Enhancing Photovoltaic Performance of Inverted Planar Perovskite

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Surfaces, Interfaces, and Applications

Enhancing Photovoltaic Performance of Inverted Planar Perovskite Solar Cells by Cobalt Doped Nickle Oxide Hole Transport Layer Yulin Xie, Kai Lu, Jiashun Duan, Youyu Jiang, Lin Hu, Tiefeng Liu, Yinhua Zhou, and Bin Hu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 05 Apr 2018 Downloaded from http://pubs.acs.org on April 5, 2018

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ACS Applied Materials & Interfaces

Enhancing Photovoltaic Performance of Inverted Planar Perovskite Solar Cells by Cobalt Doped Nickle Oxide Hole Transport Layer Yulin Xie,†,‡ Kai Lu,† Jiashun Duan,† Youyu Jiang,† Lin Hu,† Tiefeng Liu,† Yinhua Zhou,† Bin Hu*,†,§,¶

†

Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, China

‡

§

School of Electronic Information, Huanggang Normal University, Huanggang, 438000, China

Key Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing Jiaotong University, Beijing, 100044, China

¶

Department of Materials Science and Engineering, University of Tennessee, Knoxville,

Tennessee, 37996, USA.

*Corresponding author: E-mail: [email protected] (B. Hu)

1 Environment ACS Paragon Plus

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ABSTRACT: Electron and hole transport layers have critical impacts on the overall performance of perovskite solar cells (PSCs). Herein, for the first time, a solution processed cobalt (Co)-doped NiOX film was fabricated as the hole transport layer (HTL) in inverted planar PSCs, and the solar cells exhibit 18.6% power conversion efficiency (PCE). It has been found that an appropriate Co-doping can significantly adjust the work function and enhance electrical conductivity of the NiOX film. Voltage-capacitance (C-V) spectra and time-resolved photoluminescence spectra indicate clearly that the charge accumulation becomes more pronounced in the Co-doped NiOX based photovoltaic devices, it as a consequence, prevents the non-radiative recombination at the interface between the Co-doped NiOX and the photo-active perovskite layers. Moreover, field-dependent photoluminescence measurements indicate that Codoped NiOX based devices can also effectively inhibit the radiative recombination process in the perovskite layer and finally facilitate the generation of photocurrent. Our work indicates that Codoped NiOX film is an excellent candidate for high performance inverted planar PSCs.

KEYWORDS: Hole transport layer, perovskite solar cells, Co-doped NiOX, C-V spectra, nonradiative recombination


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INTRODUCTION Organic-inorganic hybrid perovskites (OIHPs) have gained tremendous interest in developing next generation photovoltaic with high certified efficiency of 22.1% over the past few years.1-5 Suitable electron and hole extraction layers are important to facilitate high efficiency PSCs, which can optimize the charge transport/extraction rates and reduce the energy losses of photogenerated carriers in perovskite absorbers. These transport layers are critically important to the PSCs, because they can reduce carrier recombination at the interface, which may influence the performance of PSCs.6 The most common HTL materials are PEDOT:PSS,7, 8 PTAA,9, 10 and P3HT,11 Spiro-OMeTAD.12,

13

Solution-processed inorganic counterparts such as CuSCN,14

NiOX,15 and CuI16 are particularly attractive as efficient HTLs owing to the superior chemical stability, low costs and simple synthesis methods. Among these, NiOX is a promising inorganic p-type semiconductor, due to its high optical transmittance and excellent valence band (VB) match with MAPbI3.17, 18 However, the pristine NiOX has relatively lower electrical conductivity, resulting in more charge recombination and inefficient hole extraction.19 Doping can effectively enhance electrical conductivity and charge carrier mobility. Recently, some dopants used for the HTL NiOX are Li,20, 21 Cu,22, 23 Mg,24 Cs,25, 26 as well as the co-doped approach, Cu-Li27, and Mg-Li25. In spite of these, Co has been expected to be an excellent dopant for fabrication HTL with desirable electrical conductivity. Nevertheless, its fabrication involves the complicated magnetron sputtering or the co-evaporation in high vacuum.



28

The method is not compatible with the solution-processed OIHP films. Moreover, high cost

and time consumption are also the problems. Hence, it is highly demanding to develop a solution based method for fabricating the Co-doped NiOX and meanwhile demonstrating a highly efficient perovskite solar cell. In this work, we have successful fabricated the Co-doped NiOX as the HTLs by the solution method and studied the optoelectronic properties of the films. Based on this, several different inverted planar perovskite solar cells with different doping levels of the Co-doped NiOX were made. We have found a significant improvement of the PCE from 16.3% to 18.6%. We believe the solution processed Co-doped NiOX HTL can effectively adjust the work function of the NiOX without doping, and enhance its electrical conductivity. As a consequence, the interfacial charge recombination can be greatly suppressed, which is evidenced by C-V measurements, stead-state and time-resolved photoluminescence spectroscopy. Therefore, the Co-doped NiOX film is expected to be one of the potential candidates for developing highly efficient inverted planar PSCs. EXPERIMENTAL SECTION Material processing and device fabrication: Prior to the fabrication, ITO coated glass substrates were cleaned. Then, they were immediately treated by oxygen plasma for 5 min. The pristine NiOX precursor was prepared with 2-Methoxyethanol solution containing 0.12 M Ni(CH3COO)2 ·4H2O with 1 molar equivalents of ethanolamine. For the preparation of Co-doped NiOX solutions, 2 mol%, 6 mol%, 10 mol% of Co(CH3COO)2 · 4H2O were used to replace the


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Ni(CH3COO)2·4H2O. Both of them were stirred in ambient at 60℃ for 4 h. After this, the Codoped NiOX solution was filtered by a 0.22 µm nylon filters. The Co-doped NiOX films was spincoated onto as prepared ITO substrates at 3500 rpm for 40 s. The Co-doped NiOX/ITO(glass) samples were initially annealed at 150℃ in ambient for 10 min, and then the temperature was rapidly increased to 400℃ for another 20 min annealing. After thermal annealing, the Co-doped NiOX/ITO(glass) samples were treated by oxygen plasma for totally 5 min before the fabrication of the perovskite film. The perovskite solution was prepared by dissolving lead iodine (PbI2) and Methylammonium iodide (MAI) with the equivalent molar ratio in a mixed solvent of Dimethyl Sulfoxide (DMSO) and γ-Butyrolactone (GBL) (volume ratio 3:7). The perovskite film was fabricated by spin coating the precursor solution onto the Co-doped NiOX/ITO(glass) with a spinning speed of 1000 rpm for 10 s, followed with 4000 rpm for another 20 s. During this process, a 260 µL toluene always dripped onto the sample as an anti-solvent. After this, all the samples were annealing at 100℃ for 10 min. The electron transport layer (ETL) such as PCBM with the thickness of 30 nm was spin-cast on top of perovskite films at 2000 rpm for 40 s, followed by 5 nm thick PEI as interface-decorating layer. Finally, 100 nm-thick silver electrode were deposited on the top of PEI with the pressure of 5×10-7 Pa. The transport areas of the devices are approximately 4.1 mm2. Device Characterization: The J-V characteristic curves of the as-fabricated devices were performed by Keithley 2400 under illumination of 1 sun with 20 mV s-1 scan rate in the glove box. The negligible hysteresis was observed for the reverse and forward scans. The external



quantum efficiency (EQE) of the inverted planar PSCs was performed by a 150 W xenon lamp (Oriel) fitted with a monochromator. The film thickness was performed by a step profiler (Bruker Corp). The work function of HTL was measured with a Kelvin probe (KP-020, KP Technology). X-ray photoelectron spectroscopy (XPS) measurements were carried out in a Thermo-VG Scientific ESCALAB 250 photoelectron spectrometer. The X-ray diffraction (XRD) spectra were carried out by X-ray diffractometer (Bruker D8 Advance). SPM9700 (Shimadzu) was used for conductive atomic force microscopy (c-AFM) measurement. Time-resolved PL decay transients were performed by a light pulse at 478 nm from the Horiba Scientific DeltaPro. FLS920 (Edinburgh) was used for the PL emission spectrum of perovskite samples. The C-V spectra were performed by Agilent4294A impedance analyzer at 1 kHz and AC oscillating amplitude was 50 mV. RESULTS AND DISCUSSION The energy level alignment of the doped and undoped NiOX for the inverted planar PSCs are given in Figure 1a, where the work functions of MAPbI3, PCBM, and Ag were cited from the literature.29 Specifically, the NiOX and Co-doped NiOX show a relative change between the probe and the surface-contact potential measured by the Kelvin probe force microscopy. Doped NiOX are coincide with the trend in PSCs employing doped organic HTLs, which is gained higher device performance.30 The J-V characteristic curves and the corresponding photovoltaic parameters are shown in Figure 1b and Table 1, respectively. Apparently, with the appropriate doping concentration of Co-doped NiOX such as molar ratio of 2 mol% and 6 mol%, the PCE


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was increased up to 17.2% and 18.6% respectively by comparing to the one without Co dopant. In fact, all the photovoltaic parameters such as JSC, VOC and FF were enhanced. Further increase of Co concentration up to 10 mol% leads to the decrease of the photovoltaic performance. In the following studies, we chose the one with 6 mol% Co and the device exhibited negligible hysteresis, as it is shown in Figure 1c. The statistics for photovoltaic parameters with NiOX and Co:NiOX HTL are presented in Table S1 and Figure S1. The EQE for NiOX and Co:NiOX HTL based PSCs are shown in Figure 1d. The integrated photocurrent densities according to EQE are to be 19.7 mA cm-2 and 21.8 mA cm-2 with NiOX and Co:NiOX HTL based devices which are coincide with the J-V curves. The conductivity of Co:NiOX film compared with NiOX film is used to explore detailed reason of reduction interface accumulation of photogenerated charge carriers. Among 3d transition metal dopants, improved electrocatalytic properties in Co-doped NiOX films have been reported.31 Here, we performed c-AFM measurements to characterize the electrical conductivity change in Co:NiOX film as compared to the pristine NiOX film, as shown in Figure 2a,b. It is clearly observed that significantly higher current is obtained in the case of Co:NiOX film, which indicates higher electrical conductivity of the doped films. Therefore, we conclude that a small amount of Co-doped NiOX can significantly improve the conductivity of HTL. The schematic diagram of c-AFM measurement was performed as described in Figure 2c. The J-V curves presented in Figure 2c demonstrated that the electrical conductivity was enhanced from 4.4×10-5 S/cm to 2.5×10-3 S/cm while Co-doping into NiOX films. Therefore, the higher electrical



conductivity in the doped film may contribute to the extract carriers, leading to the less interfacial accumulation of charge carriers. To understand the effectiveness of Co:NiOX HTL, we further investigated its surface characteristic. The incorporation of Co was confirmed by the XPS measurements of NiOX and Co:NiOX films, as shown in Figure S2. It is noted that morphology of perovskite absorber layer is crucial to the device performance. To investigate the influence of the modulated NiOX interface on perovskite crystallization, we conducted atom force microscope (AFM) measurements of the perovskite films in Supporting Information. The crystalline MAPbI3 films grown on Co:NiOX and NiOX HTLs are shown in Figure S3, and the of perovskite films deposited on Co:NiOX have a grain size comparable to that of the NiOX films. Simultaneously, the properties of perovskite films deposited on NiOX and Co:NiOX substrates were further analyzed by XRD patterns, as shown in Figure S3. Our previous experimental studies have found that charge carrier is inevitable to accumulate at the interface during transport process in PSCs.32, 33 The impedance spectroscopy can be used to investigate the interfacial charge carriers accumulation which can change the effective potential of the electrode interface in PSCs, thereby affect the VOC and JSC.34 So, we have measured impedance spectroscopy of the PSCs to explore surface charge accumulation and its effects on VOC and JSC by comparing NiOX and Co:NiOX HTLs based devices. The C-V curves of NiOX and Co:NiOX HTLs based devices were measured at different intensity of illumination, shown in Figure 3a,b. The C-V peak (Vpeak) shifts 91 mV and 47 mV for NiOX and Co:NiOX based devices, while the increasing photoexcitation intensity from dark to 1 sun. Our previous


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work has shown that photogenerated carriers accumulation at the interface leads to Vpeak shifts while increasing photoexcitation intensity in solar cells.35 The PSCs with Co:NiOx HTLs show a smaller Vpeak comparing to the PSCs with pristine NiOx HTLs, indicating less charge carrier accumulation at the electrode interface. Doping transport layer can change the transport property through two different ways by reducing the traps and increasing the electrical polarization, which decreases the interfacial charge accumulation. Less the charge carriers accumulation can augment the build-in potential and consequently boosts the VOC during device operation.33, 36, 37 The C-V curves of PSCs can serve as a signature of decreasing the charge accumulation at interface upon using Co-doped NiOX transport layer, which is responsible for the enhanced VOC through build-in potential. The C-2-V characteristics can further reveal the influence of interfacial charge accumulation on the potential barrier of VOC. The build-in potential (Vbi) can be obtained by Mott-Schottky model38: C −2 =

2(Vbi − V ) , where NA corresponds to the density of excited A 2ε N A

states, ɛ is the dielectric constant, A and V are the active surface and the applied voltage, respectively. Figure 3c, d show that the Vbi of NiOx and Co:NiOx based devices are 0.99 V and 1.07 V in dark condition, while the Vbi are 0.91 V and 1.03 V under 1 sun illumination, respectively. It can be seen that the Vbi is greatly enhanced in the Co:NiOX HTL based PSCs, with an increasing of 8% and 13% in dark and light condition, respectively. A large built-in potential can provide significant driving force to separate the photogenerated electron-hole pairs and suppress charge recombination. In particular, interfacial charge accumulation has significant



influence the effective Vbi. Clearly, Co:NiOX HTL based device owns less charge accumulation at interface, which can increase the VOC by increasing the effective potential barriers. Efficient charge transport and extraction are critical to device performance. The analyses above indicate that the conductivity is effectively enhanced after Co-doped NiOx HTL, in consequence reducing interfacial charge accumulation and improving the VOC. Interfacial charge carrier characteristics were performed by steady-state and time-resolved spectroscopy. In PSCs, the photogenerated carries will inevitably undergo forming a photovoltaic loss of non-radiative recombination and generating photovoltaic actions of radiative recombination, respectively.39 Hence, effective regulation the non-radiation/radiation recombination is crucial for improving the solar cell performance. Since the pristine NiOx and Co:NiOx are applied as hole extraction layers in the inverted planar PSCs, we conduct steady-state PL measurements to illustrate if Co:NiOx films can more efficiently transfer charge carriers from the photo-active perovskite layer. Figure 4a presented the PL spectra for perovskite absorber films related to different interfaces. Perovskite-only films on glass demonstrate the highest PL intensity due to strong radiative recombination of photogenerated charge carriers. The PL density of perovskite film on Co:NiOX HTL was apparently decreased but a higher JSC than NiOX HTL due to obvious charge carrier transfer from corresponding HTL. Simultaneously, TRPL decay measurements based on MAPbI3, NiOX/MAPbI3 and Co:NiOX/MAPbI3 films were performed, as presented in Figure 4b. The exponential decay times was used for calculating the lifetime to further illuminate the radiative recombination is weaker than undoped HTL. We can clearly observe a significant


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decrease in PL lifetime as well as PL intensity for Co:NiOx/MAPbI3. The decrease in the PL lifetime for Co:NiOx/MAPbI3 (26ns) as compared to the NiOx/MAPbI3 (49ns) indicates more effective charge transfer by Co:NiOx HTL from perovskite active layer, as expected from the increased work function of Co:NiOx. Simultaneously, charge transport characteristics of interface is revealed by bias voltages dependence of PL intensities, which is shown in Figure 4c. Intensity of field-dependent PL intensity illustrates different amount of excitons preparation for radiative recombination, which can be suppressed to generate photocurrent. On the contrary, the excitons for non-radiative recombination are unavailable for photovoltaic actions.40 The biasdependent PL were conveniently performed on perovskite solar cells applied voltage varies from JSC

to

( ∆PL =

VOC,

leading

to

the

decrease

on

PL

intensites,

generating

a

∆PL

PL(Vbias ) − PL(VOC ) ) where PL (Vbias) and PL (VOC) are measured at Vbias and VOC PL(VOC )

conditions, respectively. ∆PL reflects the effects of the built-in potential on the radiative recombination of photogenerated charge carriers. Figure 4c shows that Co-doped NiOx can decrease the radiative recombination by passivity the grain boundary defects, changing the applied voltage from open-circuit voltage to short-circuit current condition which is expected to enhance the amplitude of ∆PL. The increased ∆PL of Co-doped NiOx based device suggests that the doped HTL can reduce charge recombination, thereby increasing the photovoltaic performance. CONCLUSION



In summary, we present that cobalt was used to incorporate into the nickel oxide as an efficient HTL for inverted planar PSCs by a simple solution-based method. The work reveals that promoting charge collection/extraction and suppressing charge recombination is critical for the photovoltaic performance of the devices. The C-V results show that Co:NiOX based devices can enhance Vbi and reduce Vpeak shift compared to NiOX based devices due to the enhanced electrical conductivity of Co:NiOX HTLs. Enhancing electrical conductivity can promote charge transport, further reducing interfacial charge accumulation. Furthermore, time-resolved spectroscopy results indicate that Co:NiOX can effectively suppress charge recombination, leading to more valid excitons preparation for charge dissociation to generate photocurrent. The field-dependent PL indicates that Co:NiOX HTL based devices can also suppress the charge recombination, thereby enhancing the photovoltaic actions. Thus, Co:NiOX is an excellent hole extraction material for realizing high performance inverted planar PSCs. ACKNOWLEDGEMENTS This work was supported by the National Young Natural Science Foundation of China (Grant No. 61306067) and the National Significant Program of China (2014CB643506). NOTES The authors declare no competing financial interest.


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Figures and Tables (a)

(b) Current Density (mA/cm2)

0

Hole Transporting Layers: NiOx

-10

2 mol% Co-doped 6 mol% Co-doped 10 mol% Co-doped

-20

0.0

0.5

1.0

Voltage (V)

(d) 0

120

Forword Reverse

100 80

EQE (%)

Voc=1.05 V 2

Jsc=22.2 mA/cm FF=0.79 PCE=18.5%

-20

0.0

0.5

Voltage(V)

24

Co:NiOx 20

Co:NiOx-based device -10

NiOx

1.0

16

60

12

40

8

20

4

0 300

400

500

600

700

800

Integrated Jsc (mA/cm 2)

(c)

Current Density (mA/cm2)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 25

0 900

Wavelength (nm)

Figure 1. (a) Energy alignment diagram of the devices. (b) Current density-voltage (J-V) characteristics of the PSCs with different ratios Co in NiOX measurement under standard test conditions (AM 1.5G, 100 mW cm-2). (c) The curves of 6 mol% Co-doped NiOX was measured using forward and reverse scan mode. (d) EQE spectra with NiOX and Co:NiOX HTL. All devices were not encapsulated and all the measurements were performed in glovebox.


Page 21 of 25

(a)

(b)

(c) 40

Co:NiOx NiOx 20

I (nA)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0

-20

-40 -0.75 -0.50 -0.25

0.00

0.25

0.50

0.75

1.00

V (V)

Figure 2. (a) Conductive-AFM characteristics of the NiOX. (b) and Co:NiOX films coated on ITO glass at Vbias=1.0 V. The scan size is 2 µm × 2 µm. (c) I-V curves of pristine NiOX and Co:NiOX measured schematic diagram by c-AFM.



(a)

(b) 60

Co:NiOx based device

NiOx based device

Capacitance (nF)

Capacitance (nF)

60

45

30

1 Sun 15

0

Dark 0.0

∆Vpeak:91mV

0.4

0.8

45

30 1 Sun

15

0

1.2

∆Vpeak:47mV

Dark

0.0

0.4

Voltage (V)

0.8

1.2

Voltage (V)

(c)

(d)

12

Co:NiOx-based device

NiOx-based device 1

8

C-2 (1016F-2)

C-2 (1016F-2)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 25

Dark

4

1 Sun

Vbi=0.99V

Dark Vbi=1.07V

1 Sun Vbi=1.03V

Vbi=0.91V

0 0.0

0.4

0.8

1.2

0 0.0

Bias (V)

0.4

0.8

1.2

Bias (V)

Figure 3. (a) Capacitance-voltage (C-V) characteristics of devices with NiOX and (b) Co:NiOX HTL with different illumination intensities from -50 mV to 1.2 V. (c) The C-2-V is measured in dark and one sun illumination condition. The solid lines are linear fits in the portion obeying Mott-Schottky behavior, with the parameters Vbi=0.99 V (dark) and Vbi=0.91 V (light) at NiOX based devices. (d) Vbi=1.07 V (dark) and Vbi=1.03 V (light) at Co:NiOX based devices.


Page 23 of 25

(a)

(b) MAPbI3 NiOx/MAPbI3 Co:NiOx/MAPbI3

MAPbI3, τ=98ns NiOx/ MAPbI3, τ=49ns Co:NiOx/ MAPbI3, τ=26ns

Intensity (a.u)

Normalized PL (a.u)

1

0.1

0.01 720

765

810

60

120

180

Decay Time (ns)

Wavelength(nm)

(c) 0

NiOx-based device -30

∆ PL (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


-60

Co:NiOx-based device 0.0

0.3

0.6

0.9

Bias (V) Figure 4. (a) Steady-state photoluminescence spectra (excitation at 470 nm) of perovskite (MAPbI3) films on top of pristine NiOX (red), Co:NiOX (blue). The bare MAPbI3 (black) film was used as a reference for photoluminescence measurement. (b) time-resolved PL spectra for the same condition corresponding to figure 4a. (c) Steady-state PL spectra measured for NiOX and Co-doped based device from short-circuit condition to open-circuit condition.



Page 24 of 25

Table 1. Summary of the photovoltaic parameters of the inverted planar PSCs with Co-doped NiOX HTL x

JSC (mA cm-2)

VOC (V)

FF (%)

PCE (%)

0

20.7

1.02

77

16.3

0.02

21.3

1.04

78

17.2

0.06

22.3

1.05

79

18.6

0.1

19.8

1.04

78

16.1


Page 25 of 25


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Enhancing Photovoltaic Performance of Inverted Planar Perovskite

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