najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2024-15-6-902-909najo-195Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХSERS substrates based on opal films with gold coatingПодложки для спектроскопии ГКР на основе опаловых пленок с золотым покрытиемАстафуровМ. О.AstafurovM. O.

Mikhail O. Astafurov

119991 Leninskie gory 1, bld. 3, Moscow

mihast0707@mail.ruhttps://orcid.org/0000-0002-1489-6747ПереведенцеваЕ. В.PerevedentsevaE. V.

Elena V. Perevedentseva

Leninskii prospekt 53, 119991, Moscow

perevedencevaev@lebedev.ruhttps://orcid.org/0000-0002-0212-9903МельникН. Н.MelnikN. N.

Nikolay N. Melnik

Leninskii prospekt 53, 119991, Moscow

melniknn@lebedev.ruhttps://orcid.org/0000-0002-2378-7446БаранчиковА. Е.BaranchikovA. E.

Alexander E. Baranchikov

Leninskii prospekt 31, 119071, Moscow

a.barantchikov@yandex.ruhttps://orcid.org/0000-0003-3820-4853ДорофеевС. Г.DorofeevS. G.

Sergey G. Dorofeev

119991 Leninskie gory 1, bld. 3, Moscow

dorofeev@inorg.chem.msu.ruhttps://orcid.org/0000-0001-6221-3093ЕжовА. А.EzhovA. A.

Alexander A. Ezhov

119991 Leninskie gory 1, bld. 3, Moscow

alexander-ezhov@yandex.ruhttps://orcid.org/0000-0001-6102-9024ГригорьеваА. В.GrigorievaA. V.

Anastasia V. Grigorieva

119991 Leninskie gory 1, bld. 3, Moscow

anastasia@inorg.chem.msu.ruhttps://orcid.org/0000-0001-6102-1305КлимонскийС. О.KlimonskyS. O.

Sergey O. Klimonsky

119991 Leninskie gory 1, bld. 3, Moscow

klimonskyso@my.msu.ruLomonosov Moscow State UniversityRussian FederationP. N. Lebedev Physical Institute of the Russian Academy of SciencesRussian FederationKurnakov Institute of General and Inorganic Chemistry of the Russian Academy of SciencesRussian Federation202405062025156902909Copyright © Astafurov M.O., Perevedentseva E.V., Melnik N.N., Baranchikov A.E., Dorofeev S.G., Ezhov A.A., Grigorieva A.V., Klimonsky S.O., 20252025Астафуров М.О., Переведенцева Е.В., Мельник Н.Н., Баранчиков А.Е., Дорофеев С.Г., Ежов А.А., Григорьева А.В., Климонский С.О.Astafurov M.O., Perevedentseva E.V., Melnik N.N., Baranchikov A.E., Dorofeev S.G., Ezhov A.A., Grigorieva A.V., Klimonsky S.O.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/195

Substrates for Surface-Enhanced Raman Spectroscopy (SERS) were fabricated by gold sputtering onto surface of synthetic opal films and their characteristics were studied at wavelengths λ = 532 and 785 nm. Synthetic opal films were fabricated by self-assembly of spherical SiO2 particles on vertical substrates. It was found that at the concentration of the analyte methylene blue equal to 10−5 M the intensity of SERS at the wavelength of 785 nm increased with increasing amount of sputtered gold up to a certain optimal thickness exceeding 35 nm, while at the concentration of 10−6 M this dependence was not observed. It is assumed that this is due to the complex amount-dependent morphology of the sputtered gold coating and the presence of “hot spots” of different strengths. For the best samples at a wavelength of λ = 785 nm, the SERS enhancement factor was of 7·104 and a detection limit for methylene blue reached 3·10−7 M that exceeds the results published for similar substrates previously. The SERS parameters obtained for λ = 532 nm were less attractive, despite the additional enhancement due to this wavelength was at the edge of the photonic stop-band.

Подложки для гигантского комбинационного рассеяния (ГКР) были сформированы с помощью напыления золота на поверхность пленки синтетического опала, и их свойства были изучены при длине волны λ = 532 и 785 нм. Пленки синтетического инвертированного опала были сформированы методом самосборки сферических частиц на вертикально SiO2 ориентированных подложках. Было обнаружено, что при концентрации аналита метиленового синего порядка 10-5 M интенсивность ГКР при длине волны возбуждающего лазера 785 нм растет с увеличением количества нанесенного золота до определенной оптимальной толщины, превышающей 35 нм, в то время как при концентрации аналита 10-6 M такой зависимости не наблюдается. Предполагается, что это связано со сложной морфологией нанесеннего золотого покрытия, зависящей от количества вещества, и присутствия «горячих точек» различной силы. Для лучших образцов на длине волны λ = 785 нм коэффициент усиления ГКР составлял 7∙104 и предел обнаружения метиленового синего  составлял 3∙10-7 M, что превышает результаты, опубликованные ранее для подобных подложек. Параметры ГКР для длины волны λ = 532 нм были менее яркими, несмотря на дополнительное усиление за счет попадания длины волны лазера в край фотонной стоп-зоны.

опал диоксида кремнияпокрытие золотамикроструктура«горячие точки»гигантское комбинационное рассеяниеsilica opalgold coatingSurface-Enhanced Raman spectroscopyThe authors are grateful to the Russian Science Foundation for financial support of the present research (Grant No. 23-23-00252). This work was partially performed using the scanning probe microscope NT-MDT NTEGRA Prima upgraded up to NT-MDT NTEGRA II by Nova SPb from Program for the Development of Moscow State University. Scanning electron microscopy was performed using the equipment of the JRC PMR IGIC RAS. The authors also thank Daniil Kozlov for assistance with electron microscopy.ReferencesLiang L., Zhao X., Wen J., Liu J., Zhang F., Guo X., Zhang K., Wang A., Gao R., Wang Y., Zhang Y. Flexible SERS Substrate with a Ag–SiO2 Cosputtered Film for the Rapid and Convenient Detection of Thiram. Langmuir, 2022, 38, P. 13753–13762.Liang L., Zhao X., Wen J., Liu J., Zhang F., Guo X., Zhang K., Wang A., Gao R., Wang Y., Zhang Y. Flexible SERS Substrate with a Ag–SiO2 Cosputtered Film for the Rapid and Convenient Detection of Thiram. Langmuir, 2022, 38, P. 13753–13762.Varasteanu P., Bujor A.M., Pachiu C., Craciun G., Mihalache I., Tucureanu V., Romanitan C., Pascu R., Boldeiu A. Close-packed small nanocubes assemblies as efficient SERS substrates. J. of Molecular Structure, 2023, 1294, 136441.Varasteanu P., Bujor A.M., Pachiu C., Craciun G., Mihalache I., Tucureanu V., Romanitan C., Pascu R., Boldeiu A. Close-packed small nanocubes assemblies as efficient SERS substrates. J. of Molecular Structure, 2023, 1294, 136441.Zha Z., Liu R., Yang W., Li C., Gao J., Shafi M., Fan X., Li Z., Du X., Jiang S. Surface-enhanced Raman scattering by the composite structure of Ag NP-multilayer Au films separated by Al2O3. Optics Express, 2021, 29 (6), P. 8890–8901.Zha Z., Liu R., Yang W., Li C., Gao J., Shafi M., Fan X., Li Z., Du X., Jiang S. Surface-enhanced Raman scattering by the composite structure of Ag NP-multilayer Au films separated by Al2O3. Optics Express, 2021, 29 (6), P. 8890–8901.Cai Z., Yan Y., Liu L., Lin S., Hu X. Controllable fabrication of metallic photonic crystals for ultra-sensitive SERS and photodetectors. RSC Adv., 2017, 7, P. 55851–55858.Cai Z., Yan Y., Liu L., Lin S., Hu X. Controllable fabrication of metallic photonic crystals for ultra-sensitive SERS and photodetectors. RSC Adv., 2017, 7, P. 55851–55858.He L., Huang J., Xu T., Chen L., Zhang K., Han S., He Y., Lee S.T. Silver nanosheet-coated inverse opal film as a highly active and uniform SERS substrate. J. Mater. Chem., 2012, 22, P. 1370–1374.He L., Huang J., Xu T., Chen L., Zhang K., Han S., He Y., Lee S.T. Silver nanosheet-coated inverse opal film as a highly active and uniform SERS substrate. J. Mater. Chem., 2012, 22, P. 1370–1374.Martynova N.A., Goldt A.E., Grigorieva A.V. Au-Au composites with inverse opal structure for surface-enhanced Raman spectroscopy. Gold Bulletin, 2018, 51, P. 57–64.Martynova N.A., Goldt A.E., Grigorieva A.V. Au-Au composites with inverse opal structure for surface-enhanced Raman spectroscopy. Gold Bulletin, 2018, 51, P. 57–64.Zhu A., Zhao X., Cheng M., Chen L., Wang Y., Zhang X., Zhang Y., Zhang X. Nanohoneycomb Surface-Enhanced Raman Spectroscopy-Active Chip for the Determination of Biomarkers of Hepatocellular Carcinoma. ACS Appl. Mater. Interfaces, 2019, 11, P. 44617–44623.Zhu A., Zhao X., Cheng M., Chen L., Wang Y., Zhang X., Zhang Y., Zhang X. Nanohoneycomb Surface-Enhanced Raman Spectroscopy-Active Chip for the Determination of Biomarkers of Hepatocellular Carcinoma. ACS Appl. Mater. Interfaces, 2019, 11, P. 44617–44623.Guo H., Qian K., Cai A., Tang J., Liu J. Ordered gold nanoparticle arrays on the tip of silver wrinkled structures for single molecule detection. Sensors & Actuators: B. Chemical, 2019, 300, 126846.Guo H., Qian K., Cai A., Tang J., Liu J. Ordered gold nanoparticle arrays on the tip of silver wrinkled structures for single molecule detection. Sensors & Actuators: B. Chemical, 2019, 300, 126846.Ke X., Chen J., Chang L., Zhou Z., Zhang W. Casting liquid PDMS on self-assembled bilayer polystyrene nanospheres to prepare a SERS substrate with two layers of nanopits for detection of p-nitrophenol. Anal. Methods, 2023, 15, P. 4582–4590.Ke X., Chen J., Chang L., Zhou Z., Zhang W. Casting liquid PDMS on self-assembled bilayer polystyrene nanospheres to prepare a SERS substrate with two layers of nanopits for detection of p-nitrophenol. Anal. Methods, 2023, 15, P. 4582–4590.Wei M.-X., Liu C.-H., Lee H., Lee B.-W., Hsu C.-H., Lin H.-P., Wu Yu-C. Synthesis of High-Performance Photonic Crystal Film for SERS Applications via Drop-Coating Method. Coatings, 2020, 10, 679.Wei M.-X., Liu C.-H., Lee H., Lee B.-W., Hsu C.-H., Lin H.-P., Wu Yu-C. Synthesis of High-Performance Photonic Crystal Film for SERS Applications via Drop-Coating Method. Coatings, 2020, 10, 679.Chen G., Zhang K., Luo B., Hong W., Chen J., Chen X. Plasmonic-3D photonic crystals microchip for surface enhanced Raman spectroscopy. Biosensors and Bioelectronics, 2019, 143, 111596.Chen G., Zhang K., Luo B., Hong W., Chen J., Chen X. Plasmonic-3D photonic crystals microchip for surface enhanced Raman spectroscopy. Biosensors and Bioelectronics, 2019, 143, 111596.Chen H., Song C., Peng Z., Mao J., Zhang Y., Chen S., Zhang W., Zhang S., Zhao W., Ouyang G. The Fabrication of Photonic Crystal Microchip with Controllable Wettability and SERS Activity based on Surface Roughness for Trace Organic Compounds Determination. Adv. Mater. Interfaces, 2022, 2102178.Chen H., Song C., Peng Z., Mao J., Zhang Y., Chen S., Zhang W., Zhang S., Zhao W., Ouyang G. The Fabrication of Photonic Crystal Microchip with Controllable Wettability and SERS Activity based on Surface Roughness for Trace Organic Compounds Determination. Adv. Mater. Interfaces, 2022, 2102178.Li W., Lu X., Yang R., Liang F., Chen W., Xie Z., Zheng J., Zhu J., Huang Y., Yue W., Li L., Su Y. Highly sensitive and reproducible SERS substrates with binary colloidal crystals (bCCs) based on MIM structures. Applied Surface Science, 2022, 597, 153654.Li W., Lu X., Yang R., Liang F., Chen W., Xie Z., Zheng J., Zhu J., Huang Y., Yue W., Li L., Su Y. Highly sensitive and reproducible SERS substrates with binary colloidal crystals (bCCs) based on MIM structures. Applied Surface Science, 2022, 597, 153654.Dzhagan V., Mazur N., Kapush O., Skoryk M., Pirko Y., Yemets A., Dzhahan Vl., Shepeliavyi P., Valakh M., and Yukhymchuk V. Self-Organized SERS Substrates with Efficient Analyte Enrichment in the Hot Spots. ACS Omega, 2024, 9, P. 4819–4830.Dzhagan V., Mazur N., Kapush O., Skoryk M., Pirko Y., Yemets A., Dzhahan Vl., Shepeliavyi P., Valakh M., and Yukhymchuk V. Self-Organized SERS Substrates with Efficient Analyte Enrichment in the Hot Spots. ACS Omega, 2024, 9, P. 4819–4830.Galisteo-Lopez J.F., Ibisate M., Sapienza R., Froufe Perez L.S., Blanco A., Lopez C. Self-Assembled Photonic Structures. Adv. Mater., 2011, 23, P. 30–69.Galisteo-Lopez J.F., Ibisate M., Sapienza R., Froufe Perez L.S., Blanco A., Lopez C. Self-Assembled Photonic Structures. Adv. Mater., 2011, 23, P. 30–69.Liu J., Zhao H., Wu M., Van der Schueren B., Yu Li, Deparis O., Ye J., Ozin G.A., Hasan T., Su B.-L. Slow Photons for Photocatalysis and Photovoltaics. Adv. Mater., 2017, 29, 1605349.Liu J., Zhao H., Wu M., Van der Schueren B., Yu Li, Deparis O., Ye J., Ozin G.A., Hasan T., Su B.-L. Slow Photons for Photocatalysis and Photovoltaics. Adv. Mater., 2017, 29, 1605349.Ashurov M., Abdusatorov B., Baranchikov A., Klimonsky S. Surface-enhanced Raman scattering in ETPTA inverse photonic crystals with gold nanoparticles. Phys. Chem. Chem. Phys., 2021, 23, P. 20275–20281.Ashurov M., Abdusatorov B., Baranchikov A., Klimonsky S. Surface-enhanced Raman scattering in ETPTA inverse photonic crystals with gold nanoparticles. Phys. Chem. Chem. Phys., 2021, 23, P. 20275–20281.Jiang P., Bertone J.F., Hwang K.S., Colvin V.L. Single-Crystal Colloidal Multilayers of Controlled Thickness. Chem. Mater., 1999, 11, P. 2132–2140.Jiang P., Bertone J.F., Hwang K.S., Colvin V.L. Single-Crystal Colloidal Multilayers of Controlled Thickness. Chem. Mater., 1999, 11, P. 2132–2140.Klimonsky S.O., Bakhia T., Knotko A.V., Lukashin A.V. Synthesis of Narrow Dispersed SiO2 Colloidal Particles and Colloidal Crystal Films Based on Them. Doklady Chemistry, 2014, 457 (1), P. 115–117.Klimonsky S.O., Bakhia T., Knotko A.V., Lukashin A.V. Synthesis of Narrow Dispersed SiO2 Colloidal Particles and Colloidal Crystal Films Based on Them. Doklady Chemistry, 2014, 457 (1), P. 115–117.St¨ober W., Fink A., Bohn E. Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range. J. Colloid Interface Sci., 1968, 26, P. 62–69.St¨ober W., Fink A., Bohn E. Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range. J. Colloid Interface Sci., 1968, 26, P. 62–69.Bakhia T., Baranchikov A.E., Gorelik V.S., Klimonsky S.O. Local Optical Spectroscopy of Opaline Photonic Crystal Films. Crystallography Reports, 2017, 62 (5), P. 783–786.Bakhia T., Baranchikov A.E., Gorelik V.S., Klimonsky S.O. Local Optical Spectroscopy of Opaline Photonic Crystal Films. Crystallography Reports, 2017, 62 (5), P. 783–786.Le Ru E., Blackie E., Meyer M., Etchegoin P.G. Surface Enhanced Raman Scattering Enhancement Factors: A Comprehensive Study. J. Phys. Chem. C, 2007, 111 (37), P. 13794–13803.Le Ru E., Blackie E., Meyer M., Etchegoin P.G. Surface Enhanced Raman Scattering Enhancement Factors: A Comprehensive Study. J. Phys. Chem. C, 2007, 111 (37), P. 13794–13803.Yan Q., Zhou Z., Zhao X.S. Inward-Growing Self-Assembly of Colloidal Crystal Films on Horizontal Substrates. Langmuir, 2005, 21 (7), P. 3158–3164.Yan Q., Zhou Z., Zhao X.S. Inward-Growing Self-Assembly of Colloidal Crystal Films on Horizontal Substrates. Langmuir, 2005, 21 (7), P. 3158–3164.

The authors declare that there are no conflicts of interest present.