Ma).
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42 KEYWORDS: metallophthalocyanine, perovskite solar cells, interfacial dipole, fluorination, and
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44 open-circuit voltage
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60 ACS Paragon Plus Environment

ACS Applied Materials & Interfaces Page 2 of 28
1
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3 ABSTRACT
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7 It is well known that tailoring the interfacial structure is very important for perovskite
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solar cells, especially for its performance and stability. Here, we reported a universal and
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12 versatile method of modulating the energetic alignment between the perovskite and hole
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14 transporting layer by introducing a multi-functional dipole layer based on metallophthalocyanine
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16 derivatives copperphthalocyanine (CuPc) or highly fluorinated copper
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19 hexadecafluorophthalocyanine (F16CuPc). Both molecules were introduced through an “anti-
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21 solution” process to treat the surface of organic-inorganic CH3NH3PbI3 perovskite. The dipole
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23 layer can well align the interfacial energy levels, passivate the CH3NH3PbI3 surface and fill the
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grain boundaries, resulting in greatly suppressed charge recombination. As a result, our planar
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28 CH3NH3PbI3 perovskite devices exhibit a best power conversion efficiency (PCE) of 20.2%, with
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30 significantly enhanced open-circuit voltages (Voc) of 1.112 V (CuPc) and 1.145 V (F16CuPc),
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which is a record high Voc value for CH3NH3PbI3 thin film solar cells. More importantly, the use
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35 of highly fluorinated F16CuPc produces a significantly more hydrophobic surface, leading to
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37 dramatically improved long-term stability under ambient conditions. We believe our study offers
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39 a general approach to making multi-functional dipole layers which are necessary for achieving
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42 both stable and efficient perovskite solar cells.
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3 1. INTRODUCTION
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6 The past decade has witnessed the rapid progress of organometal halide perovskite solar
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8 cells. Solar cells have benefited from the advantages of large absorption coefficients making the
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10 perovskite films absorb enough light even with a thin film, with high charge carrier mobility as
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well as long carrier diffusion lengths. The power conversion efficiency (PCE) which is the
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15 primary feature of the perovskite solar cells (PSCs) has already boosted from ~3.0 % to 23.3 %.1-
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17 5 One of the most popular structures of high-efficiency PSCs is called the n-i-p structure. In this
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structure, titanium oxide (TiO2) acts as the electron-transporting layer (ETL), meanwhile the
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22 2,2,7,7-tetrakis(N,N’di-p-methoxyphenylamine)-9,9-spirobifluorene (Spiro-OMeTAD) is
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24 adopted to be the hole-transporting layer (HTL).3-7 The interfacial layers (ETL and HTL) are
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26 very important because they have a big influence on the charge transmission. Many reports have
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29 proved that use of these layers can strongly optimize the morphology of the films and the
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31 crystallization of the perovskite film.8,9 In addition, the risk of forming pinholes, defects, grain
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33 boundaries and unfavorable grain orientation was high during the solution process as it is not
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very precise.10,11 Hence, the discovery of a new processing method for perovskite films will help
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38 gain more control over the film crystallization and better tune the interface.
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41 In order to modify the interface morphology of perovskite solar cells, plenty of processing
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43 methods have been utilized by people, such as vacuum treatment,12 solvent vapor annealing,13
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46 gas blowing 14 and antisolvent treatment.15 Due to the simple operating process and easy way of
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48 achieving a high PCE, the anti-solvent treatment developed by Seok et al. has been widely
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50 adopted by the community. Quite recently, several researches have claimed to modify the anti-
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solvent to “anti-solution” treatment, via compounds such as amino-based organic molecules,
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55 poly(methyl methacrylate) (PMMA), PCBM in antisolvent.16-18 The aim of these methods is to
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3 passivate the defects and facilitate the crystal size and to therefore improve the efficiency and the
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6 stability of the devices. However, there are no criteria in these reports investigating the way in
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8 which to select materials. Furthermore, the reported structures of the materials have almost been
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10 settled, as a consequence, heavily limiting the further improvement of the devices. With the
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tunable structures and desired functions, organic conjugated molecules exhibit the ability to
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15 further help modulate and control the perovskite film surface and therefore boost the device
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17 efficiency as well as the hydrophobicity of the film in the latest report, which provides new
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avenues to modulate the properties of the perovskite film.19,20,26,27
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23 Highly crystalline and ordered conjugated materials have exhibited sufficient charge
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25 carrier mobilities for application in light-emitting diodes, field effect transistors and solar cells.28-
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27 30 Among these functional materials, metallophthalocyanine (Metal-Pc) complex is ubiquitous
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because of its ease of synthesis, tunable chemical structure, high carrier mobility, and high
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32 thermal stability.31-32 Metal-Pc complexes such as CuPc, FePc, ZnPc, CoPc, NiPc and MnPc
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34 have been successfully developed and adopted in various applications in the past two decades.31-
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36 38 Fortunately, CuPc and its related derivatives have been recently used in n-i-p PSCs as the
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39 hole-conductor.39-42 However, the relatively low solubility further hinders its application in
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41 solution-processable devices. To solve this critical issue, we incorporated these functional
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43 materials into the antisolvent treatment process, which has a much lower requirement of
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46 solubility. The two most representative Metal-Pc complexes, CuPc and its fluorinated derivative
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48 F16CuPc were dissolved in antisolvent chlorobenzene at a dilute concentration (0.2 mg/mL) to
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50 treat the spinning CH3NH3PbI3 (MAPbI3) perovskite films. We discovered that both CuPc and
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F16CuPc can passivate CH3NH3PbI3 and promote the formation of a molecular dipole layer.
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55 Therefore, the modified CH3NH3PbI3 films exhibit reduced grain boundaries, improved
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3 crystallinity and a higher work function compared to the control film. We further prepared
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6 conventional planar perovskite solar cells adopting CH3NH3PbI3 as the light absorber. Solar cell
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8 devices modified with F16CuPc or CuPc output record open-circuit voltages and efficiencies of
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10 1.145 V and 20.2%, 1.112 V and 19.7% respectively, while the cell without any surface
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treatment only shows a Voc of 1.068 V and efficiency of 18.7%. More importantly, as the
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15 stability problem of PSCs against moisture is also thought to be the most crucial issue hindering
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17 the commercialization of perovskite solar cells.21-25 We found that the metallophthalocyanine
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derivatives treatment, especially the fluorinated one, can also produce a more hydrophobic
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22 surface, further leading to significantly improved long-term resilience to moisture.
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25 2. EXPERIMENTAL DETAILS
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27 2.1. Materials
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CuPc and F16CuPc were purchased from Sigma-Aldrich. Methylammonium iodide
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32 (CH3NH3I), PbI2 and Spiro-OMeTAD were purchased from Xi'an Polymer Light Technology
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34 Corp. Anhydrous dimethyl sulfoxide (DMSO) and γ-butyrolactone was purchased from Alfa
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36 Aesar.
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39 2.2. Devices Fabrication
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41 PSCs were fabricated with a structure of FTO/TiO2/MAPbI3/Spiro-OMeTAD/Au. The FTO glass
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43 substrates was ultrasonically cleaned and treated with UV−ozone for 20 min. The TiO2 films
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46 were deposited onto the substrates by the hydro-thermal method. Before the deposition of the
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48 perovskite films, a 10 min UV-ozone was carried. The MAPbI3 perovskite films were deposited
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50 through a one-step spin-coating process, with antisolvent dripping. CH3NH3I and PbI2 was
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dissolved in dimethylsulfoxide (DMSO) (99.9%, Alfa Aesar) and γ-butyrolactone (GBL)
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55 (99.9%, Alfa Aesar) (3:7, v/v) at 1.2 M and stirring in room temperature for 4 hours. The
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3 MAPbI3 precursor solution was coated onto the TiO2 substrate and spun at 1000 and 4000 rpm
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6 for 10 and 40 s, respectively. The antisolvent process was utilized to make the perovskite films
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8 with a better morphology and crystallization, in which 125 μL of chlorobenzene w/wo
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10 CuPc/F16CuPc was swiftly dripped onto the substrate 20 s preliminary to the end of the program
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during the high-speed spin-coating step. Additives with different concentration were dissolved in
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15 the chlorobenzene and stirred for 4 h at 45 oC before antisolvent process. The substrate was then
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17 dried at 100 °C for 10 min. A solution of 2,2′,7,7′-tetrakis(N,N-dip-methoxyphenylamine)-9,9′-
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spirobifluorene (spiro-OMeTAD, 90 mg, 99.5%; Xi’an Polymer Light Technology Corp.) in
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22 anhydrous chlorobenzene (1 mL) was mixed with 22 μL of lithium bis-
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24 (trifluoromethanesulfonyl) imide solution (520 mg mL−1 in anhydrous acetonitrile) and 36 μL 4-
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26 tertbutylpyridine and spin-coated on the MAPbI3 film at 5000 rpm for 30 s. Then a 100 nm of Au
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29 was deposited by thermal evaporation under vacuum of 2 × 10−6 mbar. The active area of the cell
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31 was defined as 7.25 mm2 through a shadow mask. The J−V curves of the devices were obtained
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33 with a Keithley 2400 digital source meter under simulated AM 1.5G spectrum at 100 mW cm−2,
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with a solar simulator (Class AAA, 94023A-U; Newport Corporation). The light intensity was
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38 calibrated by a National Renewable Energy Laboratory-certified Oriel reference cell (91150V).
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40 The incident photon-to-electron conversion efficiency (IPCE) spectra were recorded through
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certified IPCE equipment (Solar Cell Scan 100; Zolix Instruments Co. Ltd.).
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45 2.3. Measurement and Characterization
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47 SEM measurements were performed on field emission scanning electron microscope (Carl Zeiss
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49 Supra 55), GIWAXS measurements were performed at the Shanghai Synchrotron Radiation
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52 Facility (SSRF) Laboratory on Beamline BL14B1. Time-resolved confocal imaging system: ISS
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54 Q2 laser scanning nanoscope (ISS Inc., Champaign, Illinois, USA). Kelvin probe force
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3 microscopy (KPFM) measurements were performed under ambient conditions with an Asylum
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6 Research Cypher S AFM microscope. The X-ray diffraction (XRD) measurements were carried
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8 out on a PANalytical 80 equipment.
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11 3. RESULTS AND DISCUSSION
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The planar PSC were prepared using the sandwich structure as shown in Figure 1a, in
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16 which hydrothermal titanium dioxide(TiO2)26 was treated as the ETL. The hybrid MAPbI3
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18 perovskite acts as the active layer, which is in response to absorbing light, and Spiro-OMeTAD
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is the HTL. The molecular structures of metallophthalocyanine derivatives CuPc and F16CuPc
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23 utilized in this work are shown in Figure 1a. Figure 1b shows the structure of devices as
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25 depicted by the cross-sectional scanning electron microscopy (SEM), in which we can clearly see
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27 every single layer in the device. We found that the thicknesses of the TiO2 is only 40 nm, while
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30 the active layer is 300 nm and the Spiro-OMeTAD is 150 nm. Figure 1c draws the energy-levels
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32 of different components in the device. As shown in Figure 1a, we successfully incorporated a
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34 small amount of CuPc and F16CuPc into a halide perovskite thin film during the anti-solvent
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treatment. By finely adjusting the concentration of CuPc and F16CuPc in chlorobenzene, the
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39 optimal concentration of both CuPc and F16CuPc was found to be 0.2 mg/mL (Figure S1, Table
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41 S1-S2). Conventional anti-solvent chlorobenzene with/without (w/wo) metallophthalocyanine
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derivatives was quickly dropped onto the spinning perovskite and the as-cast MAPbI3 perovskite
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46 was further annealed at 100 oC to obtain a crystalline and dense film. The current density-voltage
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48 (J-V) characteristic curves of the optimized PSC devices under the AM 1.5 G illumination w/wo
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50 metallophthalocyanine derivatives are shown in Figure 2a, and the device’s parameters of
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53 different condition are listed in Table 1. The hysteresis and different scan direction at different
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55 delay time conditions with the results are shown in Figure S2 and Figure S3, respectively. As
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3 shown in Figure S3, the hysteresis of the CuPc and F16CuPc treated is slightly decreased
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6 compared to the control devices, which may be due to the reduced interfacial recombination.
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9 The best performance of PSC is achieved with the reverse scan with a PCE of 18.7%
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11 (average efficiency of 18.3±0.31% from 20 parallel devices), the Voc of the best device is 1.068
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13 V, with a short-circuit current (Jsc) of 22.8 mA cm−2, and a fill factor (FF) up to 0.77. After CuPc
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16 treatment, the PCE of the PSC shows a steady increase in the reverse scan to 19.7% (average
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18 efficiency of 19.3±0.43% from more than 20 devices), where the best Voc is 1.112 V, Jsc is 22.7
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20 mA cm−2, and FF is 0.78. More interestingly, after F16CuPc treatment, the PCE of the PSC shows
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23 a further increase in the reverse scan to 20.2% (average efficiency of 19.7±0.49% from more
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25 than 20 devices), where the best Voc is 1.145 V, Jsc is 22.9 mA cm-2, and FF is 0.77. The F16CuPc
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27 treated devices exhibit slightly improved Voc and PCE in comparison with CuPc treated ones,
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which may be due to the increased passivation within fluorinated molecules F16CuPc for reduced
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32 interfacial recombination. Apparently, relatively low-content CuPc or F16CuPc treatment will
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34 improve the solar cell performance, stemming from the significantly enhanced Voc (Figure 2b).
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36 However, in a more than optimal amount of cases, it will decrease the device’s performance
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39 (Figure S1). Meanwhile, we realized that the addition might have an effect on both perovskite
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41 and Spiro-OMeTAD. To elucidate the possible effect of CuPc diffusion into Spiro-OMeTAD, we
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43 also fabricated the PSCs with Spiro-OMeTAD doped with various amounts of CuPc. With the
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46 addition of more CuPc, the PCE of the device gradually decreases (Figure S4), suggesting an
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48 adverse effect on device performance. Therefore, the device’s improvement can be mainly
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50 attributed to the in-situ incorporation of CuPc and F16CuPc into MAPbI3 perovskite during the
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film formation. Under the light of AM1.5 G photon flux, Figure 2c exhibits the external
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55 quantum efficiency (EQE) and the corresponding integrated products of the device with the best
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3 performance. The integrated values of short-circuit current (Jsc) are 21.0 mA cm-2 for the pristine
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6 one, 21.2 mA cm-2 for CuPc and 21.2 mA cm-2 for F16CuPc treatment. The mismatch between
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8 the integrated Jsc and the values obtained from the J-V measurements are all around 7%. To
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10 understand the stabilized power output under working conditions, we measured the photocurrent
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of the best performance as a function of time(Figure S11, Supporting Information). The
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15 photocurrent stabilizes instantly at ~22.5 mA cm−2, with a stabilized PCE of 19.4%. This J–V
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17 scans provide a more direct representation of the steady power output of our photovoltaic
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devices.
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23 To further confirm the mechanisms for device improvement, systematic characterizations
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25 were carried out to gain insight into the charge recombination kinetics, morphology,
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27 crystallization process, trap state density and the interfacial energy level alignment. Firstly, we
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study the dependency of Jsc (Figure S5) and Voc (Figure 2d) on light intensity for devices w/wo
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32 treatment. The Jsc is expected to demonstrate a power-law dependence on light intensity I, (Jsc
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34 Iα).43 The data is plotted on a log-log scale and fits to a power factor, α. The reference device
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37 yields an α = 0.97, which is similar to the devices with CuPc (α= 0.97) and F16CuPc (α= 0.98)
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39 treatment. These values were proved to be weakly dependent on the light intensity in literature.44
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41 There is also some proof suggesting that the monomolecular recommendation which was caused
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44 by defect sites is what caused carrier losses, while bimolecular recombination may have rather
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46 minor losses.45 The slope of Voc vs. light intensity is a parameter which is equal to kT/q in the
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48 ideal case(where k represents the Boltzmann constant, T is the temperature, and q is the
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quantitative value of the elementary charge) if bimolecular recombination is dominant. If Voc
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53 changes rapidly with changes in light intensity, the slope is larger than kT/q.46 We can clearly see
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55 in Figure 2d that the slope is larger in the case of CuPc (1.64 kT/q) and F16CuPc (1.62 kT/q)
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3 treatment as compared to the control one (1.89 kT/q). This suggests that the
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6 metallophthalocyanine has largely improved the device’s performance by reducing the
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8 monomolecular SRH recombination.
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11 Scanning electron microscopy (SEM) was utilized to examine the morphology of the film
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13 surface w/wo metallophthalocyanine molecules. (Figure 3)47,48 SEM images are shown in
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16 Figure 3a-3c with different MAPbI3 perovskite films w/wo metallophthalocyanine derivatives
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18 treatment. Pristine MAPbI3 has a very smooth morphology on the surface of the film. There are
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20 however obvious grain boundaries present, as demonstrated in previous reports.27, 49 To further
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23 learn about the changes in morphology in the MAPbI3 perovskite film with different anti-
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25 solution treatment, we performed a GIWAXS measurement to assess the crystallinity and crystal
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27 orientation. Figure 3d-3f illustrates the GIWAXS patterns of the investigated perovskite layer.
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The diffraction peak of CuPc and F16CuPc cannot be observed due to the strong peaks from the
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32 perovskite films as well as the small concentration used. The GIWAXS pattern of all of the films
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34 exhibit typical scattering features which are due to the pristine perovskite crystalline, with peaks
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36 being most prominent at q=10nm-1 and q=20nm-1.26,48 Additionally, we can see that the intensity
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39 of (110), especially the (220) diffraction peak of MAPbI3 perovskite is slightly enhanced after
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41 either CuPc or F16CuPc treatment. At the same time, we have found that in the 2D GIWAXS
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43 profiles a similar trend exists when we take a line-cut of the result. (Figure S6) The improved
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46 crystallinity may indicate less traps and carrier recombination. Meanwhile, all these films exhibit
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48 remarkable (110) peaks at an angle of 90o (Figure S7), while the addition of a small amount of
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50 CuPc or F16CuPc in the anti-solution process gives some improvement to the orientation of the
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crystalline.
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3 The electrical properties of MAPbI3 perovskite after treatment were then investigated by
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6 advanced time-resolved confocal imaging. The imaging experiments are described in SI. The
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8 digital frequency domain technique named FastFLIM was acquired to characterize the MAPbI3
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10 perovskite film. FastFLIM can mark down the photon counts when they pass through a certain
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number of cross-correlation phase bins and then represent the result as phase histograms.50 An
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15 advantage of FastFLIM is that it has nearly no dead time and counts the photons in 100% duty
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17 cycle, providing a very efficient method for lifetime data acquisition. This is very useful for
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accurate lifetime imaging of perovskite samples, since these samples are typically very bright
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22 and can produce very high count rates. Using time-resolved confocal lifetime imaging, both
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24 intensity and lifetime images were simultaneously obtained at a high diffraction-limit spatial
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26 resolution (~250 nm). As shown in Figure 4a, the MAPbI3 film without molecule addition
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29 shows slightly stronger photoluminescence intensity. In comparison, by adding F16CuPc, the film
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31 exhibits quenched photoluminescence, which can be ascribed to the charge transfer at their
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33 interface. The quantitative photon-counting confocal imaging gives us the chance to make out
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the photoluminescence distribution of the MAPbI3 film, which reveals the surface-trap-state
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38 information. We found that the treated films have a more homogeneous surface PL distribution,
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40 showing the modification effect of organic molecules on the perovskite surface. The Lifetime
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images, along with the lifetime histograms were compared to study the dynamics of charge
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45 carrier recombination in the MAPbI3 perovskite film after the introduction of organic molecules.
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47 Compared to conventional time-resolved photoluminescence (TRPL) spectroscopy, the time-
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49 resolved confocal imaging allows us to assess the photoluminescence lifetime distribution of the
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52 sample at a sufficient scale of 40×40 μm with a fine resolution. As expected, the addition of
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54 either CuPc or F16CuPc can increase the lifetime of MAPbI3 perovskite films. As shown in
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3 Figure 4b, the average lifetime increase from 3.3 ns (pristine MAPbI3 film) to 5.5 ns (with
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6 CuPc) and 5.1 ns (with F16CuPc). We used steady-state photoluminescence (PL) to confirm these
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8 results. The introduction of CuPc and F16CuPc into the perovskite layer quenches and slightly
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10 blue-shifts the PL peak. (Figure S8) This blue-shifting of PL peak is a result of a weaker
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spontaneous radiative recombination which is commonly thought to be caused by trap-states.18
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15 All of these results demonstrate that the addition of CuPc or F16CuPc can help passivate the
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17 surface of MAPbI3 perovskite, as consistent with the results in Figure 2d. The modification of
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perovskite films can result in enhanced exciton lifetimes, efficient charge carrier extraction, and
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22 improved photovoltaic efficiency.
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25 Although the absolute work function (WF) values from KPFM measurement may not be
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27 accurate, the relative Fermi level comparison between different samples is still valid. The detail
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30
of KPFM measurements are described in SI. As shown in Figure 4c, the 5 × 5 μm scan area is
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32 measured on perovskite samples. The mean distribution of surface potential difference (SPD)
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34 between Ti/Ir-coated tip and the samples is 321 mV, -346 mV and -532 mV for neat MAPbI3
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36 film, MAPbI3 with CuPc and MAPbI3 with F16CuPc respectively. As described in the supporting
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39 information:
. Therefore, the WF of the MAPbI3 with CuPc
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41 and F16CuPc is 0.67 eV and 0.85 eV higher than the neat MAPbI3 perovskite film. The energy
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levels alignment at the contact interfaces, including both HTL and ETL, was found to be an
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46 important factor in determining the device’s energy losses and output voltage.51 By adding a
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48 small amount of CuPc or F16CuPc in the anti-solution process, the surface potential of the
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50 MAPbI3 perovskite film was significantly impacted. Since KPFM is a surface characterization
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53 technique, a significant change in the WF is very likely due to the formation of a surface dipole
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55 layer, which has been reported in previous work by using highly ordered organic molecules.52, 53
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3 As shown in Figure 1c, the surface dipole results in a large increased offset of the energy levels
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6 between the valence band (VB) of perovskite and the HOMO level of Spiro-OMeTAD HTL.
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8 Thus, the transmission of the hole from the perovskite film to the Spiro-OMeTAD will be faster.
9
10 In addition to this, CuPc can help transfer holes since it has been used as an efficient hole
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12
13
extractor applied in perovskite solar cells.39-42 Therefore, the introduction of CuPc and F16CuPc
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15 leads to the reduced interfacial recombination and improved Voc in these devices.
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18 Finally, we investigated the effect of metallophthalocyanine molecule treatment on device
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20 stability, since long-term stability is the most critical factor for the large-scale application of
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23 current perovskite solar cells. A preliminary test of stability under ambient conditions
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25 (Temperature: ~25 oC, relative humidity: ~30%) without any encapsulation shows that the
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27 stability of devices with CuPc and F16CuPc surface treatment is improved compared to the
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30
control device (Figure 5a-5b). In the meantime, we realized that HTL Spiro-OMeTAD with
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32 lithium salt doping is sensitive to moisture exposure.54 Hence, we introduced the
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34 metallophthalocyanine molecules into the Spiro-OMeTAD HTL to enhance its resistance to
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36 moisture. Indeed, as shown in Figure 5a, the devices that have undergone simultaneous addition
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38
39 of molecules in both perovskite and HTL are significantly more resistant to ambient conditions
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41 than the control device. There is only a ~5% (F16CuPc) and ~10% (CuPc) efficiency drop after
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43 1000 hours storage in ambient conditions, whereas the PCE drops over 20 % from its initial
44
45
46 value for the control device. It is well known that organic-inorganic hybrid perovskite MAPbI3
47
48 can easily dissociate into PbI2 and volatile CH3NHI3 in the presence of moisture.55 X-ray
49
50 diffraction (XRD) (Figure 5c) analysis was then carried out to demonstrate the correlation
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52
53
between the stability degradation and the decomposition of the perovskite into PbI2. After 30
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55 days of storage under ambient conditions, a diffraction peak at 12.5o appears in the control
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59

1
2
3 sample, which corresponds to the PbI2 phase. In contrast, the addition of CuPc can effectively
4
5
6 suppress the PbI2 phase growth in the perovskite films. Treatment with F16CuPc can even fully
7
8 preserve the crystal structure of MAPbI3, indicating that the highly fluorinated molecules can
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10 provide a strong shielding effect from environmental moisture. The protection effect of these
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13
metallophthalocyanine derivatives on device films can be clearly observed, as shown in Figure
14
15 S9d-9f. To reveal the possible mechanism, we conducted contact-angle measurements in which
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17 we let a 2 μL water droplet drip on the films of pristine MAPbI3, MAPbI3 with CuPc and
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19
F16CuPc (Figure S9g-9i). The corresponding contact angles were found to be 43.53°, 65.21° and
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22 71.36°. These results demonstrate that by introducing metallophthalocyanine molecules,
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24 especially the fluorinated ones, the surface of the perovskite films will change from being
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26 hydrophilic to hydrophobic. This is an improvement to the devices in that they are more resilient
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29 to environmental moisture.
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32 4. CONCLUSION
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34 In summary, we have demonstrated a facile “anti-solution” process using
35
36 metallophthalocyanine molecules CuPc and F16CuPc to boost the performance as well as the
37
38
39 stability of MAPbI3 perovskite solar cells. Both CuPc and F16CuPc can well passivate the
40
41 CH3NH3PbI3 surface, fill the grain boundaries and improve the film quality. Hence the perovskite
42
43 solar cells with “anti-solution” treatment output an optimal Voc of 1.145 V and a high efficiency
44
45
46 of 20.2%, while the control device under same conditions gave a Voc of only 1.068 V and an
47
48 efficiency of 18.7%. More importantly, the simple treatment using the highly fluorinated
49
50 metallophthalocyanine derivative can achieve a significantly more hydrophobic surface, leading
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53
to a dramatically improved long-term stability without encapsulation against ambient conditions.
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59

1
2
3 The easy access of materials and simple solution-process reported here may provide a routine
4
5
6 treatment to achieve perovskite solar cells with longer stability and higher efficiency.
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12
FIGURES
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38 Figure 1. a) The picture on the left is schematic illustration of a perovskite solar and the
39 molecular structural formula of CuPc and F16CuPc can be seen on the right, b) cross-sectional
40 SEM image shows the side view of the devices and c) energy-level diagram of the devices in this
41 work. The dashed line indicates the perovskite film treated with CuPc or F16CuPc.
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32 Figure 2. a) J-V curves of the perovskite solar cells with/without CuPc or F16CuPc, all of the
33 measurements were conducted under AM 1.5 simulated sunlight; b) the PCE and open voltage
34 distribution of the devices with 20 devices; c) EQE and integrated Jsc spectra of the devices w/wo
35 CuPc or F16CuPc; c) d) Voc dependence on illumination intensity w/wo CuPc or F16CuPc,
36 together with linear fits.
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41 Figure 3. SEM images of the surface morphology of a) pristine MAPbI3, b) MAPbI3+CuPc and
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c) MAPbI3+F16CuPc; the results of the 2D GIWAXS measurement are presented and colored to
44 emphasis the peaks: d) pristine MAPbI3, e) MAPbI3+CuPc and f) MAPbI3+F16CuPc.
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39 Figure 4. a) The photoluminescence; b) lifetime imaging; and c) surface potential images of
40 pristine MAPbI3, MAPbI3+CuPc and MAPbI3+F16CuPc film, insert: the lifetime histogram and
41 the value of surface potential of each sample extracted from 2D lifetime images and KPFM
42 measurements, respectively.
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28 Figure 5. The stability test with different perovskite solar cells in an ambient environment
29 without encapsulate; a) pristine MAPbI3 and MAPbI3 with CuPc in CB, Spiro-OMeTAD and
30 both; b) pristine MAPbI3 and MAPbI3 with F16CuPc in CB, Spiro-OMeTAD and both; c) XRD
31 patterns before and after 30 days of corresponding films on quartz substrate, which were exposed
32 to ambient conditions.
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34
35
Table1. Perovskite based devices w/wo CuPc or F16CuPc were measured under AM 1.5 G
36 illumination.
37 Voc Jsc PCE a)
38 FF
(V) (mA/cm2) (%)
39
40 1.068 22.8 0.77 18.7
MAPbI3
41 (1.05±0.013) (22.3±0.5) (0.75±0.03) (18.3±0.31)
42
43 1.112 22.7 0.78 19.7
MAPbI3+CuPc
44 (1.09±0.012) (22.3±0.4) (0.75±0.02) (19.3±0.43)
45 1.145 22.9 0.77 20.2
46 MAPbI3+F16CuPc
(1.13±0.015) (22.4±0.5) (0.76±0.01) (19.7±0.49)
47
aeach result is measured from at least 20 devices.
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59

1
2
3 ASSOCIATED CONTENT
4
5
6
7 Supporting Information
8
9
10 The preparation of perovskite solar cell; device optimization, device performance with different
11
12 CuPc and F16CuPc addition and hysteresis results of J-V test; the line-cuts of 2d-GIWAXS,
13
14
15
steady PL, time-resolved confocal imaging and KPFM characterization. This material is
16
17 available free of charge via the Internet at http://pubs.acs.org.
18
19
20 Corresponding Author
21
22
23 jyyuan@suda.edu.cn (J. Yuan)
24
25 wlma@suda.edu.cn (W. Ma)
26
27
28 Author Contributions
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30 The manuscript was written through contributions of all authors. All authors have given approval
31
32
33 to the final version of the manuscript.
34
35
36 Notes
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38
39
The authors declare no competing financial interest.
40
41
42 ACKNOWLEDGMENT
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44 This work was supported by the National Natural Science Foundation of China (Grant No.
45
46
51761145013, 61674111, and 51773143), the National Key Research Projects (Grant No.
47
48
49 2016YFA0202402), the Natural Science Foundation of Jiangsu Province of China
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51 (BK20170337), and “111” projects. The author thanks the Collaborative Innovation Center of
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53 Suzhou Nano Science and Technology, Soochow University, the Priority Academic Program
54
55
56 Development of Jiangsu Higher Education Institutions (PAPD). We also acknowledge Dr.
57
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59

1
2
3 Yuansheng Sun from ISS, Inc. for the helpful advanced time-resolved confocal imaging
4
5
6 measurements, and Timofey Abramski for proofread the manuscript.
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8
9
10
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10 Chen, W.; Chen, S.; Huang, H.; Qi, D. C.; Gao, X. Y.; Wee, A. T. S. Molecular
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Leung, K.; Zhu, X. Understanding the Interface Dipole of Copper Phthalocyanine
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25 Reproducibility Using a Thin Film Sandwich Approach. Adv. Mater. 2014, 26, 2041-
26
27 2046.
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30 Nenon, D. P.; Christians, J. A.; Wheeler, L. M.; Blackburn, J. L.; Sanehira, E. M.; Dou,
31
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35 Solution. Energy Environ. Sci. 2016, 9, 2072-2082.
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1
2
3
4
5
6
7 TOC GRAPHICS
8
9
10
11 24
12
13 PCE=20.2%
14
H H F F
H H F F
H H F F
20
15 H H F N N F
N N
16
Current Density (mA/cm )
Cu
2
Cu
17
N N F N N F
H H
18 16 H
H
H H
H
H F
F
F F
F
F
19 CuPc F16CuPc
20
21
Dipole Layer
12
22
23
MAPbI3
24
MAPbI3
8 TiO2 Spiro-
25 FTO OMeTAD
26
Au
27
28 4
29
30
CuPc
F16CuPc Voc
31 0
32 0.0 0.2 0.4 0.6 0.8 1.0 1.2
33 Voltage (V)
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
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Metallophthalocyanine-Based Molecular Dipole Layer As A Universal and Versatile Approach To Realize Efficient and Stable Perovskite Solar Cells

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