Metal to insulator transition for conducting polymers in plasmonic nanogaps

Yuling Xiong; Rohit Chikkaraddy; Charlie Readman; Shu Hu; Kunli Xiong; Jialong Peng; Qianqi Lin; Jeremy J. Baumberg

doi:10.1038/s41377-023-01344-7

Your Location：

Home >

Browse articles >

Metal to insulator transition for conducting polymers in plasmonic nanogaps

Article

- Metal to insulator transition for conducting polymers in plasmonic nanogaps
- Metal to insulator transition for conducting polymers in plasmonic nanogaps
- LSA 2024年13卷第1期页码：23-32
- Affiliations：
- Author bio：
  
  hjjb12@cam.ac.uk
- Funds：
  
  EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council);China Scholarship Council (CSC);Royal Society;National Natural Science Foundation of China (National Science Foundation of China)
- DOI：10.1038/s41377-023-01344-7
  中图分类号：
- 收稿日期：2023-07-06，
  
  修回日期：2023-11-17，
  
  录用日期：2023-11-22，
  
  网络出版日期：2024-01-01，
  
  纸质出版日期：2024-12
- Accepted：
Scan QR Code
Metal to insulator transition for conducting polymers in plasmonic nanogaps[J]. LSA, 2024,13(1):23-32.

Yuling Xiong, Rohit Chikkaraddy, Charlie Readman, et al. Metal to insulator transition for conducting polymers in plasmonic nanogaps[J]. Light: science & applications, 2024, 13(1): 23-32.
Metal to insulator transition for conducting polymers in plasmonic nanogaps[J]. LSA, 2024,13(1):23-32. DOI： 10.1038/s41377-023-01344-7.

Yuling Xiong, Rohit Chikkaraddy, Charlie Readman, et al. Metal to insulator transition for conducting polymers in plasmonic nanogaps[J]. Light: science & applications, 2024, 13(1): 23-32. DOI： 10.1038/s41377-023-01344-7.

摘要

Abstract

Conjugated polymers are promising material candidates for many future applications in flexible displays

organic circuits

and sensors. Their performance is strongly affected by their structural conformation including both electrical and optical anisotropy. Particularly for thin layers or close to crucial interfaces

there are few methods to track their organization and functional behaviors. Here we present a platform based on plasmonic nanogaps that can assess the chemical structure and orientation of conjugated polymers down to sub-10 nm thickness using light. We focus on a representative conjugated polymer

poly(3

4-ethylenedioxythiophene) (PEDOT)

of varying thickness (2-20 nm) while it undergoes redox in situ. This allows dynamic switching of the plasmonic gap spacer through a metal-insulator transition. Both dark-field (DF) and surface-enhanced Raman scattering (SERS) spectra track the optical anisotropy and orientation of polymer chains close to a metallic interface. Moreover

we demonstrate how this influences both optical and redox switching for nanothick PEDOT devices.

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=70078766&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=70078766&type=small

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=70078766&type=middle

关键词

Keywords

references

Reynolds, J. R., Thompson, B. C. & Skotheim, T. A. Conjugated Polymers: Perspective, Theory, and New Materials. (Boca Raton: CRC Press, 2019).

A. Karki et al. , Electrical tuning of plasmonic conducting polymer nanoantennas . Adv. Mater. 34 , 2107172 ( 2022 ). http://doi.org/10.1002/adma.202107172 http://doi.org/10.1002/adma.202107172

S.Z. Chen et al. , Conductive polymer nanoantennas for dynamic organic plasmonics . Nat. Nanotechnol. 15 , 35 - 40 ( 2020 ). http://doi.org/10.1038/s41565-019-0583-y http://doi.org/10.1038/s41565-019-0583-y

D. Papkov et al. , Quantifying polymer chain orientation in strong and tough nanofibers with low crystallinity: toward next generation nanostructured superfibers . ACS Nano 13 , 4893 - 4927 ( 2019 ). http://doi.org/10.1021/acsnano.8b08725 http://doi.org/10.1021/acsnano.8b08725

B. Cho et al. , Single-crystal poly(3,4-ethylenedioxythiophene) nanowires with ultrahigh conductivity . Nano Lett. 14 , 3321 - 3327 ( 2014 ). http://doi.org/10.1021/nl500748y http://doi.org/10.1021/nl500748y

M. Campoy-Quiles , P.G. Etchegoin , D.D.C. Bradley , On the optical anisotropy of conjugated polymer thin films . Phys. Rev. B 72 , 045209 ( 2005 ). http://doi.org/10.1103/PhysRevB.72.045209 http://doi.org/10.1103/PhysRevB.72.045209

M.H. Kong et al. , Advanced optical characterization of PEDOT: PSS by combining spectroscopic ellipsometry and raman scattering . ACS Omega 7 , 39429 - 39436 ( 2022 ). http://doi.org/10.1021/acsomega.2c05945 http://doi.org/10.1021/acsomega.2c05945

M. Tanaka , R.J. Young , Review polarised Raman spectroscopy for the study of molecular orientation distributions in polymers . J. Mater. Sci. 41 , 963 - 991 ( 2006 ). http://doi.org/10.1007/s10853-006-6595-7 http://doi.org/10.1007/s10853-006-6595-7

L. Zhai et al. , Ordered conjugated polymer nano- and microstructures: structure control for improved performance of organic electronics . Nano Today 9 , 705 - 721 ( 2014 ). http://doi.org/10.1016/j.nantod.2014.10.004 http://doi.org/10.1016/j.nantod.2014.10.004

X.X. Wang et al. , High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment . Sci. Adv. 4 , eaat5780 ( 2018 ). http://doi.org/10.1126/sciadv.aat5780 http://doi.org/10.1126/sciadv.aat5780

J.J. Baumberg et al. , Extreme nanophotonics from ultrathin metallic gaps . Nat. Mater. 18 , 668 - 678 ( 2019 ). http://doi.org/10.1038/s41563-019-0290-y http://doi.org/10.1038/s41563-019-0290-y

L. Bert Groenendaal et al. , Poly(3, 4-ethylenedioxythiophene) and its derivatives: past, present, and future . Adv. Mater. 12 , 481 - 494 ( 2000 ). http://doi.org/10.1002/(SICI)1521-4095(200004)12:7<481::AID-ADMA481>3.0.CO;2-C http://doi.org/10.1002/(SICI)1521-4095(200004)12:7<481::AID-ADMA481>3.0.CO;2-C

D. Mantione et al. , Poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives: innovative conductive polymers for bioelectronics . Polym 9 , 354 ( 2017 ). http://doi.org/10.3390/polym9080354 http://doi.org/10.3390/polym9080354

N. Jiang , X.L. Zhuo , J.F. Wang , Active plasmonics: principles, structures, and applications . Chem. Rev. 118 , 3054 - 3099 ( 2018 ). http://doi.org/10.1021/acs.chemrev.7b00252 http://doi.org/10.1021/acs.chemrev.7b00252

C.P. Byers et al. , From tunable core-shell nanoparticles to plasmonic drawbridges: active control of nanoparticle optical properties . Sci. Adv. 1 , e1500988 ( 2015 ). http://doi.org/10.1126/sciadv.1500988 http://doi.org/10.1126/sciadv.1500988

J.L. Peng et al. , Scalable electrochromic nanopixels using plasmonics . Sci. Adv. 5 , eaaw2205 ( 2019 ). http://doi.org/10.1126/sciadv.aaw2205 http://doi.org/10.1126/sciadv.aaw2205

J.L. Peng et al. , In-situ spectro-electrochemistry of conductive polymers using plasmonics to reveal doping mechanisms . ACS Nano 16 , 21120 - 21128 ( 2022 ). http://doi.org/10.1021/acsnano.2c09081 http://doi.org/10.1021/acsnano.2c09081

C. Tserkezis et al. , Hybridization of plasmonic antenna and cavity modes: extreme optics of nanoparticle-on-mirror nanogaps . Phys. Rev. A 92 , 053811 ( 2015 ). http://doi.org/10.1103/PhysRevA.92.053811 http://doi.org/10.1103/PhysRevA.92.053811

R.Q. Li et al. , Transformation optics approach to plasmon-exciton strong coupling in nanocavities . Phys. Rev. Lett. 117 , 107401 ( 2016 ). http://doi.org/10.1103/PhysRevLett.117.107401 http://doi.org/10.1103/PhysRevLett.117.107401

E. Elliott et al. , Fingerprinting the hidden facets of plasmonic nanocavities . ACS Photonics 9 , 2643 - 2651 ( 2022 ). http://doi.org/10.1021/acsphotonics.2c00116 http://doi.org/10.1021/acsphotonics.2c00116

F. Benz et al. , Generalized circuit model for coupled plasmonic systems . Opt. Express 23 , 33255 - 33269 ( 2015 ). http://doi.org/10.1364/OE.23.033255 http://doi.org/10.1364/OE.23.033255

I. Zozoulenko et al. , Polarons, bipolarons, and absorption spectroscopy of PEDOT . ACS Appl. Polym. Mater. 1 , 83 - 94 ( 2019 ). http://doi.org/10.1021/acsapm.8b00061 http://doi.org/10.1021/acsapm.8b00061

S. Rudd et al. , Charge transport and structure in semimetallic polymers . J. Polym. Sci. Part B: Polym. Phys. 56 , 97 - 104 ( 2018 ). http://doi.org/10.1002/polb.24530 http://doi.org/10.1002/polb.24530

N.J. Yang , C.G. Zoski , Polymer films on electrodes: investigation of ion transport at poly(3,4-ethylenedioxythiophene) films by scanning electrochemical microscopy . Langmuir 22 , 10338 - 10347 ( 2006 ). http://doi.org/10.1021/la061167u http://doi.org/10.1021/la061167u

A. Bund , S. Neudeck , Effect of the solvent and the anion on the doping/dedoping behavior of poly(3,4-ethylenedioxythiophene) films studied with the electrochemical quartz microbalance . J. Phys. Chem. B 108 , 17845 - 17850 ( 2004 ). http://doi.org/10.1021/jp0469721 http://doi.org/10.1021/jp0469721

A. Xomalis et al. , Controlling optically driven atomic migration using crystal-facet control in plasmonic nanocavities . ACS Nano 14 , 10562 - 10568 ( 2020 ). http://doi.org/10.1021/acsnano.0c04600 http://doi.org/10.1021/acsnano.0c04600

I. Petsagkourakis et al. , Poly(3,4-ethylenedioxythiophene): chemical synthesis, transport properties, and thermoelectric devices . Adv. Electron. Mater. 5 , 1800918 ( 2019 ). http://doi.org/10.1002/aelm.201800918 http://doi.org/10.1002/aelm.201800918

K.E. Aasmundtveit et al. , Structure of thin films of poly(3,4-ethylenedioxythiophene) . Synth. Met. 101 , 561 - 564 ( 1999 ). http://doi.org/10.1016/S0379-6779(98)00315-4 http://doi.org/10.1016/S0379-6779(98)00315-4

M.N. Gueye et al. , Structure and dopant engineering in PEDOT thin films: practical tools for a dramatic conductivity enhancement . Chem. Mater. 28 , 3462 - 3468 ( 2016 ). http://doi.org/10.1021/acs.chemmater.6b01035 http://doi.org/10.1021/acs.chemmater.6b01035

N. Massonnet et al. , Metallic behaviour of acid doped highly conductive polymers . Chem. Sci. 6 , 412 - 417 ( 2015 ). http://doi.org/10.1039/C4SC02463J http://doi.org/10.1039/C4SC02463J

A. Ugur et al. , Low-dimensional conduction mechanisms in highly conductive and transparent conjugated polymers . Adv. Mater. 27 , 4604 - 4610 ( 2015 ). http://doi.org/10.1002/adma.201502340 http://doi.org/10.1002/adma.201502340

S.Z. Chen et al. , Unraveling vertical inhomogeneity in vapour phase polymerized PEDOT: tos films . J. Mater. Chem. A 8 , 18726 - 18734 ( 2020 ). http://doi.org/10.1039/D0TA06031C http://doi.org/10.1039/D0TA06031C

Z.U. Khan et al. , Acido-basic control of the thermoelectric properties of poly(3,4-ethylenedioxythiophene)tosylate (PEDOT-Tos) thin films . J. Mater. Chem. C. 3 , 10616 - 10623 ( 2015 ). http://doi.org/10.1039/C5TC01952D http://doi.org/10.1039/C5TC01952D

L.A.A. Pettersson et al. , Spectroscopic ellipsometry studies of the optical properties of doped poly(3,4-ethylenedioxythiophene): an anisotropic metal . Thin Solid Films 313-314 , 356 - 361 ( 1998 ). http://doi.org/10.1016/S0040-6090(97)00846-8 http://doi.org/10.1016/S0040-6090(97)00846-8

S. Garreau et al. , In situ spectroelectrochemical Raman studies of poly(3,4-ethylenedioxythiophene) (PEDT) . Macromolecules 32 , 6807 - 6812 ( 1999 ). http://doi.org/10.1021/ma9905674 http://doi.org/10.1021/ma9905674

B.R. Moraes , N.S. Campos , C.M.S. Izumi , Surface-enhanced Raman scattering of EDOT and PEDOT on silver and gold nanoparticles . Vibrational Spectrosc. 96 , 137 - 142 ( 2018 ). http://doi.org/10.1016/j.vibspec.2018.04.006 http://doi.org/10.1016/j.vibspec.2018.04.006

M.H. Tsai , Y.K. Lin , S.C. Luo , Electrochemical SERS for in situ monitoring the redox states of PEDOT and its potential application in oxidant detection . ACS Appl. Mater. Interfaces 11 , 1402 - 1410 ( 2019 ). http://doi.org/10.1021/acsami.8b16989 http://doi.org/10.1021/acsami.8b16989

M. Łapkowski , A. Proń , Electrochemical oxidation of poly(3,4-ethylenedioxythiophene) - “in situ” conductivity and spectroscopic investigations . Synth. Met. 110 , 79 - 83 ( 2000 ). http://doi.org/10.1016/S0379-6779(99)00271-4 http://doi.org/10.1016/S0379-6779(99)00271-4

A. Dkhissi et al. , Theoretical investigation of the nature of the ground state in the low-bandgap conjugated polymer, poly(3,4-ethylenedioxythiophene) . Chem. Phys. Lett. 359 , 466 - 472 ( 2002 ). http://doi.org/10.1016/S0009-2614(02)00651-6 http://doi.org/10.1016/S0009-2614(02)00651-6

W.W. Chiu et al. , Studies of dopant effects in poly(3,4-ethylenedi-oxythiophene) using Raman spectroscopy . J. Raman Spectrosc. 37 , 1354 - 1361 ( 2006 ). http://doi.org/10.1002/jrs.1545 http://doi.org/10.1002/jrs.1545

J.J. Baumberg , Picocavities: a primer . Nano Lett. 22 , 5859 - 5865 ( 2022 ). http://doi.org/10.1021/acs.nanolett.2c01695 http://doi.org/10.1021/acs.nanolett.2c01695

N.S. Mueller et al. , Photoluminescence upconversion in monolayer WSe 2 activated by plasmonic cavities through resonant excitation of dark excitons . Nat. Commun. 14 ,( 2023 ). http://doi.org/10.1038/s41467-023-41401-8 http://doi.org/10.1038/s41467-023-41401-8

S. Hu et al. , Full control of plasmonic nanocavities using gold decahedra-on-mirror constructs with monodisperse facets . Adv. Sci. 10 , e2207178 ( 2023 ). http://doi.org/10.1002/advs.202207178 http://doi.org/10.1002/advs.202207178

J.A. Dolan et al. , Gyroid optical metamaterials: calculating the effective permittivity of multidomain samples . ACS Photonics 3 , 1888 - 1896 ( 2016 ). http://doi.org/10.1021/acsphotonics.6b00400 http://doi.org/10.1021/acsphotonics.6b00400

A.D. Becke , Density‐functional thermochemistry. III. The role of exact exchange . J. Chem. Phys. 98 , 5648 - 5652 ( 1993 ). http://doi.org/10.1063/1.464913 http://doi.org/10.1063/1.464913

C. Lee , W.T. Yang , R.G. Parr , Development of the colle-salvetti correlation-energy formula into a functional of the electron density . Phys. Rev. B 37 , 785 - 789 ( 1988 ). http://doi.org/10.1103/PhysRevB.37.785 http://doi.org/10.1103/PhysRevB.37.785

S. Grimme , S. Ehrlich , L. Goerigk , Effect of the damping function in dispersion corrected density functional theory . J. Comput. Chem. 32 , 1456 - 1465 ( 2011 ). http://doi.org/10.1002/jcc.21759 http://doi.org/10.1002/jcc.21759

F. Weigend , R. Ahlrichs , Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy . Phys. Chem. Chem. Phys. 7 , 3297 - 3305 ( 2005 ). http://doi.org/10.1039/b508541a http://doi.org/10.1039/b508541a

Frisch, M. J. et al. Gaussian 09, Revision E.01. (2009).

Le Ru, E. C. & Etchegoin, P. G. Principles of Surface-Enhanced Raman Spectroscopy. (Amsterdam: Elsevier, 2009).

D.B. Grys et al. , Citrate coordination and bridging of gold nanoparticles: the role of gold adatoms in AuNP aging . ACS Nano 14 , 8689 - 8696 ( 2020 ). http://doi.org/10.1021/acsnano.0c03050 http://doi.org/10.1021/acsnano.0c03050

M.K. Kesharwani , B. Brauer , J.M.L. Martin , Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and Other Selected Methods): can anharmonic force fields be avoided? . J. Phys. Chem. A 119 , 1701 - 1714 ( 2015 ). http://doi.org/10.1021/jp508422u http://doi.org/10.1021/jp508422u

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

暂无数据