Maohao
Yang
a,
Wanyin
Ge
*a,
Kenshi
Matsumoto
b,
Masaki
Saruyama
b,
Ryota
Sato
b,
Haruka
Takekuma
b,
Ryo
Takahata
b and
Toshiharu
Teranishi
b
aSchool of Materials Science and Engineering, Shaanxi University of Science and Technology, Xi'an, Shaanxi 710021, P. R. China. E-mail: gewanyin@sust.edu.cn
bInstitute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
First published on 17th July 2024
Zero-dimensional (0D) lead-free perovskites have garnered significant attention due to their unique optoelectronic properties and non-toxicity. However, the single response to stimuli in lead-free perovskites limits the versatility of multifunctional compounds. In this study, we abandoned the toxic bromic acid and utilized water as the reaction medium, to achieve an environmentally friendly green chemical route. We successfully prepared a zero-dimensional lead-free halide Cs2In1−xSbxBr5(H2O) perovskite with a fractal structure using an in situ solution crystallization method. Herein, we discovered that the recrystallization occurred beneath the smooth-grown rhombic crystal surface, forming fractal branched crystals. Interestingly, reversible luminescence color transitions from orange-red to yellow and return to the initial state were achieved in response to the individual stimuli of temperature and humidity. We found that H2O molecules played a crucial role in the color tuning, enabling reversible “on–off” switching modes with rapid modulation rates. Moreover, the 0D lead-free halide perovskite Cs2InBr5(H2O):Sb3+ also exhibited excellent temperature sensitivity, with the relative sensitivity (SR) reaching up to 9.39% K−1. This study provides valuable insights for the further development of halide perovskites in design and application fields, laying a foundation for the development of multifunctional smart materials and temperature sensing applications.
Currently, the incorporation of dopants is recognized as an effective strategy for improving the luminescence efficiency of perovskites.28 Substantial advancements have been achieved in the study of the photoluminescence (PL) properties of indium-based halide perovskites doped with antimony (Sb3+). For instance, Sb3+-doping in 0D Cs2SnCl6 exhibits yellow-red emission.29,30 Compared to the undoped counterparts, the photoluminescence quantum yield (PLQY) of Sb3+-doped A2InCl5(H2O) (A = Rb, Cs) has significantly improved, increasing from below 2% to a range of 85–95%.31 In the family of Cs2InX5(H2O) (X = Cl−, Br− and I−), the octahedral units exhibit pronounced electron–phonon coupling, resulting in a substantial Stokes shift observed in these 0D perovskite compounds.32 Substitution of the halide from Cl− to Br− and I− also leads to redshifts in the photoluminescence (PL) and photoluminescence excitation (PLE) spectra of Sb3+-doped Cs2InX5(H2O) compounds.33 Additionally, applying high pressure enables precise modulation of the PL properties of Cs2InBr5(H2O), culminating in the observation of anomalous anti-Stokes emission.34 In Cs2InBr5(H2O), photogenerated charge carriers are spatially confined within isolated octahedra, enhancing the radiative recombination probability.35–38 A-site cations have a slight effect on PL,39 while water molecules, through their induced distortion of In3+ octahedra, result in a broad emission and exert a more pronounced influence on the self-trapped excitons (STEs).40
Halide perovskites are well recognized for their high sensitivity to environmental conditions, including air composition (humidity, oxygen), temperature, light exposure, and electric fields, which can lead to rapid degradation and limit their practical applications.41–46 Fortunately, the novel lead-free 0D halide perovskite Cs2InBr5(H2O) stands out for its exceptional stability and tunable crystal structure. Interestingly, its isolated octahedral structure incorporates a water molecule (H2O). As the temperature increases, the water molecule is released, modulating its luminescence from red to yellow.47,48 Furthermore, when the dehydrated octahedral structure is subjected to an atmosphere with 80% relative humidity (RH), the PL wavelength and intensity undergo gradual alterations, with the color transitioning reversibly from yellow back to red.49
High-performance functional compounds that are reversible and responsive to stimuli such as temperature or humidity are highly desirable for sophisticated anti-counterfeiting technologies. However, many existing anti-counterfeiting functional compounds exhibit limited temperature responsiveness and necessitate further development to enhance their reversibility. In this study, we report the successful synthesis of a 0D halide perovskite, Cs2In1−xSbxBr5(H2O), utilizing water as the reaction medium, thus abandoning the common chemical route involving bromic acid reported in the literature and demonstrating an environmentally friendly and green chemical approach. Furthermore, the diverse luminescence properties of Cs2InBr5(H2O):Sb3+ are of significant importance. We observed that the water molecule in the Cs2InBr5(H2O):Sb3+ molecular structure acts as a switch, facilitating an “on–off–on” cycle that can be repeated multiple times. We conducted in-depth analysis of the reversible structural and photoluminescence transitions triggered by water molecules or thermal effects. This halide perovskite, with its reversible photoluminescence properties, offers a fresh perspective, overcoming the limitations of traditional materials that exhibit singular responses. Additionally, we assessed the absolute sensitivity (SA) and relative sensitivity (SR) during temperature variations, with SA achieving a maximum value of 3.55% K−1 and SR reaching a peak of 9.39% K−1, indicating extremely high sensitivity. These research findings demonstrate the high sensitivity and responsiveness of Cs2InBr5(H2O):Sb3+ to temperature changes within a certain temperature range, providing strong support for its applications in temperature- and humidity-sensitive fields. The reversibility of water molecules as switches and their multiple cycling capabilities presented in this study bring new opportunities for the development of lead-free 0D halide perovskites. This material, with its reversible photoluminescence characteristics, holds promise as a crucial component in anti-counterfeiting technology and multifunctional smart materials, while also exhibiting significant potential in high-performance temperature sensing applications.
Figure 1d demonstrates crystallization near room temperature (around 30 °C), where the evaporative concentration of the solution droplets on glass slides leads to the emergence of dendritic crystals at the solution–glass interface. Subsequently, diamond-shaped, rectangular, and blade-like crystals nucleate and grow on the solution surface, eventually aggregating and overlaying to form butterfly-petal-shaped crystals. Notably, as the solution evaporates, leaving a partial liquid beneath the petal-shaped crystals, the solute concentration increases, altering the crystal growth conditions and kinetics, resulting in the growth of fractal dendritic crystals beneath the crystal surface, consistent with the recent literature.50 The resulting fractal structure consists of an upper-layer butterfly petal-shaped crystal and a lower-layer dendritic crystal (Fig. 1e). ESI Fig. S1b† exhibits fractal structures obtained via the in situ solution method at different temperatures. The increasing temperature correlates with a decrease in the grain size and a corresponding increase in the quantity. This trend is attributed to the accelerated evaporation rate of water molecules at elevated temperatures, which in turn shortens the duration of crystal growth. Fig. 1f displays the EDX mapping characterizing the elemental composition and distribution of petal-shaped fractal structures, with the expected elements Cs, In, Sb, Br, and O. In Fig. 1g, the elemental molar ratio Cs:In:Br = 2:1:6, implying bromine ions exceeding the stoichiometric value, is potentially attributable to defects within the fractal structure, which could account for the slight deviations or fluctuations in the chemical stoichiometry of the crystal structure.
To ascertain the 0D halide perovskite structure of the as-prepared compound, we conducted X-ray diffraction (XRD) analysis. Subsequently, the high-precision XRD data were refined to validate the compound's phase and crystallographic characteristics. The refinement results, as presented in Fig. 2a, perfectly matched the synthesized sample's XRD pattern with the PDF card (01-087-4184) for Cs2InBr5(H2O), with an Rwp value of 6.44% and a goodness-of-fit factor of 1.52, signifying a high degree of fitting accuracy. The crystallographic parameters derived were a = 14.8763 Å, b = 10.8116 Å, and c = 7.6437 Å, consistent with the pnma space group. Additionally, we observed a color change in the luminescence of Cs2InBr5(H2O):Sb3+ under UV light after annealing at different temperatures. To further investigate this phenomenon, temperature-dependent XRD tests were conducted. As depicted in Fig. 2b, significant structural differences were evident in the samples annealed at different annealing temperatures. On increasing the temperature, the intensity of the diffraction peaks of Cs2InBr5(H2O) gradually decreased, accompanied by the appearance of diffraction peaks corresponding to the Cs3In2Br9 phase. This fact indicates that with increasing temperature, water molecules are progressively released from Cs2InBr5(H2O), leading to the partial transformation of Cs2InBr5(H2O) into Cs3In2Br9. Notably, this process is reversible, as the structure of the sample can be regenerated upon exposure to a humid environment.
The octahedral structure in the Cs2InBr5(H2O):Sb3+ perovskite is composed of one indium (In) atom, five bromine (Br) atoms, and a single H2O molecule, with indium atoms being partially substituted by Sb atoms, as illustrated in the crystal structure in Fig. 2c. Two Cs+ ions are spatially separated, forming a 0D configuration. Upon exposure to thermal annealing, dehydration of the octahedral units occurs, prompting the reorganization of adjacent In–Br bonds and the formation of Cs3In2Br9. Interestingly, the reverse transformation from Cs3In2Br9 back to Cs2InBr5(H2O) is feasible upon rehydration with water molecules. This reversible hydration–dehydration process can be represented by the formula:
(1) |
The successful utilization of an in situ solution crystallization method to prepare a 0D lead-free Cs2InBr5(H2O):Sb3+ halide perovskite is demonstrated. The structural transformation of the material is intimately associated with alterations in its color properties. The XRD patterns corresponding to Cs2In1−xSbxBr5(H2O) compounds (x = 0–2.0%) are depicted in Fig. S2a.† These patterns reveal a close match between the diffraction peaks and those of the standard PDF card, indicating that introduction of Sb3+ as a dopant has a negligible impact on the overall crystal structure. Further examination of the XRD pattern at higher magnification, as shown in Fig. S2b,† unveils a noteworthy shift in diffraction peaks towards higher angles with increasing Sb3+ content. This shift can be attributed to the smaller ionic radius of Sb3+ (0.76 Å) compared to In3+ (0.80 Å), thereby suggesting that the doping concentration of Sb3+ exerts a subtle modulating effect on the structure.
Additionally, we observed that Sb3+-doped Cs2InBr5(H2O) samples exhibit bright luminescence properties, characterized by a visually perceptible “orange peel” color. To quantify this luminescence behavior, photoluminescence (PL) measurements were conducted. The photoluminescence excitation (PLE) spectrum in Fig. 2d presents a peak at 365 nm. Consequently, we selected 365 nm as the excitation source and observed an emission peak at 671 nm. Under identical conditions, the PL spectra of Cs2In1−xSbxBr5(H2O) shown in Fig. 2e exhibit intense orange-red emissions for all samples. At a doping concentration of 0.5% Sb3+, the emission intensity reaches its maximum. Therefore, the optimal doping concentration for Cs2In1−xSbxBr5(H2O) is determined to be x = 0.5%, designated as the sample group with the best performance for subsequent temperature and humidity responsiveness assessments. Many studies indicate that self-trapped excitons (STEs) are the primary mechanism underlying the broad spectral emission in the 0D Cs2InBr5(H2O):Sb3+ perovskite.38,51 As shown in Fig. S3,† the luminescence mechanism of the Cs2InBr5(H2O):Sb3+ perovskite involves the STE process.33 Through coupling with polar lattice vibrations, excitons reduce the total energy of the system due to transient lattice deformations, thereby resulting in broad spectral emissions and larger Stokes shifts. Therefore, the luminescence of Sb3+ ions in Cs2InBr5(H2O):Sb3+ is attributed to the formation of STE. The emission peaks originate from the structural distortion of Cs2InBr5(H2O):Sb3+ crystals doped with Sb3+, which promotes the emission of both singlet and triplet STEs.
We conducted a comprehensive study of the synthesized compound, Cs2InBr5(H2O):Sb3+, to assess its responsiveness to environmental changes by subjecting it to various temperature and humidity conditions. Fig. 3a shows the inscription of “SUST” on the sample after grinding the as-prepared powder with ethanol. Upon exposure to UV lamp irradiation at room temperature, the emitted light from “SUST” appeared yellow, but it changed to orange-red under humid conditions. The intensity of the emitted light decreased with increasing temperatures, resulting in a state of fluorescence thermal quenching. As depicted in Fig. 2b, elevating the sample temperature to high degrees resulted in a structural transformation from the 0D perovskite Cs2InBr5(H2O) to the Cs3In2Br9-type perovskite. In situ PL measurements under certain humidity conditions (as depicted in the inset of Fig. 3b) yielded the intensity-normalized spectrum. The PL emission peak migrated from 589 nm (red) to 671 nm (orange-red) over a period of 270 s, indicating a transition in color from yellow to orange-red light starting from 0 s after exposure to the humid environment. Furthermore, the response time for the transition from yellow to red light varies at different humidity levels. This is attributed to the formation of a distorted octahedral structure in Cs3In2Br9, where the In–Br bonds form a regular octahedron. In contrast, Cs2InBr5(H2O):Sb3+ contains five Br ions and one H2O, forming five In–Br bonds and one In–O bond, leading to a distorted octahedral structure. This distortion breaks the symmetry of Cs2InBr5(H2O):Sb3+ and results in a larger Stokes shift. Therefore, humidity levels during the reaction process are crucial for reversible processes.
Fig. 3c highlights the significant impact of environmental humidity on the luminescence properties of the material, with a notable emission peak shift observed at around 20 s from 597 nm to approximately 664 nm, accompanied by a gradual color change from yellow to orange-red, as depicted in the inset of Fig. 3c. Fig. S4a and b† show that an increase in distilled water content resulted in a redshift of the emission peak. The color alteration of Cs2InBr5(H2O):Sb3+ from green light to red light is shown in the digital photographs in Fig. S4c† after the addition of 0.05 mL of distilled water. This change further verifies the high sensitivity of Cs2InBr5(H2O):Sb3+ to humidity levels,31 enabling precise control over the material's luminescence color, as shown in Fig. 3d. We characterized the fluorescence lifetimes of Cs2InBr5(H2O):Sb3+ (red light) and Cs3In2Br9 (yellow light) to probe their photophysical properties. As shown in Fig. 3e and f, we observed a biexponential decay with an average lifetime of 0.909 μs for the 0D Cs2InBr5(H2O):Sb3+ perovskite, attributed to characteristic singlet and triplet transitions of STEs. The average fluorescence lifetime of Cs3In2Br9 decreased to 0.186 μs. Furthermore, in Fig. S5,† by employing the integrating sphere method, we measured the excitation and emission peaks, calculated the difference in their areas, and determined the photoluminescence quantum yields (PLQYs) of Cs2InBr5(H2O) and Cs3In2Br9 to be 87.8% and 22.8%, respectively. This significant contrast suggests that water molecules (H2O) may exert a notable influence on the PLQY of Cs3In2Br9. Therefore, modulating the structure of Cs3In2Br9 or doping specific ions could potentially enhance its luminescence performance, thereby increasing its practical utility.
In response to the temperature-induced alterations observed in Cs2InBr5(H2O):Sb3+, as depicted in Fig. 3a, we undertook an examination of the temperature-dependent photoluminescence (PL) spectra of Cs2In0.995Sb0.005Br5(H2O), spanning a temperature range of 293–443 K. As shown in Fig. 4a, the fluorescence intensity gradually decreases with increasing temperature. Concurrently, during the heating process, the emission peak gradually blue-shifts (Fig. 4b), and the full width at half maximum (FWHM) initially broadens and then narrows as illustrated in Fig. S6.†Fig. 4c depicts the cooling process, where the fluorescence intensity gradually increases as the temperature decreases, accompanied by a blue-shift in the emission peak (Fig. 4d), with the FWHM initially narrowing and then broadening. Fig. 4b and d insets illustrate that the sample emits orange-red light at room temperature. Upon heating to 443 K, faint yellow light is observed, and cooling back to room temperature emits bright yellow light. The cyclic process of heating (H), cooling (C), and vapors (V) of the Cs2In0.995Sb0.005Br5(H2O) sample is represented in Fig. 4e. The color change is attributed to the evaporation of water molecules from the molecular structure, leading to yellow light emission as the temperature increases. This process demonstrates reversibility, as samples emitting yellow light in a humid environment reverted to orange-red after a storage period. The temperature-dependent spectra in cycles of heating and cooling demonstrate good stability, as shown in Fig. S7.† This observation highlights the high sensitivity of Cs2In0.995Sb0.005Br5(H2O) to both temperature and humidity. The evaporation of water molecules causes the color changes. Water molecules play a crucial role in the color-changing process, allowing for repeatable and reversible color tuning. Fig. 4 shows the dynamic interaction between temperature, humidity, and molecular structure, highlighting the potential for further exploration in the manipulation and control of water molecules in these materials.
The compound's temperature sensing performance was determined using the fluorescence intensity variation shown in Fig. 4a. Given the material's broad single-peak emission profile, the conventional fluorescence intensity ratio (FIR) temperature calculation formula could not be utilized. Fig. 5a shows the fluorescence intensity values of the material at different temperatures, decreasing continuously with temperature elevation within the range of 293–413 K. By employing a nonlinear regression analysis of the data, the derived formula is:
I = Aexp(−T/B) + C. | (2) |
Fig. 5 (a) Plot of intensity at different temperatures with nonlinear fitting curves; (b) SA curve and SR curve as a function of temperature. |
The values for A, B, and C are 5.64 × 109, 28.55, and −3.41 × 103. These values can be utilized to analyze absolute sensitivity (SA) and relative sensitivity (SR) using the following formulas:52,53
(3) |
The initial fluorescence intensity and the intensity corresponding to temperature T are represented by the symbols I(0) and I(T), respectively. SA and SR of the samples at different temperatures are shown in Fig. 5b, where SA-Max is 3.55% K−1@293 K and SR-Max is 9.39% K−1@403 K. The SR-Max achieved in this study is notably higher than those of other perovskites, as indicated by a comparison with literature values for other temperature sensing materials (refer to Table 1). This discrepancy suggests the potential importance of the Cs2InBr5(H2O):Sb3+ compound in temperature sensing applications, presenting new opportunities for the advancement of higher-performance temperature sensors and other optoelectronic devices due to its enhanced temperature sensitivity.
Samples | Temperature range (K) | S R-Max temperature (K) | S R-Max (% K−1) | Ref. |
---|---|---|---|---|
Bi2Ti2O7:Yb3+/Er3+ | 298–540 | 298 | 1.53 | 54 |
Cs3Cu2I5:Mn2+ | 298–498 | 498 | 0.547 | 55 |
CsPbCl2Br:Eu3+ | 80–440 | 400 | 3.10 | 56 |
NaYbF4:Er3+ | 175–475 | 175 | 3.46 | 57 |
CaTiO3:Yb3+/Er3+ | 303–523 | 303 | 1.17 | 58 |
Cs2Ag0.6Na0.4In0.9Bi0.1Cl6 | 300–470 | 345 | 1.05 | 59 |
Cs2NaYbCl6:Er3+/Sb3+ | 80–310 | 310 | 11.21 | 60 |
Cs4PbBr6:Sm3+ | 303–423 | 303 | 3.83 | 61 |
Cs2InCl5(H2O):Te4+ | 80–380 | 320 | 6.2 | 62 |
Cs2InBr5(H2O):Sb3+ | 293–443 | 403 | 9.39 | This work |
Footnote |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4qi01164c |
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