Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes

Wenjin Yu; Mingyang Wei; Zhenyu Tang; Hongshuai Zou; Liang Li; Yu Zou; Shuang Yang; Yunkun Wang; Yuqing Zhang; Xiangdong Li; Haoqing Guo; Cuncun Wu; Bo Qu; Yunan Gao; Guowei Lu; Shufeng Wang; Zhijian Chen; Zhiwei Liu; Huanping Zhou; Bin Wei; Yingjie Liao; Lijun Zhang; Yan Li; Qihuang Gong; Edward H. Sargent; Lixin Xiao

doi:10.1002/adma.202301114

Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes

Wenjin Yu, Mingyang Wei^*, Zhenyu Tang, Hongshuai Zou, Liang Li, Yu Zou, Shuang Yang, Yunkun Wang, Yuqing Zhang, Xiangdong Li, Haoqing Guo, Cuncun Wu, Bo Qu, Yunan Gao, Guowei Lu, Shufeng Wang, Zhijian Chen, Zhiwei Liu, Huanping Zhou, Bin WeiYingjie Liao^*, Lijun Zhang^*, Yan Li, Qihuang Gong, Edward H. Sargent, Lixin Xiao^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

Colloidal perovskite nanocrystals (PNCs) display bright luminescence for light-emitting diode (LED) applications; however, they require post-synthesis ligand exchange that may cause surface degradation and defect formation. In situ-formed PNCs achieve improved surface passivation using a straightforward synthetic approach, but their LED performance at the green wavelength is not yet comparable with that of colloidal PNC devices. Here, it is found that the limitations of in situ-formed PNCs stem from uncontrolled formation kinetics: conventional surface ligands confine perovskite nuclei but fail to delay crystal growth. A bifunctional carboxylic-acid-containing ammonium hydrobromide ligand that separates crystal growth from nucleation is introduced, leading to the formation of quantum-confined PNC solids exhibiting a narrow size distribution. Controlled crystallization is further coupled with defect passivation using deprotonated phosphinates, enabling improvements in photoluminescence quantum yield to near unity. Green LEDs are fabricated with a maximum current efficiency of 109 cd A⁻¹ and an average external quantum efficiency of 22.5% across 25 devices, exceeding the performance of their colloidal PNC-based counterparts. A 45.6 h operating half-time is further documented for an unencapsulated device in N₂ with an initial brightness of 100 cd m⁻².

Original language	English (US)
Article number	2301114
Journal	Advanced Materials
Volume	35
Issue number	33
DOIs	https://doi.org/10.1002/adma.202301114
State	Published - Aug 17 2023

Funding

This study was financially supported by the National Key R&D Program of China (Nos. 2022YFB3606502 and 2022YFE0109000) and National Natural Science Foundation of China (Nos. 61935016, 52173153, 12174013, 12074011, and 92250305). The authors thank X. Wang, J. Xie, J. Su, W. Pan, M. Chen, and Y. Guan from the College of Chemistry and Molecular Engineering of Peking University for their kind help with the TEM, XPS, XRD, FTIR, TRPL, and PLQY measurements, respectively. The authors thank J. Xu from the Electron Microscopy Laboratory of Peking University for TEM sample preparation by FIB. The authors thank J. Yang and H. Li from Beijing Nuclear Magnetic Resonance Center, Peking University for NMR measurements. The authors thank Aidan Maxwell from the University of Toronto for editing the manuscript. The authors also thank D. Zhang and L. Duan from Tsinghua University for the LED measurement calibration. This study was financially supported by the National Key R&D Program of China (Nos. 2022YFB3606502 and 2022YFE0109000) and National Natural Science Foundation of China (Nos. 61935016, 52173153, 12174013, 12074011, and 92250305). The authors thank X. Wang, J. Xie, J. Su, W. Pan, M. Chen, and Y. Guan from the College of Chemistry and Molecular Engineering of Peking University for their kind help with the TEM, XPS, XRD, FTIR, TRPL, and PLQY measurements, respectively. The authors thank J. Xu from the Electron Microscopy Laboratory of Peking University for TEM sample preparation by FIB. The authors thank J. Yang and H. Li from Beijing Nuclear Magnetic Resonance Center, Peking University for NMR measurements. The authors thank Aidan Maxwell from the University of Toronto for editing the manuscript. The authors also thank D. Zhang and L. Duan from Tsinghua University for the LED measurement calibration.

Keywords

crystallization
in situ controllable synthesis
light-emitting diodes
nanocrystals
perovskites

ASJC Scopus subject areas

General Materials Science
Mechanics of Materials
Mechanical Engineering

Access to Document

10.1002/adma.202301114

Cite this

Yu, W., Wei, M., Tang, Z., Zou, H., Li, L., Zou, Y., Yang, S., Wang, Y., Zhang, Y., Li, X., Guo, H., Wu, C., Qu, B., Gao, Y., Lu, G., Wang, S., Chen, Z., Liu, Z., Zhou, H., ... Xiao, L. (2023). Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes. Advanced Materials, 35(33), Article 2301114. https://doi.org/10.1002/adma.202301114

@article{ab06fe0f72ff4396ac1c55667bb2e527,

title = "Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes",

abstract = "Colloidal perovskite nanocrystals (PNCs) display bright luminescence for light-emitting diode (LED) applications; however, they require post-synthesis ligand exchange that may cause surface degradation and defect formation. In situ-formed PNCs achieve improved surface passivation using a straightforward synthetic approach, but their LED performance at the green wavelength is not yet comparable with that of colloidal PNC devices. Here, it is found that the limitations of in situ-formed PNCs stem from uncontrolled formation kinetics: conventional surface ligands confine perovskite nuclei but fail to delay crystal growth. A bifunctional carboxylic-acid-containing ammonium hydrobromide ligand that separates crystal growth from nucleation is introduced, leading to the formation of quantum-confined PNC solids exhibiting a narrow size distribution. Controlled crystallization is further coupled with defect passivation using deprotonated phosphinates, enabling improvements in photoluminescence quantum yield to near unity. Green LEDs are fabricated with a maximum current efficiency of 109 cd A−1 and an average external quantum efficiency of 22.5\% across 25 devices, exceeding the performance of their colloidal PNC-based counterparts. A 45.6 h operating half-time is further documented for an unencapsulated device in N2 with an initial brightness of 100 cd m−2.",

keywords = "crystallization, in situ controllable synthesis, light-emitting diodes, nanocrystals, perovskites",

author = "Wenjin Yu and Mingyang Wei and Zhenyu Tang and Hongshuai Zou and Liang Li and Yu Zou and Shuang Yang and Yunkun Wang and Yuqing Zhang and Xiangdong Li and Haoqing Guo and Cuncun Wu and Bo Qu and Yunan Gao and Guowei Lu and Shufeng Wang and Zhijian Chen and Zhiwei Liu and Huanping Zhou and Bin Wei and Yingjie Liao and Lijun Zhang and Yan Li and Qihuang Gong and Sargent, \{Edward H.\} and Lixin Xiao",

note = "Publisher Copyright: {\textcopyright} 2023 Wiley-VCH GmbH.",

year = "2023",

month = aug,

day = "17",

doi = "10.1002/adma.202301114",

language = "English (US)",

volume = "35",

journal = "Advanced Materials",

issn = "0935-9648",

publisher = "Wiley-Blackwell",

number = "33",

}

Yu, W, Wei, M, Tang, Z, Zou, H, Li, L, Zou, Y, Yang, S, Wang, Y, Zhang, Y, Li, X, Guo, H, Wu, C, Qu, B, Gao, Y, Lu, G, Wang, S, Chen, Z, Liu, Z, Zhou, H, Wei, B, Liao, Y, Zhang, L, Li, Y, Gong, Q, Sargent, EH & Xiao, L 2023, 'Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes', Advanced Materials, vol. 35, no. 33, 2301114. https://doi.org/10.1002/adma.202301114

TY - JOUR

T1 - Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes

AU - Yu, Wenjin

AU - Wei, Mingyang

AU - Tang, Zhenyu

AU - Zou, Hongshuai

AU - Li, Liang

AU - Zou, Yu

AU - Yang, Shuang

AU - Wang, Yunkun

AU - Zhang, Yuqing

AU - Li, Xiangdong

AU - Guo, Haoqing

AU - Wu, Cuncun

AU - Qu, Bo

AU - Gao, Yunan

AU - Lu, Guowei

AU - Wang, Shufeng

AU - Chen, Zhijian

AU - Liu, Zhiwei

AU - Zhou, Huanping

AU - Wei, Bin

AU - Liao, Yingjie

AU - Zhang, Lijun

AU - Li, Yan

AU - Gong, Qihuang

AU - Sargent, Edward H.

AU - Xiao, Lixin

PY - 2023/8/17

Y1 - 2023/8/17

N2 - Colloidal perovskite nanocrystals (PNCs) display bright luminescence for light-emitting diode (LED) applications; however, they require post-synthesis ligand exchange that may cause surface degradation and defect formation. In situ-formed PNCs achieve improved surface passivation using a straightforward synthetic approach, but their LED performance at the green wavelength is not yet comparable with that of colloidal PNC devices. Here, it is found that the limitations of in situ-formed PNCs stem from uncontrolled formation kinetics: conventional surface ligands confine perovskite nuclei but fail to delay crystal growth. A bifunctional carboxylic-acid-containing ammonium hydrobromide ligand that separates crystal growth from nucleation is introduced, leading to the formation of quantum-confined PNC solids exhibiting a narrow size distribution. Controlled crystallization is further coupled with defect passivation using deprotonated phosphinates, enabling improvements in photoluminescence quantum yield to near unity. Green LEDs are fabricated with a maximum current efficiency of 109 cd A−1 and an average external quantum efficiency of 22.5% across 25 devices, exceeding the performance of their colloidal PNC-based counterparts. A 45.6 h operating half-time is further documented for an unencapsulated device in N2 with an initial brightness of 100 cd m−2.

AB - Colloidal perovskite nanocrystals (PNCs) display bright luminescence for light-emitting diode (LED) applications; however, they require post-synthesis ligand exchange that may cause surface degradation and defect formation. In situ-formed PNCs achieve improved surface passivation using a straightforward synthetic approach, but their LED performance at the green wavelength is not yet comparable with that of colloidal PNC devices. Here, it is found that the limitations of in situ-formed PNCs stem from uncontrolled formation kinetics: conventional surface ligands confine perovskite nuclei but fail to delay crystal growth. A bifunctional carboxylic-acid-containing ammonium hydrobromide ligand that separates crystal growth from nucleation is introduced, leading to the formation of quantum-confined PNC solids exhibiting a narrow size distribution. Controlled crystallization is further coupled with defect passivation using deprotonated phosphinates, enabling improvements in photoluminescence quantum yield to near unity. Green LEDs are fabricated with a maximum current efficiency of 109 cd A−1 and an average external quantum efficiency of 22.5% across 25 devices, exceeding the performance of their colloidal PNC-based counterparts. A 45.6 h operating half-time is further documented for an unencapsulated device in N2 with an initial brightness of 100 cd m−2.

KW - crystallization

KW - in situ controllable synthesis

KW - light-emitting diodes

KW - nanocrystals

KW - perovskites

UR - https://www.scopus.com/pages/publications/85163713304

UR - https://www.scopus.com/inward/citedby.url?scp=85163713304&partnerID=8YFLogxK

U2 - 10.1002/adma.202301114

DO - 10.1002/adma.202301114

M3 - Article

C2 - 37314026

AN - SCOPUS:85163713304

SN - 0935-9648

VL - 35

JO - Advanced Materials

JF - Advanced Materials

IS - 33

M1 - 2301114

ER -

Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this