Highly sensitive color fine-tuning of diblock copolymeric nano-aggregates with tri-metallic cations, Eu(III), Tb(III), and Zn(II), for flexible photoluminescence films (FPFs)

doi:10.1016/j.jmst.2020.04.069

Abstract

Abstract:

Luminescence materials have shown promise as display apparatus and lighting devices. The particularly interesting systems are photoluminescence materials that are capable of reversible colors emitting repeatedly on exposure to light. Here we report a series of color tunable flexible and transparent photoluminescence films consisting of multi-metals (Eu³⁺, Tb³⁺ and Zn²⁺) induced polymer aggregates (MIPAs) which are distributed uniformly in the polyacrylonitrile (PAN) films without agglomeration. MIPAs have a unique spherical structure due to the self-assembly of polystyrene-block-polyacrylic acid (PS-b-PAA) induced by metal ions. Notably, when applied in photoluminescence devices, these photoluminescence films exhibit not only red, green, blue colors (RGB) light, but also other tuned various color light covering the whole visible range upon excitation of 345 nm through adjusting the relative ratios of metal complexes. As the most important key point, non-conductive polymers can be used in photoluminescence devices as host medium, which is not realized in electroluminescent devices. Thus, the flexible photoluminescence films (FPFs) innovated herein exhibit the great potential to apply for flexible light-color and light-energy transformation devices.

Key words: Photoluminescence, Color tunable, Flexible films, Polymer aggregates

Xinzhi Wang, Yao Wang, Xinbo Zhang, Wei Ding, Longlong Li, Linjun Huang, Laurence A. Belfiore, Jianguo Tang. Highly sensitive color fine-tuning of diblock copolymeric nano-aggregates with tri-metallic cations, Eu(III), Tb(III), and Zn(II), for flexible photoluminescence films (FPFs)[J]. J. Mater. Sci. Technol., 2021, 65: 72-81.

Figures/Tables 10

Scheme 1. Schematic of the mechanism for EuCMs, TbCMs and ZnCMs.

Scheme 2. Illustration of FPFs and molecular structure.

Fig. 1. (a) UV-vis absorption spectra of PAN, EuCMs@PAN, TbCMs@PAN and ZnCMs@PAN; Inset: Photographs of (1) EuCMs @PAN, (2) TbCMs @PAN, (3) ZnCMs @PAN films under daylight and luminescence images of (4) EuCMs@PAN, (5) TbCMs@PAN, (6) ZnCMs@PAN under 365 nm UV lamp; (b) UV-vis transmittance spectra of PAN, EuCMs@PAN, TbCMs@PAN and ZnCMs@PAN; (c) FT-IR spectra of EuCMs@PAN, TbCMs@PAN, ZnCMs@PAN; (d) the magnified spectra of (c).

Fig. 2. SEM images of EuCMs@PAN (a), TbCMs@PAN (b), ZnCMs@PAN (c) and (d-g) elemental mapping of Eu, O, S and F elements in EuCMs@PAN, (h, i) elemental mapping of Tb, and O elements in TbCMs@PAN, (j-l) elemental mapping of Zn, O and S elements in ZnCMs@PAN.

Fig. 3. TEM images of (a) EuCMs, (c) TbCMs and (e) ZnCMs and molecular structure of (b) EuCMs, (d) TbCMs and (f) ZnCMs.

Fig. 4. (a) XPS survey of EuCMs, TbCMs and ZnCMs; (b) XPS spectra of the N1 s region of Phen and EuCMs; (c) XPS spectra of the O1 s region of PS-b-PAA; (d) XPS spectra of the O1 s region of EuCMs; (e) XPS spectra of the O1 s region of 4-BBA; (f) XPS spectra of the O1 s region of TbCMs; (g) XPS spectra of the N1 s region of BTZ and ZnCMs; (h) XPS spectra of the O1 s region of ZnCMs.

Fig. 5. The emission spectra of EuCMs@PAN (a), TbCMs@PAN (b), ZnCMs@PAN (c) by 365 nm UV excitation and (d) CIE coordinates, the fluorescence decay curves of (e) EuCMs@PAN and TbCMs@PAN, (f) ZnCMs@PAN (λex = 365 nm).

Table 1 LnCMs@PAN with different mole ratio of luminescent complexes marked as A to I and luminescence properties.

LnCMs@PAN	Mole ratios of luminescent complexes			CIE (x, y)	Colors under UV excitation
	Eu	Tb	Zn
A	1	5	0.5	(0.3171,0.3298)	White
B	1	0	0.5	(0.4935, 0.2829)	Orange
C	1	3	0	(0.4859, 0.4606)	Yellow
D	1	5	0	(0.3608, 0.3575)	Light Yellow
E	1	1	0.5	(0.4092, 0.2578)	Prink
F	1	0	0.8	(0.3906, 0.2439)	Rose red
G	1	0	1	(0.2985, 0.2080)	Purple
H	0	1	0.1	(0.2086, 0.3127)	Cyan
I	1	6	1	(0.2793, 0.2366)	Light blue

Fig. 6. (a) Emission spectrum, (b)luminescence intensity of peaks at 461 nm, 545 nm and 615 nm, (c) coordinate CIE coordinates and (d) luminescence images of FPFs with different mole ratios of luminescent complexes under 365 nm UV excitation.

Fig. 7. (a) Photographs (inset), photoluminescence spectra and (b) The CIE chromaticity coordinates (a. EuCMs@PAN, b. TbCMs@PAN, c. ZnCMs@PAN) of photoluminescence devices (λex = 365 nm).

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