Efficient and Stable Low-Dimensional RuddlesdenâPopper Perovskite

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Energy Conversion and Storage; Plasmonics and Optoelectronics

Efficient and Stable Low-Dimensional Ruddlesden–Popper Perovskite Solar Cells Enabled by Reducing Tunnel Barrier Lingfeng Chao, Tingting Niu, Yingdong Xia, Xueqin Ran, YongHua Chen, and Wei Huang J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.9b00276 • Publication Date (Web): 26 Feb 2019 Downloaded from http://pubs.acs.org on February 26, 2019

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The Journal of Physical Chemistry Letters

Efficient

and

Stable

Ruddlesden–Popper

Low-Dimensional

Perovskite

Solar

Cells

Enabled by Reducing Tunnel Barrier Lingfeng Chao#,†, Tingting Niu#,†, Yingdong Xia#,†, Xueqin Ran†, Yonghua Chen*,†, Wei Huang*,†,‡,§ Key Laboratory of Flexible Electronics (KLOFE) & Institution of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), Nanjing 211816, Jiangsu, China. ‡Shaanxi Institute of Flexible Electronics (SIFE), Northwestern Polytechnical University (NPU), Xi'an 710072, Shaanxi, China. §Key Laboratory for Organic Electronics & Information Displays (KLOEID), and Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications, Nanjing 210023, Jiangsu, China. †

*Email: [email protected] (Y.C) *Email: [email protected] (W.H)

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ABSTRACT Low-dimensional Ruddlesden–Popper (LDRP) perovskite solar cells (PSCs) have attracted increasing attention due to their excellent long-term stability over three dimensional (3D) counterparts. However, the introduction of insulated long-range bulkier organic ammonium spacers hindered the charge transport. Here,

the

short-range

organic

ammonium

spacers,

1-Amino-3-Butene

Hydrochloride (BEACl) and 3-Butyn-1-Amine Hydrochloride (BYACl), were employed to construct LDRP perovskites, instead of common Butylamine Hydrochloride (BACl). We found charge transport can be significantly improved by controlling the tunneling effect. Moreover, highly oriented and flat perovskite films without pinholes were obtained. Consequently, high PCEs, exceeding 16% for BEA and 15% for BYA based devices, which is much higher than that of BA based analogous device (13.8%), were achieved. Most importantly, the BEA and BYA based LDRP perovskite films and devices show much improved stability. The finding is of great significance for the exploration of new organic ammonium spacers for highly efficient and stable LDRP PSCs.

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Hybrid organic-inorganic halide perovskite (CH3NH3PbX3, X=Cl, Br, I) materials has attracted much attention in recent years.1-5 A record power conversion efficiency (PCE) of 23.7% has been reported by NREL since the first report of perovskite solar cells (PSCs) with PCE only 3.8% in 2009.6,7 However, the long-term stability of PSCs is still a huge challenge in terms of commercialization. Reducing the dimension from three dimensional (3D) perovskite to low dimensional Ruddlesden–Popper (LDRP) phase by incorporation of bulkier organic ammonium molecules has been shown to be a potential way to enhance the stability 8-11. The basic LDRP perovskite structure consists of layers of corner sharing metal halide octahedra (e.g., PbI64-) alternating with bilayers of organic ammonium spacers. The structure is stabilized by hydrogen bonds between the proton hydrogen on the two ammonium spacers and the halogen ions of the upper and lower inorganic components, and by van der Waals, forces between the tails of the two adjacent organic ammonium spacers.12,13 LDRP perovskites have many advantages due to the merit of unique architecture, including suppressed ion migration, high formation energy, low self-doping effect, and reduced carrier recombination etc.14,15 However, the LDRP PSCs exhibits poor PCE compared to the state-of-the-art 3D PSCs due to the poor charge transport in LDRP perovskites caused by the insulated nature of organic ammonium spacers. Recently, a hot-casting technique (HC) was first applied to prepare highly oriented LDRP perovskite films to facilitate charge transport, and a PCE up to 12.5% was obtained.16 Subsequently, great efforts have been explored to construct LDRP perovskites with preferential out-of-plane alignment with respect to the contacts and high PCEs were achieved by cesium doping (13.7%),17 RP phase control (14.4%),18 additive engineering (15.4%),19 and new organic ammonium spacer (18.2%).20 In the LDRP perovskites, the charge transport mainly has two parts, one is the transport along the inorganic framework, and the other is the transport between the adjacent perovskite sheets across the organic ammonium spacers.21 3



It is well known that vertical orientation of the inorganic perovskite component is a prerequisite to LDRP PSCs operation.16, 22 In the case of the latter issue, some charge carriers can be easily trapped by the quantum wells caused by organic ammonium spacers during the transport, which can seriously affect the final device performance.21, 23-25 However, very little is known about how the length of organic ammonium spacer to construct LDRP perovskite with vertical aligned phase might translate into the overall device performance. In this work, we employed short-range organic ammonium spacers, 1-Amino-3-Butene Hydrochloride (BEACl) and 3-Butyn-1-Amine Hydrochloride (BYACl), in LDRP perovskites, instead of commonly used Butylamine Hydrochloride (BACl), to significantly improve the charge transport between adjacent perovskite sheets. Consequently, the PCE of the BEA and BYA based LDRP PSCs reached 16.1% and 15.8%, respectively, compared to 13.8% PCE obtained for analogous devices using BA spacer. Moreover, the BEA and BYA based devices retain 83.1% and 77.2% of their initial PCEs after 3500 h when stored under N2-filled glovebox without encapsulation. The molecular structures of BACl, BEACl, and BYACl and the corresponding constructed LDRP perovskites are shown in Figure 1a. The lengths of BA, BEA, and BYA cations are calculated to be 6.75, 6.53, and 6.61 Ǻ, respectively (Figure 1b). The LDRP perovskites, e.g., BA2MAn-1PbnX3n+1, can be recognized as cutting the 3D MAPbI3 analogues along the crystallographic plane with BA, BEA, and BYA. The neighboring inorganic layers are bridged by the monoammonium bilayer interacted with Van der Waals forces.26-28 The layer number of inorganic components in this study were fixed at n=4 (not the real situation in films),18 which is actually calculated from the precursor stoichiometric molar ratio of 4:2:3 with a molecular structure of (BA)2Pb4MA3I13, (BA)2Pb4MA3I13, and (BA)2Pb4MA3I13 (Figure 1a). We first investigate the morphology of the LDRP perovskite films by scanning electron microscope (SEM), as shown in Figure 1c. The LDRP perovskite (BA)2(MA)3Pb4I13 and the (BYA)2(MA)3Pb4I13 films exhibit many pinholes, which probably cause a large leakage current and affect the 4


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charge transport. In addition, it is easy to be eroded by water and oxygen.29 Interestingly, the (BEA)2(MA)3Pb4I13 LDRP perovskite films present dense and high crystallinity with large crystal (about 600 nm) and pinhole free. This is maybe mainly due to the fact that BEA has a shorter chain than BA, which reduces the steric hindrance of the perovskite during self-assembly and is beneficial to the high quality crystallization of LDRP perovskites.21,27,30 The control film (BA) consists of small crystals with root-mean-squared (RMS) roughness of 13.36 nm, while films with BEA, BYA show enhanced crystallinity and reduced RMS roughness of 11.88 and 13.14 nm, respectively (Figure S1, Supporting information). Moreover, the wettability of the three films was investigated (Figure S2). We found that (BEA)2(MA)3Pb4I13 film have better hydrophobicity, which may reduce the degradation by moisture in humidity air. Therefore, three films are placed in the natural environment to detect the environmental stability (humidity ~60%-80%). Surprisingly, no matter which bulky organic ammonium molecule prepared LDRP perovskite, all films exhibited extreme better long-term stability than that of 3D analogous (Figure S3). In detail, (BEA)2(MA)3Pb4I13 and (BYA)2(MA)3Pb4I13 film were placed in the natural environment without any peak of PbI2 for one year, whereas (BA)2(MA)3Pb4I13 began to degrade after 10 months, indicating the merit of introduction of near-plane molecules remarkably improved environmental stability. The improvement in stability is attributed to the fact that the shorter interlayer distance enhances the force between the inorganic layers,27,28,31 and on the other hand, BEA and BYA stabilize the perovskite structure by reducing the spatial distortion of the molecules.18

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Figure 1. (a) Schematic diagram of LDRP perovskites. (b) Schematic diagram of organic ammonium molecular structure. (c) Top view SEM images of perovskite films with BA, BEA, and BYA. The X-ray diffraction (XRD) was used to investigate the crystallization of LDRP perovskite films (Figure 2a). All films gave strong typical reflections at 14.42ο, 28.78ο, and 43.52ο representing the (111), (202), and (313) crystal planes of the orthorhombic lattice, which are consistent with previous reports.10,16,32 This demonstrates that LDRP perovskite crystal structures do not change under BA, BEA, and BYA modification. However, the BEA and BYA LDRP perovskite films exhibited narrower full width at half maxima (FWHM) than BA based perovskites, indicating the high crystallinity induced by BEA and BYA in LDRP perovskites (Figure 2b), corresponding to the SEM observation. In addition to the high crystallization, the orientation growth of the LDRP perovskite crystals is critical for device performance due to the improved charge transport. Such alignment, the perpendicular growth to the substrate of the inorganic layers, enable the formation of continuous charge-transport channels, and thus allow efficient charge transport in the vertical direction along the inorganic components.16,22,32-34 Grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements, therefore, were performed to determine the orientation of the LDRP perovskite films, as shown in Figure 2c-2e. The control film (BA) displays 6


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obvious Debye-Scherrer rings at qz = 10, suggesting random crystal orientation within the polycrystalline film (Figure 2c). A schematic diagram of the BA LDRP perovskite with random crystal orientation is shown in Figure 2f. On the contrary, for the BEA and BYA LDRP perovskite film, the Debye-Scherrer rings are absent, and intense, sharp, and discrete Bragg spots are observed along the same q position (Figure 2d and 2e), indicating highly oriented crystal grains.16,35 A schematic diagram of the highly oriented perovskite crystal structure is shown in Figures 2g and 2h. The influence of phase transition on LDRP perovskite orientation was further investigated. The pole fgures of the Azimuth angle shows the same rings at 75°and 90° (Figure S4a) for the BA RP Perovskite, indicating that LDRP are randomly oriented in films. By contrast, the BEA and BYA film exhibits sharp, discrete Bragg spots at pole figure 90° without noticeable peaks along the same rings, indicating that the LDRP perovskites are highly oriented (Figure S4a).16,17,32 In addition, this indicates that the inorganic layers are perpendicular to the substrate to form continuous charge-transport channels, which promotes efficient charge transport in the vertical direction.32,34 The BEA RP perovskite film has a narrower FWHM and a stronger diffraction peak than the control film, indicating that the BEA LDRP perovskite has better crystallinity and higher crystal orientation (Figure S4b).10

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Figure 2. (a) XRD patterns and (b) FWHM of (110) crystal planes statistics for 15 films of each LDRP perovskite. GIWAXS patterns of LDRP perovskite films: (c) (BA)2(MA)3Pb4I13, (d) (BEA)2(MA)3Pb4I13, and (e) (BYA)2(MA)3Pb4I13. Schematic interpretation of LDRP perovskite orientations: (f) (BA)2(MA)3Pb4I13, (g) (BEA)2(MA)3Pb4I13, and (h) (BYA)2(MA)3Pb4I13. We further found that the short-range organic ammonium play an important role on the optoelectronic properties of the LDRP perovskites. As shown in Figure 3a, (BEA)2(MA)3Pb4I13 perovskite film has the strongest photoluminescence (PL) intensity over (BYA)2(MA)3Pb4I13 and (BA)2(MA)3Pb4I13, which may be attributed to the fact that BEA perovskites have fewer defects and reduced Auger recombination induced by the shorter length of organic ammonium.36,37

Interestingly,

(BYA)2(MA)3Pb4I13

and

(BA)2(MA)3Pb4I13perovskite films exhibited red shift compared to that of (BEA)2(MA)3Pb4I13 perovskite film, which is mainly attributed to defects induced PL emission (discuss below).38 The same absorption range of three perovskite 8


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films also confirm that this shift is not caused by the reduced bandgap (Figure S5). Moreover, the average lifetime of (BA)2MA3Pb4I13, (BEA)2MA3Pb4I13, and (BYA)2MA3Pb4I13 perovskite films was calculated to be 41.82 ns, 149.32 ns, and 90.17 ns fitted by exponential decay, respectively (Figure 3b). Detailed data was listed in Table S1. The significant increased exciton lifetime by the introduction of short-chain molecules further demonstrates that reducing the length of the molecule is beneficial to reduced defect density and enhanced charge carrier lifetime. In addition, to prove the effects of short-range organic ammonium on the charge extraction, we characterized the charge carriers transfer kinetics of LDRP perovskites by the LDRP perovskite/PEDOT:PSS heterojunction, as shown in Figure S6. The serious quench of PL was observed with reduced lifetime to 15.94 ns for (BA)2MA3Pb4I13, 52.21 ns for (BEA)2MA3Pb4I13, and 30.14 ns for (BYA)2MA3Pb4I13 compared to the bulk LDRP perovskite films, respectively. The higher hole extraction rates of BEA or BYA LDRP perovskites were achieved over BA perovskites with the values of 61.9%, 65.0% and 66.1%, respectively, demonstrating the good contacts with PEDOT:PSS. In order to further demonstrate the effect of short-range ammounium on charge transport of LDRP perovskites, the hole- and electron-only devices were fabricated (Figure 3c and 3d). We found that BEA perovskites have the highest current densities in the same driven voltage in both hole- and electron-only devices, which proves again that shorter-chain ammounium facilitate charge transport.39 It has been widely demonstrated that LDRP perovskites consist of multiple quantum well structure.24,25 The quantum well structure has two main functions in the charge transport process. On the one hand, it restricts ion migration and passivates defects, which is favorable for the device performance. On the other hand, it can capture charge carriers and slow down the charge transport. Two charge transport channels are actually involved in LDRP perovskites: 1) along the inorganic component; 2) across the organic ammonium by tunneling.21,26 In our case, the tunneling effect can be further enhanced by the short-chain organic ammonium BEA and BYA (Figure 3e), thereby improving the 9



charge transport.

Figure 3. (a) PL spectra and (b) Time resolved PL for LDRP perovskite films deposited on Quartz sheet substrates. (c) J-V curves of hole-only devices with the structure of ITO/PEDOT:PSS (30 nm)/perovskite (350 nm)/Spiro-OMeTAD (100 nm)/MoO3 (5 nm)/Au (100 nm). (d) J-V curves of electron-only devices with the structure of ITO/SnO2 (20 nm)/perovskite (350 nm)/PCBM (100 nm)/LiF (1 nm)/Au (100 nm). (e) Illustration of charge transport in LDRP perovskites. Having shown the excellent optoelectronics of LDRP perovskites, photovoltaic performance of was investigated with a device structure of ITO/PEDOT:PSS (30 nm)/Perovskite (350 nm)/PCBM (50 nm)/LiF (5 nm)/Al (100 nm). Figure 4a shows the J-V curves of the representative devices, which 10


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are the most outstanding results obtained for each condition. The control device based on the (BA)2(MA)3Pb4I13 LDRP perovskites showed a short-circuit current density (Jsc) of 18.43 mA cm-2, resulting in a PCE of 13.8%, which is comparable to the previous reports (13.7%).17 The PCE based on BEA and BYA LDRP perovskites (BEA)2(MA)3Pb4I13 and (BYA)2(MA)3Pb4I13 are 16.1% and 15.1%, respectively. The improved PCEs can be attributed to the enhanced Jsc and fill factor (FF), in particular, the Jsc increases from 18.43 to 19.53 mA cm-2 for (BYA)2(MA)3Pb4I11 and 20.63 mA cm-2 for (BEA)2(MA)3Pb4I13 (Table 1). Compared to the currently reported BA LDRP perovskites, device performance has been greatly improved (Table S2). This is due to the fact that the improved charge transport capability by tunneling of charge carriers across the shorter BEA and BYA molecules.21 The external quantum efficiency (EQE) is consistent with the absorption and the integrated current densities are 17.70, 19.92, and 18.89 mA cm-2 for (BA)2(MA)3Pb4I13, (BEA)2(MA)3Pb4I13 and (BYA)2(MA)3Pb4I13, respectively (Figure 4b). Moreover, histogram of the PCEs from 30 individual devices is given in Figure 4c, which exhibited good reproducibility, demonstrating the reliability of our method. More importantly, remarkable improvement

in

the

long-term

stability

of

(BEA)2(MA)3Pb4I13

and

(BYA)2(MA)3Pb4I13 LDRP perovskites over (BA)2(MA)3Pb4I13, as shown in Figure 4d. Three LDRP perovskite devices without encapsulation were placed in a glove box for 3,500 hours, and the PCEs remained 68.1%, 83.1%, and 77.2% of the original BA, BEA, and BYA devices, respectively. The introduction of short-range molecules increases the interaction between adjacent inorganic layers and reduces the charge recombination due to quantum well defects.27

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Figure 4. (a) J-V curves of the best-performing device measured under simulated AM 1.5 G sunlight of 100 mW cm-2. (b) The spectrum of EQE for (BA)2MA3Pb4I13, (BEA)2MA3Pb4I13, and (BYA)2MA3Pb4I13. (c) PCE histogram fitted with a Gaussian distribution. (d) Stability in efficiency of three LDRP devices placed in a glove box for more than 3,000 hours.

It can be seen from Figure 5a that the lowest leakage current in (BEA)2(MA)3Pb4I13 device extracted from J-V curves under dark conditions indicated that the (BEA)2(MA)3Pb4I13 LDRP perovskite could facilitate the charge transport and reduce the charge recombination due to the fewer defects.37,40 Furthermore, the VOC VS light intensity characterization confirmed that the charge recombination of the BEA and BYA based device (n=0.202, and 0.247) was substantially less than that of the BA based device (n=0.289) (Figure 5b). The linear relationship between Jsc and the light intensity on a double logarithmic scale (Jsc ∝ Iα) indicates that BEA (α=1.01) and BYA (α=0.92) devices have less space charge limiting effects and have negligible bimolecular recombination relative to BA (α=0.85) devices (Figure S7). Similarly, the 12


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photocurrent shows that the current drop of BEA is the fastest and the dark current is the lowest (Figure 5c), which is consistent with Figure 5a. The low frequency capacitance is mainly caused by the charge or ion accumulation at the perovskite interface, which leads to interfacial recombination. The BEA device has a small capacitance, which proves again that BEA RP perovskite has fewer defects and less recombination (Figure 5d). To further verify the reduction of the defect state, we fitted the J-V curve using the space-charge-limited current (SCLC) technique and calculated the defect states. The results show that the BEA device exhibited lower electron and hole defect states (Figure S8). Low defects and low recombination are one of the reasons for increasing current density.37

Figure 5. (a) J–V characteristics of devices with different LDRP perovskites under dark conditions. (b) Variation of Voc with light intensity dependence of LDRP perovskites. (c) Transient photocurrent decay of the LDRP perovskite devices. (d) Admittance spectra of BA, BEA, and BYA LDRP perovskite.

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Table 1. Summary of parameters of best-performance LDRP perovskite devices based on BA, BEA, and BYA. LDRP perovskites

Voc (V)

Jsc (mA cm-2)

FF (%)

PCE (%)

(BA)2MA3Pb4I13

0.99

18.43

75.2

13.8

(BEA)2MA3Pb4I13

1.01

20.63

78.0

16.1

(BYA)2MA3Pb4I13

1.01

19.53

76.4

15.1

In summary, we demonstrated short-range organic ammonium molecules in favor of LDRP perovskite carrier transport by increasing the probability of charge tunneling. The short-range organic ammonium molecules contribute to the high crystallization of the LDRP perovskite, forming an LDRP perovskite film having a smooth surface, high crystallinity, and low defect density. Highly stable perovskite films over one year without appreciable PbI2-impurity under humidity of 80% were observed. Importantly, charge carrier transport of LDRP perovskites prepared by short-range organic ammonium molecules has a large increase due to increased tunneling probability. (BEA)2MA3Pb4I13 perovskite device reached a high PCE of 16.1%, which is significant higher than the control device based on (BA)2MA3Pb4I13 and has an improved long-term stability. The device performance can be further improved by optimizing the device structure, interface engineering, and perovskite components.

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ASSOCIATED CONTENT The Supporting Information is available free of charge on the ACS Publications website. Experimental methods, AFM images, contact angle, film stability, pole figures, and Time-resolved PL spectra of perovskite films and tables.

AUTHOR INFORMATION Corresponding Author

*Email: [email protected] (Y.C) *Email: [email protected] (W.H) Author Contributions #L. Chao, T. Niu, and Y. Xia contributed equally to this work. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work was financially supported by the National Basic Research Program of China, Fundamental Studies of Perovskite Solar Cells (Grant 2015CB932200), the Natural Science Foundation of China (Grants 51602149, 61705102, and 91733302), Natural Science Foundation of Jiangsu Province, China (Grants BK20150064, BK20161011, and BK20161010), Young 1000 Talents Global Recruitment Program of China, Jiangsu Specially-Appointed Professor program, “Six talent peaks” Project in Jiangsu Province, China.

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