Nanostructured Organic Semiconductor Films for Molecular Detection with Surface-enhanced Raman Spectroscopy

Overview

Journal Nat Mater

Date 2017 Aug 8

PMID 28783157

Citations 41

Authors

Mehmet Yilmaz

Esra Babur

Mehmet Ozdemir

Rebecca L Gieseking

Yavuz Dede

Ugur Tamer

George C Schatz

Antonio Facchetti

Hakan Usta

Gokhan Demirel

Affiliations

Soon will be listed here.

Abstract

π-Conjugated organic semiconductors have been explored in several optoelectronic devices, yet their use in molecular detection as surface-enhanced Raman spectroscopy (SERS)-active platforms is unknown. Herein, we demonstrate that SERS-active, superhydrophobic and ivy-like nanostructured films of a molecular semiconductor, α,ω-diperfluorohexylquaterthiophene (DFH-4T), can be easily fabricated by vapour deposition. DFH-4T films without any additional plasmonic layer exhibit unprecedented Raman signal enhancements up to 3.4 × 10 for the probe molecule methylene blue. The combination of quantum mechanical computations, comparative experiments with a fluorocarbon-free α,ω-dihexylquaterthiophene (DH-4T), and thin-film microstructural analysis demonstrates the fundamental roles of the π-conjugated core fluorocarbon substitution and the unique DFH-4T film morphology governing the SERS response. Furthermore, Raman signal enhancements up to ∼10 and sub-zeptomole (<10 mole) analyte detection were accomplished by coating the DFH-4T films with a thin gold layer. Our results offer important guidance for the molecular design of SERS-active organic semiconductors and easily fabricable SERS platforms for ultrasensitive trace analysis.

Citing Articles

Nanostructured Surfaces with Plasmonic Activity and Superhydrophobicity: Review of Fabrication Strategies and Applications.

Ruzi M, Celik N, Sahin F, Sakir M, Onses M Small. 2025; 21(6):e2408189.

PMID: 39757431 PMC: 11817952. DOI: 10.1002/smll.202408189.

Machine Learning-Assisted SERS Reveals the Biochemical Signature of Enhanced Protein Secretion from Surface-Modified Magnetic Nanoparticles.

Dagci I, Solak K, Oncer N, Yildiz Arslan S, Unver Y, Yilmaz M ACS Appl Mater Interfaces. 2024; 16(51):70392-70406.

PMID: 39662987 PMC: 11672479. DOI: 10.1021/acsami.4c18591.

Impact of Surface Enhanced Raman Spectroscopy in Catalysis.

Stefancu A, Aizpurua J, Alessandri I, Bald I, Baumberg J, Besteiro L ACS Nano. 2024; 18(43):29337-29379.

PMID: 39401392 PMC: 11526435. DOI: 10.1021/acsnano.4c06192.

Multiple valence states of Fe boosting SERS activity of FeO nanoparticles and enabling effective SERS-MRI bimodal cancer imaging.

Lin J, Ma X, Li A, Akakuru O, Pan C, He M Fundam Res. 2024; 4(4):858-867.

PMID: 39156566 PMC: 11330100. DOI: 10.1016/j.fmre.2022.04.018.

Flexible 3D Plasmonic Web Enables Remote Surface Enhanced Raman Spectroscopy.

Rodriguez-Sevilla E, Alvarez-Martinez J, Castro-Beltran R, Morales-Narvaez E Adv Sci (Weinh). 2024; 11(23):e2402192.

PMID: 38582528 PMC: 11187956. DOI: 10.1002/advs.202402192.

References

Pearman W, Fountain 3rd A . Classification of chemical and biological warfare agent simulants by surface-enhanced Raman spectroscopy and multivariate statistical techniques. Appl Spectrosc. 2006; 60(4):356-65. DOI: 10.1366/000370206776593744. View

Chen A, Chatterjee S . Nanomaterials based electrochemical sensors for biomedical applications. Chem Soc Rev. 2013; 42(12):5425-38. DOI: 10.1039/c3cs35518g. View

Jensen L, Autschbach J, Schatz G . Finite lifetime effects on the polarizability within time-dependent density-functional theory. J Chem Phys. 2005; 122(22):224115. DOI: 10.1063/1.1929740. View

Wang X, Shi W, She G, Mu L . Using Si and Ge nanostructures as substrates for surface-enhanced Raman scattering based on photoinduced charge transfer mechanism. J Am Chem Soc. 2011; 133(41):16518-23. DOI: 10.1021/ja2057874. View

Zhang Y, Diao Y, Lee H, Mirabito T, Johnson R, Puodziukynaite E . Intrinsic and extrinsic parameters for controlling the growth of organic single-crystalline nanopillars in photovoltaics. Nano Lett. 2014; 14(10):5547-54. DOI: 10.1021/nl501933q. View

Korzdorfer T, Parrish R, Sears J, Sherrill C, Bredas J . On the relationship between bond-length alternation and many-electron self-interaction error. J Chem Phys. 2012; 137(12):124305. DOI: 10.1063/1.4752431. View

Lombardi J, Birke R . A unified view of surface-enhanced Raman scattering. Acc Chem Res. 2009; 42(6):734-42. DOI: 10.1021/ar800249y. View

Fan M, Brolo A . Silver nanoparticles self assembly as SERS substrates with near single molecule detection limit. Phys Chem Chem Phys. 2009; 11(34):7381-9. DOI: 10.1039/b904744a. View

Halvorson R, Vikesland P . Surface-enhanced Raman spectroscopy (SERS) for environmental analyses. Environ Sci Technol. 2010; 44(20):7749-55. DOI: 10.1021/es101228z. View

10.

Kuribara K, Wang H, Uchiyama N, Fukuda K, Yokota T, Zschieschang U . Organic transistors with high thermal stability for medical applications. Nat Commun. 2012; 3:723. DOI: 10.1038/ncomms1721. View

11.

Zang L, Che Y, Moore J . One-dimensional self-assembly of planar pi-conjugated molecules: adaptable building blocks for organic nanodevices. Acc Chem Res. 2008; 41(12):1596-608. DOI: 10.1021/ar800030w. View

12.

Capelli R, Toffanin S, Generali G, Usta H, Facchetti A, Muccini M . Organic light-emitting transistors with an efficiency that outperforms the equivalent light-emitting diodes. Nat Mater. 2010; 9(6):496-503. DOI: 10.1038/nmat2751. View

13.

Wei W, Chen K, Ge G . Strongly coupled nanorod vertical arrays for plasmonic sensing. Adv Mater. 2013; 25(28):3863-8. DOI: 10.1002/adma.201301181. View

14.

Hudson S, Chumanov G . Bioanalytical applications of SERS (surface-enhanced Raman spectroscopy). Anal Bioanal Chem. 2009; 394(3):679-86. DOI: 10.1007/s00216-009-2756-2. View

15.

Guo X, Ying Y, Tong L . Photonic nanowires: from subwavelength waveguides to optical sensors. Acc Chem Res. 2014; 47(2):656-66. DOI: 10.1021/ar400232h. View

16.

Xu W, Ling X, Xiao J, Dresselhaus M, Kong J, Xu H . Surface enhanced Raman spectroscopy on a flat graphene surface. Proc Natl Acad Sci U S A. 2012; 109(24):9281-6. PMC: 3386126. DOI: 10.1073/pnas.1205478109. View

17.

Nazeeruddin M, Wang Q, Cevey L, Aranyos V, Liska P, Figgemeier E . DFT-INDO/S modeling of new high molar extinction coefficient charge-transfer sensitizers for solar cell applications. Inorg Chem. 2006; 45(2):787-97. DOI: 10.1021/ic051727x. View

18.

Jensen L, Zhao L, Autschbach J, Schatz G . Theory and method for calculating resonance Raman scattering from resonance polarizability derivatives. J Chem Phys. 2005; 123(17):174110. DOI: 10.1063/1.2046670. View

19.

Boerigter C, Campana R, Morabito M, Linic S . Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis. Nat Commun. 2016; 7:10545. PMC: 4738363. DOI: 10.1038/ncomms10545. View

20.

Labastide J, Thompson H, Marques S, Colella N, Briseno A, Barnes M . Directional charge separation in isolated organic semiconductor crystalline nanowires. Nat Commun. 2016; 7:10629. PMC: 4773394. DOI: 10.1038/ncomms10629. View