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Engineering traps in Tm-doped calcium titanate for visible and near-infrared double band persistent luminescence bioimaging

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    1. Y surpassed Sc, La, Gd, and Lu in enhancing the persistent luminescence (PersL) of CaTiO3:Tm.

      Al, Ga, and In decreased the near-infrared (NIR) PersL of CaTiO3:Tm.

      Three basic laws were derived for optimizing the NIR PersL.

      CaTiO3:Tm, Y, Pr showed visible and NIR PersL at 613 and 803 nm, respectively.

      CaTiO3:Tm, Pr, Y was applied to multi-modal imaging both in vitro and in vivo.

  • CaTiO3:Tm (CTT) has unusual red-light charged near-infrared (NIR) persistent luminescence (PersL) property at ~ 800 nm. In this study, trap engineering was realized by co-doping CTT with 8 non-luminescent trivalent ions. Some basic laws in optimizing the NIR PersL of CTT were established based on the observation that rare earth dopants, including Sc/Y/La/Gd/Lu, at the A site of the ABO3 perovskite structure of CaTiO3 increased the PersL while the boron group dopants, including Al/Ga/In, at the B site led to decreased PersL. Y was found as an efficient co-dopant to realize enhanced NIR PersL in CaTiO3:Tm,Y (CTT-Y) with a ~60% enhancement vs. CTT. Thermal-stimulated luminescence (TSL) study indicate that Y is the most efficient element in generating abundant energy traps while slightly increased the trap depth from 320 to 326 K. Further, by choosing Pr as the 3rd dopant, visible-NIR double band fluorescence and PersL was realized in CaTiO3:Tm,Y,Pr (CTT-Y-Pr) at 613 and ~800 nm, which were ~5 and 2 times of those of CaTiO3:Tm,Pr (CTT-Pr), respectively. CTT-Y-Pr was applied to realize four-modal optical anti-counterfeiting imaging in vitro including visible fluorescence, visible PersL, invisible NIR fluorescence, and invisible NIR PersL. Moreover, visible fluorescence and NIR PersL imaging in vivo was applied to observe implanted tissue filler and its post-surgical tissue cleaning by using CTT-Y-Pr as an optical imaging contrast reagent, which was hard to retrieve once it was injected within body and formed unwanted tiny debris.
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  • [1] Jin L., Mo W., Wang Z., et al. (2025). Day-long organic persistent luminescence in flexible polymeric materials. Angew. Chem. Int. Edit. 64:e202506261. DOI:10.1002/anie.202506261

    View in Article CrossRef Google Scholar

    [2] Lin P., Shi J., Liu L., et al. (2025). Spatial confinement growth of high-performance persistent luminescence nanoparticles for image-guided sonodynamic therapy. Acta Biomater. 192:279−289. DOI:10.1016/j.actbio.2024.12.011

    View in Article CrossRef Google Scholar

    [3] Wang R., Shi J., Luo X., et al. (2025). Magnetic persistent luminescence nanoparticles repolarize tumor-associated macrophages for enhanced cancer immunotherapy. ACS Materials Lett. 7:2094−2104. DOI:10.1021/acsmaterialslett.5c00170

    View in Article CrossRef Google Scholar

    [4] Yao B., Xu F., Tian Z., et al. (2025). Strong persistent luminescence NaYF4-based nanoparticles combined with manipulated hyperfractionated irradiation for X-ray-excited photodynamic therapy enhancement. ACS Appl. Mater. Inter. 17:16561−16575. DOI:10.1021/acsami.4c20049

    View in Article CrossRef Google Scholar

    [5] Zhou L., Chen R., Li X., et al. (2025). Multicolor persistent luminescence for high-sensitivity optical temperature sensing, human motion detection, and multimodal anticounterfeiting materials. ACS Appl. Mater. Inter. 17:25451−25466. DOI:10.1021/acsami.5c01483

    View in Article CrossRef Google Scholar

    [6] Abulipizi G., Yu Z., Lin S., et al. (2023). Trap engineering in LiInSi2O6:Cr,Pr by excess cristobalite silica for X-ray activated near-infrared persistent luminescence imaging in vivo. Ceram. Int. 49:39664−39670. DOI:10.1016/j.ceramint.2023.09.321

    View in Article CrossRef Google Scholar

    [7] Chen K., Xiong Y., Wang D., et al. (2024). A facile strategy for achieving polymeric afterglow materials with wide color-tunability and persistent near-infrared luminescence. Adv. Funct. Mater. 34:202312883. DOI:10.1002/adfm.202312883

    View in Article CrossRef Google Scholar

    [8] Feng Y., Yang X., Rao Q., et al. (2024). Persistent luminescence lifetime-based near-infrared nanoplatform via deep learning for high-fidelity biosensing of hypochlorite. Anal. Chem. 96:7240−7247. DOI:10.1021/acs.analchem.4c00899

    View in Article CrossRef Google Scholar

    [9] Luo X., Shi J., Wang R., et al. (2024). Near-infrared persistent luminescence nanoprobe for early detection of atherosclerotic plaque. ACS Nano 18:6500−6512. DOI:10.1021/acsnano.3c12136

    View in Article CrossRef Google Scholar

    [10] Wang Y., Zhang P., Tian X., et al. (2025). Persistent scintillators for X-ray repetitive imaging with stable energy traps. J. Rare Earth. 43:1161−1168. DOI:10.1016/j.jre.2025.01.002

    View in Article CrossRef Google Scholar

    [11] Yan L.-X., Yan Z.-Y., Zhao X., et al. (2024). Size-independent boosting of near-infrared persistent luminescence in nano-phosphors via a magnesium doping strategy. J. Colloid. Interf. Sci. 662:11−18. DOI:10.1016/j.jcis.2024.02.008

    View in Article CrossRef Google Scholar

    [12] Zhu Y., Wen Y., Xie Y., et al. (2025). Intelligent hierarchical targeting near-infrared persistent luminescence nanosystem for improved nuclear delivery and simultaneous visualization/therapy of EBV-associated cancer. ACS Appl. Mater. Inter. 17:3072−3083. DOI:10.1021/acsami.4c20023

    View in Article CrossRef Google Scholar

    [13] Zhu Q., Xiahou J., Guo Y., et al. (2019). Zn3Ga2Ge2O10:Cr3+ uniform microspheres: Template-free synthesis, tunable bandgap/trap depth, and in vivo rechargeable near-infrared-persistent luminescence. ACS App. Bio. Mater. 2:577−587. DOI:10.1021/acsabm.8b00734

    View in Article CrossRef Google Scholar

    [14] Maldiney T., Bessiere A., Seguin J., et al. (2014). The in vivo activation of persistent nanophosphors for optical imaging of vascularization, tumours and grafted cells. Nat. Mater. 13:418−426. DOI:10.1038/Nmat3908

    View in Article CrossRef Google Scholar

    [15] Miao S. H., Lv X. L., Shan X. H., et al. (2024). Ultraviolet-B and near-infrared dual-band luminescence in Bi2+/Bi3+ codoped persistent phosphor for optical storage application. ACS Appl. Mater. Interfaces 16:23585−23595. DOI:10.1021/acsami.4c02522

    View in Article CrossRef Google Scholar

    [16] Ding Y. C., So B., Cao J. K., et al. (2023). Light delivery, acoustic read-out, and optical thermometry using ultrasound-induced mechanoluminescence and the near-infrared persistent luminescence of CaZnOS:Nd. Adv. Opt. Mater. 11:202300331. DOI:10.1002/adom.202300331

    View in Article CrossRef Google Scholar

    [17] Su J. Y., Pang R., Tan T., et al. (2024). A novel near-infrared emitting Sr2LuSbO6:Fe3+ phosphor with persistent luminescence performance. Adv. Opt. Mater. 12:202303187. DOI:10.1002/adom.202303187

    View in Article CrossRef Google Scholar

    [18] Zhou Z. H., He F. Q., Song E. H., et al. (2023). Broadband and multimode near-infrared emitter based on Cr3+-activated stannate for multifunctional applications. Adv. Opt. Mater. 11:202202466. DOI:10.1002/adom.202202466

    View in Article CrossRef Google Scholar

    [19] Zhao Y. L., Wang X. D., Wang Q. H., et al. (2024). Abnormal spectral broadening of ordered-structure near-infrared phosphor La2CaHfO6:Cr3+. J. Mater. Chem. C 12:10532−10539. DOI:10.1039/d4tc01036a

    View in Article CrossRef Google Scholar

    [20] Pan L., Delaey M., Wang Y., et al. (2024). Structural and optical properties of Cr ion-doped near-infrared long persistent luminescence silicogermanate phosphors with broad emission bands. J. Alloy. Compd. 983:173853. DOI:10.1016/j.jallcom.2024.173853

    View in Article CrossRef Google Scholar

    [21] Huang L., Lin L., Xie W., et al. (2020). Near-infrared persistent luminescence in a Cr3+-doped perovskite for low-irradiance imaging. Chem. Mater. 32:5579−5588. DOI:10.1021/acs.chemmater.0c00807

    View in Article CrossRef Google Scholar

    [22] Abulipizi G., Wang Y. X., Fang Y. L., et al. (2025). Persistent luminescent NaYTi2O6:Cr activated in the near-infrared bio-imaging window as a self-luminescent ceramic coating for visible Ti-implant in vivo. Ceram. Int. 51:6959−6967. DOI:10.1016/j.ceramint.2024.12.130

    View in Article CrossRef Google Scholar

    [23] Yu Z., Abulipizi G., Xu Y., et al. (2024). Stabilization of Ti3+ in CaTiO3 by doping Y3+ to generate visible light-activated near-infrared persistent luminescence. J. Alloy. Compd. 983:173879. DOI:10.1016/j.jallcom.2024.173879

    View in Article CrossRef Google Scholar

    [24] Xu Y., Abulipizi G., Wang Y., et al. (2024). Near-infrared persistent luminescence of CaTiO3:Cr,Y for imaging of bone implants using red-light illumination instead of X-ray. ACS Appl. Mater. Interfaces 16:55823−55831. DOI:10.1021/acsami.4c13865

    View in Article CrossRef Google Scholar

    [25] Abulipizi G., Zhou J., Qu C., et al. (2025). Unusual single band 803 nm persistent luminescence of Tm-doped calcium titanate charged in the near-infrared bio-imaging window. ACS Appl. Mater. Interfaces 17:36912−36921. DOI:10.1021/acsami.5c07800

    View in Article CrossRef Google Scholar

    [26] Kamioka H., Igarashi A., Watabe K., et al. (2025). Pr and Al doping effects on the red emission and long lasting afterglow in CaTiO3 single crystals. Opt. Mater. 159:116663. DOI:10.1016/j.optmat.2025.116663

    View in Article CrossRef Google Scholar

    [27] Yin S., Chen D. and Tang W. (2007). Combustion synthesis and luminescent properties of CaTiO3:Pr, Al persistent phosphors. J. Alloy. Compd. 441:327−331. DOI:10.1016/j.jallcom.2006.09.120

    View in Article CrossRef Google Scholar

    [28] Huang K., Li Z. J., Li Y., et al. (2021). Three-dimensional colloidal controlled growth of core-shell heterostructured persistent luminescence nanocrystals. Nano Lett. 21:4903−4910. DOI:10.1021/acs.nanolett.0c04940

    View in Article CrossRef Google Scholar

    [29] Qiao J. W., Zhang S., Zhou X. Q., et al. (2022). Near-infrared light-emitting diodes utilizing a Europium-activated calcium oxide phosphor with external quantum efficiency of up to 54.7%. Adv. Mater. 34:202201887. DOI:10.1002/adma.202201887.

    View in Article Google Scholar

    [30] Liu L., Shi J. P., Wang J. Y., et al. (2024). Biodegradable persistent luminescence nanoparticles as pyroptosis inducer for high-efficiency tumor immunotherapy. Adv. Sci. 11:202406340. DOI:10.1002/advs.202406340

    View in Article CrossRef Google Scholar

    [31] Rakov N., Matias F. and Xiao M. F. (2024). An efficient red light-emissive process from Eu3+ doped amorphous-derived CaAl2Si2O8 ceramic powders: Down-shifted luminescence with high thermal stability under 532 nm excitation. Ceram. Int. 50:16064−16075. DOI:10.1016/j.ceramint.2024.02.086

    View in Article CrossRef Google Scholar

    [32] V. Nikiforov I., V. Iliina E., Lazoryak B. I., et al. (2024). Photoluminescence, structural and antibacterial properties of co-doped β-Ca3(PO4)2-type phosphates Ca8CuRE(PO4)7 (RE = Eu-Er). J. Rare. Earth. 42:1658−1668. DOI:10.1016/j.jre.2023.07.023

    View in Article CrossRef Google Scholar

    [33] Van H. N., Cuong L. T., Nguyen D.-H., et al. (2025). Effect of Sr substituted on multifunction pure green emission of rare-earth-element doped HA/β-TCP nanocomposite for optical thermometer. Ceram. Int. 51:16894−16903. DOI:10.1016/j.ceramint.2024.07.119

    View in Article CrossRef Google Scholar

    [34] Piotrowski W. M., Ristic Z., Dramicanin M. D., et al. (2022). Modification of the thermometric performance of the lifetime-based luminescent thermometer exploiting Ti3+ emission in SrTiO3 and CaTiO3 by doping with lanthanide ions. J. Alloy. Compd. 906:164398. DOI:10.1016/j.jallcom.2022.164398

    View in Article CrossRef Google Scholar

    [35] Chen Y. F. and Pan Z. W. (2023). Red/NIR/SWIR multi-band persistent luminescent nanoparticles as ultrasensitive multi-channel tracers in water and crude oil/water emulsions. Nano Res. 16:12706−12712. DOI:10.1007/s12274-023-6116-x

    View in Article CrossRef Google Scholar

    [36] Yin X., Zhong H., Liu L., et al. (2024). X-ray-activated Bi3+/Pr3+ co-doped LiYGeO4 phosphor with UV and NIR dual-emissive persistent luminescence. J. Rare Earth. 42:955−961. DOI:10.1016/j.jre.2023.03.008

    View in Article CrossRef Google Scholar

    [37] Zhao T., Sun W., Wang S., et al. (2025). Low-dose X-ray induced long afterglow NIR luminescence from Cr3+ doped Zn1_xCdxGa2O4 spinel solid solutions. J. Rare Earth. 43:246−252. DOI:10.1016/j.jre.2023.12.006

    View in Article CrossRef Google Scholar

    [38] Wang Y., Abulipizi G., Zhou J., et al. (2025). Persistent luminescence of Dy-doped strontium pyrophosphate with double traps for room temperature qualitative and heated quantitative X-ray dosimetry by naked eyes. J. Alloy. Compd. 1022:179900. DOI:10.1016/j.jallcom.2025.179900

    View in Article CrossRef Google Scholar

    [39] Gao L., Liu Y., Su J., et al. (2025). Modulation of near-infrared afterglow luminescence in inorganic nanomaterials for biological applications. Adv. Mater. 37:202419349. DOI:10.1002/adma.202419349

    View in Article CrossRef Google Scholar

    [40] Shang R., Yang F., Gao G., et al. (2024). Bioimaging and prospects of night pearls-based persistence phosphors in cancer diagnostics. Exploration 4:20230124−20230124. DOI:10.1002/exp.20230124

    View in Article CrossRef Google Scholar

    [41] Wei Y. and Wang J. (2024). X-ray/γ-ray/ultrasound-activated persistent luminescence phosphors for deep tissue bioimaging and therapy. ACS Appl. Mater. Interfaces 16:56519−56544. DOI:10.1021/acsami.4c11585

    View in Article CrossRef Google Scholar

    [42] Yang X., Waterhouse G. I. N., Lu S., et al. (2023). Recent advances in the design of afterglow materials: mechanisms, structural regulation strategies and applications. Chem. Soc. Rev. 52:8005−8058. DOI:10.1039/d2cs00993e

    View in Article CrossRef Google Scholar

    [43] Cai G. Y., Delgado T., Richard C., et al. (2023). ZGSO Spinel nanoparticles with dual emission of NIR persistent luminescence for anti-counterfeiting applications. Materials 16:1132. DOI:10.3390/ma16031132

    View in Article CrossRef Google Scholar

    [44] Cai G. Y., Naillon T., Seguin J., et al. (2024). ZGSO:Cr3+, Ni2+ persistent phosphors with dual emission in NIR-I and SWIR ranges for bio-imaging applications. Small 20:202406507. DOI:10.1002/smll.202406507

    View in Article CrossRef Google Scholar

  • Cite this article:

    Ding L., Zhou J., Abulipizi G., et al. (2026). Engineering traps in Tm-doped calcium titanate for visible and near-infrared double band persistent luminescence bioimaging. The Innovation Materials 4:100200. https://doi.org/10.59717/j.xinn-mater.2026.100200
    Ding L., Zhou J., Abulipizi G., et al. (2026). Engineering traps in Tm-doped calcium titanate for visible and near-infrared double band persistent luminescence bioimaging. The Innovation Materials 4:100200. https://doi.org/10.59717/j.xinn-mater.2026.100200

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