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Article
Cs-incorporated AgBiI4 Rudorffite for Efficient and Stable Solar Cells
Fengyang Yu, Liang Wang, Kuankuan Ren, Shuzhang Yang, Zhenhua Xu, Qianji Han, and Tingli Ma
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.0c00496 • Publication Date (Web): 10 May 2020
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Cs-incorporated AgBiI4 Rudorffite for Efficient and
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Stable Solar Cells
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16 Fengyang Yu,† Liang Wang,*,† Kuankuan Ren,‡ Shuzhang Yang,† Zhenhua Xu,†Qianji
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19 Han,†Tingli Ma*,†,‡
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22 †Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, 2-
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24 4 Hibikino, Wakamatsu-ku, Kitakyushu, Fukuoka 808-0196, Japan
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College of Materials and Chemistry, China Jiliang University, No. 258, Xueyuan Street, Xiasha
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30 Higher Education Zone, Hangzhou, Zhejiang, 310018, P. R. China.
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33 Corresponding Authors
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35 *E-mail: tinglima@life.kyutech.jp
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37 *E-mail: wangliang@life.kyutech.ac.jp
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42 ABSTRACT
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45 The Ag-Bi-I system has recently attracted much attention as a potential material for use in Pb-free
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47 solar cells due to its low toxicity and good stability. However, the main issue of the Ag-Bi-I
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50 rudorffite solar cells is that the power conversion efficiency (PCE) is still quite low. In this study,
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52 a series of CsxAg1-xBiI4 absorbers were synthesized by introducing different amount of Cs via a
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54 simple method. It was found that Cs incorporation is promising for achieving dense and pinhole
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3 free CsxAg1-xBiI4 films. In addition, the valence band edge of 5% Cs cooperated film is slightly
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6 upshifted. The corresponding CsxAg1-xBiI4 rudorffite solar cells achieved an enhancement of 40%
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8 in PCE for both the mesoporous structure and planar structure solar cells. After the Cs cooperation,
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10 the devices also show a better long-term air stability than that of pure AgBiI4.
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KEYWORDS: rudorffite solar cells, Cs incorporation, AgBiI4, lead free, high stability.
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16 INTRODUCTION
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19 Organic−inorganic hybrid lead halide perovskite solar cells (PSCs) have attracted wide attention
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21 and the PCE increased from 3.8% to 25.2% due to its excellent photoelectric properties1-3.
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Nevertheless, there are still some issues for these PSCs, such as the use of toxic Pb and poor
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26 stability4-6. Thus, for promoting the commercial applications of the perovskite photovoltaic
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28 technology, it is essential to further explore the low-toxicity or non-toxicity, and stable light-
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30 absorbing materials7. Many researchers have recently focused on lead-free perovskite (-like)
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33 materials to solve the toxic problem8. Sn-based and Ge-based perovskites have attracted significant
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35 attention due to their similar properties to Pb. However, the undesirable oxidization of Sn2+ to Sn4+
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37 and Ge2+ to Ge4+ limits their stability9-10. Bi-based and Sb-based compounds have also been studied
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based on the A3B2I9 formula, where A is Cs+ or MA+, etc., and B is Bi3+ or Sb3+. These materials
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42 always suffer from their large band gap (Eg >2.1 eV), and do not have a 3D structure or direct
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44 bandgap11-12. Furthermore, double perovskite materials also have an unsuitable band gap for
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photovoltaics13-14.
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49 The Ag-Bi-I system has recently attracted much attention as emergent materials for high stability
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51 and low toxic absorbers in solar cells15-25. The Ag−Bi−I ternary family exhibits an edge-shared
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53 [AgI6] and [BiI6] octahedra 3D structure with the general formula of AgaBibIa+3b. The studied
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56 AgBiI4, Ag2BiI5, Ag3BiI6, and AgBi2I7 compositions display a direct band gap of 1.79 – 1.83 eV.
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3 Sargent and coworkers first reported the AgBi2I7 photovoltaic device with the PCE of 1.22% in
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6 201626. Later, Turkevych et al. reported Ag3BiI6 with the maximum efficiency of 4.3% via the
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8 solid reaction of the raw materials27. Lu et al. recently reported a photovoltaic device based on
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10 AgBiI4 with the PCE of 2.1%28. The PCE of Ag-Bi-I system solar cells increased from 1.2% to
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4.3% suggesting a significant aim for further improvements. Pai et al. reported solar cells based
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15 on silver bismuth sulfoiodides (Ag3BiI5.92S0.04) with the best PCE of 5.56% by the Ar-assisted
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17 method, where S incorporation increased the valence band edge29. By using SnO2 as an electron
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transport layer (ETL) and adding Li-TFSI, Xiao and co-workers obtained a high open-circuit
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22 voltage (VOC) for the AgBiI4 solar cells30. These results suggest that silver bismuth iodides are
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24 solution-processable, air-stable, lead-free photovoltaic materials31. However, the high
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26 performance Ag-Bi-I solar cells always rely on a special method, and a simple method for
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29 improving the performance of the solar cells is required.
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31 These studies have been carried out for enhancing the PCE of hybrid perovskites by Cs
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33 incorporation. Choi et al. reported Cs/MA mixtures increasing the perovskite PCE to 8%32. With
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the Cs incorporation, Park enhanced the PCE of FA-perovskite solar cells to 16.5%33. Furthermore,
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38 Yi et al. showed that Cs is effective in assisting the crystallization of FA-perovskite due to entropic
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40 stabilization34. Zhou et al. demonstrated that CsI pre-intercalation in the inorganic framework
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greatly impact the grain growth process and improve the device stability35. Yang et al. reported
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45 Cs-doped triple cation perovskite films leading to impressively enhanced photoluminescence
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47 lifetime and open circuit voltage (VOC)36. These studies show that Cs-incorporation is very
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49 effective for obtaining large crystal grains and a higher PCE. Inspired by the higher performance
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52 of the Cs-mixed-cation lead perovskite, the investigation of Cs-mixed-cation Ag-Bi-I compounds
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3 is highly motivating. In addition, studies about Cs in rudorffites are meaningful as CsxAg1-xBiI4
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6 has not yet been reported.
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8 In this study, we synthesized a series of CsxAg1-xBiI4 absorbers and systematically investigated the
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10 effect of Cs incorporation. The CsxAg1-xBiI4 based solar cells employed TiO2 and poly [bis (4-
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phenyl) (2,4,6-trimethylphenyl) amine] (PTAA) as the electron and hole transporting layer (HTL),
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15 respectively. Thus, the average PCE of CsxAg1-xBiI4 solar cells improved by 40% in mesoporous
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17 structure devices. For cooperating with 5% Cs, the highest PCE is 1.58%. However, the best PCE
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is about 1.05% with no Cs cooperation. In the planar SnO2-based solar cells, the VOC improved to
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22 0.8 V as reported in the literature, and Cs-containing solar cells also showed a higher PCE than
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24 that of pure AgBiI4, which are 1.38% and 0.98%, respectively. The improvements are caused by
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26 the Cs cooperation, which enhances the crystallinity and increases the valence band edges, thus
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29 reduce the non-radiative recombination and promote the carrier transport. In addition, Cs
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31 cooperated solar cells show a better long-term stability than that of pure AgBiI4.
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33 EXPERIMENTAL SECTION
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36 Materials.
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39 AgI (99.999%), BiI3 (99%), Cesium iodide (CsI, 99.9%), dimethyl sulfoxide (DMSO), N,N-
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41 dimethylformamide (DMF) and Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] PTAA were
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43 purchased from Sigma-Aldrich. SnO2 colloid (tin (IV) oxide) precursor was purchased from Alfa
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46 Aesar. SnCl2 (99.9%) was purchased from Wako. The FTO-coated and ITO-coated glass was
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48 purchased from Yingkou OPV Tech Co., Ltd. All these commercially available materials were
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50 used as received without any further purification.
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Fabrication of Electron Transport Layer.
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3 Hydrochloric acid etched FTO-coated glass substrates were cleaned with ethanol, acetone,
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6 isopropanol and ethanol by ultrasonication for 15 min, then dried in an oven, followed by treating
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8 with ultraviolet ozone for 20 min. The TiO2 compact layer was spin-coated at 3000 rpm for 30 s
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10 onto the FTO substrates, then the compact TiO2 (c-TiO2) layer was annealed at 500 ℃ for 30 min
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and cooled to room temperature. After treated with ultraviolet ozone for 20 min, the substrates
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15 were treated with a 4 × 10−3 M TiCl4 aqueous solution for 30 min at 70 °C. The FTO substrates
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17 coated with c-TiO2 were then washed with distilled water and ethanol, followed by drying in an
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oven. For the mesoporous TiO2 (m-TiO2) structure, the resultant colloid TiO2, centrifuged at a 1:6
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22 weight ratio of the colloid in ethanol, was spin-coated at 5000 rpm for 30 s onto the c-TiO2. The
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24 substrate was annealed at 450 ℃ for 30 minutes and cooled to room temperature.
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26 The SnO2 colloid precursor (Alfa Aesar, 15% in H2O colloidal dispersion) was diluted in H2O to
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29 2.67% and spin-coated onto ITO/glass substrates at 2000 rpm for 30 s, then baked on a hot plate
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31 in ambient air at 150 °C for 30 min. The SnCl2 ethanol solution (0.1 M) was then deposited on the
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33 SnO2 nanoparticles film (NPs) and baked at 100 °C for 10 min and 180 °C for 1 hour.
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Fabrication of rudorffite solar cells.
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38 The 0.6 M AgBiI4 precursor was prepared by dissolving AgI/BiI3 powders at the molar ratio of 1:1
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40 in DMSO and DMF with v/v of 4:1. As for the Cs cooperation precursor, with different amounts
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of cooperated CsI (0%, 1%, 5%, 10%, 50% and 100%), which should reduce the amount of AgI,
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45 such as a 10% cooperation, CsI is 0.06M and AgI is 0.54M, and the ratio of Cs/(Cs+Ag) is 10%.
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47 The precursor was then stirred overnight at room temperature.
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49 Spin-coating the precursor in a glovebox to obtain the AgBiI4 film followed a literature procedure28,
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52 then the film was stored at 35 oC for 5 min and subsequently at 130 oC for 15 min. We choose
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3 PTAA as the HTL by spin-coating the precursor in 3000 rpm for 30 s, and the concentration was
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6 10 mg/mL in toluene. Finally, the silver electrode was deposited by thermal evaporation.
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8 Characterization
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10 XRD patterns were recorded by using a Rigaku Co. Ltd. (Tokyo, Japan) X-ray diffractometer with
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Cu Kα radiation (λ=1.54056 Ǻ). The morphology of the absorber layers was captured by field
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15 emission SEM (FE-SEM) (JSM-6701, JEOL). XPS analysis was performed by Shimadzu Kratos
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17 AXIS-NOVA spectrometer using monochromatic AlKa (1486.6 eV) as the radiation source. The
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XPS spectra were calibrated by the binding energy of 284.8 eV for C 1s. The ultravioletvisible
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22 (UV) absorption spectra were recorded using a UV/Vis-NIR spectrophotometer with a wavelength
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24 ranging from 300–900 nm at room temperature (V-670, JASCO Co. Ltd., USA). PL (excitation at
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26 510 nm) spectra were measured using a FLS980 spectrometer (Edinburgh Instruments Ltd) and
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29 TRPL spectra were measured with a PicoQuant FluoQuant 300. Photovoltaic performances were
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31 measured using Bunko Keiki BSOX150LC solar simulator under an illumination power of 100
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33 mW cm-2 under AM 1.5G conditions with cell area was controlled at 0.08 cm2 by a black metal
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mask. The solar simulator was first calibrated with an amorphous Si photodetector (Bunko Keiki
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38 BS-520 S/N 353) prior to use. The incident photon-to-current efficiency (IPCE) was characterized
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40 by using a monochromatic Xenon lamp (Bunkouki CEP-2000SRR).
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RESTULTS AND DISCUSSION
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46 A mixture of AgI and BiI3 powders (0.6 mmoL) with the molar ratio of 1:1 was dissolved in 1 mL
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48 of a mixed solvent of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) (4:1, v/v),
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50 then the prepared solution was stirred overnight. The Ag−Bi−I films were deposited via the one-
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step spin-coating method with toluene as the anti-solvent. First, the annealing temperature had
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55 been optimized at which 130 oC and 150 oC for 15 min were employed. The current
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3 density−voltage (J−V) curves of the best PCE and statistical PCE are shown in Figure S1 and
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6 Table S1, respectively. Annealing the film at 130 oC for 15 min showed a higher short-circuit
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8 current (JSC) (2.79 mA/cm2) and the average PCE was 0.83%. Interestingly, after the precursor
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10 was spin-coated, we found that the gap time between spin-coating and annealing critically affects
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the device performance. Figure S2 and Table S2 show the best and average PCE obtained from
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15 different gap time, and 5 min gap time showed better performance. The gap time affecting the
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17 evaporation of the extra solvents, which lead to the rudorffite film obtained slow recrystallization37.
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As shown in Figure S3, the rudorffite AgBiI4 film shows fewer pinholes and flatter surfaces for
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22 the gap time of 5 min compared to the gap time of 0 min and 10 min. Besides, we indicated that
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. Thus, the best conditions for depositing AgBiI4 films are stored the film at around 35 oC for 5
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29 min and annealing it at 130 oC for 15 min.
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31 We discovered that the color of the precursor became darker as the ratio of CsI:BiI3 increased. The
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33 corresponding prepared films changed from brownish to orange, as shown in Figure S4a. The XRD
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patterns indicated that when the precursor is composed of CsI and BiI3 in the ratio of 1:1, all the
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38 peaks of the prepared film are quite consistent with the JCPDS card no. 23-0847, which indicated
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40 that Cs3Bi2I9 synthesized under this condition. As shown in Figure S4b, the main dominant 2θ
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diffraction peaks (black dotted lines and black square) at 8.34°, 16.71°and 25.17°, which are
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45 assigned to the crystallographic planes (002), (004) and (006) of the Cs3Bi2I9 hexagonal-phase,
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47 respectively. When the precursor is composed of AgI and BiI3 in the ratio of 1:1, the main
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49 dominant diffraction peaks (red dotted lines and red star) at around 2θ = 12.78°, 29.25°and 41.45°
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52 are assigned to the crystallographic planes (111), (400) and (440) of the AgBiI4 cubic-phase,
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Figure 1. (a) XRD patterns and (b) Absorption spectra of AgBiI4 films with 0%, 1%, 5% and 10%
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21 respectively. In the 10% Cs prepared film, both the AgBiI4 and Cs3Bi2I9 phases exist, thus we
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26 To improve the quality of the AgBiI4 film, CsI was employed as cooperation to the precursor
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28 solution and the concentration of CsI was 0%, 1%, 5% and 10%. As shown in Figure 1(a), the
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30 prepared CsxAg1-xBiI4 films adopt a cubic defect-spinel structure. For pristine AgBiI4 film, there
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is substrate SnO2 peak (marked as #), which is accord with the poor morphology .In addition, we
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35 observed impurity (marked as *) and the detailed XRD patterns are shown in Figure S5. The XRD
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37 intensity was enhanced as the Cs cooperation increased from 1% to 10%, indicating a higher
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crystallinity of the CsxAg1-xBiI4 film, and thus we speculate that the Cs cooperation can improve
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42 the quality of the films. Furthermore, the full width at half maximum (FWHM) values of (111),
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44 (400) and (440) planes are summarized in Table S3, the values gradually decrease as the amount
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of Cs increase, which indicate the CsxAg1-xBiI4 films achieve a higher crystallinity after Cs
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49 incorporation.
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51 The ultraviolet-visible-near infrared spectrometer (UV-vis-NIR) absorption spectra of the films
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53 are shown in Figure 1(b), and the absorption edge is around 686 nm for AgBiI4. The corresponding
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56 Tauc plot as shown in Figure S6, from which we obtained the 1.93 eV band bap of the AgBiI4
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30 Figure 2. The XPS core-level spectra of (a) Cs 3d, (b) Ag 3d, (c) Bi 4f and (d) I 3d at different Cs
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cooperation.
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35 film, which is similar to the reported literature30. The band gap of Cs cooperated films increased
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37 from 1.93 eV to 1.95 eV, and the best absorbance appears at a 5% Cs cooperation. The absorption
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39 edge has a blue shift around 10 nm for the 10% Cs cooperation, and we speculate this was caused
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42 by the impurity phase of Cs3Bi2I9 as we have discussed above, which produced a larger indirect
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44 band gap (2.23 eV)39.
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46 To illustrate the incorporation of Cs atom into rudorffite CsxAg1-xBiI4, X-ray photoelectron
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spectroscopy (XPS) measurements was conducted. As shown in Figure S7, the major elements of
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51 silver, bismuth, iodine and cesium are presented in the survey scan for the 10% Cs cooperated
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53 CsxAg1-xBiI4 film, indicating the successful incorporation of Cs into the AgBiI4 films. The small
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peaks of the oxygen, carbon and titanium are most likely from the ETL. The amount of the
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3 corresponding elements in the prepared film was calculated in Table S4. Considering the new
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6 Cs3Bi2I9 phase that emerged with the large amounts of cooperated Cs, Cs content in film is far less
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8 than precursor, and simulated XRD pattern Cs0.1Ag0.9BiI4 (Figure S8) shifted to small angle
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10 compared with AgBiI4, we speculate that the Cs atom is hard to replace Ag. Therefore, the
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incorporated Cs located in crystal vacancies. Figures 2(a)-(d) showed that the correlated Cs, Ag,
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15 Bi, and I peaks shifted toward a higher binding energy with increasing Cs cooperation
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17 concentration, which can be attributed to the stronger interaction of these atoms. In greater detail,
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the Cs 3d core-level for 5% Cs-cooperated film exhibits two intense peaks of Cs 3d3/2 and 3d5/2,
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22 and the corresponding binding energies are located at 738.8 eV and 724.2 eV, respectively. These
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24 two peaks increased to 739.2 eV and 725.2 eV with the 10% Cs cooperation40. The Ag 3d core-
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27 level for pure AgBiI4 film exhibits two intense peaks of Ag 3d3/2 and 3d5/2, and the corresponding
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29 binding energies are located at 373.3 eV and 367.2 eV, respectively. After the 5% Cs cooperation,
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the binding energy of the two peaks increased by 0.4 eV. The binding energy of the two peaks
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34 increased to 373.9 eV and 368.3 eV with the 10% Cs cooperation. Moreover, the binding energies
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36 of the Bi 4f and I 3d peaks also have the same trend as the Ag 3d peaks with the increasing Cs
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38 cooperation, indicating the strong interaction among these atoms after Cs cooperation.
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41 It is well-known that the film morphology is an important factor for the device performance. As
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shown in Figure 3, the morphology of the films incorporated with the varying amounts of Cs,
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46 which indicates that the cation composition has a strong impact on the film morphology. Figure
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48 3(a) shows large pinholes in the AgBiI4 film without the Cs cooperation. We also observed
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50 improvements in the morphology and crystal growth along with a better uniformity after the Cs
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53 cooperation (Figure 3(b)-3(c)), and displaying a pinhole free and dense CsxAg1-xBiI4 film at the 5%
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55 Cs cooperation. The white component may be BiI3 or Ag2BiI5 in the prepared CsxAg1-xBiI4
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Figure 3. SEM images of FTO/c-TiO2/m-TiO2/AgBiI4 film with different Cs cooperation
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27 concentrations. (a) 0%; (b) 1%; (c) 5% and (d) 10%.
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30 films marked with * in Figure 1 (a)25, which attribute to the highest intensity of pattern at around
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32 2θ = 25.7° and 2θ = 42.2° for 5% Cs-incorporated films showed in Figure S5. However, as shown
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in Figure 3(d), 10% Cs cooperation caused a leaky film, resulting from impurity (Cs3Bi2I9), which
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37 is similar to Cs3Bi2I9 generated in CsPbI3 system41. Meanwhile, lower surface roughness of
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39 CsxAg1-xBiI4 film is observed by atomic force microscope (AFM) in Figure S9, with the root-
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mean-square of Rq = 29.7 nm for pristine AgBiI4 film and Rq = 25.1 nm for 5% Cs incorporation
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44 film. Synthesizing above consequence, we found that Cs incorporation benefit for smoother films.
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46 To evaluate the effect of the Cs cooperation on the photovoltaic performance, the films with
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48 different Cs cation ratios were employed in devices based on the structure of FTO/c-TiO2/m-TiO2-
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51 (CsxAg1-x)BiI4/PTAA/Ag. As shown in Figure 4(a), the electron and hole transporting materials
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53 are TiO2 and PTAA, respectively. A typical cross-sectional SEM image of the device is shown in
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55 Figure 4(b), showing the thickness of the c-TiO2, m-TiO2 and CsxAg1-xBiI4 absorber layer, PTAA
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16 Figure 4. (a) Schematic illustration of the device structure. (b) The cross-sectional SEM image
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and (c) Band alignment diagram of the device.
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21 and Ag electrode are 40 nm, 300 nm, 50 nm and 200 nm, respectively. The energy level diagram
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23 of the device was plotted in Figure 4(c). The band positions of CsxAg1-xBiI4 were obtained from
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the UPS data (Figure S10). With a moderate Cs cooperation, the increased valence band edges
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28 (EVB) are beneficial for hole transport as the low-lying EVB position limits the performance of the
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30 solar cell29.
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32 Figure 5(a) shows the J−V curves of the rudorffite devices based on different cation composition
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35 films, and the device parameters are summarized in Table S5. The Cs cooperation mainly increases
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37 the JSC with small cooperation of Cs compared to that of pure AgBiI4. However, we postulate that
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39 the impurities resulted in the photovoltaic performance decrease at the 10% Cs concentration. The
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best cell based on the absorber with a 5% Cs content shows a PCE of 1.58%, with an VOC of 0.57
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44 V, JSC of 6.05 mA/cm2, and fill factor (FF) of 0.46. This PCE is higher than the device based on
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46 the pure AgBiI4 of 1.05%. This improvement is mainly due to the increase in the JSC. The PCE
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data for each condition are shown in Figure 5(b), which includes 20 devices. The average PCE for
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51 the Cs cooperation shows a 40% enhancement compared to that of the pure AgBiI4. The enhanced
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53 performance of the solar cells can be attributed to higher-quality rudorffite films and efficient
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55 carrier transport.
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Figure 5. (a) Current density-voltage (J-V) characteristic curves of best performing solar cells and
17 (b) statistics PCE of 20 devices with 0%, 1%, 5% and 10% Cs cooperation.
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20 The incident photon-to-electron conversion efficiency (IPCE) spectra of ordinary CsxAg1-xBiI4
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22 devices indicates the JSC change with an integrated JSC of 3.55 mA cm−2 and 3.01 mA cm−2 for
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25 with and without Cs cooperation, respectively (Figure 6(a)). The higher JSC partly attributed to the
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27 dense light absorber layer because of its stronger light absorption ability. We also studied the
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29 stability of CsxAg1-xBiI4 solar cells, which were stored without any encapsulation in desiccator
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(temperature, 20−30 °C; relative humidity, 23%). As shown in Figure 6(b), the PCE of the AgBiI4
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34 solar cells slightly decreased compared to the initial performance after storage for 500 h, and the
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36 Cs-incorporated devices displayed a higher PCE after the 500 h storage, indicating that the Cs
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cooperation enhanced the stability of the devices.
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53 Figure 6. (a) IPCE spectra of CsxAg1-xBiI4 solar cells. (b) Stability of CsxAg1-xBiI4 devices without
54 any encapsulation.
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3 We have fabricated electron-only devices (FTO/c-TiO2/m-TiO2-CsxAg1-xBiI4/PCBM/Ag) to
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6 measure the trap-state density of absorber by space charge limited current (SCLC) measurement,
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8 as shown in. Figure S11. In ohmic regime, the trap-state density can be determined by the trap-
9
10 filled limit voltage (VTFL) using the following equation:
11
12
13 𝑒𝑛𝑡 𝐿2
𝑉𝑇𝐹𝐿 = (1)
14 2𝜀𝜀0
15
16 where L is the thickness of film, ε0 is the vacuum permittivity and ε is the relative dielectric
17
18
19 constant. Lower VTFL was connected with lower concentration of trap states. The VTFL of the
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21 pristine AgBiI4 film and 5% Cs incorporated film are 0.36 and 0.18 V, respectively. Therefore, the
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23 trap-state density for AgBiI4 film and 5% Cs incorporated film were determined to be 1.92 × 1015
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25
26
and 9.56× 1014 cm−3, respectively. The 5% Cs incorporated film presents a reduced trap density,
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28 indicating that the film quality is much improved. In Child region, the carrier mobility (μ) can be
29
30 calculated with Mott–Gurney’s equation:
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32
9𝜀𝜀0 𝜇𝑉𝑏2
33 𝐽𝐷 = (2)
34 8𝐿3
35
36 where JD is the current density and Vb is the applied voltage. The resulted μ of 5% Cs incorporated
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38 film is 5.11× 10−3 cm2 s−1 V−1, which is larger than that calculated for AgBiI4 film (6.50 × 10−4
39
40
41 cm2 s−1 V−1). Apparently, Cs incorporation contribute to reduce the trap density and improve
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43 carrier mobility could possibly be the result of better crystallinity35, 42-43.
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45 To determine the impact of Cs on the rudorffite absorber layer, the steady-state photoluminescence
46
47
48
(PL) was measured for the CsxAg1-xBiI4 films. As shown in Figure 7(a), the Cs incorporated films
49
50 show a higher PL intensity than that of pure AgBiI4 film, indicating a decrease in the non-radiative
51
52 recombination44. The 5% Cs incorporated film also shows the highest PL intensity, indicating a
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better crystallinity of the as-deposited film45. For the 10% Cs cooperation, the PL peak shows a
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Figure 7. (a) PL spectra of 0%, 1%, 5% and 10% Cs cooperation film. (b) TRPL spectra of 0%
17 and 5% Cs cooperation film on TiO2.
18
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20 blue shift around 10 nm, which is consistent with the absorption spectra (Figure 1(b)). We
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22 performed time-resolved photoluminescence (TRPL) measurements to investigate the dynamics
23
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25 of recombination through the lifetime of the photo-excited carriers in the different materials, as
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27 shown in Figure 7(b). The decay time (t) was calculated using the biexponential function of time
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29 (F(t)= Σ ai e -τ/τi
, i=1, 2), which contains a fast decay time component and a slow decay time
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31
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component46. TRPL measurements of the CsxAg1-xBiI4 layer show a decrease in the PL lifetime
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34 (0.336 ns) compared to the AgBiI4 layer (0.655 ns) in the presence of TiO2, indicating a faster and
35
36 more effective carrier transport. Cs cooperation suppresses the charge recombination at the
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CsxAg1-xBiI4/ETL interface and reduced non-radiative recombination. These results indicated an
39
40
41 improved charge collection efficiency of the CsxAg1-xBiI4-based solar cells compared to that in the
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43 pristine AgBiI4, which is consistent with the improved performance of those perovskite devices47-
44
45 48
. The increases of JSC and enhancement of the solar cell performance mainly attributed to the
46
47
48 higher quality of rudorffite film with 5% Cs incorporation, resulting in reduced defect density,
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50 suppressed recombination and promoted carrier transport.
51
52 We also fabricated the rudorffite solar cells based on the planar structure of “ITO/SnO2/CsxAg1-
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54
xBiI4/PTAA/Ag”. The CsxAg1-xBiI4 films morphology based on SnO2 were investigated in Figure
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3 S12. With Cs cooperation, the film is dense and pinhole free compared to that of pure AgBiI4. As
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5
6 shown in Figure S13 and Table S6, the VOC in the planar structure obviously increased to 0.8 V
7
8 compared to the mesoporous structure devices, which is in accordance with the reported literature30.
9
10 The PCE increased from 0.98% to 1.38% after the Cs cooperation, the PCE shows a 40%
11
12
13
enhancement and this improvement is mainly due to the higher quality deposited CsxAg1-xBiI4 film,
14
15 which increased the JSC from 2.46 to 3.34 mA/cm2.
16
17 CONCLUSIONS
18
19
20 In summary, we synthesized a series of Pb-free CsxAg1-xBiI4 films through a one-step spin-coating
21
22
23 process followed by a mild thermal annealing method. By optimizing the annealing process, we
24
25 obtained a good crystalline AgBiI4 film. Furthermore, we obtained dense and pinhole free films
26
27 after optimizing the concentration of the Cs cooperation. Cs cooperated devices exhibit around a
28
29
30
40% improvement in the PCE, both in the mesoporous structure and in the planar structure. The
31
32 devices also show a long-term stability in ambient environment, particularly for the Cs cooperated
33
34 ones. This study points out the significance of the film quality improvement, interface charge
35
36 extraction, and other cooperated cations on improving the performance of AgBiI4 solar cells.
37
38
39
ASSOCIATED CONTENT
40
41
42
43 Supporting Information.
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45 J-V curves and statistics PCE of different devices; SEM of different gap time films; Different Cs
46
47 concentration precursor and films photo and XRD patterns of different films; detailed XRD
48
49
patterns; Tauc plot of different films; XPS survey scan of 10% Cs cooperation film; Simulated
50
51
52 XRD pattern of Cs0.1Ag0.9BiI4 film; Different films AFM images; Different films UPS spectra;
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54 Dark I–V measurement of different devices; SEM of different films on SnO2; Average Performance
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3 Parameters of different devices; FWHM of different films; Elements content of 10% Cs
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6 cooperation film. This material is available free of charge via the Internet at http://pubs.acs.org.
7
8 AUTHOR INFORMATION
9
10
11 Corresponding Authors
12
13 *E-mail: tinglima@life.kyutech.jp
14
15
16 *E-mail: wangliang@life.kyutech.ac.jp
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18 Tel: +81-936956045
19
20 Notes
21
22
23 The authors declare no competing financial interest.
24
25 ACKNOWLEDGMENTS
26
27
28 This work was supported by the National Natural Science Foundation of China (Grant No.
29
30 51772039 and 51972293).
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32
33
REFERENCES
34
35
36
37 (1) Im, J. H.; Jang, I. H.; Pellet, N.; Gratzel, M.; Park, N. G. Growth of CH3NH3PbI3 cuboids with
38 controlled size for high-efficiency perovskite solar cells. Nat. Nanotechnol. 2014, 9, 927-32, DOI
39 10.1038/NNANO.2014.181.
40 (2) Son, D.-Y.; Lee, J.-W.; Choi, Y. J.; Jang, I.-H.; Lee, S.; Yoo, P. J.; Shin, H.; Ahn, N.; Choi,
41 M.; Kim, D.; Park, N.-G. Self-formed grain boundary healing layer for highly efficient
42 CH3NH3PbI3 perovskite solar cells. Nature Energy 2016, 1, 16081, DOI
43
44
10.1038/NENERGY.2016.81.
45 (3) https://www.nrel.gov/pv/assets/pdfs/best-research-cell-efficiencies.20200406.pdf
46 (4) Nie, R.; Mehta, A.; Park, B. W.; Kwon, H. W.; Im, J.; Seok, S. I. Mixed Sulfur and Iodide-
47 Based Lead-Free Perovskite Solar Cells. J. Am. Chem. Soc. 2018, 140, 872-875, DOI
48 10.1021/jacs.7b11332.
49 (5) Zhang, C.; Gao, L.; Hayase, S.; Ma, T. Current Advancements in Material Research and
50 Techniques Focusing on Lead-free Perovskite Solar Cells. Chem. Lett. 2017, 46, 1276-1284 DOI
51
52
10.1246/cl.170345.
53 (6) Habisreutinger, S. N.; Leijtens, T.; Eperon, G. E.; Stranks, S. D.; Nicholas, R. J.; Snaith, H. J.
54 Carbon nanotube/polymer composites as a highly stable hole collection layer in perovskite solar
55 cells. Nano lett. 2014, 14, 5561-8, DOI 10.1021/nl501982b.
56
57
58
59
60 ACS Paragon Plus Environment
 ACS Sustainable Chemistry & Engineering Page 18 of 22

1
2
3 (7) Zhu, Z.; Bai, Y.; Liu, X.; Chueh, C. C.; Yang, S.; Jen, A. K. Enhanced Efficiency and Stability
4
5
of Inverted Perovskite Solar Cells Using Highly Crystalline SnO2 Nanocrystals as the Robust
6 Electron-Transporting Layer. Adv. Mater. 2016, 28, 6478-84, DOI 10.1002/adma.201600619.
7 (8) Shi, Z.; Guo, J.; Chen, Y.; Li, Q.; Pan, Y.; Zhang, H.; Xia, Y.; Huang, W. Lead-Free Organic-
8 Inorganic Hybrid Perovskites for Photovoltaic Applications: Recent Advances and Perspectives.
9 Adv. Mater. 2017, 29, 1605005, DOI 10.1002/adma.201605005.
10 (9) Wang, F.; Ma, J.; Xie, F.; Li, L.; Chen, J.; Fan, J.; Zhao, N. Organic Cation-Dependent
11
Degradation Mechanism of Organotin Halide Perovskites. Adv. Funct. Mater. 2016, 26, 3417-
12
13
3423, DOI 10.1002/adfm.201505127.
14 (10) Noel, N. K.; Stranks, S. D.; Abate, A.; Wehrenfennig, C.; Guarnera, S.; Haghighirad, A.-A.;
15 Sadhanala, A.; Eperon, G. E.; Pathak, S. K.; Johnston, M. B.; Petrozza, A.; Herz, L. M.; Snaith, H.
16 J. Lead-free organic–inorganic tin halide perovskites for photovoltaic applications. Energy
17 Environ. Sci. 2014, 7, 3061-3068, DOI 10.1039/c4ee01076k.
18 (11) Park, B. W.; Philippe, B.; Zhang, X.; Rensmo, H.; Boschloo, G.; Johansson, E. M. Bismuth
19
Based Hybrid Perovskites A3Bi2I9 (A: Methylammonium or Cesium) for Solar Cell Application.
20
21 Adv. Mater. 2015, 27, 6806-13, DOI 10.1002/adma.201501978.
22 (12) Lyu, M.; Yun, J.-H.; Cai, M.; Jiao, Y.; Bernhardt, P. V.; Zhang, M.; Wang, Q.; Du, A.; Wang,
23 H.; Liu, G.; Wang, L. Organic–inorganic bismuth (III)-based material: A lead-free, air-stable and
24 solution-processable light-absorber beyond organolead perovskites. Nano Research 2016, 9, 692-
25 702, DOI 10.1007/s12274-015-0948-y.
26 (13) Greul, E.; Petrus, Michiel L.; Binek, A.; Docampo, P.; Bein, T. Highly stable, phase pure
27
28
Cs2AgBiBr6 double perovskite thin films for optoelectronic applications. J. Mater. Chem. A 2017,
29 5, 19972-19981, DOI 10.1039/C7TA06816F.
30 (14) Wu, C.; Zhang, Q.; Liu, Y.; Luo, W.; Guo, X.; Huang, Z.; Ting, H.; Sun, W.; Zhong, X.; Wei,
31 S.; Wang, S.; Chen, Z.; Xiao, L. The Dawn of Lead-Free Perovskite Solar Cell: Highly Stable
32 Double Perovskite Cs2AgBiBr6 Film. Advanced science 2018, 5, 1700759, DOI
33 10.1002/advs.201700759.
34
(15) Jung, K. W.; Sohn, M. R.; Lee, H. M.; Yang, I. S.; Sung, S. D.; Kim, J.; Wei-Guang Diau, E.;
35
36
Lee, W. I. Silver bismuth iodides in various compositions as potential Pb-free light absorbers for
37 hybrid solar cells. Sustainable Energy Fuels 2018, 2, 294-302, DOI 10.1039/C7SE00477J.
38 (16) Zhu, H.; Pan, M.; Johansson, M. B.; Johansson, E. M. J. High Photon-to-Current Conversion
39 in Solar Cells Based on Light-Absorbing Silver Bismuth Iodide. ChemSusChem 2017, 10, 2592-
40 2596, DOI 10.1002/cssc.201700980.
41 (17) Koedtruad, A.; Goto, M.; Amano Patino, M.; Tan, Z.; Guo, H.; Nakamura, T.; Handa, T.;
42
Chen, W.-T.; Chuang, Y.-C.; Sheu, H.-S.; Saito, T.; Kan, D.; Kanemitsu, Y.; Wakamiya, A.;
43
44 Shimakawa, Y. Structure–property relations in Ag–Bi–I compounds: potential Pb-free absorbers
45 in solar cells. J. Mater. Chem. A 2019, 7, 5583-5588, DOI 10.1039/C8TA11227D.
46 (18) Shao, Z.; Le Mercier, T.; Madec, M. B.; Pauporté, T. AgBi2I7 layers with controlled surface
47 morphology for solar cells with improved charge collection. Mater. Lett. 2018, 221, 135-138, DOI
48 10.1016/j.matlet.2018.03.085.
49 (19) Khazaee, M.; Sardashti, K.; Chung, C.-C.; Sun, J.-P.; Zhou, H.; Bergmann, E.; Dunlap-Shohl,
50
51
W. A.; Han, Q.; Hill, I. G.; Jones, Jacob L.; Lupascu, D. C.; Mitzi, D. B. Dual-source evaporation
52 of silver bismuth iodide films for planar junction solar cells. J. Mater. Chem. A 2019, 7, 2095-
53 2105, DOI 10.1039/c8ta08679f.
54 (20) Sansom, H. C.; Whitehead, G. F. S.; Dyer, M. S.; Zanella, M.; Manning, T. D.; Pitcher, M. J.;
55 Whittles, T. J.; Dhanak, V. R.; Alaria, J.; Claridge, J. B.; Rosseinsky, M. J. AgBiI4 as a Lead-Free
56
57
58
59
60 ACS Paragon Plus Environment
Page 19 of 22 ACS Sustainable Chemistry & Engineering

1
2
3 Solar Absorber with Potential Application in Photovoltaics. Chem. Mater. 2017, 29, 1538-1549,
4
5
DOI 10.1021/acs.chemmater.6b04135.
6 (21) Shao, Z.; Le Mercier, T.; Madec, M. B.; Pauporté, T. Exploring AgBixI3x+1 semiconductor
7 thin films for lead-free perovskite solar cells. Mater. Des. 2018, 141, 81-87, DOI
8 10.1016/j.matdes.2017.12.036.
9 (22) Hosseini, S. S.; Adelifard, M.; Ataei, M. An investigation on physical properties of Ag2BiI5
10 absorber layers synthesized by microwave assisted spin coating technique. J. Mater. Sci.: Mater.
11
Electron. 2019, 30, 5021-5029, DOI 10.1007/s10854-019-00799-y.
12
13
(23) Baranwal, A. K.; Masutani, H.; Sugita, H.; Kanda, H.; Kanaya, S.; Shibayama, N.; Sanehira,
14 Y.; Ikegami, M.; Numata, Y.; Yamada, K.; Miyasaka, T.; Umeyama, T.; Imahori, H.; Ito, S. Lead-
15 free perovskite solar cells using Sb and Bi-based A3B2X9 and A3BX6 crystals with normal and
16 inverse cell structures. Nano convergence 2017, 4, 26, DOI 10.1186/s40580-017-0120-3.
17 (24) Oldag, T.; Aussieker, T.; Keller, H.-L.; Preitschaft, C.; Pfitzner, A. Solvothermale Synthese
18 und Bestimmung der Kristallstrukturen von AgBiI4 und Ag3BiI6. Z. Anorg. Allg. Chem. 2005, 631,
19
677-682, DOI 10.1002/chin.200523007.
20
21 (25) Ghosh, B.; Wu, B.; Guo, X.; Harikesh, P. C.; John, R. A.; Baikie, T.; Arramel; Wee, A. T. S.;
22 Guet, C.; Sum, T. C.; Mhaisalkar, S.; Mathews, N. Superior Performance of Silver Bismuth Iodide
23 Photovoltaics Fabricated via Dynamic Hot-Casting Method under Ambient Conditions. Adv.
24 Energy Mater. 2018, 8, 1802051, DOI 10.1002/aenm.201802051.
25 (26) Kim, Y.; Yang, Z.; Jain, A.; Voznyy, O.; Kim, G. H.; Liu, M.; Quan, L. N.; Garcia de Arquer,
26 F. P.; Comin, R.; Fan, J. Z.; Sargent, E. H. Pure Cubic-Phase Hybrid Iodobismuthates AgBi2I7 for
27
28
Thin-Film Photovoltaics. Angew. Chem. Int. Ed. 2016, 55, 9586-90, DOI 10.1002/ange.201603608.
29 (27) Turkevych, I.; Kazaoui, S.; Ito, E.; Urano, T.; Yamada, K.; Tomiyasu, H.; Yamagishi, H.;
30 Kondo, M.; Aramaki, S. Photovoltaic Rudorffites: Lead-Free Silver Bismuth Halides Alternative
31 to Hybrid Lead Halide Perovskites. ChemSusChem 2017, 10, 3754-3759, DOI
32 10.1002/cssc.201700980.
33 (28) Lu, C.; Zhang, J.; Sun, H.; Hou, D.; Gan, X.; Shang, M.-h.; Li, Y.; Hu, Z.; Zhu, Y.; Han, L.
34
Inorganic and Lead-Free AgBiI4 Rudorffite for Stable Solar Cell Applications. ACS Appl. Mater.
35
36
Interfaces 2018, 1, 4485-4492, DOI 10.1021/acsaem.8b01202.
37 (29) Pai, N.; Lu, J.; Gengenbach, T. R.; Seeber, A.; Chesman, A. S. R.; Jiang, L.; Senevirathna, D.
38 C.; Andrews, P. C.; Bach, U.; Cheng, Y. B.; Simonov, A. N. Silver Bismuth Sulfoiodide Solar
39 Cells: Tuning Optoelectronic Properties by Sulfide Modification for Enhanced Photovoltaic
40 Performance. Adv. Energy Mater. 2018, 1803396, DOI 10.1002/aenm.201803396.
41 (30) Zhang, Q.; Wu, C.; Qi, X.; Lv, F.; Zhang, Z.; Liu, Y.; Wang, S.; Qu, B.; Chen, Z.; Xiao, L.
42
Photovoltage Approaching 0.9 V for Planar Heterojunction Silver Bismuth Iodide Solar Cells with
43
44 Li-TFSI Additive. ACS Appl. Mater. Interfaces 2019, 2, 3651-3656, DOI
45 10.1021/acsaem.9b00366.
46 (31) Kulkarni, A.; Jena, A. K.; Ikegami, M.; Miyasaka, T. Performance enhancement of AgBi2I7
47 solar cells by modulating a solvent-mediated adduct and tuning remnant BiI3 in one-step
48 crystallization. Chem. Commun. 2019, 55, 4031-4034, DOI 10.1039/C9CC00733D.
49 (32) Choi, H.; Jeong, J.; Kim, H.-B.; Kim, S.; Walker, B.; Kim, G.-H.; Kim, J. Y. Cesium-doped
50
51
methylammonium lead iodide perovskite light absorber for hybrid solar cells. Nano Energy 2014,
52 7, 80-85, DOI 10.1016/j.nanoen.2014.04.017.
53 (33) Lee, J.-W.; Kim, D.-H.; Kim, H.-S.; Seo, S.-W.; Cho, S. M.; Park, N.-G. Formamidinium and
54 Cesium Hybridization for Photo- and Moisture-Stable Perovskite Solar Cell. Adv. Energy Mater.
55 2015, 5, 1501310, DOI 10.1002/aenm.201501310.
56
57
58
59
60 ACS Paragon Plus Environment
 ACS Sustainable Chemistry & Engineering Page 20 of 22

1
2
3 (34) Yi, C.; Luo, J.; Meloni, S.; Boziki, A.; Ashari-Astani, N.; Grätzel, C.; Zakeeruddin, S. M.;
4
5
Röthlisberger, U.; Grätzel, M. Entropic stabilization of mixed A-cation ABX3 metal halide
6 perovskites for high performance perovskite solar cells. Energy Environ. Sci. 2016, 9, 656-662,
7 DOI 10.1039/c5ee03255e.
8 (35) Zhou, N.; Shen, Y.; Zhang, Y.; Xu, Z.; Zheng, G.; Li, L.; Chen, Q.; Zhou, H. CsI Pre-
9 Intercalation in the Inorganic Framework for Efficient and Stable FA1-xCsxPbI3 (Cl) Perovskite
10 Solar Cells. Small 2017, 13, 1700484, DOI 10.1002/smll.201700484.
11
(36) Wang, C.; Zhang, C.; Wang, S.; Liu, G.; Xia, H.; Tong, S.; He, J.; Niu, D.; Zhou, C.; Ding,
12
13 K.; Gao, Y.; Yang, J. Low‐Temperature Processed, Efficient, and Highly Reproducible Cesium‐
14 Doped Triple Cation Perovskite Planar Heterojunction Solar Cells. Sol. RRL 2018, 2, 1700209,
15 DOI 10.1002/solr.201700209.
16 (37) Dubey, A.; Adhikari, N.; Mabrouk, S.; Wu, F.; Chen, K.; Yang, S.; Qiao, Q. A strategic review
17 on processing routes towards highly efficient perovskite solar cells. J. Mater. Chem. A 2018, 6,
18
19
2406-2431, DOI 10.1039/c7ta08277k.
20 (38) Sanni, D. M.; Chen, Y.; Yerramilli, A. S.; Ntsoenzok, E.; Asare, J.; Adeniji, S. A.; Oyelade,
21 O. V.; Fashina, A. A.; Alford, T. L. An approach to optimize pre-annealing aging and anneal
22 conditions to improve photovoltaic performance of perovskite solar cells. Mater. Renew. Sustain.
23 Energy. 2018, 8, 3-12, DOI 10.1007/s40243-018-0139-3.
24 (39) Yu, B.-B.; Liao, M.; Yang, J.; Chen, W.; Zhu, Y.; Zhang, X.; Duan, T.; Yao, W.; Wei, S.-H.;
25
He, Z. Alloy-induced phase transition and enhanced photovoltaic performance: the case of
26
27
Cs3Bi2I9−xBrx perovskite solar cells. J. Mater. Chem. A 2019, 7, 8818-8825, DOI
28 10.1039/C9TA01978B.
29 (40) Akin, S.; Altintas, Y.; Mutlugun, E.; Sonmezoglu, S. Cesium lead based inorganic perovskite
30 quantum-dots as interfacial layer for highly stable perovskite solar cells with exceeding 21%
31 efficiency. Nano Energy 2019, 60, 557-566, DOI 10.1016/j.nanoen.2019.03.091.
32 (41) Hu, Y.; Bai, F.; Liu, X.; Ji, Q.; Miao, X.; Qiu, T.; Zhang, S. Bismuth Incorporation Stabilized
33
α-CsPbI3 for Fully Inorganic Perovskite Solar Cells. ACS Energy Letters 2017, 2, 2219-2227, DOI
34
35 10.1021/acsenergylett.7b00508.
36 (42) Hu, W.; He, X.; Fang, Z.; Lian, W.; Shang, Y.; Li, X.; Zhou, W.; Zhang, M.; Chen, T.; Lu,
37 Y.; Zhang, L.; Ding, L.; Yang, S. Bulk heterojunction gifts bismuth-based lead-free perovskite
38 solar cells with record efficiency. Nano Energy 2020, 68, 104362, DOI
39 10.1016/j.nanoen.2019.104362.
40 (43) Li, W. G.; Wang, X. D.; Liao, J. F.; Jiang, Y.; Kuang, D. B. Enhanced On–Off Ratio
41
42 Photodetectors Based on Lead‐Free Cs3Bi2I9 Single Crystal Thin Films. Adv. Func.l Mater. 2020,
43 30, 1909701, DOI 10.1002/adfm.201909701.
44 (44) Alharbi, E. A.; Dar, M. I.; Arora, N.; Alotaibi, M. H.; Alzhrani, Y. A.; Yadav, P.; Tress, W.;
45 Alyamani, A.; Albadri, A.; Zakeeruddin, S. M.; Gratzel, M. Perovskite Solar Cells Yielding
46
47
Reproducible Photovoltage of 1.20 V. Research 2019, 2019, 8474698, DOI
48 10.34133/2019/8474698.
49 (45) Chang, J.; Zhu, H.; Li, B.; Isikgor, F. H.; Hao, Y.; Xu, Q.; Ouyang, J. Boosting the
50 performance of planar heterojunction perovskite solar cell by controlling the precursor purity of
51 perovskite materials. J. Mater. Chem. A 2016, 4, 887-893, DOI 10.1039/C5TA08398B.
52 (46) Yang, D.; Zhou, X.; Yang, R.; Yang, Z.; Yu, W.; Wang, X.; Li, C.; Liu, S.; Chang, R. P. H.
53
Surface optimization to eliminate hysteresis for record efficiency planar perovskite solar cells.
54
55 Energy Environ. Sci. 2016, 9, 3071-3078, DOI 10.1039/c6ee02139e.
56
57
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3 (47) Pham, N. D.; Tiong, V. T.; Chen, P.; Wang, L.; Wilson, G. J.; Bell, J.; Wang, H. Enhanced
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perovskite electronic properties via a modified lead(ii) chloride Lewis acid–base adduct and their
6 effect in high-efficiency perovskite solar cells. J. Mater. Chem. A 2017, 5, 5195-5203, DOI
7 10.1039/C6TA11139D.
8 (48) Guo, Z.; Teo, S.; Xu, Z.; Zhang, C.; Kamata, Y.; Hayase, S.; Ma, T. Achievable high Voc of
9 carbon based all-inorganic CsPbIBr2 perovskite solar cells through interface engineering. J. Mater.
10 Chem. A 2019, 7, 1227-1232, DOI 10.1039/c8ta09838g.
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19 By introducing Cs into Pb-free AgBiI4 films, the devices achieve a 40% enhancement in PCE
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