椭偏仪在位表征电化学沉积的系统搭建（三十一）- 单波长实时监测

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椭偏仪在位表征电化学沉积的系统搭建（三十一）- 单波长实时监测

同样选择-0.4mA作为沉积电流，然后进行椭偏仪的单波长实时在位测量，测量角度65°，测量波长380nm。

图4-24是沉积1080s后进行SEM测试得到的薄膜表面形貌图，在1μm标尺下看到沉积的薄膜颗粒大小不等，小到几纳米大到几百纳米，形态上为不规则棱柱状。和前面准在位监测沉积1080s的对比发现此处得到的薄膜小颗粒更少，岛状更加明显。

图4-24 -0.4mA连续沉积1080s后的SEM图

把上节层状生长得到的平均生长速率和岛状生长得到的厚度时间关系计算得到相应厚度和时间的变化如图4-24(a)所示。利用两个不同厚度随时间的变化和沉积1080s拟合得到的n、k值，输入Film Wizard软件中模拟计算得到不同厚度下的Psi和Delta，并和实验值进行对比，如图4-24(b)和(c)所示，其中Experiment value是在位监测得到的椭偏参数实验值，0.34nm/s是用层状生长平均速率得到的模拟计算值，0.005t^0.72nm/s是用岛状生长平均速率得到的模拟计算值，图4-24(b)为Psi值，(c)图为Delta值。可以看到实验值和模拟计算得到的Psi和Delta值整体上的变化趋势一致，但是在数值及峰位上存在差别。对于实验值，随着沉积时间的增加，Psi值在0-125s从32°减小到25°，在125s-500s增加，500s-1080s减小；Delta值变化趋势和Psi一致。层状生长模拟计算的Psi值整体上比实验的小，在0-250s内减小，250-1080s先增后减，变化不明显；Delta值整体上比实验值小，在0-150s内减小，150s-1080s先增后减。岛状生长模拟计算的Psi和Delta值整体和层状生长的比较相似，在500s-1080s基本重合。和层状模式相比，在0-500s数值峰位存在向右移动，Psi值的波谷由250s附近移动到了375s附近，Delta值的波谷由150s附近移动到了275s附近。在0-250s内减小，250-1080s先增后减，变化不明显；Delta值整体上比实验值小，在0-150s内减小，150s-1080s先增后减。实验值和模拟计算出的值对比有明显的差别。

实验值包含了测试过程中光经过的所有介质(TIO、溶液、沉积物和Au/Si基底)，反映的是测试池体整体信息。模拟值用的n、k及厚度用的是准在位拟合出来的沉积层的值，计算的是沉积层的信息。所以实验值和模拟计算的Psi和Delta值会有差别，这也就是上述图线出现差异的原因。这种差异的存在同时也验证了建模拟合的可行性。同时，从SEM的对比发现，沉积得到的CU²O表面形貌差异也可能是导致上述用Psi和Delta随时间的变化实验值和计算值不同的原因。

图4-25(a)层状(0.34nm/s)和岛状(0.005t^0.72nm/s)生长得到生长速率下厚度随时间变化及单波长380nm实时在位监测得到的椭偏参数实验值和模拟计算值图(b)Psi和(c)Delta

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参考文献

[1] WONG H S P, FRANK D J, SOLOMON P M et al. Nanoscale cmos[J]. Proceedings of the IEEE, 1999, 87(4): 537-570.

[2] LOSURDO M, HINGERL K. ellipsometry at the nanoscale[M]. Springer Heidelberg New York Dordrecht London. 2013.

[3] DYRE J C. Universal low-temperature ac conductivity of macroscopically disordered nonmetals[J]. Physical Review B, 1993, 48(17): 12511-12526. DOI:10.1103/PhysRevB.48.12511.

[4] CHEN S, KÜHNE P, STANISHEV V et al. On the anomalous optical conductivity dISPersion of electrically conducting polymers: Ultra-wide spectral range ellipsometry combined with a Drude-Lorentz model[J]. Journal of Materials Chemistry C, 2019, 7(15): 4350-4362.

[5] 陈篮，周岩. 膜厚度测量的椭偏仪法原理分析[J]. 大学物理实验, 1999, 12(3): 10-13.

[6] ZAPIEN J A, COLLINS R W, MESSIER R. Multichannel ellipsometer for real time spectroscopy of thin film deposition from 1.5 to 6.5 eV[J]. Review of Scientific Instruments, 2000, 71(9): 3451-3460.

[7] DULTSEV F N, KOLOSOVSKY E A. Application of ellipsometry to control the plasmachemical synthesis of thin TiONx layers[J]. Advances in Condensed Matter Physics, 2015, 2015: 1-8.

[8] DULTSEV F N, KOLOSOVSKY E A. Application of ellipsometry to control the plasmachemical synthesis of thin TiONx layers[J]. Advances in Condensed Matter Physics, 2015, 2015: 1-8.

[9] YUAN M, YUAN L, HU Z et al. In Situ Spectroscopic Ellipsometry for Thermochromic CsPbI3 Phase Evolution Portfolio[J]. Journal of Physical Chemistry C, 2020, 124(14): 8008-8014.

[10] 焦杨景.椭偏仪在位表征电化学沉积的系统搭建.云南大学说是论文,2022.

[11] CANEPA M, MAIDECCHI G, TOCCAFONDI C et al. Spectroscopic ellipsometry of self assembLED monolayers: Interface effects. the case of phenyl selenide SAMs on gold[J]. Physical Chemistry Chemical Physics, 2013, 15(27): 11559-11565. DOI:10.1039/c3cp51304a.

[12] FUJIWARA H, KONDO M, MATSUDA A. Interface-layer formation in microcrystalline Si:H growth on ZnO substrates studied by real-time spectroscopic ellipsometry and infrared spectroscopy[J]. Journal of Applied Physics, 2003, 93(5): 2400-2409.

[13] FUJIWARA H, TOYOSHIMA Y, KONDO M et al. Interface-layer formation mechanism in (formula presented) thin-film growth studied by real-time spectroscopic ellipsometry and infrared spectroscopy[J]. Physical Review B - Condensed Matter and Materials Physics, 1999, 60(19): 13598-13604.

[14] LEE W K, KO J S. Kinetic model for the simulation of hen egg white lysozyme adsorption at solid/water interface[J]. Korean Journal of Chemical Engineering, 2003, 20(3): 549-553.

[15] STAMATAKI K, PAPADAKIS V, EVEREST M A et al. Monitoring adsorption and sedimentation using evanescent-wave cavity ringdown ellipsometry[J]. Applied Optics, 2013, 52(5): 1086-1093.

[16] VIEGAS D, FERNANDES E, QUEIRÓS R et al. Adapting Bobbert-Vlieger model to spectroscopic ellipsometry of gold nanoparticles with bio-organic shells[J]. Biomedical Optics Express, 2017, 8(8): 3538.

[17] ARWIN H. Application of ellipsometry techniques to biological materials[J]. Thin Solid Films, 2011, 519(9): 2589-2592.

[18] ZIMMER A, VEYS-RENAUX D, BROCH L et al. In situ spectroelectrochemical ellipsometry using super continuum white laser: Study of the anodization of magnesium alloy [J]. Journal of Vacuum Science & Technology B, 2019, 37(6): 062911.

[19] ZANGOOIE S, BJORKLUND R, ARWIN H. Water Interaction with Thermally Oxidized Porous Silicon Layers[J]. Journal of The Electrochemical Society, 1997, 144(11): 4027-4035.

[20] KYUNG Y B, LEE S, OH H et al. Determination of the optical functions of various liquids by rotating compensator multichannel spectroscopic ellipsometry[J]. Bulletin of the Korean Chemical Society, 2005, 26(6): 947-951.

[21] OGIEGLO W, VAN DER WERF H, TEMPELMAN K et al. Erratum to ― n-Hexane induced swelling of thin PDMS films under non-equilibrium nanofiltration permeation conditions, resolved by spectroscopic ellipsometry‖ [J. Membr. Sci. 431 (2013), 233-243][J]. Journal of Membrane Science, 2013, 437: 312..

[22] BROCH L, JOHANN L, STEIN N et al. Real time in situ ellipsometric and gravimetric monitoring for electrochemistry experiments[J]. Review of Scientific Instruments, 2007, 78(6).

[23] BISIO F, PRATO M, BARBORINI E et al. Interaction of alkanethiols with nanoporous cluster-assembled Au films[J]. Langmuir, 2011, 27(13): 8371-8376.

[24] 李广立. 氧化亚铜薄膜的制备及其光电性能研究[D]. 西南交通大学, 2016.

[25] 董金矿. 氧化亚铜薄膜的制备及其光催化性能的研究[D]. 安徽建筑大学, 2014.

[26] 张桢. 氧化亚铜薄膜的电化学制备及其光催化和光电性能的研究[D]. 上海交通大学材料科 学与工程学院, 2013.

[27] DISSERTATION M. Cellulose Derivative and Lanthanide Complex Thin Film Cellulose Derivative and Lanthanide Complex Thin Film[J]. 2017.

[28] NIE J, YU X, HU D et al. Preparation and Properties of Cu2O/TiO2 heterojunction Nanocomposite for Rhodamine B Degradation under visible light[J]. ChemistrySelect, 2020, 5(27): 8118-8128.

[29] STRASSER P, GLIECH M, KUEHL S et al. Electrochemical processes on solid shaped nanoparticles with defined facets[J]. Chemical Society Reviews, 2018, 47(3): 715-735.

[30] XU Z, CHEN Y, ZHANG Z et al. Progress of research on underpotential deposition——I. Theory of underpotential deposition[J]. Wuli Huaxue Xuebao/ Acta Physico - Chimica Sinica, 2015, 31(7): 1219-1230.

[31] PANGAROV n. Thermodynamics of electrochemical phase formation and underpotential metal deposition[J]. Electrochimica Acta, 1983, 28(6): 763-775.

[32] KAYASTH S. ELECTRODEPOSITION STUDIES OF RARE EARTHS[J]. Methods in Geochemistry and Geophysics, 1972, 6(C): 5-13.

[33] KONDO T, TAKAKUSAGI S, UOSAKI K. Stability of underpotentially deposited Ag layers on a Au(1 1 1) surface studied by surface X-ray scattering[J]. Electrochemistry Communications, 2009, 11(4): 804-807.

[34] GASPAROTTO L H S, BORISENKO N, BOCCHI N et al. In situ STM investigation of the lithium underpotential deposition on Au(111) in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide[J]. Physical Chemistry Chemical Physics, 2009, 11(47): 11140-11145.

[35] SARABIA F J, CLIMENT V, FELIU J M. Underpotential deposition of Nickel on platinum single crystal electrodes[J]. Journal of Electroanalytical Chemistry, 2018, 819(V): 391-400.

[36] BARD A J, FAULKNER L R, SWAIN E et al. Fundamentals and Applications[M]. John Wiley & Sons, Inc, 2001.

[37] SCHWEINER F, MAIN J, FELDMAIER M et al. Impact of the valence band structure of Cu2O on excitonic spectra[J]. Physical Review B, 2016, 93(19): 1-16.

 [38] XIONG L, HUANG S, YANG X et al. P-Type and n-type Cu2O semiconductor thin films: Controllable preparation by simple solvothermal method and photoelectrochemical properties[J]. Electrochimica Acta, 2011, 56(6): 2735-2739.

[39] KAZIMIERCZUK T, FRÖHLICH D, SCHEEL S et al. Giant Rydberg excitons in the copper oxide Cu2O[J]. Nature, 2014, 514(7522): 343-347.

[40] RAEBIGER H, LANY S, ZUNGER A. Origins of the p-type nature and cation deficiency in Cu2 O and related materials[J]. Physical Review B - Condensed Matter and Materials Physics, 2007, 76(4): 1-5.

[41] 舒云. Cu2O薄膜的电化学制备及其光电化学性能的研究[D]. 云南大学物理与天文学院，2019.