基于金属锡掺杂浓度变化的光学性能可调谐ITO薄膜制备研究

摘要/Abstract

摘要： 本文通过电子束蒸发技术制备了金属锡掺杂浓度不同的一系列ITO薄膜。采用X射线衍射仪、原子力显微镜、紫外-可见光-近红外分光光度计、四探针测电阻仪和Z扫描系统分别对ITO薄膜的物相结构、微观形貌、光学吸收、方块电阻和非线性光学性能进行测试和表征。结果表明,随着金属锡掺杂浓度由10%增加到30%:ITO薄膜的结晶质量增加;薄膜表面粗糙度增加,晶粒尺寸逐渐增大;等离子体吸收增强,且吸收峰的位置发生红移,光学带隙变窄;薄膜的方块电阻不断减小;非线性吸收系数逐渐增加,绝对值最大可以增至2.59×10^-7 cm/W。时域有限差分拟合结果表明金属锡掺杂浓度不同的ITO薄膜电场强度变化规律与实验结果相一致。

关键词: 氧化铟锡, 局部表面等离子体共振, 非线性光学响应, Z扫描, 增强电场, 掺杂, 电子束蒸发

Abstract: In this paper, a series of ITO thin films with different concentrations of metal Sn doping were prepared by electron beam evaporation technique. X-ray diffractometer, atomic force microscope, UV-Vis-NIR spectrophotometer, four-probe resistivity meter and Z-scan system were used to measure and characterize the physical phase structure, microscopic morphology, optical absorption, square resistance and nonlinear optical properties of ITO films, respectively. The test results show that, with the increase of metal Sn doping concentration from 10% to 30%: the crystalline quality of the ITO film is enhanced; the surface roughness of the film increases and the grain size gradually increases; the plasma absorption is enhanced and the position of the absorption peak is red-shifted and the optical band gap is narrowed; the square resistance of the film continuously reduces; the nonlinear absorption coefficient gradually increases, and the maximum absolute value can be increased to 2.59× 10^-7 cm/W. The finite-difference fitting results in the time domain show that the variation pattern of electric field intensity of ITO thin film samples with different metal Sn doping concentrations is consistent with the experimental results.

Key words: ITO, LSPR, nonlinear optical response, Z-scan, enhanced electric field, doping, electron beam evaporation

中图分类号:

O484.1
O437

南博洋, 洪瑞金, 陶春先, 王琦, 林辉, 韩朝霞, 张大伟. 基于金属锡掺杂浓度变化的光学性能可调谐ITO薄膜制备研究[J]. 人工晶体学报, 2023, 52(9): 1617-1623.

NAN Boyang, HONG Ruijin, TAO Chunxian, WANG Qi, LIN Hui, HAN Zhaoxia, ZHANG Dawei. Fabrication of Metal Sn Doping Concentration Dependency of ITO Thin Films with Tunable Optical Properties[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(9): 1617-1623.

参考文献

[1] LI G R, XU Q, SINGH R, et al. Graphene oxide/multiwalled carbon nanotubes assisted serial quadruple tapered structure-based LSPR sensor for glucose detection[J]. IEEE Sensors Journal, 2022, 22(17): 16904-16911.
[2] REN B S, LUAN Q R, MA L L, et al. Amorphous domain induced LSPR Zn-Cr-In-S solid solution with enhanced visible photocatalytic H₂ production[J]. Materials Chemistry and Physics, 2022, 285: 126100.
[3] LV S J, DU Y P, WU F T, et al. Review on LSPR assisted photocatalysis: effects of physical fields and opportunities in multifield decoupling[J]. Nanoscale Advances, 2022, 4(12): 2608-2631.
[4] WEST J L, HALAS N J. Engineered nanomaterials for biophotonics applications: improving sensing, imaging, and therapeutics[J]. Annual Review of Biomedical Engineering, 2003, 5: 285-292.
[5] LIN M, LU M D, LIANG Y Z, et al. Polyelectrolyte-enhanced localized surface plasmon resonance optical fiber sensors: properties interrogation and bioapplication[J]. ACS Applied Nano Materials, 2022, 5(5): 6171-6180.
[6] ATWATER H A, POLMAN A. Erratum: plasmonics for improved photovoltaic devices[J]. Nature Materials, 2010, 9(10): 865.
[7] YANG Y, NOGAMI M, SHI J L, et al. Controlled surface-plasmon coupling in SiO₂-coated gold nanochains for tunable nonlinear optical properties[J]. Applied Physics Letters, 2006, 88(8): 081110.
[8] BOUHELIER A, BACHELOT R, LERONDEL G, et al. Surface plasmon characteristics of tunable photoluminescence in single gold nanorods[J]. Physical Review Letters, 2005, 95(26): 267405.
[9] SHAN H F, MA W J, YANG H H, et al. Fabrication of Cu-doped molybdenum oxide for bifunctional SERS and photothermal conversion[J]. Materials Chemistry and Physics, 2022, 292: 126775.
[10] AUGUSTINE S, SAINI M, K P S, et al. Au/Ag SERS active substrate for broader wavelength excitation[J]. Optical Materials, 2023, 135: 113319.
[11] BAKKER R M, YUAN H K, LIU Z T, et al. Enhanced localized fluorescence in plasmonic nanoantennae[J]. Applied Physics Letters, 2008, 92(4): 043101.
[12] SINGLA S, ABHISHEK, BANSAL N, et al. Analysis of gold nanoparticles dispersed bismuth borate glass: effect of size and concentration[J]. Journal of Materials Science: Materials in Electronics, 2023, 34(6): 526.
[13] BARBIC M, MOCK J J, SMITH D R, et al. Single crystal silver nanowires prepared by the metal amplification method[J]. Journal of Applied Physics, 2002, 91(11): 9341-9345.
[14] KOTTMANN J P, MARTIN O J F, SMITH D R, et al. Plasmon resonances of silver nanowires with a nonregular cross section[J]. Physical Review B, 2001, 64(23): 235402.
[15] WANG L R, FANG Y. The investigation of a series of n-hydroxybenzoic acids (n=p, m, o) on a new surface enhanced Raman scattering active substrate[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2005, 62(4/5): 958-963.
[16] HOU X M, FANG Y. Investigation of p-hydroxybenzoic acid from a new surface-enhanced Raman scattering system[J]. Journal of Colloid and Interface Science, 2007, 316(1): 19-24.
[17] REN Y, LIU P, LIU R X, et al. The key of ITO films with high transparency and conductivity: grain size and surface chemical composition[J]. Journal of Alloys and Compounds, 2022, 893: 162304.
[18] TCHENKA A, AGDAD A, BOUSSETA M, et al. Effect of vacuum annealing and position of metal Cu on structural, optical, electrical and thermoelectrical properties of ITO/Cu/ITO multilayers prepared by RF sputtering[J]. Optical Materials, 2022, 131: 112634.
[19] XIA Y N, XIONG Y J, LIM B, et al. Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics?[J]. Angewandte Chemie, 2009, 48(1): 60-103.
[20] HONG R J, SONG X, TAO C X, et al. Surface-enhanced Raman scattering of silver thin films on as-roughened substrate by reactive ion etching[J]. Applied Physics A, 2016, 122(3): 178.
[21] MALATHY V, SIVARANJANI S, VIDHYA V S, et al. Amorphous to crystalline transition and optoelectronic properties of nanocrystalline indium tin oxide (ITO) films sputtered with high RF power at room temperature[J]. Journal of Non-Crystalline Solids, 2009, 355(28/29/30): 1508-1516.
[22] SZKUTNIK P D, ROUSSEL H, LAHOOTUN V, et al. Study of the functional properties of ITO grown by metalorganic chemical vapor deposition from different indium and tin precursors[J]. Journal of Alloys and Compounds, 2014, 603: 268-273.
[23] BOUOUDINA M, OMRI K, EL-HILO M, et al. Structural and magnetic properties of Mn-doped ZnO nanocrystals[J]. Physica E: Low-Dimensional Systems and Nanostructures, 2014, 56: 107-112.
[24] LIU X J, JIA L J, FAN G P, et al. Au nanoparticle enhanced thin-film silicon solar cells[J]. Solar Energy Materials and Solar Cells, 2016, 147: 225-234.
[25] KANEHARA M, KOIKE H, YOSHINAGA T, et al. Indium tin oxide nanoparticles with compositionally tunable surface plasmon resonance frequencies in the near-IR region[J]. Journal of the American Chemical Society, 2009, 131(49): 17736-17737.
[26] KIM S S, CHOI S Y, PARK C G, et al. Transparent conductive ITO thin films through the sol-gel process using metal salts[J]. Thin Solid Films, 1999, 347(1/2): 155-160.
[27] RAND B P, PEUMANS P, FORREST S R. Long-range absorption enhancement in organic tandem thin-film solar cells containing silver nanoclusters[J]. Journal of Applied Physics, 2004, 96(12): 7519-7526.
[28] SZCZESNY R, SCIGALA A, DERKOWSKA-ZIELINSKA B, et al. Synthesis, optical, and morphological studies of ZnO powders and thin films fabricated by wet chemical methods[J]. Materials, 2020, 13(11): 2559.
[29] RAMANATHAN G, MURALI K R. Optical performance of Tin doped indium oxide (ITO) thin films prepared by sol gel dip coating techniques using acrylamide route[J]. Optical and Quantum Electronics, 2022, 54(10): 1-12.
[30] LIU T T, LIU Q Y, JIANG Y K, et al. Enhancement of nonlinear optical property of Cu₂O/Ag/Cu₂O composite films induced by laser irradiation[J]. Journal of Materials Science, 2021, 56(16): 9871-9882.
[31] SERNA J, RUEDA E, GARCÍA H. Nonlinear optical properties of bulk cuprous oxide using single beam Z-scan at 790 nm[J]. Applied Physics Letters, 2014, 105(19): 191902.
[32] GANESH V, YAHIA I S, ALFAIFY S, et al. Sn-doped ZnO nanocrystalline thin films with enhanced linear and nonlinear optical properties for optoelectronic applications[J]. Journal of Physics and Chemistry of Solids, 2017, 100: 115-125.
[33] BIKORIMANA S, LAMA P, WALSER A, et al. Nonlinear optical responses in two-dimensional transition metal dichalcogenide multilayer: WS₂, WSe₂, MoS₂ and Mo_0.5W_0.5S₂[J]. Optics Express, 2016, 24(18): 20685.