Ranran Fan, Shaofan Fang, Chengchuan Liang, Zhaoxing Liang, Haizhe Zhong. Controllable one-step doping synthesis for the white-light emission of cesium copper iodide perovskites[J]. Photonics Research, 2021, 9(5): 694
- Photonics Research
- Vol. 9, Issue 5, 694 (2021)
Abstract
1. INTRODUCTION
Halide perovskites are prospective materials for optoelectronics because of the remarkable properties, such as low manufacturing cost, high luminescence efficiency, and tunable light emission characters due to their abundant variety of compositions [1–4]. Among the numerous applications, the white-light emission of organic-inorganic hybrids and all inorganic halide perovskites have received special attention [5–7]. Through flexible regulation of halogen elements in (X = Cl, Br, I), the white emission with a diverse color temperature and index can be generated [8,9]. However, the anion exchange derived from mixtures of different halide perovskites, and the relatively narrow coverage of lead (Pb) in halide-based perovskites’ luminescent spectra are important factors hindering the development of white lighting [10–12]. Meanwhile, the problems of thermal instability in organic systems and toxicity caused by the heavy Pb limit their further commercial applications [13,14]. In view of this situation, all-inorganic lead-free metal halide perovskites will have more promising prospects in an efficient, stable, and eco-friendly white lighting.
Control of material dimensionality enables them to form various structure types and light emission features [15–17]. The typical 3D and 2D metal halides have been widely investigated because of their excellent optical and electronic characteristics. Nevertheless, low-dimensional 1D and 0D materials exhibit more unique photophysical properties, such as a large Stokes shift, broadband emission, and high photoluminescence quantum yield (PLQY) due to the self-trapped excitons or excited state structural reorganization [18–20]. Recently, Cu-based metal halide perovskites are gradually coming into view because of their abundance, low environmental impact, high efficiency, and low-dimensional structures. For instance, green emission and nanocrystals [21], blue-green luminescence (X = Cl, Br, Br/I) perovskite quantum dots [22], blue light emission () with near-unity PLQY [23], and (X =Cl, Br, I) with improved air and thermal stability [24] have been recently reported. Specifically, with a 0D electronic structure, large Stokes shift, and strong blue emission has been fabricated and applied for LED devices [25,26]. Another phase of cesium copper iodide, , shows broadband yellow emission [24], and the stable yellow LED based on it was successfully realized [27]. Additionally, single crystals with a high-PLQY due to strongly localized 1D excitonic recombination have been reported [28]. As both and are pure iodide phases, the general mixed halide’s exchange existing in perovskite’s mixtures could be avoided, and pure white emission can be further achieved by appropriate mixing of these phases. Previously, a pure white-light emission has been successfully realized by adjusting the appropriate mixing ratio of these two phases [29,30]. Nevertheless, these methods always needed to fabricate two pure phases of blue emission and yellow emission , and then precisely control the mixing ratio of these individual luminescent materials, which was intricate and inconvenient for the practical application. Therefore, developing a simple intrinsic white-light emission of a cesium copper iodide system will become an effective approach. It has been reported that through a controllable CsI–CuI phase transformation by solvent treatment, stable was obtained from , and a single white-emission layer could be prepared [31]. In addition, Shi’s group has reported the electroluminescent white-light emitting diodes in terms of Cu-based halide materials [32].
In this paper, we have successfully prepared the white luminescent material by a one-step doping method, achieving full coverage of the visible spectrum. Through adding impurities into the system, high efficiency and stable was successfully synthesized, and the coexistence of varied high luminescence phases realized the white lighting. By means of the disposable preparation of and phases, a high-quality and more uniform white luminescence with CIE coordinates of (0.3397, 0.3325) and a CRI reaching 90 could be generated in a simple way.
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2. MATERIALS AND METHODS
Cesium iodide (CsI, 99.9%), copper (I) iodide (CuI, 99.999%), neodymium iodide (, 99.9%), terbium iodide (, 99.99%), praseodymium iodide (, 99.9%), bismuth iodide (, 99.9%), -dimethylformamide (DMF, 99.9%), and isopropanol (99.5%) were directly used without further purification.
The cesium copper iodide perovskites were synthesized via an antisolvent infiltration method, which was performed at room temperature by adding the precursor solution within a good solvent into a nonpolar poor solvent. The blend of two various solvents induced a transient supersaturation, leading to the nucleation and form of perovskites. Cesium iodide, copper (I) iodide, and impurity materials (in this paper, , , , and were used as impurities, respectively) in different molar ratios were firstly dissolved in DMF to get a precursor solution. Then, the solution was rapidly dropped into the antisolvent of isopropanol to form a precipitate, and the resulting products were the mixture of and . With the increase in the molar ratio of doping materials, a mixture with different proportions of and could be obtained. The specific synthesis procedures are as below.
Adding into the system. In the synthesis of molar ratios of 9 mol%, CsI (0.6 mmol), CuI (0.364 mmol), and (0.036 mmol) were dissolved in DMF (4 mL). The mixture was stirred for 2 h at 80°C, then we let it cool naturally to room temperature. Next the precursor solution was rapidly added into isopropanol (20 mL) with vigorous stirring under air ambient at room temperature, and a precipitate was produced immediately during this process. Then, the resulting precipitate was filtered and washed with isopropanol; the yield of the product was about 75%. The other three concentrations were obtained by three corresponding molar doses: 3 mol% (0.6 mmol CsI, 0.388 mmol CuI, and 0.012 mmol ), 5 mol% (0.6 mmol CsI, 0.38 mmol CuI, and 0.02 mmol ), and 7 mol% (0.6 mmol CsI, 0.372 mmol CuI, and 0.028 mmol ).
Adding , , and into a system. The impurities were chosen as 9 mol% (0.6 mmol CsI, 0.364 mmol CuI, and 0.036 mmol for , , and , respectively); the synthesis process was the same as above.
Adding into the system. The impurities were chosen as 9 mol% (0.3 mmol CsI, 0.546 mmol CuI, and 0.054 mmol ), and the synthesis process was the same as above.
Synthesis of pure CsI and 0.4 mmol CuI were used; the synthesis process was the same as above.
Synthesis of pure CsI and 0.6 mmol CuI were used; the synthesis process was the same as above.
Photoluminescence (PL), photoluminescence excitation (PLE), and photoluminescence quantum yield (PLQY) measurements were performed at ambient temperature by an FS5 fluorescence spectrometer equipped with a xenon lamp and an integrating sphere. Powder X-ray diffraction (PXRD) measurements were performed by the Rigaku MiniFlex600 system equipped with a Cu-Kα radiation source (). All scans were performed at room temperature with a step size of 0.02˚. X-ray photoelectron spectroscopy (XPS) analyses were conducted using an ESCALAB 250Xi spectrometer. Scanning electron microscope (SEM) measurements were performed by a ZEISS SUPRA 55 from Carl Zeiss, Germany. High resolution transmission electron microscopy (HRTEM) images were measured by the JEM-3200FS (JEOL).
3. RESULTS AND DISCUSSION
Figure 1.(a) SEM, (b) EDS mapping, and (c) TEM images of the sample with
Figure 2.(a) PL spectra of pure
Figure 3.Crystal structures of (a)
Figure 4.(a) PL spectra under excitation wavelength of 320 nm. (b) XRD patterns of the samples with
Figure 5.(a) PL spectra of samples with 9 mol% concentration of
4. CONCLUSIONS
In conclusion, a controllable one-step doping method was adopted in the cesium copper iodide perovskite’s luminescence, and the results indicated that a system including and with high quality had been successfully prepared. Through comparing the PL efficiency of samples under various molar ratios and materials, it has been investigated that the amount of combining with the uniformity and quality of and was the key factor affecting the white-lighting. Therefore, a high-quality white-emission with CIE coordinates of (0.3397, 0.3325) and CRI of 90 was obtained in a convenient way. This work provides a new approach for the investigation of Cu-based metal halide perovskites and will be helpful for the exploration of lead-free perovskites.
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