Study on the properties of perovskite materials under light and different temperatures and electric fields based on DFT

Abstract

The photoelectric conversion efficiency of perovskite solar cells has improved rapidly, but their stability is poor, which is an important factor that restricts their commercial production. This paper studies the physical and chemical stability of perovskite solar cells based on first principles. It is well known that methylamido lead iodide compounds and methylamino lead iodide compounds are easily degraded into NH₂CH=NH₂I, CH₃NH₃I and PbI₂. First, the chemical stability of the above two perovskite-type solar cell materials is discussed by calculating the binding energy. Then, their phonon scattering lines, state density and thermodynamic properties are calculated and analyzed, and the work functions of different types of crystals along different planes such as [1 0 0], [0 1 0 0], [0 0 1] and [1 1 1] are calculated. The results show that the work function of the methylamine iodized lead compound is greater than that of the methylamidine iodized lead compound, which means that the electrons of the methylamidine iodized lead compound escape more easily and the carrier transfer efficiency is higher under the same conditions. Finally, the effects of different temperatures, different electric fields and light on the two kinds of crystal materials are analyzed. This provides theoretical guidance for us to improve the stability of perovskite materials experimentally.

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1 Introduction

In recent years, the increasing demand for photovoltaic products has brought opportunities for new photovoltaic technologies. So far, the development of solar cells has gone through three generations: silicon-based cells, multi-component composite thin film cells, organic thin film solar cells and dye-sensitized solar cells. Perovskite solar cells (PSCs), as the third generation of solar cells, have attracted wide attention due to the continuous improvement of power conversion efficiency (PCE), low material cost and simple manufacturing process.^1–6 PSC, which first appeared in 2009 with an efficiency of 3.8%, has achieved a laboratory-scale photoelectric conversion efficiency of 25.2%.^7–10 Perovskite solar cells have a broad development prospect, but the main reason perovskite solar cells cannot be used on a large scale is the battery stability. At present, perovskite-type solar cells can only work for several months under active conditions, while conventional silicon cells can work for more than 25 years. How to improve the stability of perovskite batteries and make them as good as commercial polysilicon solar cells is the most important problem in the field of perovskite solar cells. The instability of organic–inorganic hybrid perovskite, such as the volatilization of organic cations in (MAPbI₃)·CH₃NH₃PbI₃ and (FAPbI₃)·NH₂CH=NH₂PbI₃ under thermal stress, has become a major limiting factor for its long-term practical application. Ze Wang etc.¹¹ studied the effects of ambient temperature and humidity on the chemical stability of perovskites, and found that the degradation reaction CH₃NH₃PbI₃ → CH₃NH₃I + PbI₂ and CH₃NH₃I → CH₃NH₂ + HI would occur when MAPbI₃ was exposed to light illumination and different temperatures. Nick Aristidou and his colleagues¹² investigated the moisture stability mechanisms of perovskite solar cell materials in a mixture of water and oxygen. In fact, it is not known whether the iodine and hydrogen atoms in the perovskite materials are more readily dissociated to form PbI₂ and HI ions. In this paper, the formation energy in the degradation reaction is calculated based on the first principle, which can help us analyze which dissociation reaction is easier to carry out. That's something you can't do experimentally. At the same time, the phonon dispersion spectrum, density of states and thermodynamic properties of the crystals are calculated and analyzed. The work functions of different types of crystals along different planes [1 0 0] [0 1 0][0 0 1] [1 1 1] are also calculated. Finally, the effects of different temperature, different electric field and light on the two kinds of crystal materials are analyzed. This provides theoretical guidance for us to improve the stability of perovskite materials experimentally.

For convenient observation of crystal structure, we build the supercells of two crystals with 2 × 3 × 1 mesh which was shown as Fig. 1, and the lattice parameters are as following: (a) a = 12.58 Å, b = 18.69 Å, c = 6.37 Å, α = 90.00°, β = 88.74°, γ = 89.98°, (b) a = 12.82 Å, b = 19.01 Å, c = 6.27 Å, α = β = γ = 90°. Space group crystal system of two crystals are triclinic.

Fig. 1 Structure diagram of two crystals.

2 Computational methods

In this paper, two perovskite crystal materials NH₂CH=NH₂PbI₃ and CH₃NH₃PbI₃ were calculated based on DFT method, and the simulation package (CASTEP and Dmol³) was used to complete the calculation. The part from 3.1 to 3.4 in this paper is calculated by the CASTEP module.^13–15 The exchange–correlation effects were still treated by Perdew–Burke–Ernzerh (PBE) of function in the generalized gradient approximation (GGA).^16,17 The cut-off energy of plane wave basis set is 340 eV, and the SCF (self-consistent field) tolerance of the total energy change of each atom is set as 1 × 10⁻⁵ eV per atom. The maximum force of each atom is less than 0.01 eV Å⁻¹ and the optimization is less than 0.0005 Å. The existence of tightly bound core electrons is represented by supersoft pseudopotential.^18,19 The integral of Brillouin region is replaced by the discrete summation of a set of special K points using Monkhorst–pack scheme. And in the part 3.5, the study on the properties of applying electric field to crystals are calculated by Dmol³ package. And the details of the calculations were as follows: the exchange–correlation effects were treated by Generalized Gradient Approximation (GGA) version of Perdew–Wang-1991(PW91),²⁰ and the basis set was 3.5 double numerical plus d-functions basis (DND), the qualities were selected as “fine”.

3 Results and discussion

3.1. Thermal stability studies

With the improvement of the understanding of the instability of component materials under the conditions of humidity, heat, light and oxygen, more researches have been carried out on the long-term stability of perovskite materials.^21–28 Perovskite materials degrade rapidly when exposed to humid environment.^29–34 Our previous work³⁵ has explored the structural stability of perovskite crystal and its adsorption properties for water molecules. Many papers^36–39 reported that the perovskite materials CH₃NH₃PbI₃ and NH₂CH=NH₂PbI₃ will decompose into CH₃NH₂, NH₂CH=NH, PbI₂ and HI at above 150 °C. The decomposition of perovskite is the reverse reaction of perovskite formation, and the instability caused by humidity and heat generally exists in organic–inorganic hybrid perovskite. The current mixed perovskite is facing another challenge: they are unstable to light.^40–44 The possible mechanism of decomposition on exposure to light is as follows

In the superlattices of MAPbI₃ and FAPbI₃, there is one lead (Pb) atom, three iodine(I) atoms and one group. However, the dissociation energies of I atoms at different positions are not equal. We can use formation energy to express its stability. If the absolute value of crystal formation energy is small, it indicates that its stability is poor. The formula of formation energy can be written as follows:

ΔE = E_CH3NH3PbI3 − E_CH3NH3I − E_PbI2 (3)

where E_CH3NH3PbI3, E_CH3NH3I, E_PbI2 are the optimized energy of the crystal. The total energy of reaction for degradation pathways in a number of different ambient environments are calculated by DFT methods and shown in Table 1.

Table 1 Formation energy of CH₃NH₃PbI₃

	CH3NH3PbI3		CH3NH3I	PbI2
Degradation pathway 1					ΔE
	−3125.36 eV		−837.04 eV	−2287.04 eV	−1.28 eV
Degradation pathway 2					ΔE
	−3125.36 eV		−836.89 eV	−2287.03 eV	−1.44 eV
Degradation pathway 3					ΔE
	−3125.36 eV		−836.93 eV	−2287.03 eV	−1.40 eV

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It can be seen from Table 1 that CH₃NH₃PbI₃ absorbing light and heat is decomposed into CH₃NH₂I and PbI₂. The energy required to dissociate ions at different positions of the crystal is not equal, and its magnitude is −1.28 eV, −1.44 eV and −1.40 eV, respectively. The results show that the first form of degradation is more likely to occur. For NH₂CH=NH₂PbI₃ crystal, the formation energy can be expressed as:

ΔE = E_CH3NH3I − E_CH3NH2 − E_HI (4)

We know that NH₂CH=NH₂PbI₃ absorbs energy to decomposed into NH₂CH=NH₂I and PbI₂. The dissociation of I and Pb atoms at different locations requires different energies to form PbI₂. The greater the absolute value of the energy required for dissociation, the more difficult the reaction. Table 2 shows that these three reaction formation energies are −1.28 eV, −0.95 eV and −1.53 eV, respectively. The result shows that the second form of degradation is easier to occur, while the third form of degradation is the most difficult.

Table 2 Formation energy of NH₂CH=NH₂PbI₃

	NH2CH=NH2PbI3		NH2CH=NH2I	PbI2
Degradation pathway 1					ΔE
	−3380.1 eV		−1091.68 eV	−2287.14 eV	−1.28 eV
Degradation pathway 2					ΔE
	−3380.1 eV		−1092.10 eV	−2287.05 eV	−0.95 eV
Degradation pathway 3					ΔE
	−3380.1 eV		−1091.52 eV	−2287.05 eV	−1.53 eV

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The possible mechanism of further decomposition on exposure to the environments of light illumination, different temperatures which is as follows¹¹:

We further analyzed the dissociation energies required for ion separation at different sites to help us explore which chemical reactions are more likely to occur. The different hydrogen (H) and iodine (I) atoms in the crystal are labeled as follows. Consider the combination of hydrogen (H) ions and iodine (I) atoms in different positions to form HI as a product. The difficulty of this reaction is determined by calculating the formation energies of the reactants and products.

ΔE = E_CH3NH3I − E_CH3NH2 − E_HI or ΔE = E_CH3NH3I − E_CH2NH3 − E_HI (7)

ΔE = E_NH2CH=NH2I − E_NH2CH=NH − E_HI or ΔE = E_NH2CH=NH2I − E_NH2C=NH2 − E_HI (8)

where E_CH3NH3I, E_NH2CH=NH2I are the optimized energy of reactants, and E_NH2CH=NH, E_CH3NH2, E_HI, are the optimized energy of products.

In this part, we can discuss the possibility of its further degradation reaction by calculating its formation energy, and the results shown in Tables 3 and 4. For convenience, we have numbered each atom in the crystal, as shown in left figure in the table. The superscript number of the element indicates the position number of the atom in the crystal, such as H¹I¹.

Table 3 Formation energy of CH₃NH₃I

		CH2NH3 + H^1I^1	CH2NH3 + H^1I^2	CH2NH3 + H^1I^3
		(a)	(b)	(c)
	ΔE (eV)	−6.01	−6.36	−5.73
		CH2NH3 + H^2I^1	CH2NH3 + H^2I^2	CH2NH3 + H^2I^3
		(d)	(e)	(f)
	ΔE (eV)	−7.64	−6.33	−4.72
		CH2NH3 + H^3I^1	CH3NH2 + H^3I^2	CH3NH2 + H^3I^3
		(g)	(h)	(i)
	ΔE (eV)	−6.32	−6.20	−6.37
		CH3NH2 + H^4I^1	CH3NH2 + H^4I^2	CH3NH2 + H^4I^3
		(j)	(k)	(l)
	ΔE (eV)	−6.13	−6.24	−6.39
		CH3NH2 + H^5I^1	CH3NH2 + H^5I^2	CH3NH2 + H^5I^3
		(m)	(n)	(o)
	ΔE (eV)	−6.35	−6.33	−6.46
		CH3NH2 + H^6I^1	CH3NH2 + H^6I^2	CH3NH2 + H^6I^3
		(p)	(q)	(r)
	ΔE (eV)	−5.51	−6.47	−7.60

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Table 4 Formation energy of NH₂CH=NH₂I

		NHCH = NH2 + H^4I^7	NHCH = NH2 + H^4I^8	NHCH = NH2 + H^4I^9
		(A)	(B)	(C)
	ΔE (eV)	−12.48	−12.95	−12.21
		NHCH = NH2 + H^5I^7	NHCH = NH2 + H^5I^8	NHCH = NH2 + H^5I^9
		(D)	(E)	(F)
	ΔE (eV)	−12.44	−13.02	−11.52
		NH2C=NH2 + H^2I^7	NH2C=NH2 + H^2I^8	NH2C=NH2 + H^2I^9
		(G)	(H)	(I)
	ΔE (eV)	−7.05	−7.13	−6.97

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The results show that the combination of H⁴, H⁵, and H⁶ with iodide (I) ions is unstable, and it is easier to decompose into H⁺ and I⁻ ions. From the left figure of Table 3, it can be seen that the hydrogen atom at positions 4, 5 and 6 is outside the supercell. The HI formed by iodine is unstable. This kind of iodine amine compound is easier to dissociate and has poor stability. The font color in Table 3 is blue, indicating that the product HI is unstable. They are easy to generate as H₂ and I₂

It can be seen from Fig. 2 this reaction of CH₂NH₃ + H²I³ is easier to carry out, and I₂ and H₂ gas will continue to be generated. And then the easier degraded reactions were (c) CH₂NH₃ + H¹I³ and (p) CH₃NH₂ + H⁶I¹.

Fig. 2 Formation energy curve of CH₃NH₃I.

Compared with the energy required for various degradation reactions in Table 4, the energy required for further dissociation of amidine iodide is in the order of (I) < (G) < (H) < (F) < (C) < (D) < (A) < (B) < (E). The reactions of (G), (H) and (I) are more likely to occur. This result is even more obvious in Fig. 3. And the degradation reaction of eqn (6) is more difficult than that of eqn (5).

Fig. 3 The formation energy of NH₂CH=NH₂I.

For convenience, we define eqn (1) and (2) as first-order degradation reactions and eqn (5) and (6) as second-order degradation reactions. It can be seen that the energy required for the primary degradation reaction is 1.56 eV, while the energy required for the secondary degradation reaction is greater than 6.24 eV, indicating that the secondary degradation reaction is more difficult than the primary degradation reaction.

3.2. Research on thermodynamic properties

In order to further study the stability of these two kinds of crystals, we optimized their phonon dispersion spectrum and distribution curve of phonon density of state, as shown in Fig. 4. First of all, the structure is optimized by using the CASTEP package, then the phonon dispersion spectrum, density of states and thermodynamic properties of two kinds of crystals are calculated and obtained.

Fig. 4 (a) Thermodynamic properties of CH₃NH₃PbI₃, (b) thermodynamic properties of NH₂CH=NH₂PbI₃, (c) Debye temperature of two crystals, (d) heat capacity of two crystals.

In Fig. 4 (a) and (b), zero point energy of CH₃NH₃PbI₃ is 2.09 eV, which is slightly larger than that of NH₂CH=NH₂PbI₃ (1.902 eV). The free energy of the two crystals decreases with the increase of temperature. Their enthalpy increases with the increase of temperature. Fig. 4(c) shows that the Debye temperature corresponds to the highest frequency of lattice vibration. It is actually a characteristic quantity of the strongest bond between crystals. Which can reflect the size of the bonding force between atoms. The Debye temperature of different materials is different, the melting point is high, that is, the stronger the atomic bond of the material is, the higher the Debye temperature is. It can be seen from Fig. 4(d) that the change trend of the bond energy between atoms of the two crystals is basically the same with the increase of temperature. The binding capacity of NH₂CH=NH₂PbI₃ is slightly higher than CH₃NH₃PbI₃. The heat capacity of NH₂CH=NH₂PbI₃ is lower than that of CH₃NH₃PbI₃.

3.3. Phonon spectrum of crystals

It can be inferred from Fig. 5 that CH₃NH₃PbI₃ and NH₂CH=NH₂PbI₃ are unstable because they have imaginary frequencies in the phonon spectrum, which is consistent with their small formation energy (see Tables 1 and 2). Also it tells us that phonon spectrum band gap of CH₃NH₃PbI₃ is similar as that of NH₂CH=NH₂PbI_3. However, the frequency of MAPbI₃ is between 45 and 85 THz, and the frequency of FAPbI₃ is between 52 and 92 THz. We know that with the decrease of the moment of inertia of the oscillator, the natural frequency of the oscillator will increase and the position frequency of the local resonance band gap will also increase. The position frequency of the local resonance band gap caused by the rotating oscillator is close to the fixed frequency of the oscillator. However, different from the linear displacement oscillator, with the decrease of the dimensionless mass, the band width shows an increasing trend. And rotational inertia of FAPbI₃ is smaller than that of MAPbI₃.

Fig. 5 Phonon dispersion and density of states of two kinds of crystals.

3.4. Calculation of work function

In our calculations, the metal slab is placed in the center of a cell and a 20 Å vacuum is introduced along the z direction. In the following, our approach to calculate the electrochemical potential and the total energy will be given in detail. In order to calculate the electrochemical potential (U) of a system, the following equations can be used according to the definition of absolute electrochemical potential. The work function reflects the minimum energy required for electrons to move from the interior of a solid to the surface of the object, , where E_VAC is the energy of a static electron in a vacuum and EF is Fermi level. Since the work function W depends on the crystal structure and crystal orientation, the crystal structure of the bulk material should be optimized before the two-dimensional array is constructed. So we build two kinds of crystals along different surface [0 0 1][0 1 0][1 0 0][1 1 1]. And a vacuum layer with a thickness of 20 Å, fix the surface atoms, and optimize the crystal structure, then calculate the corresponding work function, as shown in the following Fig. 6:

Fig. 6 FAPbI₃ cleave surface [1 0 0].

For comparison purposes, I constructed a vacuum layer (20 Å) for FAPbI₃ and MAPbI₃ crystal. In the calculation results of FAPbI₃, the electrostatic energy values of the vacuum top electron and the vacuum bottom electron appear on the plane [1 0 0] and [1 1 1] respectively. Its operating function is between 5.811–3.799 eV and 6.238–5.552 eV. In MAPbI₃, the work function has no obvious fluctuation, and the surface work function is 5.054 eV, 4.96 eV, 5.946 eV, 5.194 eV at surface [0 0 1], [0 1 0], [1 0 0], [1 1 1], respectively. Also we can find that the work function of MAPbI₃ is greater than that of FAPbI₃ for [1 0 0] plane, the work functions in other planes for FAPbI₃ and MAPbI₃ crystal are similar, as shown in the Fig. 7.

Fig. 7 Thermodynamic properties of two kinds of crystals.

From Fig. 8(a), we find that the work function of FAPbI₃ has a minimum value (3.799 eV) along the [1 0 0] plane, while the work function of MAPbI₃ is the minimum value in the [0 1 0] plane. We further explored the changes of band gap on different cutting planes, which were [1 0 0], [0 1 0], [0 0 1], and [1 1 1], and calculated the corresponding band gap using CASTEP module. As can be seen from Fig. 8(b), the band gap of MAPbI₃ varies greatly along different cleavage planes, while the band gap of FAPbI₃ varies little.

Fig. 8 (a) Work function and (b) band gap of two kinds of crystals.

3.5. Perovskite crystal stability at different temperatures

As solar cells, they are exposed to the sun all year round and their temperature varies greatly. It is necessary to analyze the influence of temperature on perovskite materials. We can now focus on the analysis of different environments (250 K, 273 K, 300 K 350 K, 373 K, 400 K, 450 K) to calculate their free energy and kinetic energy to analyze the change of crystal stability at different temperatures. The result shows as Fig. 9(a) and (b).

Fig. 9 (a) Kinetic energy and (b) free energy of crystals at different temperatures.

For macroscopic systems such as crystals, the principle follows the lowest free energy F = U−TS, where U is the potential energy and TS is the kinetic energy. Fig. 10 tells us that MAPbI₃ obtain the minimum kinetic energy at a temperature of 273 K (0 °C) and the maximum value at 373 K (100 °C). FAPbI₃ also achieved a maximum at 373 K (100 °C). And FAPbI₃ suddenly increased to −3379.80 eV at 273 K (0 °C), which means that the stability of this crystal decreased at 0 °C. The free energy for MAPbI₃ does not change much at different temperatures.

Fig. 10 (A)–(H) are thermodynamic properties of two kinds of crystals.

3.6. Apply an electric field in different directions

Perovskite solar cells always work at a certain voltage, so we discuss the effect of electric field on the crystal stability in different directions. Because the CASETP package of material Studio software cannot analyze the application electric field during calculation, but the Dmol³ package can apply an electric field to the bulk crystal. In this part, we use the Dmol³ package for calculation, and the parameter setting is described in part 2. After applying the electric field 0.005 a.u or 0.01 a.u. in the x, y and z directions, the corresponding free energy, bond energy, exchange energy, kinetic energy of the system molecule, Fermi energy level, conduction band and valence state are obtained (1 a.u. ≈ 5.14 × 10¹¹ V m⁻¹).

The calculation results are shown in Fig. 10(A–H). It can be seen from Fig. 10(A) that the system free energy of crystal FAPbI₃ is higher than that of MAPbI₃. Fig. 10(B) shows that the bond energy of FAPbI₃ is lower than that of MAPbI₃. Because the bonding energy is lower, its stability is relatively poor, and the naturally the free energy is high, which is consistent with the theory of solid physics. Fig. 10(E–H) shows that the free energy and bond energy of the electric field have little change after the application of the electric field, which means that the electric field has little influence on its stability. However, after the electric field is applied, its Fermi level position increases slightly, as shown in Fig. 10(C) and (D). The Fermi energy level increases with the increase of voltage. When the electric field is applied along the z-axis, the change is more obvious. From the point of view of molecular kinetic energy and exchange energy of the system, the energy increases significantly after the application of electric field, and increases with the increase of voltage.

4 Conclusion

In this paper, the stability of two important organic–inorganic perovskite solar cell materials, FAPbI₃ and MAPbI₃, under different light, temperature and electric field were studied in detail. Firstly, the chemical degradation reactions of the two organic–inorganic perovskite crystals material
were studied under heat condition. Moreover, the photoactive layer of CH₃NH₃PbI₃ and NH₂CH=NH₂PbI₃ can be rapidly decomposed into a Al₂O₃ mesoporous structures under light and drying conditions, generating products such as CH₃NH₂, NH₂CH=NH₂, HI and I₂. Since iodine (I) atoms in different parts of the crystal need different energies to react with hydrogen, which reaction form is more likely to occur can be determined according to the energy required for the reaction. By calculating the formation energy, it is found that CH₃NH₃PbI₃ is more likely to undergo the first type of degradation reaction, while NH₂CH=NH₂PbI₃ is more likely to undergo the second type of degradation reaction. The above results cannot be specifically determined by experiments. Furthermore, 18 possible CH₃NH₃I degradation reactions and 9 possible NH₂CH=NH₂I degradation schemes were analyzed. The calculation results show that the hydrogen atoms H⁴, H⁵, and H⁶ are not stable in combination with iodine ions, and are easier decompose into H⁺ and I⁻ ions. It can be seen from the figure that the reactions of (G), (H) and (I) are more likely to occur when the hydrogen atoms at positions 4, 5 and 6 are outside the supercell unit.

Then, the phonon dispersion spectrum, thermodynamic properties, and work functions of the two crystals are discussed. The phonon dispersion curve shows that the moment of inertia of FAPbI₃ is smaller than that of MAPbI₃. The FAPbI₃ system has the maximum free energy and kinetic energy at 373 K (100 °C), but the free energy of MAPbI₃ does not change much at different temperatures. The free energy of FAPbI₃ suddenly increases to −3379.80 eV at 273 K (0 °C), which means that it has the lowest temperature dependence at 0 °C. The work function of MAPbI₃ is greater than that of FAPbI₃ for [1 0 0] plane, which means that the electrons of FAPbI₃ are easier to escape and its carrier transfer efficiency is higher with the same conditions. In other planes, the work functions of the two crystals are similar.

Finally, the stability of the two kinds of crystals under different temperature and electric field is discussed. The free energy of crystal FAPbI₃ is higher than that of MAPbI₃. When the electric field is applied, the free energy and bond energy of the two crystals do not change significantly, which means that the electric field has little influence on their stability. However, the molecular kinetic energy and exchange energy of the two crystalline materials increase obviously and increase with the increase of the voltage. This provides theoretical guidance for us to improve the stability of perovskite materials experimentally.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work is supported by the National Natural Science Foundation of China Program (Grant No. 11164004), Guizhou Provincial Photonic Science and Technology Innovation team (Qianke Joint talents team [2015]4017), the Industrial Research Project of Guizhou Province (GY[2012]3060), the Growth Foundation for Young Scientists of Guizhou Provincial Department of Education (Grant no. QJH KY [2018]265), Special Laboratory Fund of Guizhou Education Department of Education (GY[2014]217), First class discipline education science construction project of Guizhou Education University [2019YLXK C05]

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