Conventional perovskite solar cells (PSCs) have adapted the organic–inorganic hybrid perovskites as the absorption layer due to low processing temperature, superior optoelectronic properties, and simple solution processing. However, hybrid perovskites are more vulnerable to heat compared to inorganic perovskites. For long-term operation, heat stability is essential for the commercialization of PSCs based on hybrid perovskite. In this study, we synthesized inorganic halide perovskite CsPbBr₃ with SiO₂ shell to ensure stability against heat. However, due to the lattice mismatch between the SiO₂ shell and CsPbBr₃, we introduced nickel doping using nickel acetate to reduce this mismatch. The nickel-doped CsPbBr₃–SiO₂ core–shell perovskite exhibited superior thermal stability, maintaining the 92% of its initial performance after 12 h at 353 K.

1. Introduction

Halide perovskites have an ABX₃ structure as well as wide-ranging photoelectric properties that are attributed to the various combinations of ions in the A⁺, B²⁺, and X⁻ sites [1, 2]. Based on diverse properties such as high absorption coefficient, long carrier diffusion length, and high carrier mobility, perovskites have been used in various applications, such as in solar cells [3–8], light-emitting diodes (LEDs) [9–15], detectors [16, 17], and sensors [18, 19]. Perovskite solar cells (PSCs) have seen rapid advancements over the past 15 years, with power conversion efficiency (PCE) increasing from 3.8% to 26.08% [20, 21]. However, the conventional lead halide perovskites (LHPs) used in PSCs are typically organic–inorganic hybrid perovskites, which suffer from stability issues due to the organic cations’ vulnerability to external factors such as heat and moisture.

In contrast to organic–inorganic hybrid perovskites, inorganic LHPs are commonly applied in LEDs because of their defect tolerance, high photoluminescence quantum yield (PLQY), and superior stability [22–30]. Inorganic LHPs, such as CsPbI₃ [31–33], CsPbI_3-xBr_x [34–36], and CsPbBr₃ [37–42], have also been applied as the absorption layer in solar cells, leading to an improvement in PCE from 2.9% [43] to 21.5% [37] over 10 years. Inorganic LHPs are promising candidates for replacing the traditional organic–inorganic hybrid perovskites, with methods such as quantum dot (QD) solutions, spin-coating, and thermal evaporation being explored [38]. One strategy to further enhance efficiency is the use of tandem structures with other absorption layers [39]. Among inorganic LHPs, CsPbBr₃ is a strong candidate for stable performance under heat, with improvements achieved through doping and structural adjustments. CsPbBr₃ also demonstrates a stable crystal structure due to its higher Goldschmidt tolerance factor compared to other inorganic LHPs. Using a raw material source that combines transition metals and ligands, extensive studies have reported that the stability of halide perovskites is improved by simultaneously applying metal ion doping and core/shell structure formation [44–48]. Appropriate metal ions, such as Mg²⁺ and Ni²⁺, were incorporated into perovskite to modulate its optical properties and stability [49, 50]. Additionally, thiocyanate was introduced to adjust the growth rate of the perovskite [51]. The synthesis of perovskite with a core–shell structure is progressing, involving the encapsulation of perovskite with polymers, other perovskites, and metal oxides. The core–shell structure typically enhances stability against external factors, and synthesized core–shell perovskites have been applied in various fields, including 3D printing [52]. Therefore, this study also aims to provide a theoretical foundation for the improvement of LHPs induced by the synergistic effect of transition metal doping and core/shell structure formation [53]. A previous study synthesized a core/shell perovskite with an SiO₂ shell, which exhibited weakened optical properties compared to pristine perovskite owing to lattice mismatches.

In this work, we synthesized the CsPbBr₃ perovskites with nickel doping and SiO₂ shell for enhancing the stability with alleviating the lattice mismatch. The sources of doping and shell were nickel acetate and 3-aminopropyltriethoxysilane (APTES). Comparing to other nickel source, the nickel acetate can be dissolved in low temperature that be able to synthesize in lower temperature than conventional hot injection methods. The reduction in synthesis temperature indicated a decline in the overall cost of the synthesis process. APTES was integrated with perovskite at the A-site, filling the point vacancy of the Cs ion. As a result, nickel-doped CsPbBr₃ with a SiO₂ shell (Ni–SiO₂) perovskite maintained 92% of their initial performance after 120 h at 353 K. The superior heat stability demonstrated that Ni–SiO₂ perovskite is suitable for application as an absorption layer in PSCs.

2. Experimental

2.1. Materials

All chemicals were utilized without further purification. Cesium carbonate (Cs₂CO₃, 99.9%, Sigma–Aldrich), oleic acid (OA, 90%, Sigma–Aldrich), 1-octadecene (ODE, 90%, Sigma–Aldrich), PbBr₂, nickel acetate, APTES (99%, Sigma–Aldrich), and oleylamine (OLA, 70%, Sigma–Aldrich) were purchased for synthesis.

2.2. Synthesis of Pristine CsPbBr₃ and Ni-Doped QDs

The procedure used for synthesizing CsPbBr₃ and Ni-doped CsPbBr₃ QDs was similar to the conventional hot injection method with minor modifications. The Cs–oleate was synthesized by stirring 5 mL of ODE, 0.25 mmol of Cs₂CO₃, and 0.5 mL of OA in 250 mL three-neck flask under N₂ at 110 for 1 h. For utilizing the Cs–oleate precursor again, we preheated the precursor at 100°C. For CsPbBr₃ synthesis, 5 mL of ODE, 0.188 mmol of PbBr₂, and 0.47 mmol of nickel acetate were added to a 250 mL three-neck round-bottom flask and dried under vacuum at 110°C for 1 h. The flask was filled with N₂, and 2 mL of OA and 2 mL of OLA were injected into the flask, which was preheated to 70°C. Subsequently, the flask was heated at 130°C until PbBr₂ and nickel acetate completely reacted with OA and OLA, following which the temperature was increased to 160°C. The Cs–oleate precursor (0.4 mL) was rapidly injected into the Pb–oleate solution, and the solution was maintained at 160°C for 5 s to allow for the growth of the QDs. Subsequently, the solution was cooled by immersing the flask in a cold-water bath.

2.3. Synthesis of CsPbBr₃ and Ni-Doped CsPbBr₃ QDs With SiO₂ Shell

The procedures used for synthesizing CsPbBr₃ and nickel-doped CsPbBr₃ QDs with SiO₂ shell were similar to the conventional hot injection method with minor modifications [54]. Briefly, 5 mL of ODE, 0.188 mmol of PbBr₂, and 0.47 mmol of nickel acetate were added to a 250-mL three-neck round-bottom flask and dried under vacuum at 110°C for 1 h. The flask was filled with N₂, and OA (2 mL) and APTES (2 mL) were injected into the flask, which was preheated to 70°C. Subsequently, the flask was maintained at 110°C until PbBr₂ and nickel acetate completely reacted with OA and APTES; subsequently, the temperature was increased to 130°C. The Cs–oleate precursor (0.4 mL) was rapidly injected into the Pb–oleate solution, and the solution was maintained at 130°C for 5–10 s to allow for the growth of the QDs. The solution was cooled by immersing the flask in a cold-water bath.

2.4. Purification and Dispersion

The as-synthesized samples were purified by centrifugation at 13,500 RPM for 5 min. After centrifugation, the bright green supernatants were discarded, and the precipitates were collected, dispersed in 2 mL of hexane, and centrifuged at 3000 RPM for 5 min. During the purification process, perovskite solution was exposed to air for supplementing the H₂O. The resulting supernatants were collected and stored in a vial, which was encased with aluminum foil to prevent light exposure.

2.5. Characterization

Field-emission scanning electron microscopy (FE-SEM) (Carl Zeiss SIGMA 300 and Hitachi SU-8100) and field-emission transmission electron microscopy (FE-TEM; JEOL JEM-F200) were used to characterize the morphology and lattice structures of the synthesized colloidal QD samples. An X-ray diffractometer (Bruker-AXS, XRD New D8-Advance) was used to record the XRD patterns. NMR (NMR 600 Hz, Varian, VNS) was used to analyze the behavior of the ligands. A spectrofluorometer (Jasco, FP-8550) was used to analyze the PL intensity, absorbance, and PLQY of the synthesized colloidal QD samples. The XPS survey (K-alpha+, Thermo Fisher Scientific) was measured for analyzing the chemical effect of the nickel and SiO₂.

3. Result and Discussion

3.1. Analysis for Perovskites

As shown in Figure 1a, changing the passivation material to alleviate the lattice mismatch can maintain or improve the existing optical properties. The Goldschmidt tolerance factor (T) and octahedral factor (μ) are the main parameters that indicate the nature of the existing perovskite phases and structures. The structures of halide perovskites are shown in Figure 1b–d, and the expressions for calculating these factors are given in Equations (1) and (2). These factors are determined by the radii of the A⁺, B²⁺, and X⁻ ions and are denoted as R_A, R_B, and R_X, respectively. In particular, the tolerance factor is expressed as the ratio of A⁺ to Pb²⁺ ions, and the octahedral factor is determined by the [BX₆]⁴⁻ octahedra, which indicate the radii of the Pb²⁺ and X⁻ ions. Typically, LHPs are nonradiative phases in terms of these two factors.

Details are in the caption following the image — **Figure 1**
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(a) Schematic of lattice-mismatched and lattice-matched structures due to the smaller relative ion size of Ni²⁺ compared to Pb²⁺. (b) Octahedral structure of lead halide perovskite. Indication of ionic radii: (c) front view of lead halide perovskite and (d) diagonal view of lead halide perovskite. Each ionic radius is indicated by R_A, R_B, and R_X (radii of the A⁺, B²⁺, and X⁻ ions, respectively).

In the synthesis of radiative perovskites structures, ionic radii and structural properties should also be considered.

(1)

(2)

Halide vacancy is a common defect in LHPs. Moreover, LHPs are known to be defect tolerant owing to Pb²⁺ ions. For example, in the case of CsPbBr₃, Cs ions do not affect the band states of the LHP. The top of the valence bands in CsPbBr₃ forms via s–p antibonding between the empty Pb p orbital and the Br p orbital, resulting in a shallow defect energy level. Moreover, the empty Pb p orbital causes a conduction band minimum, which further contributes to the shallow defect energy level. Although Pb ions endow structural defect tolerance characteristics, a small amount of nickel ion doping enhances Pb–Br binding, which inhibits halide vacancy formation.

Many transition metals have been used in studies on LHP doping. Among them, research has been conducted to increase the stability and optical efficiency of LHPs by doping. Generally, when doping a transition metal, a material that has an ionic bond between the transition metal and halide is used to obtain a halide-rich environment, reduce the number of halide vacancies, and dope the transition metal, which usually exists as bivalent ions, on the Pb site [55–59]. However, these halide metals have strong ionic bonds and require elevated temperatures or additional energy to enable their utilization as a precursor for synthesis in the presence of an organic solvent. Therefore, the use of an ionic compound composed of a transition metal and an acetate ion as a doping source is also evaluated. To develop the SiO₂ shell, APTES was added to the precursor solution after doping. The process of forming the SiO₂ shell is shown in Equations (3), (4), and (5) [60].

(3)

(4)

(5)

APTES binds to the perovskite at the A-site vacancy through its amine functional group, and the formation of the SiO₂ shell inhibits the generation of surface and point defects. The processes of doping and SiO₂ shell formation are summarized in Figure S1. The optical properties of the CsPbBr₃ depending on the presence of Ni²⁺ and SiO₂ shell were shown in Figure 2. In Figure 2a, the UV-vis absorbance spectra of pristine, nickel-doped CsPbBr₃ (Ni), SiO₂-encapped CsPbBr₃ (SiO₂), and Ni–SiO₂ perovskite are shown. The peak edge of each sample located at 511, 514, 527.5, and 521.5 nm coincided with PL peak position in Figure 2b. Also, the full width half maximum (FWHM) of the samples were 20.7, 19.5, 20.00, and 21.2 nm as shown in Figure 2b. The red shift of the PL peak position was attributed to difference in size as shown in Figure S2. In Figure S2a,b, the TEM images of the pristine and SiO₂ perovskite and the size distributions of each sample was shown in the inset image of Figure S1a,b. The average size of SiO₂ perovskites was larger than the pristine CsPbBr₃ that contribute to the red shift in PL peak position. The perovskites Ni and Ni–SiO₂ showed the difference in PL peak position that shifted smaller than nondoped perovskites. It was attributed to the reduction in lattice mismatch. The introduction of SiO₂ also decreases to the PLQY because of the lattice distortion between the perovskite and SiO₂ shell.

The nickel doping alleviated the lattice distortion, and the gap of PL intensity between the Ni and Ni–SiO₂ perovskites was smaller than pristine and SiO₂ perovskites. The peak position, FWHM, and PLQY of perovskites were summarized in Table 1.

Table 1. Optical properties of perovskites according to the presence of nickel doping and SiO₂ shell.

Sample	Pristine	Ni	SiO₂	Ni–SiO₂
PL peak (nm)	511	514	527.5	521.5
FWHM (nm)	20.7	19.5	20.0	21.2
PLQY (%)	62	71	51	65

Abbreviations: FWHM, full width half maximum; PLQY, photoluminescence quantum yield.

For identifying the phase stability of synthesized perovskites, TEM images of perovskites after 5 days were measured as shown in Figure 3a,–d, and as-prepared perovskites were shown in Figure S1a–d. In Figure 3a, the boundaries of the square CsPbBr₃ crystals faded after 5 days, and hexagonal structures with a spherical shape were formed. These hexagonal structures have a very similar shape to that of previously reported Cs₄PbBr₆ crystals [61, 62]. The pristine perovskite showed the phase transition from CsPbBr₃ to Cs₄PbBr₆, and the SiO₂ perovskite partially transformed to Cs₄PbBr₆ because of the defect. The Ni perovskite showed the black dots and large grain that the morphology was shown as nanorods. In Figure 3b,c, the black dots were Pb⁰ originated from the lack of surface passivating ligands [59]. The low-temperature synthesis of perovskite influenced the morphology of nanorods, which can be attributed to the excess nickel content. The variation of morphologies attributed to the excess of nickel was shown in Figure S3a−c. Ni–SiO₂ perovskites preserved the CsPbBr₃ phase because the surface was successfully passivated both A-site and B-site by APTES and nickel doping as shown in Figure 3d. For atomic-scale analysis, we magnified the TEM images, as shown in Figure S4a–d. The nickel ion has a smaller ionic radius than the lead ion, and the formation of the SiO₂ shell affected the size of the perovskite QD. As a result, compared to pristine perovskite, the other perovskites exhibited a reduction in planar distance. In Figure S4c,d, the SiO₂ shell is shown covering the perovskite QD, with the Ni–SiO₂ perovskite demonstrating greater coverage than the SiO₂ perovskite, which is attributed to the alleviation of lattice mismatch.

The XRD pattern of the as-prepared perovskites and perovskites after 5 days were shown in Figure 3e,f. In Figure 3e, all XRD patterns showed the same positions for two peaks. The peaks located near 15.2° and 30.6° signified the (100) and (200) planes of cubic CsPbBr₃ that coincided with JCPDS no. 54-0752. In Figure 3f, each XRD patterns showed that maintained existing peaks. However, the pristine, SiO₂, and Ni perovskites showed the additional peaks near 12.6° and 25.4° that signified the (012) and (240) planes of Cs₄PbBr₆, and those peaks were coincided with JCPDS no. 73-2478 that denoted Cs₄PbBr₆. The existence of additional peaks attributed to transition from CsPbBr₃ to Cs₄PbBr₆ was consistent with the TEM images in Figure 3a–d. Despite the other XRD patterns showed additional peak, Ni–SiO₂ perovskite retain the original pattern, and it signified that the chemical stability was improved.

For identifying the chemical environment of perovskites, we measured the XPS spectra of pristine, SiO₂, Ni, and Ni–SiO₂ perovskites as shown in Figure 4a–c and Figure S5a and S4b. In Figure 4a, the XPS survey spectra of pristine and Ni–SiO₂ perovskite was displayed. The Si 2p and O 1s peaks were shown in Ni–SiO₂ spectra that signified the presence of SiO₂ on the surface of perovskites. For identifying the introduction of the nickel, we measured the XPS Ni 2f spectra of Ni–SiO₂ perovskite as shown in Figure S4. However, the amount of the nickel was too small to measure by XPS spectra that showed the peak near 856 eV with weak intensity. For clarifying the presence of nickel, we measured the TEM-energy-dispersive spectroscopy (TEM-EDS) of pristine and Ni–SiO₂ perovskites as shown in Figure S6. In Figure S7a, the TEM-EDS mapping of pristine perovskites showed that Cs, Pb, and Br was detected and the ratios of Pb/Cs and Br/Cs were nearly 1, and 3. Those ratios were proved the CsPbBr₃ phase was dominated. In Ni–SiO₂ perovskites, as shown in Figure S7b, the TEM-EDS detected the Cs, Pb, Br, Si, O, and Ni that the presence of Ni was proved and SiO₂ shell was detected. We introduced the nickel acetate in the precursor that was the same ratio with lead bromide, but the doped nickels were not coincided with the number of leads. Figure 4b,c showed the XPS Br 3d and Pb 4f spectra of Ni–SiO₂. Both spectra showed the peak shift to low binding energy and that the strong interaction between CsPbBr₃ and SiO₂ affected the chemical environment [63]. In Figure 4c, the edge of the Pb 4f_5/2 and Pb 4f_7/2 peaks in XPS Pb 4f spectra of pristine perovskite showed additional peaks in low binding energy. The presence of those peaks was attributed to the Pb⁰ defects [64]. In XPS Pb 4f spectra of Ni–SiO₂, those edge peak disappeared and that the surface of the perovskite was successfully passivated by nickel and SiO₂ shell.

NMR is an effective analytical method for confirming the presence of ligands in samples. 1D NMR was performed using CDCl₃ as a reference solvent, which exhibited a peak at ~7.3 ppm that did not overlap with those of the ligands, such as OA, oleylamine, and APTES, to be verified. A total of four ligands were detected. The NMR spectra of OA and oleylamine were shown in Figure S8a,b; the peaks observed at 2 ppm or less were attributed to the hydrogen attached to alkyl chains. In addition, the peaks observed at 2.4 and 2.7 ppm were attributed to the hydrogen attached to alkene carbons. APTES formed an SiO₂ shell via hydrolysis, and the NMR peak varied as the chemical bonds of the silane group changed. As shown in Figure S8c and S7d, the APTES peak changed before and after hydrolysis from 3.8 to 3.5 ppm, because the three ethoxide groups of APTES were transformed into hydroxyl groups. Figure 4d shows the NMR data for the Ni perovskite prepared using APTES. The peaks indicated by the red circles in the chemical shift range of 2 ppm or less correspond with those of the alkyl chain of OA. Therefore, it is concluded that OA remained in the sample after synthesis. The peaks indicated by the green circle at ~3.8 ppm confirm that APTES was hydrolyzed. Compared with the peak position shown in Figure S6c, the shift in the peak to higher ppm values is ascribed to the decrease in electron density that occurs when APTES combines with the perovskite. The weak intensity of some peaks is attributed to the presence of ethanol during hydrolysis. Consequently, when APTES is injected during perovskite synthesis, NMR analysis can be used to confirm the synthesis of the halide perovskite with the desired core/shell structure by combining hydrated APTES with Ni perovskite.

3.2. Stability Challenges

Conventional QD-sensitized solar cells were fabricated using inorganic QDs such as CdS, ZnS, and ZnO as the active layer, with many QDs encapsulated or treated with various metal oxides [63, 65]. Notably, ZnO nanorods were commonly synthesized with CdS/CdSe QDs or CdS/CdSe/ZnS QDs. Another treatment method involved a two-step process: first, CdS/CdSe QDs were applied, followed by the insertion of ZnS/Al₂S₃ QDs into the ZnO nanorods to reduce back electron recombination.

Perovskite QDs exhibited a lower density of surface defects compared to inorganic QDs; however, they were also vulnerable to external stimuli such as water, heat, and oxygen. For applying electric devices, the thermal stability of perovskites especially has to improve the optical stability of perovskites which was improved by the passivation in previous works [66, 67]. For comparing the thermal stability of pristine and Ni–SiO₂ perovskites, we conducted the measurement of PL intensity against 353 K in time-dependent as shown in Figure 5 and Figure S9. In Figure 5a, time-dependent PL spectra of pristine perovskites under 353K were measured. The PL intensity of the pristine perovskite declined to 2.6% of initial intensity during 12 h under 353 K. Also, the PL peak position was shifted from 511 to 514 nm and that the size of the perovskites was increased because of the annealing. In Figure S9, time-dependent PL spectra were displayed according to the treatment of APTES and nickel. In Figure S9a, the SiO₂ perovskite showed decreased in the PL intensity to 64.6% of initial intensity, and the peak position was red shifted for 5.5 nm. In Figure S9b, the Ni perovskites retained the 56.1% of initial intensity, and the peak position was red shifted from 514 to 518 nm. On the other hand, the Ni–SiO₂ perovskites showed the superior stability that the PL intensity preserved 92.0% of the initial intensity after 12 h under 353 K. The preservation of the PL intensity proved that the encapsulation of perovskites was successfully conducted. The improved stability signified that the nickel doping and SiO₂ shell simultaneously affect the thermal stability. As a result, the Ni–SiO₂ perovskite maintained more PL intensity than other perovskites.

3.3. Feasibility and Implementation Challenges

To fabricate PSCs based on the synthesized Ni–SiO₂, two processing steps were necessary. First, the perovskite film deposition needed to be optimized. The Ni–SiO₂ perovskites were in solution form, with QDs dispersed in the solvent. Conventionally, perovskite films are fabricated using spin-coating methods, with parameters such as time, RPM, and annealing temperature optimized. Second, the structure of the Ni–SiO₂-based PSCs required optimization. Many PSCs use a TiO₂ layer as the electron transport layer, while various materials, such as NiOx and CuSCN, are selected as the hole transport layer. An interlayer is also applied to PSCs to alleviate interface defects between the perovskite and the charge transport layer. A comparison of this work with conventional research is provided in Table 2. The active layers were either single structures or tandem structures with other absorption materials.

Table 2. Comparison of perovskites applied to PSCs with/without additional materials by diverse strategies with stability and performance.

Perovskite	Treated material	Method	PCE	Stability	References
MAPbI₃	—	—	—	25°C, N₂, 50 h	[68]
CsPbI₂Br	—	—	9.3%	25°C, N₂, 1500 h	[68]
CsPbI_3-xBr_x	MMI	Interlayer	20.6%	65°C, N₂, 265 h	[69]
CsPbI₃	DMF/DMSO	Solvent engineering	15.7%	25°C, N₂, 500 h	[70]
CsPbBr₃	SiO₂	Core–shell	—	85°C, air, 120 h	This work

Abbreviation: PCE, power conversion efficiency.

The fabrication process order also influenced the PSC structure, such as normal or inverted structures. As a result, the optimized PSCs demonstrated superior heat stability, which is advantageous for modules. The summarized process for application is shown in Figure 6.

4. Conclusion

This study aimed to increase the stability of perovskites, which is the main issue limiting their application. Perovskite materials with improved optical characteristics and high stability were synthesized by combining the advantages of doping and core/shell structures. The source of nickel ions was nickel acetate, which reduced the synthesis temperature from 170−195°C to 130°C. This decrease in temperature indicated a more cost-efficient process. The formation of the SiO₂ shell and nickel doping was confirmed by TEM images and NMR. Stability tests showed that the Ni–SiO₂ perovskite maintained over 90% of its initial intensity at 80°C for 120 h. The superior thermal stability enhances its suitability for outdoor applications in PSCs.

This study, as well as further research on the stability of perovskites, will facilitate the research and development of photoluminescent perovskites. Moreover, perovskites, which possess high absorption coefficient and long carrier diffusion length are promising next-generation materials for solar cell. The inorganic LHP recently applied to the solar cell and the efficiency of them improved with time. Therefore, this study contributed to development of solar cell with clarifying the chemical properties of inorganic LHP with shell for stability.

Conflicts of Interest

The authors declare no conflicts of interest.

Author Contributions

Myeong Jin Seol: conceptualization, investigation, writing–original draft. Seunghwan Hwang: conceptualization, investigation, writing–original draft. Soo Young Kim: project administration, supervision, writing–review and editing. Myeong Jin Seol and Seunghwan Hwang contributed equally to this work.

Funding

This research was supported by the National Research Foundation (NRF) of Korea (Grant numbers 2020R1A2C2100670 and 2022M3H4A1A04096380).

Acknowledgments

This research was supported by the National Research Foundation (NRF) of Korea (Grant numbers 2020R1A2C2100670 and 2022M3H4A1A04096380).

Supporting Information

Additional supporting information can be found online in the Supporting Information section.

Open Research

Data Availability Statement

The data supporting this article have been included as part of the ESI.

Supporting Information

References

1 Hu D. Y., Zhao X. H., Tang T. Y., Lu L. M., Gao L. K., and Tang Y. L., Study on the Structural, Electronic and Optical Properties of Double-Perovskite Halides Cs₂AgSbX₆ (X = I, Br, Cl) Based on First-Principles, Materials Science Semiconductor Processing. (2022) 152, 107077.
10.1016/j.mssp.2022.107077
CAS Google Scholar
2 Ren Y., Hua J., Han Z., Sun M., and Lu S., Brightly Luminescent Green-Emitting Halide Perovskite Light Emitting Diode by Employing the Whole Single Crystal, Chemical Engineering Journal. (2023) 452, 139160.
10.1016/j.cej.2022.139160
CAS Google Scholar
3 Zhong F., He Y., Sun Y., Dong F., and Sheng J., Metal-Doping of Halide Perovskite Nanocrystals for Energy and Environmental Photocatalysis: Challenges and Prospects, Journal of Materials Chemistry A. (2022) 43, 22915–22928.
10.1039/D2TA06851F
Google Scholar
4 Zhou R., Cheng C. A., and Wang X., et al.Metal Halide Perovskite Nanocrystals With Enhanced Photoluminescence and Stability Toward Anticounterfeiting High-Performance Flexible Fibers, Nano Research. (2022) 16, 3542–3551.
10.1007/s12274-022-5041-8
Google Scholar
5 Zhou W., Pan T., and Ning Z. J., Strategies for Enhancing the Stability of Metal Halide Perovskite Towards Robust Solar Cells, Science China Materials. (2022) 65, 3190–3201.
10.1007/s40843-022-2277-9
CAS Web of Science® Google Scholar
6 Park H. H., Transparent Electrode Techniques for Semitransparent and Tandem Perovskite Solar Cells, Electronic Materials Letters. (2021) 17, 18–32.
10.1007/s13391-020-00259-4
CAS Web of Science® Google Scholar
7 Zhang Y., Wang Z., and Liu T., et al.Effects of Spin-Casting Speed on Solar Cell Performances and Corresponding Films Morphology and Optical Properties Using 2D Perovskite of PEA₂MA₂Pb₃I₁₀, Electronic Materials Letters. (2022) 18, 282–293.
10.1007/s13391-022-00343-x
CAS Google Scholar
8 Ahn Y. J., Ji S. G., and Kim J. Y., Monolithic All-Perovskite Tandem Solar Cells: Recent Progress and Challenges, Journal of Korean Ceramic Society. (2021) 58, 399–413.
10.1007/s43207-021-00117-5
CAS Web of Science® Google Scholar
9 Ye F., Wang H., Ke W., Tao C., and Fang G., Unveiling the Key Factor Affecting the Illumination Deterioration and Response Measures for Lead Halide Perovskite Solar Cells, Journal of Energy Chemistry. (2021) 73, 429–435.
10.1016/j.jechem.2022.05.011
Google Scholar
10 Shen C., Sun D., and Dang Y., et al.(C₄H₁₀NO)PbX₃ (X = Cl, Br): Design of Two Lead Halide Perovskite Crystals With Moderate Nonlinear Optical Properties, Inorganic Chemistry. (2021) 61, 16936–16943.
10.1021/acs.inorgchem.2c03042
Google Scholar
11 Rana M. M., Khan A. A., and Zhu W., et al.Enhanced Piezoelectricity in Lead-Free Halide Perovskite Nanocomposite for Self-Powered Wireless Electronics, Nano Energy. (2022) 101, https://doi.org/10.1016/j.nanoen.2022.107631, 107631.
10.1016/j.nanoen.2022.107631
CAS Web of Science® Google Scholar
12 Nie Z., Huang Z., and Zhang M., et al.Hot Phonon Bottleneck Stimulates Giant Optical Gain in Lead Halide Perovskite Quantum Dots, ACS Photonics. (2022) 9, no. 10, 3457–3465, https://doi.org/10.1021/acsphotonics.2c01394.
10.1021/acsphotonics.2c01394
CAS Google Scholar
13 Lin X., Chen L., and He C., et al.Vapor Phase Growth of Centimeter-Sized Band Gap Engineered Cesium Lead Halide Perovskite Single-Crystal Thin Films With Color-Tunable Stimulated Emission, Advanced Functional Materials. (2023) 33, https://doi.org/10.1002/adfm.202210278, 2210278.
10.1002/adfm.202210278
CAS Web of Science® Google Scholar
14 Seol M. J., Han J. W., Hwang S. H., and Kim S. Y., Recent Research Trends for Improving the Stability of Organo/Inorgano Halide Perovskites, Korean Journal of Metals and Materials. (2022) 60, no. 1, 1–13, https://doi.org/10.3365/KJMM.2022.60.1.1.
10.3365/KJMM.2022.60.1.1
CAS Web of Science® Google Scholar
15 Crandhi G. K., Kim H. J., and Viswanath N. S. M., et al.Strategies for Improving Luminescence Efficiencies of Blue-Emitting Metal Halide Perovskites, Journal of the Korean Ceramic Society. (2021) 58, no. 1, 28–41, https://doi.org/10.1007/s43207-020-00100-6.
10.1007/s43207-020-00100-6
Google Scholar
16 Zhang P., Hua Y., and Xu Y., et al.Ultrasensitive and Robust 120 keV Hard X-Ray Imaging Detector Based on Mixed-Halide Perovskite CsPbBr_3−nI_n Single Crystals, Advanced Materials. (2022) 34, no. 12, https://doi.org/10.1002/adma.202106562, e2106562.
10.1002/adma.202106562
CAS PubMed Web of Science® Google Scholar
17 Aamir M., Shahiduzzaman M., and Taima T., et al.On the Development of Metal Halide Perovskite-Based Fluorescent Sensors and Radiation Detectors, Advanced Optical Materials. (2021) 9, no. 24, 2101276.
10.1002/adom.202101276
CAS Web of Science® Google Scholar
18 Wang K., Li G., and Wang S., et al.Dark-Field Sensors Based on Organometallic Halide Perovskite Microlasers, Advanced Materials. (2018) 30, no. 32, https://doi.org/10.1002/adma.201801481, 2-s2.0-85051116511, e1801481.
10.1002/adma.201801481
PubMed Web of Science® Google Scholar
19 Ruan S., Lu J., and Pai N., et al.An Optical Fibre-Based Sensor for the Detection of Gaseous Ammonia With Methylammonium Lead Halide Perovskite, Journal of Materials Chemistry C. (2018) 6, 6988–6995.
10.1039/C8TC01552J
CAS Web of Science® Google Scholar
20 Kojima A., Teshima K., shirai Y., and Miyasaka T., Oraganometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells, Journal of the American Chemical Society. (2009) 131, no. 17, 6050–6051, https://doi.org/10.1021/ja809598r, 2-s2.0-70149102912.
10.1021/ja809598r
CAS PubMed Google Scholar
21 Park J., Kim J., and Yub H.-S., et al.Controlled Growth of Perovskite Layers With Volatile Alkylammonium Chlorides, Nature. (2023) 616, 724–730, https://doi.org/10.1038/s41586-023-05825-y.
10.1038/s41586-023-05825-y
CAS PubMed Web of Science® Google Scholar
22 Xie K., Zhang S., and Wang X., et al.Post-Synthetic Ammonium Hexafluorophosphate Treatment Enables CsPbBr₃ Perovskite Quantum Dots Exhibiting Robust Photoluminescence and Environmental Stability for White Light-Emitting Diodes, Journal of Luminescence. (2022) 252, 119401.
10.1016/j.jlumin.2022.119401
CAS Google Scholar
23 Xiao B., Qian Y., and Li X., et al.Enhancing the Stability of Planar Perovskite Solar Cells by Green and Inexpensive Cellulose Acetate Butyrate, Journal of Energy Chemistry. (2023) 76, 259–265.
10.1016/j.jechem.2022.09.039
CAS Web of Science® Google Scholar
24 Wang W., Song S., Li J., Cao B., and Liu Z., Single Silica-Coated Mn-Doped CsPbCl₃ Perovskite Quantum Dots With Enhanced Stability and Excellent Optical Properties, Journal of Luminescence. (2022) 252, 119361.
10.1016/j.jlumin.2022.119361
CAS Google Scholar
25 Peng K., Yu L., and Zhang M., Synthesis of CsPbX₃ Lead Halide Perovskite Nanocrystals in Flower-Like TiO₂ Matrices With Enhanced Stability, Journal of Luminescence. (2023) 253, 119428.
10.1016/j.jlumin.2022.119428
CAS Web of Science® Google Scholar
26 Li H., Wang Z., and Wang L., et al.Dual-Passivation Strategy on CsPbI₂Br Perovskite Solar Cells for Reduced Voltage Deficit and Enhanced Stability, Nano Energy. (2022) 103, 107792.
10.1016/j.nanoen.2022.107792
CAS Google Scholar
27 Hao M., Wang Q., Li J., Xiang W., Fan H., and Liang X., An Environment-Friendly Backlight Display Material: Dy³⁺-Doped CsPbBr₃ Perovskite Quantum Dot Glass With Super High Stability and Ultra-Wide Color Gamut, Materials Today Chemistry. (2022) 26, 101020.
10.1016/j.mtchem.2022.101020
CAS Google Scholar
28 Gao Z., Zhou H., and Dong K., et al.Defect Passivation on Lead-Free CsSnI₃ Perovskite Nanowires Enables High-Performance Photodetectors With Ultra-High Stability, Nano-Micro Letters. (2022) 14, https://doi.org/10.1007/s40820-022-00964-9, 20225987.
10.1007/s40820-022-00964-9
Google Scholar
29 Chen Y., Mei E., Liang X., Chen Q., and Xiang W., CaO Modulated Dual-Phase CsPb₂Br₅/CsPbBr₃ Perovskite Nanocrystal Glasses With Enhanced Stability for Backlit Display, Journal of Luminescence. (2023) 253, 119456.
10.1016/j.jlumin.2022.119456
CAS Google Scholar
30 Kim H., Gu H., and Song M., et al.Study on A-Site Compositional Mixing for the Shear Coating Process of FA-Based Lead Halide Perovskites, Korean Journal of Metal and Materials. (2021) 59, no. 5, 321–328.
10.3365/KJMM.2021.59.5.321
CAS Google Scholar
31 Wang J., Che Y., and Duan Y., et al.21.15%-Efficiency and Stable γ-CsPbI₃ Perovskite Solar Cells Enabled by an Acyloin Ligand, Advanced Materials. (2023) 35, no. 12, 2210223.
10.1002/adma.202210223
CAS PubMed Web of Science® Google Scholar
32 Zou H., Duan Y., and Yang S., et al.20.67%-Efficiency Inorganic CsPbI₃ Solar Cells Enabled by Zwitterion Ion Interface Treatment, Small. (2023) 19, no. 2, https://doi.org/10.1002/smll.202206205, e2206205.
10.1002/smll.202206205
CAS PubMed Web of Science® Google Scholar
33 Duan Y., Wang J., and Xu D., et al.21.41%-Efficiency CsPbI3 Perovskite Solar Cells Enabled by an Effective Redox Strategy With 4-Fluorobenzothiohydrazide in Precursor Solution, Advanced Functional Materials. (2024) 34, no. 10, 2312638.
10.1002/adfm.202312638
CAS Web of Science® Google Scholar
34 Zhang H., Xiang W., and Zuo X., et al.Fluorine-Containing Passivation Layer via Surface Chelation for Inorganic Perovskite Solar Cells, Angewandte Chemie. (2023) 135, no. 6, e202216634.
10.1002/ange.202216634
Google Scholar
35 Xiao H., Zuo C., and Yan K., et al.Highly Efficient and Air-Stable Inorganic Perovskite Solar Cells Enabled by Polylactic Acid Modification, Advanced Energy Materials. (2023) 13, no. 32, 2300738.
10.1002/aenm.202300738
CAS Web of Science® Google Scholar
36 Wang Z., Tian Q., and Zhang H., et al.Managing Multiple Halide-Related Defects for Efficient and Stable Inorganic Perovskite Solar Cells, Angewandte Chemie. (2023) 62, no. 30, https://doi.org/10.1002/anie.202305815, e202305815.
10.1002/anie.202305815
CAS Google Scholar
37 Mali S. S., Patil J. V., and Shao J.-Y., et al.Phase-Heterojunction All-Inorganic Perovskite Solar Cells surpassing 21.5% Efficiency, Nature Energy. (2023) 8, 989–1001.
10.1038/s41560-023-01310-y
CAS Web of Science® Google Scholar
38 Park J. H., Yoon Y. S., and Kim J. Y., Fabrication Processes for All-Inorganic CsPbBr₃ Perovskite Solar Cells, EcoMat. (2023) 5, no. 11, e12407.
10.1002/eom2.12407
CAS Google Scholar
39 Liu L., Xiao H., and Jin K., et al.4-Terminal Inorganic Perovskite/Organic Tandem Solar Cells Offer 22% Efficiency, Nano-Micro Letters. (2023) 15, 23.
10.1007/s40820-022-00995-2
CAS Google Scholar
40 Yuan B., Zhou Y., Liu T., Li C., and Cao B., Extending the Absorption Spectra and Enhancing the Charge Extraction by the Organic Bulk Heterojunction for CsPbBr₃ Perovskite Solar Cells, ACS Sustainable Chemistry & Engineering. (2023) 11, no. 2, 718–725.
10.1021/acssuschemeng.2c05859
CAS Web of Science® Google Scholar
41 Hossain M. K., Mohammed M. K. A., and Pandey R., et al.Numerical Analysis in DFT and SCAPS-1D on the Influence of Different Charge Transport Layers of CsPbBr₃ Perovskite Solar Cells, Energy & Fuels. (2023) 37, no. 8, 6078–6098.
10.1021/acs.energyfuels.3c00035
CAS Web of Science® Google Scholar
42 Zhang Z., Zhu W., and Han T., et al.Accelerated Sequential Deposition Reaction via Crystal Orientation Engineering for Low-Temperature, High-Efficiency Carbon-Electrode CsPbBr₃ Solar Cells, Energy & Environmental Materials. (2024) 7, no. 1, e12524.
10.1002/eem2.12524
CAS Google Scholar
43 Eperon G. E., Paterno G. M., and Sutton R. J., et al.Inorganic Caesium Lead Iodide Perovskite Solar Cells, Journal of Materials Chemistry A. (2015) 3, 19688–19695.
10.1039/C5TA06398A
CAS Web of Science® Google Scholar
44 Qiao B., Song P., and Cao J., et al.Water-Resistant, Monodispersed and Stably Luminescent CsPbBr₃/CsPb₂Br₅ Core-Shell-Like Structure Lead Halide Perovskite Nanocrystals, Nanotechnology. (2017) 28, 445602.
10.1088/1361-6528/aa892e
PubMed Web of Science® Google Scholar
45 Ahmed G. H., Yin J., Bakr O. M., and Mohammed O. F., Successes and Challenges of Core/Shell Lead Halide Perovskite Nanocrystals, ACS Energy Letters. (2021) 6, no. 4, 1340–1357.
10.1021/acsenergylett.1c00076
CAS Web of Science® Google Scholar
46 Wang F., Li J., and Zhang X., et al.Structural Design for Controlling the Lattice Strain Relaxation Process in TiO₂/SiO₂ Core-Shell Nanoparticles, Sustainable Chemistry Engineering. (2021) 9, no. 49, 16796–16807.
10.1021/acssuschemeng.1c06572
CAS Google Scholar
47 Strasser P., Koh S., and Anniyev T., et al.Lattice-Strain Control of the Activity in Dealloyed Core-Shell Fuel Cell Catalysts, Nature Chemistry. (2010) 2, no. 6, 454–460, https://doi.org/10.1038/nchem.623, 2-s2.0-77952794660.
10.1038/nchem.623
CAS PubMed Web of Science® Google Scholar
48 Jiang M.-C. and Pan C.-Y., Research on the Stability of Luminescence of CsPbBr₃ and Mn: CsPbBr₃ PQDs in Polar Solution, RSC Advances. (2022) 12, no. 24, 15420–15426, https://doi.org/10.1039/d2ra02165j.
10.1039/D2RA02165J
CAS PubMed Google Scholar
49 Thapa S., Zhu H., Grigoriev A., and Zhu P., Novel Composite of Nickel Thiocyanate-Based All-Inorganic Lead Bromide Perovskite Nanocrystals With Enhanced Luminescent and Stability for White Light-Emitting Diodes, Advanced Materials, Interfaces. (2022) 9, 2200710.
10.1002/admi.202200710
CAS Web of Science® Google Scholar
50 Adhikari G. C., Thapa S., Zhu H., and Zhu P., Mg²⁺-Alloyed All-Inorganic Halide Perovskites for White Light-Emitting Diodes by 3D-Printing Method, Advanced Optical Materials. (2019) 7, 1900916.
10.1002/adom.201900916
CAS Web of Science® Google Scholar
51 Thapa S., Adhikari G. C., Zhu H., and Zhu P., Scalable Synthesis of Highly Luminescent and Stable Thiocyanate Based CsPbX₃ Perovskite Nanocrystals for Efficient White Light-Emitting Diodes, Journal of Alloys and Compounds. (2021) 860, 158501.
10.1016/j.jallcom.2020.158501
CAS Web of Science® Google Scholar
52 Zhu P., Thapa S., and Zhu H., et al.Solid-State White Light-Emitting Diodes Based on 3D-Printed CsPbX₃-Resin Colar Conversion Layers, ACS Applied Electron Materials. (2023) 5, 5316–5324.
10.1021/acsaelm.2c01778
CAS Google Scholar
53 Zhu J., Zhou L., and Zhu Y., et al.Stable Bismuth-Doped Lead Halide Perovskite Core-Shell Nanocrystals by Surface Segregation Effect, Small. (2022) 18, no. 3, https://doi.org/10.1002/smll.202104399, e2104399.
10.1002/smll.202104399
CAS PubMed Web of Science® Google Scholar
54 Kim H., Bae S., and Lee T. H., et al.Enhanced Optical Properties and Stability of CsPbBr₃ Nanocrystals Through Nickel Doping, Advanced Functional Materials. (2021) 31, no. 28, 2102770.
10.1002/adfm.202102770
CAS Web of Science® Google Scholar
55 Zheng Y., Yuan X., and Yang J., et al.Cu Doping-Enhanced Emission Efficiency of Mn²⁺ in Cesium Lead Halide Perovskite Nanocrystals for Efficient White Light-Emitting Diodes, Journal of Luminescence. (2020) 227, 117586.
10.1016/j.jlumin.2020.117586
CAS Web of Science® Google Scholar
56 Wang X., Ali N., and Bi G., et al.Lead-Free Antimony Halide Perovskite With Heterovalent Mn²⁺ Doping, Inorganic Chemistry. (2020) 59, no. 20, 15289–15294.
10.1021/acs.inorgchem.0c02252
CAS PubMed Web of Science® Google Scholar
57 Park C., Choi J., Min J., and Cho K., Suppression of Oxidative Degradation of Tin−Lead Hybrid Organometal Halide Perovskite Solar Cells by Ag Doping, ACS Energy Letters. (2020) 5, no. 10, 3285–3294.
10.1021/acsenergylett.0c01648
CAS Web of Science® Google Scholar
58 Naresh V. and Lee N., Zn(II)-Doped Cesium Lead Halide Perovskite Nanocrystals With High Quantum Yield and Wide Color Tunability for Color-Conversion Light-Emitting Displays, ACS Applied Nano Materials. (2020) 3, no. 8, 7621–7632.
10.1021/acsanm.0c01254
CAS Web of Science® Google Scholar
59 Thawarkar S., Jyoti P., Rana S., Narayan R., and Singh S. P., Ni-Doped CsPbBr₃ Perovskite: Synthesis of Highly Stable Nanocubes, Langmuir. (2019) 35, no. 52, 17150–17155, https://doi.org/10.1021/acs.langmuir.9b02450.
10.1021/acs.langmuir.9b02450
CAS PubMed Web of Science® Google Scholar
60 Sun C., Zhang Y., and Ruan C., et al.Efficient and Stable White LEDs With Silica-Coated Inorganic Perovskite Quantum Dots, Advanced Materials. (2016) 28, no. 45, 10088–10094, https://doi.org/10.1002/adma.201603081, 2-s2.0-84988812035.
10.1002/adma.201603081
CAS PubMed Web of Science® Google Scholar
61 Ma Z., Liu Z., and Lu S., et al.Pressure-Induced Emission of Cesium Lead Halide Perovskite Nanocrystals, Nature Communication. (2018) 9, 4506.
10.1038/s41467-018-06840-8
PubMed Web of Science® Google Scholar
62 Seth S. and Samanta A., Fluorescent Phase-Pure Zero-Dimensional Perovskite-Related Cs₄PbBr₆ Microdisks: Synthesis and Single-Particle Imaging Study, Journal of Physical Chemistry Letters. (2017) 8, no. 18, 4461–4467, https://doi.org/10.1021/acs.jpclett.7b02100, 2-s2.0-85029748099.
10.1021/acs.jpclett.7b02100
CAS PubMed Web of Science® Google Scholar
63 Wang P., Wu Z., Wu M., Wei J., Sun Y., and Zhao Z., All-Solution-Processed, Highly Efficient and Stable Green Light-Emitting Devices Based on Zn-Doped CsPbBr₃/ZnS Heterojunction Quantum Dots, Journal of Materials Science. (2021) 56, 4161–4171.
10.1007/s10853-020-05527-0
CAS Web of Science® Google Scholar
64 Zhang F., Chen J., Zhou Y., He R., and Zheng K., Effect of Synthesis Methods on Photoluminescent Properties for CsPbBr₃ Nanocrystals: Hot Injection Method and Conversion Method, Journal of Luminescence. (2020) 220, 117023.
10.1016/j.jlumin.2019.117023
CAS Google Scholar
65 Kumar P. N., Kolay A., and Kumar S. K., et al.Counter Electrode Impact on Quantum Dot Solar Cell Efficiencies, ACS Applied Materials & Interfaces. (2016) 8, no. 41, 27688–27700, https://doi.org/10.1021/acsami.6b08921, 2-s2.0-84992217915.
10.1021/acsami.6b08921
CAS PubMed Web of Science® Google Scholar
66 Liu X., Zhang X., and Li L., et al.Stable Luminescence of CsPbBr₃/nCdS Core/Shell Perovskite Quantum Dots With Al Self-Passivation Layer Modification, ACS Applied Materials Interfaces. (2019) 11, no. 43, 40923–40931, https://doi.org/10.1021/acsami.9b14967, 2-s2.0-85073726347.
10.1021/acsami.9b14967
CAS PubMed Web of Science® Google Scholar
67 Lv W., Li L., and Xu M., et al.Improving the Stability of Metal Halide Perovskite Quantum Dots by Encapsulation, Advanced Materials. (2019) 31, no. 28, https://doi.org/10.1002/adma.201900682, 2-s2.0-85065960267, e1900682.
10.1002/adma.201900682
PubMed Web of Science® Google Scholar
68 Zhou W., Zhao Y., and Zhou X., et al.Light-Independent Ionic Transport in Inorganic Perovskite and Ultrastable Cs-Based Perovskite Soar Cells, The Journal of Physical Chemistry Letters. (2017) 8, no. 17, 4122–4128.
10.1021/acs.jpclett.7b01851
CAS PubMed Web of Science® Google Scholar
69 Xu T., Xiang W., and Yang J., et al.Interface Modification for Efficient and Stable Inverted Inorganic Perovskite Solar Cells, Advanced Materials. (2023) 35, no. 31, https://doi.org/10.1002/adma.202303346, e2303346.
10.1002/adma.202303346
CAS PubMed Google Scholar
70 Wang P., Zhang X., and Zhou Y., et al.Solvent-Controlled Growth of Inorganic Perovskite Films in Dry Environment for Efficient and Stable Solar Cells, Nature Communications. (2018) 9, https://doi.org/10.1038/s41467-018-04636-4, 2-s2.0-85048277823, 2225.
10.1038/s41467-018-04636-4
PubMed Web of Science® Google Scholar

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Enhanced Structural and Chemical Stability of New Inorganic Halide Perovskite Solar Cell Structures via Nickel Doping and Silicon Dioxide Encapsulation

Abstract

1. Introduction