低成本氧化铟锡基底的制备及其SERS活性

摘要/Abstract

摘要： 本文采用脉冲激光沉积和真空退火的方法在铝箔上制备氧化铟锡(indium tin oxide, ITO)表面增强拉曼散射(surface-enhanced Raman scattering, SERS)活性基底,并研究了ITO基底的SERS特性。沉积了700、1 000、1 300、1 600、2 000五组脉冲数的基底,测量结果显示薄膜厚度与脉冲数接近线性关系,当ITO薄膜厚度为60.80 nm(脉冲数为1 300)时,拉曼信号的增强程度达到最大值,其拉曼强度是Au基底的2~3倍。研究表明,真空退火能够显著提升ITO基底的拉曼增强效果,不同厚度的ITO薄膜基底均具有明显的SERS增强效果,可以通过控制薄膜厚度对ITO基底进行SERS调控。这些研究结果可为后续ITO材料SERS研究及应用提供参考依据。

关键词: 氧化铟锡, 脉冲激光沉积, 真空退火, 脉冲数, 表面增强拉曼散射, 表面等离激元, 低成本

Abstract: In this paper, the surface-enhanced Raman scattering (SERS) active substrates of indium tin oxide (ITO) were prepared on aluminum foil by laser pulse deposition and vacuum annealing, and the SERS characteristics of ITO substrates were investigated. Five substrates with pulse numbers of 700, 1 000, 1 300, 1 600 and 2 000 were deposited. The measurements show that the film thickness is close to the linear relationship with the pulse number. When the thickness of ITO film is 60.80 nm with the pulse number of 1 300, the enhancement degree of Raman signal reaches the maximum, and the Raman intensity of the prepared ITO substrate is about 2 to 3 times that of the Au substrate. The results show that vacuum annealing can significantly improve the Raman enhancement effect of ITO substrates. All substrates with different thicknesses of ITO films have obvious SERS enhanced effect. SERS enhancement effect of the ITO substrates can be adjusted by varying the film thickness. These results provide a reference for subsequent SERS research and application of indium tin oxide.

Key words: ITO, laser pulse deposition, vacuum annealing, pulse number, SERS, surface plasmon, low-cost

中图分类号:

O657.37

朱化强, 龙开琳, 刘风坤. 低成本氧化铟锡基底的制备及其SERS活性[J]. 人工晶体学报, 2022, 51(2): 263-270.

ZHU Huaqiang, LONG Kailin, LIU Fengkun. Low-Cost Indium Tin Oxide Substrates: Preparation and Its Surface Enhanced Raman Scattering Effect[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(2): 263-270.

参考文献

[1] FAN M K, ANDRADE G F S, BROLO A G. A review on recent advances in the applications of surface-enhanced Raman scattering in analytical chemistry[J]. Analytica Chimica Acta, 2020, 1097: 1-29.
[2] 陈思远,杨苗,刘晓云,等.载Au@Ag核壳复合双金属纳米棒的复合滤纸用作SERS基底[J].光谱学与光谱分析,2018,38(6):1747-1752.
CHEN S Y, YANG M, LIU X Y, et al. Study on Au@Ag core-shell composite bimetallic nanorods laoding filter paper as SERS substrate[J]. Spectroscopy and Spectral Analysis, 2018, 38(6): 1747-1752(in Chinese).
[3] 陈颖,吴振刚,魏恒勇,等.静电纺丝法制备柔性SERS基底及性能研究[J].人工晶体学报,2020,49(9):1667-1672.
CHEN Y, WU Z G, WEI H Y, et al. Preparation and properties of flexible SERS substrates by electrospinning[J]. Journal of Synthetic Crystals, 2020, 49(9): 1667-1672(in Chinese).
[4] NOGINOV M A, GU L, LIVENERE J, et al. Transparent conductive oxides: plasmonic materials for telecom wavelengths[J]. Applied Physics Letters, 2011, 99(2): 021101.
[5] 李晓晖,宋凯强,丛大龙,等.高透明低发射率ITO薄膜的制备及其光电性能研究[J].表面技术,2020,49(7):126-132.
LI X H, SONG K Q, CONG D L, et al. Preparation and photoelectric properties of ITO thin films with high transparency and low emissivity[J]. Surface Technology, 2020, 49(7): 126-132(in Chinese).
[6] 王欣月,张兆诚,黎智杰,等.基底加热温度对ITO薄膜的性能影响研究[J].人工晶体学报,2021,50(5):858-865.
WANG X Y, ZHANG Z C, LI Z J, et al. Effects of the substrate heating temperature on properties of ITO films[J]. Journal of Synthetic Crystals, 2021, 50(5): 858-865(in Chinese).
[7] FRANZEN S, RHODES C, CERRUTI M, et al. Plasmonic phenomena in indium tin oxide and ITO-Au hybrid films[J]. Optics Letters, 2009, 34(18): 2867.
[8] LOSEGO M D, EFREMENKO A Y, RHODES C L, et al. Conductive oxide thin films: model systems for understanding and controlling surface plasmon resonance[J]. Journal of Applied Physics, 2009, 106(2): 024903.
[9] MATSUI H, FURUTA S, TABATA H. Role of electron carriers on local surface plasmon resonances in doped oxide semiconductor nanocrystals[J]. Applied Physics Letters, 2014, 104(21): 211903.
[10] 蒋行,周玉荣,刘丰珍,等.后退火处理对铟锡氧化物表面等离激元共振特性的影响[J].物理学报,2018,67(17):177802.
JIANG H, ZHOU Y R, LIU F Z, et al. Effect of annealing treatment on characteristics of surface plasmon resonance for indium tin oxide[J]. Acta Physica Sinica, 2018, 67(17): 177802(in Chinese).
[11] MCGHEE J R, GOULAS A, SOUTHEE D J, et al. Indium tin oxide nanowires manufactured via printing and laser irradiation[J]. Applied Materials Today, 2020, 21: 100835.
[12] FRANZEN S. Surface plasmon polaritons and screened plasma absorption in indium tin oxide compared to silver and gold[J]. The Journal of Physical Chemistry C, 2008, 112(15): 6027-6032.
[13] RHODES C, CERRUTI M, EFREMENKO A, et al. Dependence of plasmon polaritons on the thickness of indium tin oxide thin films[J]. Journal of Applied Physics, 2008, 103(9): 093108.
[14] HAN B B, CHEN L, JIN S L, et al. Modulating mechanism of the LSPR and SERS in Ag/ITO film: carrier density effect[J]. The Journal of Physical Chemistry Letters, 2021, 12(31): 7612-7618.
[15] PHUNG V D, JUNG W S, KIM J H, et al. Gold nanostructures electrodeposited on graphene oxide-modified indium tin oxide glass as a surface-enhanced Raman scattering-active substrate for ultrasensitive detection of dopamine neurotransmitter[J]. Japanese Journal of Applied Physics, 2018, 57(8S2): 08PF02.
[16] LU H, HAN G X, CAO J P, et al. Large-area and patternable nano-dot array from electrolysis of ITO film for surface-enhanced Raman spectroscopy[J]. Nanoscale Research Letters, 2020, 15(1): 1-10.
[17] 马可可,周宁,袁梦,等.单分散氧化铟锡纳米晶的合成及其增强表面拉曼性能的研究[J].光散射学报,2014,26(2):140-143.
MA K K, ZHOU N, YUAN M, et al. Synthesis of monodisperse indium tin oxide nanocrystals and surface enhanced Raman performance research[J]. The Journal of Light Scattering, 2014, 26(2): 140-143(in Chinese).
[18] YANG Y M, QIU T, OU H L, et al. Modulation of surface-enhanced Raman spectra by depth selective excitation of embedded indium tin oxide nanoisland arrays[J]. Journal of Physics D: Applied Physics, 2011, 44(21): 215305.
[19] YANG Y M, QIU T, KONG F, et al. Interference effects on indium tin oxide enhanced Raman scattering[J]. Journal of Applied Physics, 2012, 111(3): 033110.
[20] YANG Y M, QIU T, LIU Z C, et al. Surface and interference co-enhanced Raman scattering from indium tin oxide nanocap arrays[J]. Applied Surface Science, 2013, 280: 343-348.
[21] 司丽芳,范兴策,侯翔宇,等.氧化铟锡纳米阵列中的协同增强拉曼散射现象研究[J].光散射学报,2021,33(1):32-39.
SI L F, FAN X C, HOU X Y, et al. Assembly of indium tin oxide nanoarrays for synergistically enhanced Raman scattering[J]. The Journal of Light Scattering, 2021, 33(1): 32-39(in Chinese).
[22] ADURODIJA F O, BRÜNING R, ASIA I O, et al. Effects of laser irradiation energy density on the properties of pulsed laser deposited ITO thin films[J]. Applied Physics A, 2005, 81(5): 953-957.
[23] KIM K H, CHOI K, CHOI E S, et al. Indium tin oxide thin films deposited by RF-magnetron sputtering for organic electro-luminescence devices[J]. Journal of Ceramic Processing Research, 2003, 4(2): 96-100.
[24] AOUAJ M A, DIAZ R, BELAYACHI A, et al. Comparative study of ITO and FTO thin films grown by spray pyrolysis[J]. Materials Research Bulletin, 2009, 44(7): 1458-1461.
[25] ALAM M J, CAMERON D C. Optical and electrical properties of transparent conductive ITO thin films deposited by sol-gel process[J]. Thin Solid Films, 2000, 377/378: 455-459.
[26] SAWADA Y, KOBAYASHI C, SEKI S, et al. Highly-conducting indium-tin-oxide transparent films fabricated by spray CVD using ethanol solution of indium (Ⅲ) chloride and tin (Ⅱ) chloride[J]. Thin Solid Films, 2002, 409(1): 46-50.
[27] KIM J H, AHN B D, LEE C H, et al. Enhancement in electrical and optical properties of indium tin oxide thin films grown using a pulsed laser deposition at room temperature by two-step process[J]. Thin Solid Films, 2007, 515(7/8): 3580-3583.
[28] MERGEL D, QIAO Z. Dielectric modelling of optical spectra of thin In₂O₃∶Sn films[J]. Journal of Physics D: Applied Physics, 2002, 35(8): 794-801.
[29] DINIZ A S A C, KIELY C J. Crystallisation of indium-tin-oxide (ITO) thin films[J]. Renewable Energy, 2004, 29(13): 2037-2051.
[30] QIU T, ZHANG W J, LANG X Z, et al. Controlled assembly of highly Raman-enhancing silver nanocap arrays templated by porous anodic alumina membranes[J]. Small, 2009, 5(20): 2333-2337.
[31] ZHANG Y, YAO L S, LIU L X, et al. Shape-diversified silver nanostructures on Al foil fabricated in micellar template for high performance surface enhanced Raman scattering applications[J]. Optical Materials, 2021, 121: 111629.
[32] GUTÉS A, CARRARO C, MABOUDIAN R. Silver dendrites from galvanic displacement on commercial aluminum foil as an effective SERS substrate[J]. Journal of the American Chemical Society, 2010, 132(5): 1476-1477.
[33] DONG J, ZHENG H R, YAN X Q, et al. Fabrication of flower-like silver nanostructure on the Al substrate for surface enhanced fluorescence[J]. Applied Physics Letters, 2012, 100(5): 051112.
[34] MUKANOVA Z, GUDUN K, ELEMESSOVA Z, et al. Detection of paracetamol in water and urea in artificial urine with gold nanoparticle@Al foil cost-efficient SERS substrate[J]. Analytical Sciences, 2018, 34(2): 183-187.
[35] ISIYAKU A K, ALI A H, NAYAN N. Structural optical and electrical properties of a transparent conductive ITO/Al-Ag/ITO multilayer contact[J]. Beilstein Journal of Nanotechnology, 2020, 11: 695-702.
[36] YESHCHENKO O A, KOZACHENKO V V, NAUMENKO A P, et al. Gold nanoparticle plasmon resonance in near-field coupled Au NPs layer/Al film nanostructure: dependence on metal film thickness[J]. Photonics and Nanostructures-Fundamentals and Applications, 2018, 29: 1-7.
[37] ALI D, BUTT M Z, MUNEER I, et al. Correlation between structural and optoelectronic properties of tin doped indium oxide thin films[J]. Optik, 2017, 128: 235-246.
[38] 孟庆哲,方允樟,马云,等.退火温度对ITO薄膜电导率的影响[J].材料科学,2013,3(1):45-49.
MENG Q Z, FANG Y Z, MA Y, et al. Influence of Annealing Temperature on Conductivity of ITO Films[J]. Material Sciences, 2013, 3: 45-49(in Chinese).
[39] 肖和平,郭冠军,马祥柱,等.热退火处理对氧化铟锡薄膜光电特性的影响[J].激光与光电子学进展,2017,54(1):013102.
XIAO H P, GUO G J, MA X Z, et al. Influence of thermal annealing on photoelectrical properties of indium-tin oxide thin films[J]. Laser & Optoelectronics Progress, 2017, 54(1): 013102(in Chinese).
[40] 刘钰,徐抒平,唐彬,等.表面等离子体共振与表面增强拉曼散射相关性研究[J].光散射学报,2010,22(1):29-33.
LIU Y, XU S P, TANG B, et al. Study on the relationship of surface plasmon and resonance surface-enhanced Raman scattering[J]. The Journal of Light Scattering, 2010, 22(1): 29-33(in Chinese).