Journal of Physics and Chemistry of Solids 61 (2000) 837845 www.elsevier.

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Preparation and characterization of natural lower dimensional layered perovskite-type compounds

Y. Tabuchi a,b,*, K. Asai a,b, M. Rikukawa b,c, K. Sanui b,c, K. Ishigure a
a

Department of Quantum Engineering and Systems Science, University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 1130033, Japan b CREST Japan, Science and Technology Corporation (JST), 7-3-1, Hongo, Bunkyo-ku, Tokyo 1130033, Japan c Department of Chemistry, Sophia University, 7-1, Kioi-cho, Chiyoda-ku, Tokyo 1028554, Japan Received 9 July 1999; accepted 12 November 1999

Abstract Thin lms of layered perovskite compounds (CnH2n 1NH3)2(CH3NH3)m 1PbmBr3m 1 m 1; 2 and 3) were prepared by the spin-coating method from their DMF (N,N-dimethylformamide) solutions. The control of the inorganic layer thickness in layered perovskites can be achieved by changing the ratio of the two amines (CnH2n 1NH3/CH3NH3). The layered perovskite lms showed a strong, clear exciton absorption peak at room temperature due to their large exciton binding energy. With increasing numbers of inorganic layers, a red shift of the exciton absorption was observed due to the decrease in transfer energy. X-ray diffraction patterns clearly demonstrated that the spin-coated lm was highly oriented normal to the surface, which is consistent with mono, bi, and tri layer structures, respectively. The effect of the alkyl chain length of the organic part was also investigated. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: A. Quantum wells; A. Thin lms; C. X-ray diffraction

1. Introduction Over the past 10 years, much attention has been paid to nding suitable materials with large nonlinearity and short responses for optical signal processing and optical computing [1]. The optical properties of exciton materials such as semiconductor Multiple Quantum Wells (MQW) have been intensively studied [2]. The multi-quantum-well structure is very useful for optical application because the exciton binding energy and optical nonlinearity have been found to become larger in two-dimensional (i.e. low dimensional) than in three-dimensional materials. Extensive studies on semiconductor quantum wells have resulted in better understanding of the low-dimensional electronic systems. Hanamura et al. [3] have proposed a new two-dimensional system in which the quantum well is sandwiched by a barrier material of a large bandgap and smaller dielectric constant to increase the exciton binding energy and optical
* Corresponding author. Tel.: 81-3-5841-6978; fax: 3818-3455. E-mail address: tabuchi@langmuir.q.t.u-tokyo.ac.jp (Y. Tabuchi). 0022-3697/00/$ - see front matter PII: S0022-369 7(99)00402-3 81-3-

nonlinearity. Such low-dimensional electronic systems and related quantum-well structures can be fabricated by Molecular Beam Epitaxy (MBE), Metal Organic Chemical Vapor Deposition (MOCVD) or Electron Beam Lithography techniques. Even with these techniques, nanometer structures are still difcult to realize because of the inevitable monolayer uctuation. On the other hand, organicinorganic perovskites have recently attracted much attention due to their unique electrical and optical properties, as well as their lm processability [46]. Hybrid organicinorganic materials offer scientically and technologically signicant opportunities for combining the attractive features of both systems within a single material. Layered perovskite-type compounds with the general formula (CnH2n 1NH3)2(CH3NH3)m 1MmX3m 1 (M group IVB metal, X halogen) are such materials and naturally form the quantum-well structure consisting of a metal halide semiconductor sheet sandwiched between organic insulator layers. Due to the low dimensionality of these semiconductor sheets, the exciton has a large binding energy of several millielectron volts, which enables strong photoluminescence even at room temperature sufcient to offer potential applications in emitter materials in

2000 Elsevier Science Ltd. All rights reserved.

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improve the stability. The lms were characterized by Xray diffraction and optical absorption.

2. Layered perovskite compounds In general, the layered perovskites have the chemical formula (RNH3)2MX4, which corresponds to the simplest material m 1 of the (CnH2n 1NH3)2(CH3NH3)m 1 MmX3m 1, where M is a divalent metal, X is a halide and R can be a wide range of organic moieties. The schematic structure of these layered perovskite compounds is shown in Fig. 1. The two-dimensional inorganic layer and an organic ammonium layer are alternately stacked. The inorganic layer is comprised of a two-dimensional sheet of [MX6] 4 octahedra which are connected at the four corners with halide ions on the plane. The six halogen ions X surround M 2 , forming an octahedral [MX6] 4 cluster as shown in Fig. 2. Therefore, the inorganic layer is as thin as a few atomic layers. The NH3 ends of the cations bind to the anion layers of [MX6] 4 in a specic orientation determined by hydrogen bonding with both equatorial and axial halide ions. A multi-layer structure is organized by neutralizing [MX6] 4 with alkylammonium ions. The adjacent alkyl chains interact with each other by van der Waals interaction, and they may or may not overlap, depending on the size of the ions in the inorganic layer and the cationic molecules. This perovskite family based on [MX6] 4 has the possibility of considerable structural exibility in the nature of the organic cations. In order to form a crystal out of the building blocks, cations are required to neutralize the electrical charge. When they combine with a cation having a long tail such as an n-decylammonium ion (C10H21NH3 ), they sandwich a two-dimensional plane to form a two-dimensional structure as shown in Fig. 3(a). On the contrary, in the case where they combine with small cations such as the NH4 or CH3NH3 , the cations are embedded into the voids to form a three-dimensional structure as shown in Fig. 3(b). Recently, a group at Du Pont expanded the eld by showing that there exists a family of layered inorganic organic perovskites, (CnH2n 1NH3)2(CH3NH3)m 1MmX3m 1, CnMmX3m 1 for short, which has CH3NH3MX3 perovskite sheets with the accumulation number of m sandwiched with alkylammonium bilayers. Here, m is the number of the metal-ion monolayer sheets. The organicinorganic compounds (CnH2n 1NH3)2(CH3NH3)m 1MmX3m 1 form natural multi-quantum-well structures, with variable well thickness (controlled by m) and even well depth (controlled by metal), providing an ideal model for tailoring the optical properties [1620]. Methylammonium ts in the center of eight MX6 corner-shared octahedra, while a long-chain alkylammonium ts only the periphery of a set of four MX6 octahedra. To maintain the charge neutrality, methylammonium ions incorporate into the structure and function as counterions to cohere the two layers. The extreme

Fig. 1. Schematic structure of layered perovskite compound (CnH2n 1NH3)2MX4.

electroluminescent devices [7,8]. Moreover, the organic inorganic layered perovskites can be easily obtained by conventional spin-coating method. One can prepare thin lms of perovskite structure with good optical quality and a plain surface at an atomic level without difculty. Among these compounds, optical properties of (CnH2n 1NH3)2(CH3NH3)m 1PbmI3m 1 have been mainly discussed because they show a strong exciton peak in the visible region [714]. However, it has been observed that the crystal of (CnH2n 1NH3)2(CH3NH3)m 1PbmI3m 1 is not stable toward moisture and light and gradually decomposes [15]. In this study, we tried to fabricate a series of layered perovskites, (CnH2n 1NH3)2(CH3NH3)m 1PbmX3m 1 lms which have [PbBr6] 4 as the semiconductor layers to

Fig. 2. Unit structure of perovskites: closed circle, ammonium ion; shaded circle, metal cation M 2 ; open circle, anion X .

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Fig. 3. Structures based on [MX6] 4 octahedra: (a) CnMBr4; and (b) CH3NH3MBr3.

member of this class of compounds is CH3NH3MX3 for m : This structure lacks barrier layers and can be considered as a three-dimensional variation of the generic compounds, where [MX6] 4 octahedra share no corners and are isolated. In this study, we tried to fabricate (CnH2n 1NH3)2 (CH3NH3)m 1PbmBr3m 1 which have a mono m 1; bi m 2; or tri m 3 layer of inorganic two-dimensional sheets. The structure of the thin lms was characterized by X-ray diffraction and optical absorption. The effect of the length of the alkylamines on the formation of twodimensional materials was also investigated.

3. Experimental 3.1. Sample preparation 3.1.1. Amine hydrobromides N-alkylamines (CnH2n 1NH2), and hydrobromic acid (HBr) (aqueous solution, 48%) are commercially available. Stoichiometric amounts of hydrobromic acid and alkylamine are mixed in a ask cooled with water in order to remove the reaction heat. After the reaction, water should be evaporated by elevating the temperature followed by washing with diethylether. 3.1.2. Tetrabromoplumbate perovskite compounds The monolayer (i.e. m 1 compounds, (CnH2n 1NH3)2 PbBr4 n 2; 3, 4, 6 and 10)), were prepared by treating puried CnH2n 1NH3Br with a stoichiometric amount of PbBr2 in N,N-dimethylformamide (DMF) at room tempera-

ture in N2 atmosphere. The bilayer m 2 perovskites, (CnH2n 1NH3)2(CH3NH3)Pb2Br7 n 2;3,4 and 6), were prepared by reacting CnH2n 1NH3Br and CH3NH3Br with PbBr2 in DMF. As the reaction proceeds, PbBr2 dissolves in DMF. The monolayer and bilayer compounds are obtained as a precipitate, when the reaction solutions were poured into a poor solvent such as acetone. The trilayer m 3 compound, (CnH2n 1NH3)2(CH3NH3)2Pb3Br10 n 6; was obtained by adding excess amount of CH3NH3Br to stoichiometry. The DMF solutions with CH3NH3Br/CnH2n 1NH3Br in a molar ratio of 1.5 were mixed with PbBr2 at 35 C. Thin lms of microcrystalline (CnH2n 1NH3)2 (CH3NH3)m 1PbmBr3m 1 were fabricated on glass slides by the spin-coating method. The scan speed was electrically controlled to approximately 6000 rpm. 3.2. Measurements Optical absorption spectra of the lms on glass or SiO2 substrates were taken using a conventional UVvisible spectrophotometer (HITACHI, U-3300) at room temperature. Room temperature photoluminescence (PL) spectra were also measured. A monochromated Xe lamp was used as an excitation source for the PL measurement (HITACHI spectrophotometer). The lm on the substrate was irradiated by the light beam at an angle of 45 . Excited wavelengths ranged from 250 to 550 nm, depending on the samples. The crystallinity and orientation of the powder samples and spin-coated lms were determined by X-ray diffraction. X-ray diffraction measurements recorded with a 2u ranging

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Fig. 4. X-ray diffraction proles of (a) powder; and (b) spin-coated lm of (C6H13NH3)2PbBr4(C6PbBr4).

from 1.5 to 40 were performed on a Rigaku RAD-IIA with  a CuKa target l 1:5418 A at 40 kV and 25 mA. All the samples were measured at room temperature. Differential scanning calorimetry (DSC) measurements were performed in the temperature range between 150 and 20 C under N2 atmosphere (SEIKO Instruments).

4. Results and discussion 4.1. Control of the thickness of the inorganic quantum-well in perovskites Layered perovskite compounds, (CnH2n 1NH3)2 (CH3NH3)m 1PbmBr3m 1 m 13; which consist of different inorganic thicknesses were successfully obtained using different sizes of alkylammonium ions with a controlled ratio of the two amines. Mono- m 3 and bilayer m 2 are prepared by stoichiometric reaction. On the contrary, pure trilayer m 3 compounds can be obtained only when an excess of CH3NH3Br is added. Optimum experimental conditions for preparing the trilayer lms involve using CnH2n 1NH3Br/CH3NH3Br in a molar ratio at 1.5 and maintaining the temperature at 35 C. 4.1.1. X-ray diffraction Fig. 4 shows X-ray diffraction proles of a powder and a spin-coated lm of monolayer perovskites, (C6H13NH3)2PbBr4 which has hexylamine as a longer alkylamine (abbreviated C6PbBr4). In the diffraction proles of the powder sample, a series of (001) diffractions corresponding to the interlayer spacing is mainly observed with small peaks assigned to other reection planes in the low 2u

region. This result shows that the perovskite structure with chemical formula of (CnH2n 1NH3)2(CH3NH3)m 1PbmBr3m 1 has already formed in the powder sample. In contrast, only the diffraction patterns from the (001) plane are observed in the spin-coated lm. This evidence led us to strongly support the fact that these lms were highly oriented with the c-axis perpendicular to the substrate. Moreover, the observation of higher order peaks indicates that the perovskite lms are well crystallized. From the diffraction peaks, the long cell dimension along the c-axis was calculated to be 18.0 A. X-ray diffraction proles of (C6H13NH3)2(CH3NH3)m 1 PbmBr3m 1 m 2 and 3) fabricated under optimum conditions are depicted in Fig. 5. The (C6H13NH3)2 (CH3NH3)Pb2Br7 m 2 lms also exhibited an X-ray diffraction pattern which corresponded to a layered perovskite structure suggesting primarily c-axis orientation. No evidence for lower order (i.e. m 1 or higher order m 2 members of the perovskite family could be detected using X-ray diffraction. Similarly, a clear diffraction pattern is observed in the case of (C6H13NH3)2(CH3NH3)Pb3Br10 m 3: However, the half width at half maximum of the peak of the trilayer compound is wider than that of the mono- and bilayer compounds. This is thought to be derived from the smaller grain size of the perovskite crystal or distortion of the inorganic layers. The interlayer d-spacing values calculated from the X-ray diffraction are 23.2, and 28.5 A for C6Pb2Br7 and C6Pb3Br10 spin-coated lms, respectively. An increase in layer spacing was observed. The increase from the n 1 to the n 2 structure is 5.2 A, and that from n 2 to n 3 is 5.3 A. These values are nearly equal to the lattice constant 5.8 A of the cubic perovskite, CH3NH3PbBr3. The increase observed

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Fig. 5. X-ray diffraction patterns of spin-coated lms of (C6H13NH3)2(CH3NH3)m 1PbmBr3m

m 2 and 3).

in these systems is the result of inserting two or three more CH3NH3PbBr3 perovskite layers per unit cell. These X-ray diffraction results clearly demonstrated that the spin-coated lm was highly oriented normal to the surface, which is consistent with mono, bi, and tri layer structures, respectively.

4.1.2. Absorption spectra Fig. 6 shows the optical absorption spectra of (C6H13NH3)2(CH3NH3)m 1PbmBr3m 1 m 13 at room temperature. The monolayer m 1 exhibits a strong and sharp absorption at 395 nm even at room temperature as shown in Fig. 6(a), which is assigned to the exciton from

Fig. 6. Absorption spectra of spin-coated lms of (C6H13NH3)2(CH3NH3)m 1PbmBr3m

m 13:

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Fig. 7. d-spacing value of CnPbBr4 and CnPb2Br7 spin-coated lms as a function of carbon atoms in the alkyl chains.

the [PbBr6] 4 inorganic layer. The exciton is considered to be formed by the transition of the Pb 2 (6s) orbital hybridized with the Br (4p) orbital to the Pb 2 (6p) orbital and is conned two-dimensionally by the organic layers. Thin lms of the bilayer m 2 and trilayer m 3 also show strong, sharp exciton absorption due to their large exciton binding energy. A red shift of the exciton absorption was observed with increasing numbers of inorganic layers, m. There might be two reasons for the red shift. The rst reason is the decrease in the quantum connement effect because of the expansion of the exciton Bohr radius, which causes a decrease in exciton binding energy. The second reason is the decrease in the bandgap. As the inorganic sheet thickness increases, the conduction and the valence bands become wider because the transfer energy among [PbBr6] 4 octahedra becomes larger. These perovskite lms showed strong photoluminescence even at room temperature sufcient to detect with an aided eye. The luminescence originates from electronic transitions within the inorganic perovskite layer, rather than the organic layer, because the simple organic molecules being employed are transparent in the visible reigon.
Table 1 The D-spacing value of CnPbBr4 and CnPb2Br7 spin-coated lms Monolayer C2PbBr4 C3PbBr4 C4PbBr4 C6PbBr4 C10PbBr4 d-spacing (A) 11.62 12.62 13.80 18.02 23.86 Bilayer C2Pb2Br7 C3Pb2Br7 C 4Pb2Br7 C6Pb2Br7 d-spacing (A) 22.64 18.39 19.62 23.23

4.2. The effect of alkyl sidechain length on the twodimensional structure Fig. 7 demonstrates the dependence of the layer d-spacing of mono and bi layer perovskites upon alkyl chain length. The d-spacing values of each layer with various alkylammonium molecules are summarized in Table 1. Layer spacing is increased linearly with increasing alkyl chain length in monolayer perovskites. This result shows that the distances between the inorganic layers are controllable by changing the alkyl chain length. The relationship between the d-spacing and alkyl chain length is derived from the results for monolayer compounds expressed as  d A 8:05 1:59 n (here, n is the number of carbon atoms of the alkylamines). Considering that the chain length of a normal hydrocarbon increases by 2.5 A per carbon atom, the alkyl chain is supposed to be tilted or interdigitated. A usual result was obtained with the bilayer system. Although the d-spacing increases linearly similar to the monolayer system in the case that alkylamines are longer than propylamine n 3; C2Pb2Br7 deviates from linearity. The absorption spectra of the monolayer, CnPbBr4 n 2 and 6), are shown in Fig. 8. Fig. 9 displays the exciton absorption peaks of the monolayer, CnPbBr4, as a function of alkyl chain length. C6PbBr4 showed a single clear exciton peak at 395 nm due to the two-dimensionality as described previously. All of the CnPbBr4 lms, except for n 2; show an exciton peak at around 390 nm. Although the distance between the adjacent lead bromide layers changes from 12.62 A for n 3 to 18.02 A for n 6; the qualitative features of the absorption spectra are essentially the same. This demonstrates that the interaction between the layers is weak enough to treat them as two-dimensional. On the contrary, C2PbBr4 showed two absorption peaks at 390

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Fig. 8. Absorption spectra of CnPbBr4 n 2 and 6) spin-coated lms.

and 402 nm. This result revealed that C2PbBr4 does not have enough distance to neglect the percolation of wave function. 4.3. Thermal analysis of layered perovskite-type compounds Fig. 10 shows the simultaneous thermogravimetric analysis (TGA) and differential thermal analysis (DTA) scan for the C6PbBr4. All of the layered perovskite compounds treated in this paper are stable to heat up to 200 C but gradually decompose above that point. DSC studies on the perovskites were undertaken demonstrating structural transitions below the melting/decomposition point for many of these compounds. These transitions are driven primarily by orderdisorder transitions of the

alkylammonium cations, and for the longer alkyl chain compounds, by conformational and melting transitions within the organic layer. Decomposition of the (CnH2n 1NH3)2MX4 compounds often occurs through the simultaneous loss of organic amines and HX from the compound below the melting temperature. Fig. 11 shows the DSC thermographs of CnPbBr4 with n 4 and 6, respectively. All of the monolayer perovskites, CnPbBr4, except for the n 4 compound, are found to show a structural phase transition under room temperature. On the other hand, CnPbBr4 shows a structural transition at around 110 C as shown in Fig. 11(a). This is an important merit for application to an optical device because of the exciton peak does not skip at the low temperature.

Fig. 9. Exciton absorption peaks of CnPbBr4 as a function of the carbon number in the alkyl chains.

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Fig. 10. TgDTA for C6PbBr4.

Fig. 11. DSC curves of CnPbBr4 for (a) n 4; and (b) n 6:

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5. Conclusion The layered perovskite compounds (CnH2n 1NH3)2 (CH3NH3)m 1PbmBr3m 1, of which the inorganic layer thickness in the layered perovskites ranges from one to three, can be achieved by changing the ratio of the two amines (CnH2n 1NH3/CH3NH3). The layered perovskite lms showed strong, clear exciton absorption peak at room temperature due to their large exciton binding energy. With an increasing number of inorganic layers, a red shift of the exciton absorption was observed due to the decrease in transfer energy. No difference in the absorption peak was observed in the case of alkylamines as long as propylamine. Acknowledgements This work was supported by the Core Research for Evolution Science and Technology (CREST) of the Japan Science and Technology Corporation (JST). References
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