LCP /TLC based composite multi-dimensional polarization-dependent anti-counterfeiting device

Zhu Yu-Wen; Yuan Cong-Long; Liu Bing-Hui; Wang Xiao-Qian; Zheng Zhi-Gang

doi:10.7498/aps.72.20230850

Abstract

Modern anti-counterfeiting technology can effectively suppress and combat forgery and counterfeiting behaviors, which is of great significance in information security, national defense and economy. However, the realization of multi-dimensional, integrated, difficult-to-copy and easy-to-detect optical anti-counterfeiting devices is still a challenge. In this paper, a multi-dimensional and polarization-dependent anti-counterfeiting device with structure color is designed, which is composed of patterned liquid crystal polymer (LCP) nematic layer and thermotropic cholesteric liquid crystal (TLC) layer. It has the advantages of displaying and hiding polarization states, wide color tuning range, convenient operation, high integration and security. For incident light with a specific polarization state, the patterned nematic phase LCP layer can carry out regionalized phase editing and polarization state modulation, while the TLC layer can selectively reflect the incident light. Therefore, a patterned structural color security label is subtly realized. The anti-counterfeiting device can realize the display, hiding, color adjustment and image/background conversion of patterns by adjusting the polarization direction of incident light. In addition, the TLC layer in the device can meet the application requirements of the anti-counterfeit device at different environmental temperatures through the flexible design of the system weight ratio. Furthermore, the device can be easily heated by body temperature, realize dynamic real-time wide-spectrum color modulation and reversible pattern erasure, and further enhance its security dimension and security. The multi-polarization-type anti-counterfeiting device has three-dimensional anti-counterfeiting efficacy. The first dimensional anti-counterfeiting efficacy is achieved by the thermochromic liquid crystal layer. The thermochromic liquid crystal layer has no reflection color outside the operating temperature range of TLC material, and the entire device displays black background. The second and the third dimensional anti-counterfeiting efficacy are related to the polarization state of the incident light and the linear polarization direction, respectively. Only when the incident light is linearly polarized light and its polarization direction makes an angle of 45° or –45° with respect to the optical axis of the liquid crystal, will the device show the designed pattern. Consequently, our proposed anti-counterfeiting device is expected to provide a new idea for developing the anti-counterfeiting field.

Keywords:

Authors and contacts

1.
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
2.
School of Physics, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Wang Xiao-Qian, xqwang@ecust.edu.cn

Funds: Project supported by the National Key Research and Development Program of China (Grant No. 2022YFA1203700), the National Natural Science Foundation of China (Grant Nos. 61822504, 62275081, 62035008), the “Shuguang” Program of Shanghai, China (Grant No. 21SG29), the Shanghai Municipal Education Commission, China, and the Scientific Innovation Major Program of Shanghai Scientific and Technology Committee, China (Grant No. 2021-01-07-00-02-E00107).

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References

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Cited By

图 1 胆甾醇衍生物COC, CN, CD的化学结构

Figure 1. Chemical structures of the cholesterol derivatives COC, CN, and CD.

DownLoad: Full-Size Img PowerPoint

图 2 集成式防伪器件的结构.

Figure 2. The structure of integrally anti-counterfeiting device.

DownLoad: Full-Size Img PowerPoint

图 3 复合多维偏振型防伪器件的防伪工作原理示意图

Figure 3. Schematic drawing of working principle of composite multi-dimensional polarization dependent anti-counterfeiting device.

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图 4 样品 S2 的 (a) 反射光谱及 (b) 织构随温度的变化. 正交双箭头代表正交偏振片

Figure 4. The variation of (a) the reflection spectra and (b) the textures of sample S2 with temperature. Orthogonal double arrows represent the crossed polarizers.

DownLoad: Full-Size Img PowerPoint

图 5 基于热致变色理论模型的拟合结果. 其中, 实线代表拟合值, 点代表实验测量值

Figure 5. The fitting results based on thermochromic theoretical model. Herein, the solid lines represent the fitting values and the points represent the experimental measurement values

DownLoad: Full-Size Img PowerPoint

图 6 自然光及不同偏振方向入射光下样品图案的温度依赖性. Δα = α_i – α_v 代表入射光偏振方向 α_i 与箭头区域光轴方向 α_v 之间的夹角. 白色箭头代表不同区域相应的光轴方向

Figure 6. Temperature dependence of sample pattern under natural light and linearly polarized light with different polarization directions. Δα = α_i – α_v represents the angle between the polarization direction of the incident light α_i and the optical axis direction of the arrow region α_v. The white arrows represent the corresponding optical axis directions in different regions.

DownLoad: Full-Size Img PowerPoint

图 7 线偏振入射光(α_i = π/4)照射下, S1, S3及S6体系制备的多维偏振型防伪器件在10—40 ℃的热致变色效果

Figure 7. Thermochromic effect of multi-polarization security devices prepared by S1, S3 and S6 systems under linearly polarized incident light (α_i = π/4) at 10 ℃ to 40 ℃

DownLoad: Full-Size Img PowerPoint

表 1 不同样品中COC/CN/CD混合材料与TEB300的质量分数和温度参数

Table 1. Weight content and temperature parameters of COC/CN/CD material and TEB300 in different samples.

样品 COC/CN/
CD/% TEB300/% 可见光波段
显色温度
范围/℃ 温宽/℃

S1 100.0 0 29.3—37.5 8.2
S2 97.0 3.0 22.5—32.5 10.0
S3 96.3 3.7 20.0—29.5 9.5
S4 95.3 4.7 17.5—28.5 10.5
S5 94.3 5.7 15.0—26.5 11.5

DownLoad: CSV

表 2 基于热致变色理论模型的各系数拟合值

Table 2. The fitting value of each coefficient based on thermochromic theoretical model.

λ₀/nm T_c/℃ c′/(nm·℃^ν) ν

S1 198.575 25.742 1299.893 0.699
S2 172.004 18.026 1607.392 0.699
S3 141.651 15.014 1852.118 0.699
S4 124.274 11.431 2188.508 0.699
S5 120.653 8.554 2288.744 0.699

DownLoad: CSV

[1]	Kim J M, Bak J M, Lim B, Jung Y J, Park B C, Park M J, Park J M, Lee H I, Jung S 2022 Nanoscale 14 5377 Google Scholar
[2]	Gu Y Q, He C, Zhang Y Q, Lin L, Thackray B D, Ye J 2020 Nat. Commun. 11 516 Google Scholar
[3]	Peng S, Sun S, Zhu Y, Qiu J, Yang H 2023 Virtual Phys. Prototyping 18 e2179929 Google Scholar
[4]	Huo Y, Yang Z, Wilson T, Jiang C 2022 Adv. Mater. Interfaces 9 2200201 Google Scholar
[5]	Xu C, Huang C, Yang D, Luo L, Huang S 2022 ACS Omega 7 7320 Google Scholar
[6]	Yang D, Liao G, Huang S 2019 J. Mater. Chem. C 7 11776 Google Scholar
[7]	Qin L, Liu X J, He K Y, Yu G D, Yuan H, Xu M, Li F Y, Yu Y L 2021 Nat. Commun. 12 699 Google Scholar
[8]	Wei J, Ou W, Luo J, Kuang D 2022 Angew. Chem. Int. Ed. 61 e202207985
[9]	Xu J, Zhu T, Chen X, Zhao D, Li Y, Zhang L, Bi N, Gou J, Jia L 2023 J. Lumin. 256 119647 Google Scholar
[10]	Yao W, Lan R, Li K, Zhang L 2021 ACS Appl. Mater. Interfaces 13 1424 Google Scholar
[11]	Liu Y, Han F, Li F, Zhao Y, Chen M, Xu Z, Zheng X, Hu H, Yao J, Guo T, Lin W, Zheng Y, You B, Liu P, Li Y, Qian L 2019 Nat. Commun. 10 2409 Google Scholar
[12]	Chen Q, Huang X, Yang D, Le Y, Pan Q, Li M, Zhang H, Kang J, Xiao X, Qiu J, Yang Z, Dong G 2023 Adv. Opt. Mater. 11 2300090 Google Scholar
[13]	Han W, Wen X, Ding Y, Li Z, Lu M, Zhu H, Wang G, Yan J, Hong X 2022 Appl. Surf. Sci. 595 153563 Google Scholar
[14]	Jung C, Kim G, Jeong M, Jang J, Dong Z G, Badloe T, Yang J K W, Rho J 2021 Chem. Rev. 121 13013 Google Scholar
[15]	Yao B, Lin P, Sun H, Wang S, Luo C, Li Z, Du X, Ding Y, Xu Y, Wan H, Zhu W 2021 Adv. Opt. Mater. 9 2001434 Google Scholar
[16]	Duan X, Kamin S, Liu N 2017 Nat. Commun. 8 14606 Google Scholar
[17]	Jung C, Yang Y, Jang J, Badloe T, Lee T, Mun J, Moon S W, Rho J 2021 Nanophotonics 10 919
[18]	Daqiqeh Rezaei S, Dong Z, Wang H, Xu J, Wang H, Tavakkoli Yaraki M, Choon Hwa Goh K, Zhang W, Ghorbani S R, Liu X, Yang J K W 2023 Mater. Today 62 51 Google Scholar
[19]	Wu Y, Sun R, Ren J, Zhang S, Wu S 2022 Adv. Funct. Mater. 33 2210047
[20]	Hou J, Li M, Song Y 2018 Angew. Chem. Int. Ed. 57 2544 Google Scholar
[21]	Li T, Liu G, Kong H, Yang G, Wei G, Zhou X 2023 Coord. Chem. Rev. 475 214909 Google Scholar
[22]	Rezaei S D, Dong Z G, Chan J Y E, Trisno J, Ng R J H, Ruan Q F, Qiu C W, Mortensen N A, Yang J K W 2021 ACS Photonics 8 18
[23]	Li J, Guan Z, Liu H, He Z, Li Z, Yu S, Zheng G 2023 Laser Photonics Rev. 17 2200342 Google Scholar
[24]	Huang H, Li H, Yin J, Gu K, Guo J, Wang C 2023 Adv. Mater. 35 2211117 Google Scholar
[25]	Zheng Z, Hu H, Zhang Z, Liu B, Li M, Qu D, Tian H, Zhu W, Feringa B L 2022 Nat. Photonics 16 226
[26]	Hu H L, Liu B H, Li M Q, Zheng Z G, Zhu W H 2022 Adv. Mater. 34 2110170 Google Scholar
[27]	Bisoyi H K, Li Q 2022 Chem. Rev. 122 4887 Google Scholar
[28]	Chen P, Wei B, Hu W, Lu Y 2020 Adv. Mater. 32 1903665
[29]	Zhu L, Xu C T, Chen P, Zhang Y, Liu S, Chen Q, Ge S, Hu W, Lu Y 2022 Light-Sci. Appl. 11 135 Google Scholar
[30]	Shopsowitz K E, Qi H, Hamad W Y, MacLachlan M J 2010 Nature 468 422 Google Scholar
[31]	Mitov M 2012 Adv. Mater. 24 6260 Google Scholar
[32]	Faryad M, Lakhtakia A 2014 Adv. Opt. Photonics 6 225 Google Scholar
[33]	Liu B, Yuan C, Hu H, Sun P, Yu L, Zheng Z 2022 J. Mater. Chem. C 10 16924 Google Scholar
[34]	Kelly J A, Giese M, Shopsowitz K E, Hamad W Y, MacLachlan M J 2014 Acc. Chem. Res. 47 1088 Google Scholar
[35]	Bisoyi H K, Bunning T J, Li Q 2018 Adv. Mater. 30 1706512 Google Scholar
[36]	Wang L, Li Q 2016 Adv. Funct. Mater. 26 10 Google Scholar
[37]	Xu C, Chen P, Zhang Y, Fan X, Lu Y, Hu W 2021 Appl. Phys. Lett. 118 151102 Google Scholar
[38]	Lu L F, Chen X F, Liu W, Li H K, Li Y, Yang Y G 2023 Liq. Cryst. DOI: 10.1080/02678292.2023. 2200266
[39]	Yang C, Wu B, Ruan J, Zhao P, Chen L, Chen D, Ye F 2021 Adv. Mater. 33 2006361 Google Scholar
[40]	Williams M W, Wimberly J A, Stwodah R M, Nguyen J, D’Angelo P A, Tang C 2023 ACS Appl. Polym. Mater. 5 3065 Google Scholar
[41]	Zhang Z, Chen Z, Wang Y, Zhao Y, Shang L 2022 Adv. Funct. Mater. 32 2107242 Google Scholar
[42]	Ma L L, Wu S B, Hu W, Liu C, Chen P, Qian H, Wang Y D, Chi L F, Lu Y Q 2019 ACS Nano 13 13709 Google Scholar
[43]	Liu C, Hsu C, Cheng K 2020 Opt. Laser Technol. 126 106060 Google Scholar
[44]	van der Werff L C, Robinson A J, Kyratzis I L 2012 ACS Comb. Sci. 14 605 Google Scholar
[45]	Pindak R S, Huang C C, Ho J T 1974 Phys. Rev. Lett. 32 43 Google Scholar

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