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Yan ZJ, Liu Z, Yang X, et al. Perovskite quantum dot color conversion Micro-LEDs: progress in stability and patterning[J]. Opto-Electron Eng, 2024, 51(7): 240088. doi: 10.12086/oee.2024.240088
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Perovskite quantum dot color conversion Micro-LEDs: progress in stability and patterning
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Abstract
Micro light-emitting diode (Micro-LED) display is considered the "next-generation" ultimate display technology due to its excellent display performance and optoelectronic properties. In order to meet the requirements of near-eye display applications, further miniaturization and integration of Micro-LED are necessary. With the continuous innovation of micro/nanopatterning technology, the fluorescent color conversion layer method has significant advantages such as low manufacturing cost. Compared to the three-color chip method, it is more suitable for virtual/augmented reality display applications that demand higher color gamut and resolution. Perovskite quantum dots (PQDs) are the most promising fluorescent color conversion materials. However, the inherent lattice instability of PQDs and degradation caused by external environmental factors pose significant challenges. Furthermore, it is crucial to develop micro-scale fluorescent array patterns that match the Micro-LED chip array. Therefore, this paper first discusses the factors that affect the structural instability of perovskite quantum dots. Then, it summarizes the applications of strategies such as ligand exchange, ion doping, surface coating, and chemical cross-linking in enhancing the stability of perovskite quantum dots. Finally, the latest research progress for fabricating high-resolution perovskite quantum dot fluorescent arrays using photolithography and inkjet printing techniques is summarized. -
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References
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Overview
Micro-LEDs, as microscale light-emitting diode displays, are widely regarded as the ultimate choice for next-generation display technology due to their exceptional display performance and optoelectronic properties. Through miniaturization and high integration, Micro-LEDs have surpassed LCD and OLED technologies. Currently, the methods employed to achieve full-color Micro-LEDs primarily involve the use of trichromatic chips and photoluminescent quantum dot (PQD) conversion layers. However, one of the major challenges faced by the trichromatic chip approach is large-scale transfer technology, which affects transfer efficiency, precision, and yield. Moreover, the demand for ultra-high pixel density displays has led to a further reduction in Micro-LED chip size, increasing the difficulty of chip transfer and resulting in high manufacturing costs. Additionally, the impact of sidewall damage during the fabrication process on the performance of small-sized Micro-LEDs cannot be overlooked. In recent years, the fabrication of patterned full-color Micro-LED displays using PQDs conversion layers has garnered significant attention. However, a PQD possess ionic properties and low surface energy, making them highly susceptible to the external environment, including water, oxygen, heat, and light. The high dissociation of long-chain surface ligands leads to increased surface defects and particle aggregation, severely impacting the performance of PQD-based Micro-LED displays. To overcome these challenges, several strategies have been proposed, including ligand exchange, ion doping, surface encapsulation, and chemical cross-linking. These methods effectively passivate surface defects of PQDs, enhance lattice stability, and suppress non-radiative recombination pathways. By employing stability-enhancing techniques such as strong ligand bonding, lattice adjustment, organic/inorganic shell encapsulation, and covalent cross-linking, ion diffusion in PQDs can be inhibited, thereby improving their environmental stability. For achieving exceptional full-color Micro-LEDs, these stability-enhancing approaches can be combined with photolithography and inkjet printing techniques to fabricate PQDs conversion layers with high resolution, stability, and luminance. This review begins by elucidating the causes of structural instability in PQDs. Subsequently, it summarizes the applications of ligand exchange, ion doping, surface encapsulation, and chemical cross-linking in enhancing the stability of perovskite quantum dots. Finally, the latest research advancements in photolithography and inkjet printing techniques for fabricating high-resolution perovskite quantum dot fluorescent arrays are presented. By synthesizing these findings, this comprehensive review specifically emphasizes the strategies employed to enhance the stability and performance of patterned Micro-LED displays with perovskite quantum dot conversion layers.
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Yan ZJ, Liu Z, Yang X, et al. Perovskite quantum dot color conversion Micro-LEDs: progress in stability and patterning[J]. Opto-Electron Eng, 2024, 51(7): 240088. doi: 10.12086/oee.2024.240088
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Figure 1.
PQD-based Micro-LEDs full-color technology and stability solution[23]. (a) Ligand exchange[24]; (b) Ion doping[25]; (c) Surface coating[26]; (d) Chemical cross-linking[27]
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Figure 2.
(a) Schematic of a typical ABX3 crystal structure of halide perovskite[33] ; (b) Possible pathways for phase transitions of CsPbI3[39] ; (c) Photo-oxidation mechanism of CsPbI3[43]; (d) Schematic of the interaction between water and PNCs[47]; (e) Schematic of photo-induced agglomeration of CsPbBr3[45]
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Figure 3.
(a) Structure of CsPbI3-DDAB and CsPbI3-OA/OLA[52]; (b) PLQY stability of CsPbI3-DDAB and CsPbI3-OA/OLA[52]; (c) TEM image of CsPbI3-DDAB after 60 days of storage in a dark environment[52]; (d) Strategy of HI-induced in situ exchange strategy of 5AVA ligand with OA/OLA ligand[54]; (e) Schematic of the passivation of amphipathic ionic ligands (sulfobetaine, phosphocholine and γ-aminoacids)[58]; (f) DDAB and DLPS dual ligand passivation strategies[59]; (g) PL stability of three QDs in natural environments[59]
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Figure 4.
(a) Schematic diagram of in-situ synthesized Ni2+ doped CsPbI3 PQD[75]; (b) Variation of PLQY with storage time for undoped and Ni-doped CsPbI3 PQD[75]; (c) Stabilization mechanism of Zn2+ doped CsMnCl3 PQD[77]; (d) PLQY at different Zn/Mn mass ratios[77]; (e) Process flowchart for the preparation of CsPbBr3 PQDs doped with NdCl3[79]; (f) PLQY stability of CsPbBr3 PQDs with different dopants in a natural environment[79]
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Figure 5.
(a) Schematic structure of CsPbBr3/LLPDE[83]; (b) Degradation of CsPbBr3 and CsPbBr3/LLPDE in natural environment[83]; (c) Degradation of CsPbBr3 and CsPbBr3/LLPDE under 365 nm light irradiation[83]; (d) Flowchart for preparation of polymerisable CsPbX3 PQD ink[87]; (e) Ligand exchange and ALD-Al2O3 encapsulation flowchart[97]; (f) CsPbBr3/CdS and CsPbBr3/Cs4PbBr6 encapsulation methods and energy maps[103]; (g) Degradation of various QD materials in aqueous environment (left) and 365 nm light environment (right)[103]
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Figure 6.
(a) Schematic diagram of the preparation of CsPbBr3 perovskite PQD in LHD nanosheets[107]; (b) PL stability of CsPbBr3 and LDH-CP-CsPbBr3 at high temperatures[107]; (c) Schematic diagram of in-situ growth of CsPbBr3 QDs on hydrophobic silica aerogel[108]; (d) PL stability of PQDs after heating at high temperatures for 1 hour[108]; (e) Design schematic of CsPbBr3 PQD composite materials[109]; (f) Fluorescence characteristics of CsPbBr3 PQD composite materials during heating-cooling cycles[109]; (g) PL stability of PQDs with the addition of ethyl cellulose in a natural environment[110]
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Figure 7.
(a) Schematic diagram of PQD thin film preparation using photolithographic masking method[113]; (b) PQD array with feature sizes as small as 3 µm[113]; (c) Schematic diagram of PQD thin film preparation using photolithographic peeling method[114]; (d) PQD dot array with a radius size of 5 µm[114]; (e) Schematic diagram of in-situ fabrication of PQD patterns using lead bromide complex[115]; (f) PQD fluorescence array with a resolution of up to 2450 PPI [115]; (g) Photopatterning mechanism of PZ ligands[116]; (h) High-resolution PQD pattern with a line spacing of 4 µm[116]
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Figure 8.
(a) Reaction mechanism between PTMP and PQD (top) and schematic diagram of direct photolithographic fabrication of PQD patterns (bottom)[119]; (b) PQD fluorescence array with a resolution of 12700 PPI[119]; (c) Schematic diagram of PQD fluorescence array prepared by microsphere filling method[120]; (d) High-resolution PQD fluorescence array with pixel size of 2 µm[120]; (e) High-resolution dual-color PQD pattern[120].
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Figure 9.
(a) Schematic diagram of PQD color conversion layer prepared by aerosol inkjet printing technique[125]; (b) PQD pattern with a line width of 13 µm [125]; (c) Schematic diagram of EHD inkjet printing[126]; (d) PQD pattern with a resolution of 10 µm [126]; (e) Red PQD fluorescence array with a resolution of 2540 DPI [127]; (f) Full-color PQD color conversion layer with subpixel diameter of 10 µm [127]; (g) Schematic diagram of red PQD fluorescence array prepared by ligand exchange and EHD inkjet printing process[127]
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Figure 10.
(a) Schematic diagram of ink preparation and printing[129]; (b) PQD fluorescence array with a resolution of up to 22718 DPI[129]; (c) Fabrication process of mixed QD nanoring Micro-LED with line width less than 2 µm[130]; (d) QD pattern with a line width of 1.65 µm[130]; (e) Patterns of perovskite dot arrays with diameters of 1 µm, 2 µm, and 3 µm[131]
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