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Abstract

Introduction

Protocol

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Engineering

Ultrafast Laser-Ablated Nanoparticles and Nanostructures for Surface-Enhanced Raman Scattering-Based Sensing Applications

Published: June 16th, 2023

DOI:

10.3791/65450

1Advanced Centre for Research in High Energy Materials (ACRHEM), DRDO Industry Academia - Centre of Excellence (DIA-COE), University of Hyderabad

Ultrafast laser ablation in liquid is a precise and versatile technique for synthesizing nanomaterials (nanoparticles [NPs] and nanostructures [NSs]) in liquid/air environments. The laser-ablated nanomaterials can be functionalized with Raman-active molecules to enhance the Raman signal of analytes placed on or near the NSs/NPs.

The technique of ultrafast laser ablation in liquids has evolved and matured over the past decade, with several impending applications in various fields such as sensing, catalysis, and medicine. The exceptional feature of this technique is the formation of nanoparticles (colloids) and nanostructures (solids) in a single experiment with ultrashort laser pulses. We have been working on this technique for the past few years, investigating its potential using the surface-enhanced Raman scattering (SERS) technique in hazardous materials sensing applications. Ultrafast laser-ablated substrates (solids and colloids) could detect several analyte molecules at the trace levels/mixture form, including dyes, explosives, pesticides, and biomolecules. Here, we present some of the results achieved using the targets of Ag, Au, Ag-Au, and Si. We have optimized the nanostructures (NSs) and nanoparticles (NPs) obtained (in liquids and air) using different pulse durations, wavelengths, energies, pulse shapes, and writing geometries. Thus, various NSs and NPs were tested for their efficiency in sensing numerous analyte molecules using a simple, portable Raman spectrometer. This methodology, once optimized, paves the way for on-field sensing applications. We discuss the protocols in (a) synthesizing the NPs/NSs via laser ablation, (b) characterization of NPs/NSs, and (c) their utilization in the SERS-based sensing studies.

Ultrafast laser ablation is a rapidly evolving field of laser-material interactions. High-intensity laser pulses with pulse durations in the femtosecond (fs) to picosecond (ps) range are used to generate precise material ablation. Compared to nanosecond (ns) laser pulses, ps laser pulses can ablate materials with higher precision and accuracy due to their shorter pulse duration. They can generate less collateral damage, debris, and contamination of the ablated material due to fewer thermal effects. However, ps lasers are typically more expensive than ns lasers and need specialized expertise for operation and maintenance. The ultrafast laser pulses enable precise contr....

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A typical protocol flowchart of the application of ultrafast ablated NPs or NSs in the trace detection of molecules via SERS is shown in Figure 1A.

1. Synthesizing metal NPs/NSs

NOTE: Depending on the requirement/application, choose the target material, the surrounding liquid, and the laser ablation parameters.
Here:
Target materials: Ag
Surrounding liquid: 10 mL of DI
Laser parameters: 35.......

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Silver NPs were synthesized via ps laser ablation in liquid technique. Here, a ps laser system with a pulse duration of ~30 ps operating at a 10 Hz repetition rate and with a wavelength of one of 355, 532, or 1,064 nm was used. The input pulse energy was adjusted to 15 mJ. The laser pulses were focused using a plano-convex lens with a focal length of 10 cm. The laser focus should be exactly on the material surface during laser ablation because the laser energy is most concentrated at the focal point, where it ca.......

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In ultrasonication cleaning, the material to be cleaned is immersed in a liquid and high-frequency sound waves are applied to the liquid using an ultrasonic cleaner. The sound waves cause the formation and implosion of tiny bubbles in the liquid, generating intense local energy and pressure that dislodge and remove dirt and other contaminants from the surface of the material. In laser ablation, a Brewster polarizer and a half-wave plate combination were used to tune the laser energy; the polarizer is typically placed bef.......

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We thank the University of Hyderabad for support through the Institute of Eminence (IoE) project UOH/IOE/RC1/RC1-2016. The IoE grant obtained vide notification F11/9/2019-U3(A) from the MHRD, India. DRDO, India is acknowledged for funding support through ACRHEM [[#ERIP/ER/1501138/M/01/319/D(R&D)]. We acknowledge the School of Physics, UoH, for the FESEM characterization and XRD facilities. We would like to extend our sincere gratitude to Prof SVS Nageswara Rao and his group for their valuable collaboration contributions and support. We would like to express our appreciation to past and present lab members Dr. P Gopala Krishna, Dr. Hamad Syed, Dr. Chandu Byram, Mr.....

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Name Company Catalog Number Comments
Alloys Local goldsmith N/A 99% pure
Axicon Thorlabs N/A 100, IR range, AR coated, AX1210-B
Ethanol Supelco, India CAS No. 64-17-5
Femtosecond laser femtosecond  (fs)  laser amplifier  Libra HE, Coherent N/A Pulse duraction 50 fs;
wavelenngth 800 nm;
Rep rate 1 KHz;
Pulse Energy: 4 mJ
FESEM Carl ZEISS, Ultra 55 N/A
Gatan DM3 www.gatan.com Gatan Microscopy Suite 3.x
Gold target  Sigma-Aldrich, India 99% pure
HAuCl4.3H2O Sigma-Aldrich, India CAS No. 16961-25-4
High resolution translational stages Newport SPECTRA PHYSICS GMBI N/A M-443 High-Performance Low-Profile Ball Bearing Linear Stage;
The stage is only 1 inch high, and has 2 inches of travel. 
Micro Raman Horiba LabRAM N/A Grating-1,800 and 600 grooves/mm;
Wavelength of excitation-785 nm,632 nm, 532 nm, 325 nm;
Objectives 10x, 20x, 50 x, 100x;
CCD detector
Mirrors Edmund Optics N/A Suitable mirrors for specific wavelength of laser
Motion controller NEWPORT SPECTRA PIYSICS GMBI N/A ESP300 Controller-3 axes control
Origin www.originlab.com Origin 2018
Picosecond laser EKSPLA 2251 N/A Pulse duraction 30ps;
wavelenngth 1064 nm, 532 nm, 355 nm;
Rep rate 10 Hz;
Pulse Energy: 1.5 to 30 mJ
Planoconvex lens N/A focal length 10 cm
Raman portable i-Raman plus,  B&W Tek, USA N/A 785 nm, ~ 100 µm laser spot  fiber optic probe excitation and collection
Silicon wafer Macwin India Ltd. 1–10 Ω-cm, p (100)-type
Silver salt (AgNO3) Finar, India CAS No. 7783-90-6 
Silver target Sigma-Aldrich, India CAS NO 7440-22-4 99% pure
TEM Tecnai TEM N/A
TEM grids Sigma-Aldrich, India TEM-CF200CU Copper Grid Carbon Coated  200 mesh
Thiram Sigma-Aldrich, India CAS No. 137-26-8
UV Jasco V-670 N/A
XRD Bruker D8 advance N/A

  1. Theerthagiri, J., et al. Fundamentals and comprehensive insights on pulsed laser synthesis of advanced materials for diverse photo-and electrocatalytic applications. Light: Science & Applications. 11 (1), 250 (2022).
  2. Byram, C., et al. Review of ultrafast laser ablation for sensing and photonic applications. Journal of Optics. 25, 043001 (2023).
  3. Barcikowski, S., et al. . Handbook of laser synthesis of colloids. , (2016).
  4. Pariz, I., Goel, S., Nguyen, D. T., Buckeridge, J., Zhou, X. A critical review of the developments in molecular dynamics simulations to study femtosecond laser ablation. Materials Today: Proceedings. 64 (3), 1339-1348 (2022).
  5. Naser, H., et al. The role of laser ablation technique parameters in synthesis of nanoparticles from different target types. Journal of Nanoparticle Research. 21, 249 (2019).
  6. Zhang, D., Wada, H. Laser ablation in liquids for nanomaterial synthesis and applications. Handbook of Laser Micro-and Nano-Engineering. , 1-35 (2020).
  7. Yang, G. W. Laser ablation in liquids: Applications in the synthesis of nanocrystals. Progress in Materials Science. 52 (4), 648-698 (2007).
  8. Yu, J., et al. Extremely sensitive SERS sensors based on a femtosecond laser-fabricated superhydrophobic/-philic microporous platform. ACS Applied Materials & Interfaces. 14 (38), 43877-43885 (2022).
  9. Obilor, A. F., Pacella, M., Wilson, A., Silberschmidt, V. V. Micro-texturing of polymer surfaces using lasers: A review. The International Journal of Advanced Manufacturing Technology. 120 (1-2), 103-135 (2022).
  10. Beeram, R., Soma, V. R. Ultra-trace detection of diverse analyte molecules using femtosecond laser structured Ag-Au alloy substrates and SERRS. Optical Materials. 137, 113615 (2023).
  11. Yu, Y., Lee, S. J., Theerthagiri, J., Lee, Y., Choi, M. Y. Architecting the AuPt alloys for hydrazine oxidation as an anolyte in fuel cell: Comparative analysis of hydrazine splitting and water splitting for energy-saving H2 generation. Applied Catalysis B: Environmental. 316, 121603 (2022).
  12. Yu, Y., et al. Integrated technique of pulsed laser irradiation and sonochemical processes for the production of highly surface-active NiPd spheres. Chemical Engineering Journal. 411, 128486 (2021).
  13. Yu, Y., et al. Reconciling of experimental and theoretical insights on the electroactive behavior of C/Ni nanoparticles with AuPt alloys for hydrogen evolution efficiency and non-enzymatic sensor. Chemical Engineering Journal. 435, 134790 (2022).
  14. Shreyanka, S. N., Theerthagiri, J., Lee, S. J., Yu, Y., Choi, M. Y. Multiscale design of 3D metal-organic frameworks (M−BTC, M: Cu, Co, Ni) via PLAL enabling bifunctional electrocatalysts for robust overall water splitting. Chemical Engineering Journal. 446, 137045 (2022).
  15. Atta, S., Vo-Dinh, T. Ultra-trace SERS detection of cocaine and heroin using bimetallic gold-silver nanostars (BGNS-Ag). Analytica Chimica Acta. 1251, 340956 (2023).
  16. Mandal, P., Tewari, B. S. Progress in surface enhanced Raman scattering molecular sensing: A review. Surfaces and Interfaces. 28, 101655 (2022).
  17. Anh, N. H., et al. Gold nanoparticle-based optical nanosensors for food and health safety monitoring: recent advances and future perspectives. RSC Advances. 12 (18), 10950-10988 (2022).
  18. Zhao, Z., et al. Core-shell structured gold nanorods on thread-embroidered fabric-based microfluidic device for ex situ detection of glucose and lactate in sweat. Sensors and Actuators B: Chemical. 353, 131154 (2022).
  19. Chung, T., Lee, S. -. H. Quantitative study of plasmonic gold nanostar geometry toward optimal SERS detection. Plasmonics. 17 (5), 2113-2121 (2022).
  20. Mangababu, A., et al. Gold nanoparticles decorated GaAs periodic surface nanostructures for trace detection of RDX and tetryl. Surfaces and Interfaces. 36, 102563 (2023).
  21. Kang, H. -. S., et al. High-index facets and multidimensional hotspots in Au-decorated 24-faceted PbS for ultrasensitive and recyclable SERS substrates. Journal of Materials Chemistry C. 10 (3), 958-968 (2022).
  22. Chirumamilla, A., et al. Lithography-free fabrication of scalable 3D nanopillars as ultrasensitive SERS substrates. Applied Materials Today. 31, 101763 (2023).
  23. Meyer, S. M., Murphy, C. J. Anisotropic silica coating on gold nanorods boosts their potential as SERS sensors. Nanoscale. 14 (13), 5214-5226 (2022).
  24. Mangababu, A., et al. Multi-functional gallium arsenide nanoparticles and nanostructures fabricated using picosecond laser ablation. Applied Surface Science. 589, 152802 (2022).
  25. Krajczewski, J., et al. The battle for the future of SERS - TiN vs Au thin films with the same morphology. Applied Surface Science. 618, 156703 (2023).
  26. Naqvi, T. K., et al. Hierarchical laser-patterned silver/graphene oxide hybrid SERS sensor for explosive detection. ACS Omega. 4 (18), 17691-17701 (2019).
  27. Song, X., et al. Vertically aligned Ag-decorated MoS2 nanosheets supported on polyvinyl alcohol flexible substrate enable high-sensitivity and self-cleaning SERS devices. Journal of Environmental Chemical Engineering. 11 (2), 109437 (2023).
  28. Byram, C., Moram, S. S. B., Rao, S. V. Femtosecond laser-patterned and Au-coated iron surfaces as SERS platforms for multiple analytes detection. 2019 Workshop on Recent Advances in Photonics (WRAP). IEEE. , 1-3 (2019).
  29. Yao, H., et al. Functional cotton fabric-based TLC-SERS matrix for rapid and sensitive detection of mixed dyes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 280, 121464 (2022).
  30. Bharati, M. S. S., Soma, V. R. Flexible SERS substrates for hazardous materials detection: recent advances. Opto-Electronic Advances. 4 (11), 210048 (2021).
  31. Banerjee, D., Akkanaboina, M., Kanaka, R. K., Soma, V. R. Femtosecond Bessel beam induced ladder-like LIPSS on trimetallic surface for SERS-based sensing of Tetryl and PETN. Applied Surface Science. 616, 156561 (2023).
  32. Moram, S. S. B., Byram, C., Shibu, S. N., Chilukamarri, B. M., Soma, V. R. Ag/Au nanoparticle-loaded paper-based versatile surface-enhanced Raman spectroscopy substrates for multiple explosives detection. ACS Omega. 3 (7), 8190-8201 (2018).
  33. Byram, C., Rathod, J., Moram, S. S. B., Mangababu, A., Soma, V. R. Picosecond laser-ablated nanoparticles loaded filter paper for SERS-based trace detection of Thiram, 1, 3, 5-trinitroperhydro-1, 3, 5-triazine (RDX), and Nile blue. Nanomaterials. 12 (13), 2150 (2022).
  34. Moram, S. S. B., Byram, C., Soma, V. R. Femtosecond laser patterned silicon embedded with gold nanostars as a hybrid SERS substrate for pesticide detection. RSC Advances. 13 (4), 2620-2630 (2023).
  35. Zhang, D., Li, Z., Sugioka, K. Laser ablation in liquids for nanomaterial synthesis: diversities of targets and liquids. Journal of Physics: Photonics. 3 (4), 042002 (2021).
  36. Verma, A. K., Soni, R. K. Laser ablation synthesis of bimetallic gold-palladium core@shell nanoparticles for trace detection of explosives. Optics & Laser Technology. 163, 109429 (2023).
  37. Verma, A. K., Soni, R. K. Laser-textured hybrid tin-gold SERS platforms for ultra-trace analyte detection from contaminants. Optical Materials. 139, 113820 (2023).
  38. Podagatlapalli, G. K., Hamad, S., Rao, S. V. Trace-level detection of secondary explosives using hybrid silver-gold nanostructures and nanoparticles achieved with femtosecond laser ablation. The Journal of Physical Chemistry. C. 119 (29), 16972-16983 (2015).
  39. Hamad, S., Podagatlapalli, G. K., Mohiddon, M., Soma, V. R. Cost effective nanostructured copper substrates using ultrashort laser pulses for explosives detection using surface enhanced Raman spectroscopy. Applied Physics Letters. 104, 263104 (2014).
  40. Chandu, B., Bharati, M., Rao, S. V. Ag nanoparticles coupled with Ag nanostructures as efficient SERS platform for detection of 2, 4-Dinitrotoluene. 2017 IEEE Workshop on Recent Advances in Photonics (WRAP). IEEE. , 1-3 (2017).
  41. Naqvi, T. K., et al. Ultra-sensitive reusable SERS sensor for multiple hazardous materials detection on single platform. Journal of Hazardous Materials. 407, 124353 (2021).
  42. Byram, C., Moram, S. S. B., Soma, V. R. SERS based multiple analyte detection from explosive mixtures using picosecond laser fabricated gold nanoparticles and nanostructures. Analyst. 144 (7), 2327-2336 (2019).
  43. Byram, C., Moram, S. S. B., Shaik, A. K., Soma, V. R. Versatile gold based SERS substrates fabricated by ultrafast laser ablation for sensing picric acid and ammonium nitrate. Chemical Physics Letters. 685, 103-107 (2017).

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