Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2025 May;12(18):e2412459.
doi: 10.1002/advs.202412459. Epub 2025 Mar 17.

In Situ Halide Vacancy Tuning of Low-Dimensional Lead Perovskites to Realize Multiple Adjustable Luminescence Performance

Chen Sun  1   2 , Chang-Qing Jing  1   3 , Dong-Yang Li  1   2 , Meng-Han Dong  1 , Ming-Xue An  1 , Zhong-Hui Zhang  1 , Cheng-Yang Yue  1 , Honghan Fei  2 , Xiao-Wu Lei  1
Affiliations

In Situ Halide Vacancy Tuning of Low-Dimensional Lead Perovskites to Realize Multiple Adjustable Luminescence Performance

Chen Sun et al. Adv Sci (Weinh). 2025 May.

Abstract

Surface defects play a crucial role in the photophysical properties and optoelectronic applications of perovskite materials. Although luminescent efficiency is improved through post-synthetic defect passivation, comprehensive optimization of photoluminescent performance via defect chemistry remains a significant challenge. Herein, a successful defect engineering strategy is demonstrated toward 0D perovskite of [DADPA]PbBr5 (DADPA = diaminodipropylamine) single crystal to achieve multiple adjustable luminescent properties. Through fine-tuning the crystallization environment to diminish Br vacancy (VBr), [DADPA]PbBr5 displays gradually evolutionary luminescence range from broadband blue-white to narrow green light emissions, with continuously adjustable dominant wavelengths (445-535 nm) and linewidths (134-27 nm). Meanwhile, the quantum yields increase significantly from 3.7% to 80.8%, and lifetime extends from 5.4 to 57.7 ns. This is the pioneering discovery in perovskite chemistry for simultaneous modification of multi-dimensional luminescent performances. Combined spectroscopic investigations and first-principles calculations indicate that the reducing VBr significantly narrows the bandgap and inhibits nonradiative recombination, which attenuates interband trap-state-associated broadband emission and facilitates the formation of bound exciton for enhanced emission efficiency. More remarkably, this universal strategy can be extended to other perovskite systems with similar luminescent adjustability, paving the way for applications of diverse perovskites with improved optoelectronic performance.

Keywords: 0D organic‐inorganic halide perovskites; adjustable emission; defect passivation; halogen vacancies.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Schematic illustration of surface defect engineering on exciton diffusion processes, electronic in‐gap states, and luminescence transformation in lead halide perovskites. The dashed circles represent V Br.
Figure 1
Figure 1
a) Solvothermal preparation process for serial [DADPA]PbBr5 single crystals; b) corresponding photo images under sunlight and 365 nm UV light; c) evolutional PL emission spectra from white to green light emission.
Figure 2
Figure 2
a) The crystal structures of [Pb2Br10]6− dimers (up) and packing crystal structure (down) of [DADPA]PbBr5; b) average ratio of Pb and Br based on the ICP results (atom %); c) powder X‐ray diffraction patterns of W‐, B‐, and G‐[DADPA]PbBr5; d,e) detailed comparison of powder X‐ray diffraction patterns between 22–31° and 7–15° for W‐, B‐, and G‐[DADPA]PbBr5; f) logarithmic absorption coefficient extracted from optical absorption spectra as a function of photon energy, and corresponding Urbach energies for W‐, B‐, and G‐[DADPA]PbBr5; g) comparison of the HRXPS peaks for Br‐3d, Pb‐4f, C‐1s, N‐1s of W‐, B‐, and G‐ [DADPA]PbBr5.
Figure 3
Figure 3
Systematical characterizations of PL properties for W‐, B‐ and G‐[DADPA]PbBr5; a–c) absorption and emission spectra of W‐, B‐ and G‐[DADPA]PbBr5 respectively; d–f) power density dependent PL emission intensity of W‐, B‐ and G‐[DADPA]PbBr5 respectively; g) time‐resolved PL spectroscopy of W‐, B‐ and G‐[DADPA]PbBr5; h) the absolute PLQYs of W‐, B‐ and G‐[DADPA]PbBr5; i) the radiative and nonradiative recombination rate (K r and K nr) for W‐, B‐ and G‐[DADPA]PbBr5.
Figure 4
Figure 4
Fs‐TA spectra of W‐ (up) and G‐[DADPA]PbBr5 (down): a and d) Pseudo contour plot as a function of wavelength and delay time; c and d) Decay associated TA spectra recorded at different delay times calculated by singular value decomposition analysis; e and f) Normalized PIA decay dynamics of fs‐TA signals.
Figure 5
Figure 5
a–c) 3D color maps of PL emission at varied temperatures for W‐, B‐ and G‐[DADPA]PbBr5; d–f) experimental and fitted emission intensity versus reciprocal temperature for W‐, B‐ and G‐[DADPA]PbBr5; g–i) calculated band structure and DOS of W‐, B‐ and G‐[DADPA]PbBr5.
Figure 6
Figure 6
a) The simulated adsorption models of DMA and NMA molecule; b,c) charge density difference and adsorption formation energies of DMA b) and NMA c) molecule on the [DADPA]PbBr5 perovskite surface via N‐, O‐ and double N‐, O‐band connections. d) Schematic illustration of the possible photophysical mechanism for the W‐, B‐, and G‐[DADPA]PbBr5.
Figure 7
Figure 7
Structural and PL characterizations of [TMPDA]2Pb3Br10 family: a) The packing structure based on [TMPDA]2+ cation and 1D [Pb3Br10]4− chain; b) powder X‐ray diffraction patterns; c) absorption and emission spectra (inset: structural diagram and photo images under UV light); d) radar map of comparisons for λ em (nm), FWHM (nm), PLQY (%), time‐resolved PL decay (ns), radiative (K r) and nonradiative (K nr) recombination rates of W‐, B‐ and G‐ [TMPDA]2Pb3Br10.
See this image and copyright information in PMC

References

    1. a) Du Z., Lai Y., Bai R., Wang B., Zheng Q., Xu C., Lu T., Pei J., Li W., Wu Y.‐N., Liu K., Liu Y., Fu E., Li J.‐F., Yang Y., Li Q., Adv. Mater. 2023, 35, 2212213; - PubMed
    2. b) Cahn R. W., Nature 1999, 397, 656;
    3. c) Szot K., Speier W., Bihlmayer G., Waser R., Nat. Mater. 2006, 5, 312; - PubMed
    4. d) Park J.‐S., Calbo J., Jung Y.‐K., Whalley L. D., Walsh A., ACS Energy Lett. 2019, 4, 1321.
    1. a) Pastor E., Sachs M., Selim S., Durrant J. R., Bakulin A. A., Walsh A., Nat. Rev. Mater. 2022, 7, 503;
    2. b) Sun X., Zhang X., Xie Y., Matter 2020, 2, 842.
    1. a) Xiong J., Di J., Xia J., Zhu W., Li H., Adv. Funct. Mater. 2018, 28, 1801983;
    2. b) Wang R., Liu Q., Dai S., Liu C.‐M., Liu Y., Sun Z.‐Y., Li H., Zhang C.‐J., Wang H., Xu C.‐Y., Shao W.‐Z., Meixner A. J., Zhang D., Li Y., Zhen L., Small 2024, 20, 2305658; - PubMed
    3. c) Li H., Zhou Y., Tu W., Ye J., Zou Z., Adv. Funct. Mater. 2015, 25, 998.
    1. a) Park K., Lee J.‐H., Lee J.‐W., ACS Energy Lett. 2022, 7, 1230;
    2. b) Seth S., Ahmed T., De A., Samanta A., ACS Energy Lett. 2019, 4, 1610;
    3. c) Srivastava V., Liu W., Janke E. M., Kamysbayev V., Filatov A. S., Sun C.‐J., Lee B., Rajh T., Schaller R. D., Talapin D. V., Nano Lett. 2017, 17, 2094. - PubMed
    1. Gruber A., Dräbenstedt A., Tietz C., Fleury L., Wrachtrup J., Borczyskowski C. v., Science 1997, 276, 2012.

LinkOut - more resources