通过聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸改性实现高性能蓝色钙钛矿发光二极管

doi:10.6023/A23070344

摘要/Abstract

金属卤化物钙钛矿材料因其独特的光电特性, 在光电器件领域引起了相当大的关注和研究. 特别是近年来, 绿色和红色钙钛矿发光二极管(PeLEDs)研究取得了显著进展. 然而, 蓝色PeLEDs的发展落后于绿光和红光PeLEDs, 效率也要低得多. 其中一个主要原因是空穴传输层与蓝色钙钛矿材料的能级不匹配. 在这项研究中, 通过使用聚(4-苯乙烯磺酸钠)(PSS-Na)和溴化钾(KBr)改性空穴传输层材料聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS), 抑制PEDOT:PSS与钙钛矿材料界面之间的非辐射复合. 并通过降低膜的粗糙度来提高钙钛矿膜的质量. 结果表明, PSS-Na和KBr有效地提高了空穴传输能力, 从而提高了PeLEDs器件的整体性能. 通过PSS-Na改性PEDOT:PSS制备的蓝色PeLEDs具有低启亮电压(仅为3.3 V)和高外量子效率(EQE)(达到4.12%). 随着PEDOT:PSS中进一步加入KBr, 蓝色PeLEDs最大EQE达到6.25%, 启亮电压降至3 V. 此外, 与其他蓝光钙钛矿器件相比, 该器件在不同电压下也表现出了良好的光谱稳定性. 说明通过改性空穴传输层, 可以提高钙钛矿发光器件的效率和稳定性, 显示出钙钛矿发光二极管在彩色显示器和固态照明中的潜力.

关键词: 钙钛矿材料, 蓝光PeLEDs, 空穴传输层, 改性

Metal halide perovskite materials, with their high stability and excellent optical properties, have attracted considerable attention and research in the field of optoelectronic devices. Especially in recent years, the research of green and red perovskite light-emitting diodes (PeLEDs) has made remarkable progress. However, the development of blue PeLEDs has lagged behind that of green and red PeLEDs, and is much less efficient, limiting the applications of perovskite light-emitting devices in color displays and solid-state lighting. One of the main reasons is the mismatch between the energy levels of the hole transporting layer and the blue perovskite material. In this study, we inhibited the non-radiative recombination between the interface of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and perovskite materials by first modifying the hole transporting layer material PEDOT:PSS with poly(sodium 4-styrenesulfonate) (PSS-Na) and potassium bromide (KBr). The quality of the perovskite layer film was improved by optimizing the fabrication process to reduce the roughness of the hole transporting layer film. Finally, perovskite light emitting devices are fabricated by vacuum evaporation. It is shown that the use of PSS-Na and KBr can effectively increase the hole transporting capacity and thus improve the overall performance of the PeLEDs device. Moreover, the blue PeLEDs prepared by PEDOT:PSS modified by PSS-Na alone have low on-voltage (only 3.3 V) and high external quantum efficiency (EQE) (up to 4.12%). With the further addition of KBr to the modified PEDOT:PSS of PSS-Na, the maximum EQE of the final blue PeLEDs reaches 6.25%, the on-chip voltage drops to 3 V, and the peak wavelength is 488 nm, which is a blue sky perovskite light emitting device. In addition, compared to other blue-emitting perovskite devices, this device also exhibits excellent spectral stability at different voltages. The efficiency and stability of perovskite light-emitting devices can be improved by modifying the hole transporting layer, showing the potential of perovskite light-emitting diodes for color displays and solid-state lighting.

Key words: perovskite material, blue PeLEDs, hole transporting layer, modification

引用此文

张璇, 熊军, 张旺. 通过聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸改性实现高性能蓝色钙钛矿发光二极管[J]. 化学学报, 2023, 81(12): 1695-1700.

Xuan Zhang, Jun Xiong, Wang Zhang. High Performance Blue Perovskite Light Emitting Diode Realized by Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Modification[J]. Acta Chimica Sinica, 2023, 81(12): 1695-1700.

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图/表 8

图1. (a)钙钛矿薄膜在不同空穴传输层上的XRD; (b)紫外-可见吸收光谱; (c) PL和365 nm紫光激发下的相片; (d)基于PEDOT:PSS、m-PEDOT:PSS和m-PEDOT:PSS＋KBr薄膜的钙钛矿TRPL光谱

Figure 1. (a) XRD of perovskite thin film on different HTLs; (b) UV-vis absorption spectra; (c) PL and photograph under 365 nm excitation; (d) TRPL spectra of the perovskites based on PEDOT:PSS, m-PEDOT:PSS and m-PEDOT:PSS＋KBr films

图2. (a) PEDOT:PSS, (b) m-PEDOT:PSS, (c) m-PEDOT:PSS＋KBr, (d) PEDOT:PSS/PVSK, (e) m-PEDOT:PSS/PVSK和(f) m-PEDOT:PSS＋KBr/PVSK的AFM图像

Figure 2. AFM images of (a) PEDOT:PSS, (b) m-PEDOT:PSS, (c) m-PEDOT:PSS＋KBr, (d) PEDOT:PSS/PVSK, (e) m-PEDOT:PSS/ PVSK and (f) m-PEDOT:PSS＋KBr/PVSK

图3. (a) PEDOT:PSS, (b) m-PEDOT:PSS, (c) m-PEDOT:PSS＋KBr, (d) PEDOT:PSS/PVSK, (e) m-PEDOT:PSS/PVSK和(f) m-PEDOT:PSS＋KBr/PVSK的SEM图像

Figure 3. SEM images of (a) PEDOT:PSS, (b) m-PEDOT:PSS, (c) m-PEDOT:PSS＋KBr, (d) PEDOT:PSS/PVSK, (e) m-PEDOT:PSS/ PVSK and (f) m-PEDOT:PSS＋KBr/PVSK

图4. 不同空穴传输层的XPS谱. (a)空穴传输层的XPS测量光谱; (b) K 2p核能级能谱; (c) Na 1s核能级能谱; (d) S 2p核能级能谱

Figure 4. XPS spectra of different HTLs. (a) XPS survey spectra of the HTLs; (b) the K 2p core-level energy spectra; (c) the Na 1s core-level energy spectra; (d) the S 2p core-level energy spectra

图5. (a)样品的UPS光谱; (b) ITO、PEDOT:PSS、m-PEDOT:PSS、m-PEDOT:PSS＋KBr和钙钛矿的能级

Figure 5. (a) UPS spectra of samples; (b) energy levels for ITO, PEDOT:PSS, m-PEDOT:PSS, m-PEDOT:PSS＋KBr and perovskite

图6. 不同空穴传输层的PeLEDs器件性能图. (a)电压-电流密度(V-J)曲线; (b)发光-电压曲线(L-V); (c)电压-电流效率(V-CE)曲线; (d)电压-外量子效率(V-EQE)曲线

Figure 6. Performance diagram of PeLED device with different HTLs. (a) Voltage-current density (V-J) curve; (b) luminance-voltage curve (L-V); (c) voltage-current efficiency (V-CE) curve; (d) voltage-external quantum efficiency (V-EQE) curve

HTL层材料	V_on/V	L_max/(cd•m⁻²)	EQE_max/%	CE_max/(cd•A⁻¹)
PEDOT:PSS	4.1	1843	0.86	1.30
m-PEDOT:PSS	3.3	1930	4.14	8.62
m-PEDOT:PSS＋KBr	3	2322	6.25	12.56

表1. PEDOT:PSS、m-PEDOT:PSS和m-PEDOT:PSS＋KBr的PeLEDs性能

Table 1. Device performances of PeLEDs with PEDOT:PSS, m-PEDOT:PSS and m-PEDOT:PSS＋KBr

图7. (a) PEDOT:PSS、m-PEDOT:PSS和m-PEDOT:PSS＋KBr天蓝光PeLEDs的EL光谱; (b)不同电压下PEDOT:PSS PeLEDs的EL光谱; (c)不同电压下m-PEDOT:PSS PeLEDs的EL光谱; (d)不同电压下m-PEDOT:PSS＋KBr PeLEDs的EL光谱

Figure 7. (a) EL spectra of PEDOT:PSS, m-PEDOT:PSS and m-PEDOT:PSS＋KBr sky blue PeLEDs; (b) EL spectra of PEDOT:PSS PeLED at different voltage; (c) EL spectra of m-PEDOT:PSS PeLED at different voltage; (d) EL spectra of m-PEDOT:PSS＋KBr PeLED at different voltage

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