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Controllable p- and n-type behaviours in emissive perovskite semiconductors

Nature volume 633, pages 344–350 (2024)Cite this article

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Abstract

Reliable control of the conductivity and its polarity in semiconductors is at the heart of modern electronics1,2,3,4,5,6,7, and has led to key inventions including diodes, transistors, solar cells, photodetectors, light-emitting diodes and semiconductor lasers. For archetypal semiconductors such as Si and GaN, positive (p)- and negative (n)-type conductivities are achieved through the doping of electron-accepting and electron-donating elements into the crystal lattices, respectively1,2,3,4,5,6. For halide perovskites, which are an emerging class of semiconductors, mechanisms for reliably controlling charge conduction behaviours while maintaining high optoelectronic qualities are yet to be discovered. Here we report that the p- and n-type characteristics in a wide-bandgap perovskite semiconductor can be adjusted by incorporating a phosphonic acid molecular dopant with strong electron-withdrawing abilities. The resultant carrier concentrations were more than 1013 cm−3 for the p- and n-type samples, with Hall coefficients ranging from −0.5 m3 C−1 (n-type) to 0.6 m3 C−1 (p-type). A shift of the Fermi level across the bandgap was observed. Importantly, the transition from n- to p-type conductivity was achieved while retaining high photoluminescence quantum yields of 70–85%. The controllable doping in the emissive perovskite semiconductor enabled the demonstration of ultrahigh brightness (more than 1.1 × 106 cd m−2) and exceptional external quantum efficiency (28.4%) in perovskite light-emitting diodes with a simple architecture.

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Fig. 1: n-type to p-type transition in a wide-bandgap perovskite through molecular doping.
Fig. 2: DFT calculations for the molecular doping process.
Fig. 3: Device architecture and performance of HTL-free PeLEDs.
Fig. 4: Origins of device performance improvements.

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information. The source data files are available at Figshare (https://doi.org/10.6084/m9.figshare.26048218)56.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (grant no. 2022YFA1204800), the National Natural Science Foundation of China (grant nos. 62274144 and 62005243), the Zhejiang Provincial Government, the Natural Science Foundation of Zhejiang Province (grant no. LR21F050003) and the Fundamental Research Funds for the Central Universities. We acknowledge W. Guo and J. Zhang of Juanhu Lake Laboratory for the KPFM measurements, T. Sun and Z. Wang of Zhejiang University of Technology for the STEM measurements, and Y. Yang of the International Research Center for Functional Polymers at Zhejiang University for NMR and FTIR measurements. We thank the technicians at Shenzhen Huasuan Technology for their assistance with the theoretical calculations. We thank J. Sun from Shiyanjia Lab for the inductively coupled plasma optical emission spectroscopy (ICP-OES) measurements. We thank T. Liu of Guangxi University for assistance with device encapsulation.

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Authors and Affiliations

  1. State Key Laboratory of Extreme Photonics and Instrumentation, College of Optical Science and Engineering, International Research Center for Advanced Photonics, Zhejiang University, Hangzhou, China

    Wentao Xiong, Weidong Tang, Gan Zhang, Yichen Yang, Yangning Fan, Ke Zhou, Chen Zou, Baodan Zhao & Dawei Di

  2. ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, China

    Chen Zou, Baodan Zhao & Dawei Di

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  1. Wentao Xiong
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Contributions

D.D., B.Z. and W.X. conceived the study. W.X. planned the experiments under the guidance of D.D and B.Z. W.X. fabricated the efficient and bright HTL-free PeLEDs, characterized the devices and analysed the data. W.X. prepared the doped perovskite samples. W.X. and W.T. performed the UPS and XPS measurements. G.Z. performed the device simulations using COMSOL. W.X. and W.T. prepared the perovskite p–n junction diodes. C.Z., Y.Y. and Y.F. performed the transient photoluminescence measurements. W.X., W.T. and K.Z. performed the Hall effect measurements. W.X. prepared the initial draft of the manuscript, which was revised by D.D. and B.Z. All authors contributed to the work and commented on the paper. D.D. and B.Z. supervised the project.

Corresponding authors

Correspondence to Baodan Zhao or Dawei Di.

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Competing interests

D.D., W.X. and B.Z. are inventors on CN patent application no. 202410202637.2. The other authors declare no competing interests.

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Extended data figures and tables

Extended Data Fig. 1 Structural characterization of undoped and 4PACz-doped perovskite samples.

a, XRD patterns. b,c, The STEM images of undoped and 4PACz-doped perovskite samples, respectively. d,e, The SEM images of undoped and 4PACz-doped perovskite samples, respectively (scale bar: 500 nm). f,g, The AFM height images of undoped and 4PACz-doped perovskite samples, respectively (scale bar: 400 nm). Rq denotes the root mean square (r.m.s.) of roughness.

Extended Data Fig. 2 Characterization of chemical interactions in solution and solid films.

a, 31P NMR spectra of 4PACz, and 4PACz with PbBr2 in deuterated DMSO. Compared with pure 4PACz compound, the 31P NMR signals of 4PACz/PbBr2 undergo an upfield shift, indicating the binding between the PA moiety on 4PACz and the Pb2+ cations. b, 1H NMR of 4PACz in deuterated-DMSO solution with FABr. * indicates protons on ammonium. The 1H NMR results demonstrate the formation of hydrogen bonding between 4PACz and FA+, which could significantly affect the crystallization process of perovskite films during spin-coating. c, XPS spectra (O 1s) of 4PACz and 4PACz-doped perovskites. Two peaks (P-OH groups at 533.6 eV, and P=O group at 532.3 eV) can be identified from the O 1s spectrum of 4PACz, while the O 1s spectrum of 4PACz-doped perovskites can be constructed by three peaks (P-OH groups at 532.6 eV, P=O group at 531.6 eV, and P-O-Pb group at 530.7 eV). The emergence of the new peak at around 530.7 eV indicates the presence of covalent bonding between Pb2+ and the P-OH group on 4PACz through deprotonation process. d, XPS spectra (P 2p) of 4PACz and 4PACz-doped perovskite. P 2p spectrum of 4PACz show the main peak at 134.6 eV, while shifting to 133.2 eV after doping into perovskites. The P 2p spectra of 4PACz (134.6 eV) and 4PACz-doped perovskite (133.2 eV) show similar spectral shapes, indicating that no bonding is formed between the perovskite and the P atom on 4PACz. e, XPS spectra (Pb 4f) of undoped and 4PACz-doped perovskite samples. The Pb 4f peak of the perovskite films show a shift of ~0.2 eV to higher binding energies with the incorporation of 4PACz. This may be attributed to the formation of new Pb-O-P bonds in the solid films. The XPS results show that the electron densities on O and P atoms increase as the electron density around Pb2+ decreases, highlighting the important role of the electron-withdrawing process during 4PACz doping. f, FTIR spectra of pristine 4PACz and 4PACz-doped perovskite. The stretching vibration peak of the P-O bond in 4PACz at 1058 cm−1 shifts to 1051 cm−1 with PbBr2, indicating the interactions between the PA group on 4PACz and Pb2+.

Extended Data Fig. 3 Additional device performance data of HTL-free PeLEDs.

a, Current density–voltage curves. b, Luminance-voltage curves. c, EQE-luminance curves. d, EL spectra.

Extended Data Fig. 4 Performance of undoped PeLEDs based on bare and 4PACz-coated ITO.

a, Current density–voltage curves. b, Luminance-voltage curves. c, EQE-luminance curves. g, ηECE-luminance curves.

Extended Data Fig. 5 Performance of doped PeLEDs based on bare and 4PACz-coated ITO.

a, Current density–voltage curves. b, Luminance-voltage curves. c, EQE-luminance curves.

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Xiong, W., Tang, W., Zhang, G. et al. Controllable p- and n-type behaviours in emissive perovskite semiconductors. Nature 633, 344–350 (2024). https://doi.org/10.1038/s41586-024-07792-4

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