Simultaneous broadening and enhancement of Cr³⁺ photoluminescence in Ba₃ZrTa₄O₁₅ by chemical unit co-substitution

Abstract

Long-wavelength broadband near-infrared (NIR) phosphors serve as a cornerstone for versatile NIR spectroscopy applications. However, achieving simultaneous enhancement in both bandwidth and luminescence intensity at long wavelengths remains a significant challenge. Here, we report two novel NIR phosphors, Ba₃ZrTa₄O₁₅:Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:Cr³⁺, both exhibiting dual luminescent centers (Cr1 and Cr2). Ba₃ZrTa₄O₁₅:0.04Cr³⁺ emits at 905 nm with a bandwidth of 239 nm under 470 nm excitation. Upon substituting Zr⁴⁺–Zr⁴⁺ with Al³⁺–Ta⁵⁺, the bandwidth increases to 290 nm (room temperature), and the luminescence intensity rises 4 fold. The enhanced luminescence intensity is attributed to lattice contraction, which not only suppresses the non-radiative transitions of Cr1 but also reduces the energy transfer distance between Cr1 and Cr2. This finding offers a new avenue for improving the performance of ultra-broadband NIR phosphors.

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1. Introduction

Near-infrared (NIR) spectroscopy has emerged as a powerful analytical tool across numerous fields, including food quality control, biomedical imaging, and non-destructive testing.^1–4 Its unique ability to penetrate biological tissues, avoid visible light interference, and interact with molecular vibrations (e.g., O–H and C–H bonds) makes it indispensable for applications requiring high sensitivity and minimal invasiveness.^5–9 The development of efficient, broadband NIR light sources is essential to fully harness these applications. Traditional NIR light sources often suffer from narrow emission bands or bulky designs, limiting their utility in portable devices and spectral analysis.^10–13 Phosphor-converted light-emitting diodes (pc-LEDs), which combine NIR phosphors with commercial blue chips, have emerged as a promising alternative, offering tunable emission and compact form factors.^14–17 However, developing high-performance NIR phosphors remains a critical challenge.

Cr³⁺ stands out as a compelling activator for NIR luminescence, owing to its unique 3d³ electronic configuration that enables tunable emission via crystal field modulation.^18–20 In octahedral coordination environments, Cr³⁺ exhibits two characteristic emission modes: sharp-line emissions from spin-forbidden ²E_g → ⁴A_2g transitions under strong crystal fields and broadband emissions from spin-allowed ⁴T_2g → ⁴A_2g transitions under weak crystal fields.^21–24 This versatility has driven its widespread exploration in NIR phosphors. However, in weak crystal fields that emit at longer wavelengths (≥850 nm), the luminescence efficiency plummets.^25–28 This is attributed to enhanced electron–phonon coupling, which increases the probability of non-radiative transitions.^29,30 To overcome these limitations, strategies that simultaneously broaden the emission bandwidth and improve long-wavelength emission intensity are essential.

Expanding the emission bandwidth through multi-site occupation strategies is a current research focus.^31–37 In such materials, Cr³⁺ ions occupy multiple distinct crystallographic sites, each experiencing a unique crystal field strength and thereby emitting light at different peak wavelengths. The superposition of these individual emission bands results in an ultra-broadband spectrum, which is highly suitable for applications requiring wide spectral coverage.^15,38,39 In our previous work, by substituting In³⁺ for M in Na₄M₃Ta(PO₄)₆ (M = Al³⁺, Ga³⁺), the bandwidth expanded from 134 nm for a single luminescent center to 232 nm for a two-luminescent-center system.⁴⁰ These achievements highlight the potential of multisite engineering to overcome the narrowband constraint of single-center Cr³⁺ luminescence. However, a critical bottleneck persists: the longer-wavelength emission centers in these multi-site systems cannot deliver sufficient intensity due to the inherent properties of weak crystal fields. This limits the practical utility of ultra-broadband phosphors, as the long-wavelength components are vital for deep-tissue imaging and spectral analysis of long-wavelength-absorbing molecules. Resolving this disparity requires strategies to boost the emission strength of long-wavelength centers while preserving the broadband advantage of multisite occupation.

Here, we report a chemical unit co-substitution strategy to simultaneously broaden and enhance Cr³⁺ photoluminescence. In both Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and its modified Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺, two distinct Cr³⁺ emission centers (Cr1 and Cr2) are identified, between which energy transfer occurs. Substitution of Zr⁴⁺–Zr⁴⁺ pairs with Al³⁺–Ta⁵⁺ units effectively suppresses non-radiative transitions at the Cr1 site and promotes efficient energy transfer from Cr1 to Cr2. Following substitution, the overall emission intensity of Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ increased 4 fold compared to that of Ba₃ZrTa₄O₁₅:0.04Cr³⁺, with a bandwidth of up to 290 nm at room temperature. These findings offer a new pathway for enhancing the performance of Cr³⁺-activated NIR phosphors.

2. Materials preparation and characterization

2.1 Sample preparation

Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ phosphors were synthesised via a solid-state reaction method. High-purity starting materials, including BaCO₃ (AR), Al₂O₃ (AR), ZrO₂ (AR), Cr₂O₃ (AR), and Ta₂O₅ (AR), were weighed according to the stoichiometric ratios of the respective chemical formulae. The thoroughly mixed reactants were sintered at 1400 °C for 5 h. The resulting products were subsequently cooled to room temperature, ground into fine powders, and ultimately obtained as the final phosphor materials.

2.2 Characterization

The crystal structure information was identified using a BRUKER D8 ADVANCE X-ray diffractometer. GSAS software was employed to perform Rietveld refinement.⁴¹ An Edinburgh FLS-1000 fluorescence spectrophotometer was used to acquire and analyse the excitation, emission spectra, thermal stability, and fluorescence lifetime. SEM photographs and elemental mapping were obtained using a JEOL JEM-2100F scanning electron microscope equipped with an Oxford Xplore 30 attachment. Diffuse reflection spectra were acquired using a Shimadzu UV-3600i Plus. X-ray photoelectron spectroscopy (XPS) was performed using a Thermo Scientific K-Alpha. The quantum yield (QY) was assessed with the Quantaurus-QY Plus C13534-11 (Hamamatsu Photonics).

3. Results and discussion

3.1 Crystal structure

Ba₃ZrTa₄O₁₅ belongs to the tetragonal crystal system and has the P4bm space group.⁴² As shown in Fig. 1, the structure contains four distinct coordination polyhedra: Ba1O₁₂, Ba2O₁₅, (Zr/Ta)1O₆, and (Zr/Ta)2O₆. The Ba1O₁₂ and Ba2O₁₅ polyhedra interconnect via face-sharing, extending along the a and b axes. The (Zr/Ta)1O₆ and (Zr/Ta)2O₆ octahedra occupy interstices within the three-dimensional framework formed by Ba1O₁₂/Ba2O₁₅ polyhedra and exhibit face-sharing connectivity with both polyhedral types. The two octahedra provide alternative occupation sites for Cr³⁺ ions. These four polyhedral units stack sequentially along the c-axis to form a layered architecture. Within the octahedral layer, (Zr/Ta)1O₆ and (Zr/Ta)2O₆ exhibit vertex-sharing connectivity. The ratio of the two octahedra in the unit cell is (Zr/Ta)1O₆ : (Zr/Ta)2O₆ = 1 : 4.

Fig. 1 Crystal structure of Ba₃ZrTa₄O₁₅.

The X-ray diffraction (XRD) peaks of the Ba₃ZrTa₄O₁₅:0.04Cr³⁺ phosphor precisely match the ICSD#151421 (Ba₃ZrTa₄O₁₅) reference pattern, confirming successful synthesis. After substituting Zr⁴⁺ (0.72 Å, CN = 6) with 0.5Al³⁺ + 0.5Ta⁵⁺ (0.535 Å and 0.64 Å, CN = 6), the diffraction peaks of the resultant Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ phosphor shift toward higher angles, demonstrating lattice contraction, as shown in Fig. 2a. To quantify lattice parameter changes before and after substitution, Rietveld refinements were performed for Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. As shown in Fig. 2b, the calculated diffraction patterns highly match the measured diffraction data with the reliability factors (R_p, R_wp, χ²) converging to (3.74%, 5.23%, 1.58) and (4.46%, 5.79%, 1.60) for Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺, respectively. The final crystallographic data are summarised in Table 1, with detailed atomic coordinates provided in Table S1 in the SI. Upon Al³⁺–Ta⁵⁺ co-substitution for Zr⁴⁺–Zr⁴⁺, the lattice parameters a and b contract from 12.6843(2) to 12.5613(4) Å and c contracts from 3.9918(6) to 3.9473(2) Å, resulting in a unit cell volume reduction from 642.2583 to 622.8368 ų.

Fig. 2 (a) XRD patterns, (b) Rietveld refinement results, (c) XPS spectra, and (d) EDS mapping images of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺.

Table 1 Crystallographic data of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺

Samples	Ba3ZrTa4O15:0.04Cr^3+	Ba3Al0.5Ta4.5O15:0.04Cr^3+
Crystal system	Tetragonal
Space group	P4bm
Lattice parameters
a/b (Å)	12.6843(2)	12.5613(4)
c (Å)	3.9918(6)	3.9473(2)
α/β/γ (°)	90	90
Cell volume (Å^3)	642.2583	622.8368
R p	3.74	4.46
R wp	5.23	5.79
χ ^2	1.58	1.60

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Fig. 2c presents the XPS of the synthesised samples, while Fig. 2d displays the corresponding elemental mapping. These results confirm the homogeneous spatial distribution of the constituent elements. High-resolution XPS analysis (inset of Fig. 2c) verifies the exclusive presence of Cr³⁺ species.

3.2 Photoluminescence

Fig. 3a shows the diffuse reflectance (DR) spectra of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. Three broad absorption bands are observed in the ranges 300–400 nm, 400–600 nm, and 600–700 nm, which correspond to the spin-allowed transitions ⁴A_2g → ⁴T_1g (⁴P), ⁴A_2g → ⁴T_1g (⁴F), and ⁴A_2g → ⁴T_2g (⁴F) of Cr³⁺, respectively.^43–45 The excitation spectra (Fig. 3b) exhibit bands consistent with those in the DR spectra. Under 470 nm excitation, Ba₃ZrTa₄O₁₅:Cr³⁺ shows a broad emission spanning 650–1200 nm with a full width at half maximum (FWHM) of 239 nm, attributed to the ⁴T_2g → ⁴A_2g transition of Cr³⁺.⁴⁶ After substituting Zr⁴⁺ with Al³⁺–Ta⁵⁺, the bandwidth remained unchanged, while the emission band exhibited a slight red shift, accompanied by a 2.8-fold increase in luminescence intensity and an increase in QY from 8.48% to 18.87%, as shown in Fig. 3b and Fig. S1 and S2. Additionally, the spectral shape changed, with a clear peak emerging at 754 nm for Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. Both samples exhibited a weak peak at 679 nm, originating from the ²E_g → ⁴A_2g transition of Cr³⁺. When excited by 328 nm light, the emission intensity of Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ increased 4 fold compared to that of Ba₃ZrTa₄O₁₅:0.04Cr³⁺. Meanwhile, the peak at 754 nm becomes sharper, with the FWHM at room temperature expanding to 290 nm. Such a broad emission band is highly advantageous for NIR spectral applications.

Fig. 3 (a) DR spectra, (b) excitation spectra, and (c) emission spectra of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. (d) The excitation spectra at different monitoring wavelengths, and (e) emission spectra at different excitation wavelengths. (f) Decay curves at different monitoring wavelengths.

The significant change in the emission peak shape suggests the potential existence of two luminescent centers. To investigate the properties of these two luminescent centers, the excitation spectra of Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ phosphor were studied at different monitoring wavelengths, along with its emission spectra under different excitation conditions, as shown in Fig. 3d and e. When monitoring at 679 nm, the excitation spectrum exhibits two peaks at 396 and 470 nm. Based on comparison with the Tanabe–Sugano diagram, the sharp peak at 470 nm is assigned to the ⁴A_2g → ²T_2g (²G) transition of Cr³⁺.^47,48 Monitoring at 754 nm results in a significant decrease in the 470 nm excitation peak, a broadening of the 396 nm peak, and the emergence of two additional excitation bands at 300 and 620 nm. As the monitoring wavelength increases, a broad excitation band appears in the 400–500 nm range, and the excitation peaks at 300 nm and 620 nm exhibit a red shift. Selective emission spectra reveal a gradual decrease in the 754 nm emission component with increasing excitation wavelength, whereas the 908 nm emission remains unchanged. When excited at 720 nm, the 754 nm peak vanishes entirely. Furthermore, luminescence decay lifetimes at 908 and 1200 nm are nearly identical, while the lifetime at 754 nm is significantly longer (Fig. 3f). Similar behaviour is observed in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ (Fig. S3 in the SI). Fig. S4 shows the emission spectra of low-doping-concentration samples (Ba₃ZrTa₄O₁₅:0.005Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.005Cr³⁺). The emission spectra exhibit two well-resolved emission peaks. The clear separation of the two peaks directly demonstrates that they originate from Cr³⁺ occupying two distinct crystallographic sites. All these results demonstrate the presence of two luminescent centers in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺, with emission wavelengths at 754 nm (Cr1) and 908 nm (Cr2), respectively.

To investigate the mechanism underlying the enhanced luminescence intensity resulting from Al³⁺–Ta⁵⁺ substitution for Zr⁴⁺–Zr⁴⁺, emission spectra at 80 K were measured, as shown in Fig. 4a. The Cr1 emission component is significantly more intense in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ than in Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺, while Cr2 remains comparable between the two. At 80 K, the shorter decay lifetime of Cr1 in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ suggests a higher radiative transition rate (Fig. 4b). When the temperature rises to room temperature, the lifetime of Cr1 in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ remains shorter than that in Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ (Fig. 4c). Since the emission intensity of Cr1 in Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ at room temperature is significantly higher than that in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ (Fig. 3c), we can deduce that Cr1 in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ undergoes more severe non-radiative transitions compared to Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. This indicates that Al³⁺–Ta⁵⁺ substitution for Zr⁴⁺–Zr⁴⁺ suppresses the non-radiative transitions of Cr1.

Fig. 4 (a) The emission spectra of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ at 80 K. (b–f) Decay curves of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ monitored at 754 and 908 nm at temperatures of 80 and 298 K.

Under 720 nm excitation, which exclusively activates Cr2 emission (as shown in Fig. 3e), the decay profiles of both compounds can be fitted by a mono-exponential function (Fig. 4d). In contrast, under 328 nm excitation, the decay curves of both Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ exhibit an additional slow-decay component distinct from that of Cr1. Additionally, the radiative probability of the fast-decaying component of Cr³⁺ in both Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ increases, demonstrating a higher radiative probability of Cr2, suggesting a potential energy transfer mechanism between Cr1 and Cr2 (Fig. 4e). Spectral overlap between the Cr1 emission and Cr2 excitation bands provides further evidence for energy transfer between Cr1 and Cr2 (Fig. 3d and e). At 298 K, as shown in Fig. 4f, Ba₃ZrTa₄O₁₅:0.04Cr³⁺ decays faster than Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺, indicating a larger non-radiative transition probability. These results demonstrate energy transfer between Cr1 and Cr2.

Fig. 5 illustrates the changes in the octahedral coordination environments before and after substitution. Following the replacement of 0.5Zr⁴⁺–0.5Zr⁴⁺ with 0.5Al³⁺–0.5Ta⁵⁺, the elemental ratio within the octahedra shifts from Zr : Ta = 1 : 4 to Al : Ta = 1 : 9. The average bond length of the (Zr/Al/Ta)1O₆ octahedron decreases from 2.0011 to 1.8539 Å, accompanied by a contraction in volume from 10.4974 to 8.3656 ų. The distances in octahedra are listed in Table S2. This reduction in bond length results from the smaller ionic radius of Al³⁺/Ta⁵⁺ compared to Zr⁴⁺. In contrast, the average bond length of the (Zr/Al/Ta)2O₆ octahedron increases slightly from 2.0015 to 2.0161 Å, with a marginal volume expansion from 10.7278 to 10.8034 ų. This change is abnormal, as the substitution of larger Zr⁴⁺ with smaller Al³⁺/Ta⁵⁺ should cause contraction, yet it coincides with the spectral redshift. This may be related to the contraction of the neighboring polyhedra Ba1O₁₂ and Ba2O₁₅. Anomalous expansion also occurs in LiGaP₂O₇:Cr³⁺.⁴⁹ Based on the spectral profiles, we assign the Cr1 center to the (Zr/Al/Ta)1O₆ site and Cr2 to the (Zr/Al/Ta)2O₆ site. The structural analysis indicates that the compression of the (Zr/Al/Ta)1O₆ octahedron enhances its structural rigidity, thereby reducing the probability of non-radiative transitions at the Cr1 site. Furthermore, the distance between the (Zr/Al/Ta)1O₆ and (Zr/Al/Ta)2O₆ octahedra decreases from 3.755 to 3.725 Å after substitution, facilitating more efficient energy transfer between the two luminescent centers.

Fig. 5 Variation in the octahedral coordination environment before and after substitution.

Fig. 6a and b present the temperature-dependent emission spectra (80–483 K) of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺, respectively. Both compounds exhibit two distinct emission bands, consisting of a narrow and a broad component. At low temperatures, the broadband emission dominates the spectrum. As the temperature increases, the overall intensity (Cr1 + Cr2) gradually decreases due to thermal quenching and shows a consistent declining trend in both materials.^50,51 At 80 K, Cr1 in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ exhibits a sharper and more intense emission peak compared to that in Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. With increasing temperature, the emission intensity of Cr1 in both compounds rapidly weakens. However, the decay rate in Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ is significantly slower than that in Ba₃ZrTa₄O₁₅:0.04Cr³⁺ (Fig. 6c), indicating that Al³⁺–Ta⁵⁺ substitution effectively suppresses non-radiative transitions at the Cr1 sites. This finding is consistent with previous structural and spectroscopic analyses. Additionally, as the temperature increases, the emission spectrum undergoes a blue shift (Fig. S5 in the SI), further confirming the presence of multiple luminescent centers.

Fig. 6 Temperature-dependent emission spectra of (a) Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and (b) Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. (c) Normalized emission intensity and (d) FWHM of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ at different temperatures.

Fig. 6d shows the temperature dependence of FWHM. Between 80 and 230 K, FWHM is primarily controlled by Cr2, with Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺ exhibiting nearly identical FWHM values that gradually increase with rising temperature, indicating enhanced electron–phonon coupling.^52,53 Above 230 K, both Cr1 and Cr2 contribute to the FWHM. Owing to Cr1's superior thermal stability in Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺, a remarkable FWHM of 295 nm is achieved at 333 K through the combined emission from both centers, which is highly favourable for spectroscopic applications. As shown in Fig. 7, the characteristic absorption peaks of water and ethanol can be calculated from the emission spectra before and after transmission through water and ethanol. The results indicate that the characteristic absorption of water occurs at approximately 960 and 1154 nm, while that of ethanol occurs at approximately 908, 1014, and 1185 nm. This demonstrates its potential application in NIR spectroscopy technology.

Fig. 7 The calculated transmission spectra of (a) water and (b) alcohol measured using Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺.

4. Conclusion

In summary, this study systematically investigated the NIR luminescence properties and enhancement mechanisms of Ba₃ZrTa₄O₁₅:0.04Cr³⁺ and the Al³⁺–Ta⁵⁺ co-substituted sample Ba₃Al_0.5Ta_4.5O₁₅:0.04Cr³⁺. The results indicate that Al³⁺–Ta⁵⁺ substitution significantly enhances luminescence performance, with the emission intensity increasing by 2.8 times under 470 nm excitation. When the excitation wavelength is shifted to 328 nm, the emission intensity further increases by 4 times. Spectral and lifetime analyses confirmed the presence of two luminescent centers, Cr1 (754 nm) and Cr2 (908 nm), originating from (Zr/Al/Ta)1O₆ and (Zr/Al/Ta)2O₆ octahedra, respectively. The dual-emission center enables ultra-broadband emission up to 290 nm. The enhancement mechanism stems from the synergistic effects of structural modification and energy transfer. Al³⁺–Ta⁵⁺ substitution shortens the bond length of (Zr/Al/Ta)1O₆ and increases its rigidity, thus suppressing the non-radiative transitions of Cr1. Simultaneously, the structural modification reduces the inter-octahedral spacing (3.755 → 3.725 Å), facilitating energy transfer from Cr1 to Cr2. This study provides a novel approach for enhancing the luminescence performance of Cr³⁺-activated long-wavelength NIR phosphors. The prepared broadband NIR phosphors hold potential value for spectral applications.

Conflicts of interest

There are no conflicts to declare.

Data availability

The supporting data are included in the supplementary information (SI). Supplementary information (SI): Supplementary Tables S1 and S2, and Figures S1–S5. Supplementary information is available. See DOI: https://doi.org/10.1039/d5qi02501j.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (12504465 and 12474415), the Natural Science Foundation of Liaoning Province (2025-BS-0441), and the Natural Science Foundation of Jilin Province (20220101208JC).

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