High-Temperature Dielectric Switching and Photoluminescence in a

Jul 19, 2019 - ... was discovered undergoing a high-temperature reversible phase transition ... new fertile ground to discover more potentially useful...
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High-Temperature Dielectric Switching and Photoluminescence in a Corrugated Lead Bromide Layer Hybrid Perovskite Semiconductor Hao-Jie Li,† Yu-Ling Liu,‡ Xiao-Gang Chen,† Ji-Xing Gao,† Zhong-Xia Wang,*,‡ and Wei-Qiang Liao*,†,‡ †

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Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics, Southeast University, Nanjing, 211189, People’s Republic of China ‡ Ordered Matter Science Research Center, Nanchang University, Nanchang 330031, People’s Republic of China S Supporting Information *

ABSTRACT: Layered lead−halide organic−inorganic hybrid perovskites have shown great application prospects in photovoltaics and optoelectronics because of their diverse structural assemblies and richness in physical properties. In this report, a rare corrugated layer lead bromide hybrid perovskite of (demethyltropinone)4Pb3Br10 was discovered undergoing a high-temperature reversible phase transition at 410 K, which is induced by the order−disorder transition of organic cation response to the variation of external temperature. The title compound exhibits prominent switchable dielectric behavior, coupled with semiconducting property and brilliant orange fluorescence under UV excitation. The integrated multifunction ability indicates the emergence of new promising materials and provides new fertile ground to discover more potentially useful materials.

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INTRODUCTION Hybrid organic−inorganic metal halides (HOMHs) have attracted considerable attention in recent years due to their promising use in optical and optoelectronic fields.1−4 The reason is that HOMHs have a big ability to embrace diverse organic ammonium cations interacting with inorganic metal halides, producing all sorts of fresh architectures and intriguing physical properties.5,6 As one of the hottest topics in the energy field, three-dimensional (3D) CH3NH3PbI3 perovskite has been experiencing a comprehensive inspection that will give full play to its advantages in photovoltaic application.3,7 However, the 3D lead iodide perovskites are tightly confined to a few cases, which makes them extremely challenging to evolve other capabilities in the current system. Significantly, research is already on its way to two-dimensional (2D) HOMHs, which can conceptually be thought of as a structure derived from a specific slice of 3D HOMHs.8,9 The 2D HOMHs have greater prospects for structural manipulation to discover more diverse structures with promising physical properties in contrast to the 3D HOMHs since they possess the ability to match larger and more complex organic cations.10−12 As the representative of 2D HOMHs, layered structures comprise the organic cations that are located in the cavities enclosed by the metal−halide octahedron.13 The weak hydrogen-bonding interactions between organic and inorganic composites create suitable room for the thermally activated motions of the cations under external stimulus including temperature, pressure and electric field, etc.14−16 This kind of cationic motion would trigger the distortion of lattice and © XXXX American Chemical Society

further change the crystal structure. Therefore, layered HOMHs are seemingly inherent with the potential for structural phase transition. Besides this, molecular dynamics of order−disorder transition are generally accompanied by a variation of dipole moments in molecules, in which the structural phase transition along with symmetry breaking might be responsible for important switchable dielectrics, ferroelectrics, etc.17−23 Very recently, 2D layered HOMHs with the molecular formula of A2BX4, where A is monovalent or divalent (ABX4) organic cation, B is divalent transition metal, and X is halogen, have been proven to be commendable candidates for phase transition materials.24 Other coupled versatilities can be achieved by introduction of a special metal into phase transition compounds, such as the magnetic and luminescent manganese, semiconducting lead, etc.25−30 For example, many cases of layered cadmium HOMHs demonstrate remarkable switchable dielectric responses because of the order−disorder transition of organic cations in the cavities.31,32 Interestingly, the important photoluminescent feature is bringing in based on layered manganese HOMHs, making them promising luminescence-dielectric phase transition materials.33,34 It is notable that structural phase transitions in layered lead HOMHs have been reported showing excellent dielectric switches and ferroelectric semiconductors. However, the phase transition coupled with high-temperature switchable dielectric, Received: May 24, 2019

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DOI: 10.1021/acs.inorgchem.9b01538 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

were used to estimate the band gap by converting reflectance data to absorbance according to the Kubelka−Munk equation: F(R∞) = (1 − R∞)2/(2R∞) = α/S (R∞, α, and S represent reflectance, absorption, and scattering coefficients, respectively).37 The optical band gap were determined by the variant of the Tauc equation: (hν × F(R∞))2 = A(hν − Eg), where h is the Planck’s constant, ν is the frequency of vibration, A is the proportional constant, and Eg is the band gap.38 Photoluminescence Measurements. The large crystals were used to measure the emission and excitation spectra on an Edinburgh FLS-920 fluorescence spectrometer. Electronic Structure Calculations. Energy band structure and DOS were processed with the DFT method within the CASTEP code.39,40 The initial structure is based on the single-crystal structure at 293 K and was used for calculations after structural optimization. The Perdew−Burke−Ernzerhof in the generalized gradient approximation was employed to take the exchange and correlation effects into consideration.41 The core−electrons interactions between the ionic cores and the electrons were described by the norm-conserving pseudopotential with the following valence electron configurations: Pb-5s25p65d106s26p2, Br-4s24p5, C-2s22p2, N-2s22p3, O-2s22p4, and H1s1.

semiconducting and photoluminescent properties involved in the corrugated layer architecture with the analogue of Cs4Mg3F10 have been scarcely discovered.35 Herein, we constructed a new 2D corrugated layer of lead bromide HOMH, namely, (dmte)4Pb3Br10 (dmte = demethyltropinone) (1). 1 experiences a reversible structural phase transition at 410 K (Tc) with prominent switchable dielectric behavior and semiconducting property. Moreover, the obvious orange light emission is observed under UV excitation owing to the special corrugated structural stacking.11,36 Multiple physical characterizations reveal the order−disorder transition of dmte organic cation accounts for the significant dielectric transition. The finding of multiple coupling of semiconductor, luminescence and dielectric switching in corrugated layer lead bromide hybrid perovskite would make HOMHs more substantial and further boost the development of multifunctional materials.

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EXPERIMENTAL SECTION

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Materials. Demethyltropinone hydrochloride (Accela, 97%), lead bromide (Aladdin, AR 99.0%), and hydrobromic acid (Aladdin, CP, 40%) were used as received without further purification. Synthesis. Lead bromide (10.0 mmol, 3.67 g) was dissolved in hydrobromic acid (20.0 mL). Then demethyltropinone hydrochloride (10.0 mmol, 1.62 g) was added to the above solution and heated to 100 °C. The colorless crystals of 1 were harvested by slow evaporation at 60 °C for 1 week (Figure S1). IR, TGA, and PXRD Measurements. IR spectra of 1 in KBr pellets were recorded on a Shimadzu IR Prestige-21 instrument at room temperature. Thermogravimetric analyses (TGA) were carried out on a TA Q50 system with a heating rate of 10 K min−1 under a nitrogen atmosphere. PXRD measurements were taken on a Rigaku D/MAX 2000 PC X-ray diffraction instrument in the 2θ range of 5− 50° with a step size of 0.02°. The purity of the bulk phase was verified by powder X-ray diffraction (PXRD) and IR spectra (Figure S2 and Figure S3). Thermogravimetric analysis (TGA) demonstrates that 1 was thermally stable up to about 536 K (Figure S4). DSC Measurements. Differential scanning calorimeter (DSC) measurements for 1 (19.6 mg) were carried out on a PerkinElmer Diamond DSC instrument in the temperature range from 293 to 443 K with a heating rate of 10 K/min under nitrogen atmosphere. Single-Crystal X-ray Crystallography. Variable-temperature Xray single crystal diffractions were performed on Rigaku Oxford Diffraction 2018 with Mo−Kα radiation (λ = 0.71073 Å) and the crystal data were collected at 293 K (low-temperature phase, LTP) and 443 K (high-temperature phase, HTP), respectively. The CrystalClear software package (Rigaku, 2018) was used to process crystal data. The variable-temperature crystal structures were solved using a direct method, and the SHELXLTL software package (SHELXLTL-2014) was used for the refinement of crystal structures on F2 using full-matrix least-squares refinement. The anisotropically of non-hydrogen atoms were refined for all reflections with I > 2σ(I), and the positions of the hydrogen atoms were generated geometrically. The crystallographic data and structure refinement are listed at 293 and 443 K in Table S1. The DIAMOND software (Brandenburg and Putz, 2005) was used to draw asymmetric units and package views. Dielectric Measurements. For complex dielectric measurements, the polycrystalline samples were ground into powder and then pressed into a thin plate. The large crystal was cut into three thin slices along the a-axis, b-axis, and c-axis, respectively, which were used to measure the dielectric anisotropy. The complex dielectric constants (ε = ε′ − iε″, where ε′ is the real part, and ε″ represents the imaginary parts) were measured by a TongHui TH2828A instrument in the frequency range of 5−1000 kHz with a temperature range of 300−430 K. Optical Absorption Spectrum. Ultraviolet−vis spectral measurements were performed using a Shimadzu UV-2450 spectrophotometer operating from 220 to 850 nm at room temperature with BaSO4 sample as the 100% reflectance reference. The reflectance data

RESULTS AND DISCUSSION Thermal Analysis. DSC is the primary tool for thermal analysis to detect whether compound exists a reversible phase transition under the stimulation of temperature. As shown in Figure 1, a pair of thermal anomalies including a sharp

Figure 1. DSC curve of 1 measured in the temperature range 293− 443 K.

endothermic peak at 410 K and an exothermic peak at 370 K indicates a reversible phase transition. Large thermal hysteresis of 40 K together with the Lambda type peaks reveals a firstorder phase transition involved in 1.42 Besides, enthalpy change (ΔH) was recorded as 6709.67 J mol−1 and the corresponding entropy change (ΔS) was calculated to be 16.38 J mol−1 K−1 based on the equation ΔS = ΔH/Tc. According to the Boltzmann equation ΔS = R ln(N), where R is the gas constant, and N represents the proportion of the number of possible orientations for the whole disordered system, the N value was determined as 5.36 for 1, pointing to an order− disorder feature of phase transition.43 Crystal Structures. To determine the structural details and the microscopic mechanism of phase transition in 1, variabletemperature X-ray diffraction data were collected at 293 and 443 K. At 293 K, 1 crystallizes in an orthorhombic crystallographic system with a space group of Pbca (No. 61). The cell parameters was refined as a = 20.9220(5) Å, b = B

DOI: 10.1021/acs.inorgchem.9b01538 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry 9.1743(2) Å, c = 23.6345(6) Å, Z = 1, and V = 4536.52(19) Å3. The asymmetric unit consists of two protonated dmte cations, one and a half Pb atoms and five Br atoms (Figure 2a

Figure 2. Asymmetric unit of 1 at 293 K (a) and 443 K (b). All the hydrogen atoms were omitted for clarity.

and Figure S5a). As the temperature increases from 293 to 443 K, 1 enters into a higher symmetry of Cmca (No. 64) with a = 9.3779(3) Å, b = 23.5404(9) Å, c = 21.1914(8) Å, Z = 2, and V = 4678.2(3) Å3. Obviously, the relationship of cell parameters between LTP and HTP is shown as aHTP ≈ bLTP, bHTP ≈ cLTP, and cHTP ≈ aLTP. The asymmetric unit of 1 in HTP is equivalent to the half of that in LTP, in which the cations and inorganic framework are equally divided by the mirror parallel to the c-axis (Figure 2b and Figure S5b). In LTP, the packing structure of 1 comprises face-sharing PbBr6 octahedra connected by angular shared bridging bromide to form a wave-like 2D layered HOMPs, in which dmte cations locate in the cavities between the inorganic layers (Figure 3a and Figure S6). The Pb−Br bond lengths are in the range 2.8427−3.2131 Å and the angles of adjacent Br−Pb−Br varying from 76.208° to 83.696°, revealing the slightly distorted of the octahedrons (Table S2). The organic cations lay on the general position with the ordered state so that there is no any additional symmetry operations. Moreover, the dmte cations are linked to the inorganic framework through N−H··· Br and N−H···O hydrogen bonding interactions with the donor−acceptor distance of 3.386 (3) Å and 2.867 (6) Å (Figure S7 and Table S3). The weak interactions provide appropriate freedom for the motion of cations. When the temperature goes to the HTP, the Pb−Br bond lengths and Br−Pb−Br bond angles of 1 are slightly different from those in LTP (Figure 3b and Table S4). Significantly, the protonated dmte cations in HTP occupy the special position, so that the cations demonstrate highly disordered to satisfy the requirement of the mirror symmetry. The order−disorder transition of dmte cations accompanied by crystallographic axis transform from LTP to HTP confirm the occurrence of phase transition, being in good agreement with the results derived from DSC measurements. To further confirm the phase transition in 1, variabletemperature PXRD measurements were performed at 293, 353, 413, 423, and 433 K, respectively (Figure 4). The experimental PXRD patterns obtained at 293 and 443 K match well with the simulated ones in LTP (the bottom line) and HTP (the top line), respectively. When the measured temperatures are above Tc (i.e., 413, 423, and 433 K), the PXRD pattern exhibits a significant change compared to those in LTP. For instance, the diffraction peaks at 17.06° split into two diffractions at 16.96° and 17.15° in the area of part A. At the B region, a new diffraction peak appears at 23.58°. Moreover, two peaks at 29.46° and 29.89° undergo combination as a new peak at

Figure 3. Comparison of the packing structures between LTP and HTP. (a) Crystal packing of 1 in LTP (293 K) viewed along b-axis. Inset: the ordered dmte cation. (b) Crystal packing of 1 in HTP (443 K) viewed along a-axis. Inset: the disordered dmte cation. All of the atoms of the highly disordered cation have been replaced by C atoms, and all of the hydrogen atoms are omitted for clarity.

Figure 4. Variable-temperature PXRD pattern of 1 obtained in the temperature range 293−433 K.

29.58° from LTP to HTP in part C. In addition, one peak at 35.95° vanishes as shown in part D. The obvious variation of PXRD patterns confirms the existence of phase transition in 1, coinciding with the DSC results and structural analyses. C

DOI: 10.1021/acs.inorgchem.9b01538 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 5. (a) Temperature-dependence of the real part (ε′) of the polycrystalline sample of 1 at 1000 kHz and the inset shows the real part (ε′) of 1 at frequencies from 5 to 1000 kHz. (b) The recoverable switching of the dielectric measurement for the polycrystalline sample at 1000 kHz. Temperature-dependence of dielectric constants of 1 measured on crystal samples along (c) a-axis, (d) b-axis, and (e) c-axis at 1000 kHz. Inset: the real part (ε′) of 1 at frequencies from 5 to 1000 kHz.

Figure 6. (a) UV−vis absorption spectra. Inset: the Tauc plot for 1. (b) Calculated energy band structure of 1 (Eg = 2.94 eV). (c) Partial density of states (PDOS) for 1. (d) Photoluminescence (PL) spectrum of 1 from 340 to 365 nm at 293 K. Inset: colorless crystals of 1 under ambient light.

Dielectric Properties. As an important property of crystalline material, dielectric response generally demonstrates changes significantly in the vicinity of Tc, which has been proven to be an important method to prove structural phase transition. For 1, both the real part (ε′) and the imaginary part (ε″) of complex permittivity were first measured using polycrystalline powder in the temperature range of 300 and 430 K. As shown in Figure 5a, the value of ε′ changes little in the temperature interval of ca. 90 K only from ca. 14 to ca. 16 at 1000 kHz below 400 K, corresponding to a low dielectric state. Then the ε′ shows an increase by leaps and bounds from ca. 16 to ca. 20 in the vicinity of 405 K. As the temperature continues to rise, the ε′ increases slowly and enters into a high

dielectric state. The unstable dielectric value in LTP and HTP indicates the competition between molecular thermal dynamic and orientational polarization of the applied electric field. The ε′ experiences an obvious step-like change with an about 1.3fold increase from low dielectric state to high dielectric state. Upon cooling, the ε′ demonstrates a similar curve to that in the process of heating, but it presents a significant thermal hysteresis of ca. 35 K, indicating the first-order transition feature. The reversible dielectric behavior confirms the occurrence of phase transition, agreeing well with the results of DSC and structural analyses. The transition of high and low dielectric state denotes the dielectric switching of 1. Moreover, 1 is frequency sensitive so that the ε′ increases with the D

DOI: 10.1021/acs.inorgchem.9b01538 Inorg. Chem. XXXX, XXX, XXX−XXX

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PbBr4 (3.12 eV).48 The assigned result of the bands according to the partial density of states (PDOS) is shown in Figure 6c. The H-1s state overlaps fully with C-2s2p, N-2s2p, and O-2s2p in the organic part from −25 to 5 eV. In the vicinity of the Fermi level (Ef) of PDOS, two peaks are localized in around −0.91 and +3.04 eV, which originate from the π−π* of C−O bands in the cations. For the inorganic component, Pb-5s/p/d, 6s/p and Br-4s/p states overlap obviously, revealing the strong interactions between Pb and Br. Therefore, the VBM bands originate from the nonbonding states of Br-4p and Pb-6p orbitals account for the CBM bands. Such prominent coupling of electronic states between Pb and Br atoms denotes that the band gap of 1 is mainly determined by the Pb3Br10 framework. Besides a sharp absorption edge under UV−vis spectrum, 1 also demonstrates excellent PL spectra with broadband emission at room temperature. The colorless crystals of 1 show brightly orange light under 365 nm UV lamp (Figure 6d, inset). According to the fluorescence emission measurements and UV−vis spectra, the absorption transitions appear at 315, 340, and 367 nm (Figure 6a). The peak position of the emission spectra at 556 nm is consistent with the color observed by the naked eye and the highest peak at 360 nm excitation (Figure 6d). The broad orange PL luminescence at the excitation of the UV lamp is comparable to that recently few discovered compounds such as [trimethylsulfonium]4Pb3Br10.36

decrease of applied frequency (Figure 5a, inset), owing to the reason for the inconsistency occurred between applied frequencies and alternating electric field.44 Simultaneously, the heating−cooling cycle dielectric measurements of 1 at 1000 kHz were performed as shown in Figure 5b, demonstrating the switchings between high dielectric state (switch ON) and low dielectric state (switch OFF). The intensity of the dielectric signals appears virtually unchanged compared with the initial value, suggesting that 1 is a potential candidate for excellent stimuli-responsive electrical switch material and molecular electronic devices. Anisotropy as a typical feature of crystalline materials can be well represented by dielectric anomalies. The ε′ of singlecrystal sample was measured along the three different crystallographic axes from in the temperature range 300−430 K. As depicted in Figure 5, parts c, d, and e, corresponding to the dielectric responses along the a-, b-, and c-axes, respectively, the similar step-like dielectric behavior including the switches between high and low dielectric states were reached compared with the one measured on polycrystalline sample (Figure S8). In a different manner, a much larger variation of dielectric value around Tc was recorded along the b-axis, whereas the smaller ones were obtained in the direction of a- and c-axes. Generally, the value of ε′ is closely related to the variation of the molecular dipole moment in the crystal structure. Therefore, the origin of prominent dielectric anisotropy can be summarized in combination with the analyses of structural transition. On the basis of the structures of 1 in LTP and HTP, the dmte cations possess the position of mirror plane, in which the orientationally disordered cations are distributed equally along the b-axis. Therefore, the dynamic motions of organic cations mainly appear in the direction of baxis, leading to the most contribution of dielectric value. It also makes sense that the comparatively small ones can be observed along the a- and c-axes. The dielectric data also show obvious dependence of frequencies, being consistent with the one in the polycrystalline pellet. Optical Properties and Electronic Structure. For a new compound, it is of fundamental importance to study the optical properties and electronic structure of 1 for potential application in the future. As shown in Figure 6a, the measurements of UV−vis absorption spectra were carried out. The converted Tauc plot with a band gap of 3.23 eV observed by diffuse reflectance spectroscopy indicates that 1 is a semiconductor and potential optoelectronic candidate (Figure 6a, inset).45 The semiconducting property is closely related with the structural assembly, that is the connectivity model of the inorganic framework, where the band gap shows the rules of “corner-sharing < edge-sharing < face-sharing”.46,47 Therefore, density functional theory (DFT) calculations for the electronic structure of 1 were performed. As plotted in Figure 6b, both the valence band maximum (VBM) and the conduction band minimum (CBM) are located at point G, indicating a direct band gap semiconductor. The calculated band gap is 2.94 eV smaller than the derived value of 3.23 eV from UV−vis spectra, owing to the limitation of DFT calculation. On the basis of the molecular components, 1 integrates the corner-sharing and face-sharing octahedral, and thus the value of band gap is obtained as 2.94 eV, which is comparable to those with similar inorganic skeleton and less than those with face-sharing octahedral of (hexamethylenimine)PbBr3 (3.50 eV) and higher than the ones with corner-sharing octahedral of (1-ethylpiperazine)-

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CONCLUSION In summary, a new corrugated 2D layer organic−inorganic hybrid perovskite [demethyltropinone]4Pb3Br10 with multiple coupling of high-temperature switchable dielectric, semiconducting and photoluminescent properties was presented and characterized. The prominent step-like dielectric anomalies induced by the order−disorder transition of organic component suggest that 1 is a promising candidate for stimuliresponsive electrical switch materials. The 2D inorganic Pb3Br10 layer determines the wider optical band gap of (Eg = 3.23 eV), indicating that 1 shows potential in the semiconducting application. Together with the bright orange photoluminescent property, 1 demonstrates the great prospects of solid-state multifunctional materials combined with excellent electronic and optical properties in the field of optoelectronics.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b01538. PXRD, IR, TGA, crystal structures and crystallographic data (PDF) Accession Codes

CCDC 1915620−1915621 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*(Z.-X.W.) E-mail: [email protected]. E

DOI: 10.1021/acs.inorgchem.9b01538 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry *(W.-Q.L.) E-mail: [email protected].

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ORCID

Ji-Xing Gao: 0000-0002-5605-0766 Zhong-Xia Wang: 0000-0002-9012-5653 Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (21703033 and 91856114), the Young Elite Scientists Sponsorship Program by CAST (2018QNRC001), and the Natural Science Foundation of Jiangsu Province (BK20170658).

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DOI: 10.1021/acs.inorgchem.9b01538 Inorg. Chem. XXXX, XXX, XXX−XXX