Corresponding Author

Ling-jie LI(LJLi@cqu.edu.cn)


Ellipsometry is an optical technique with high-sensitivity to quantitatively obtain surface/interface properties such as thickness andrefractive index by analyzing the changes in polarized light reflected from the surface/interface. Its noncontacting and nondestructivenature makes it possible to acquire thein situreal-time information of the change at the surface/interface. Therefore, ellipsometry has been used widely in the electrochemical investigations. In this paper, based on the brief introduction of the measurementprinciple of ellipsometry, the current progress and the future trends of ellipsometry in electrochemistry arediscussed. The applications of ellipsometry in the fields of conversion and storage of electrochemical energy, electrochemistry ofmaterials science,electroanalysisand bioelectrochemistry are reviewed.

Graphical Abstract


ellipsometry, spectroelectrochemistry, interface, surface

Publication Date


Online Available Date


Revised Date


Received Date



[1] Azzam R M A., Bashara N M. Ellipsometry and polarized light[M]. New York: North-Holland Publishing Co., 1977: 270.

[2] Fujiwara H. Spectroscopic ellipsometry: Principles and applications[M]. West Sussex: John Wiley & Sons, Inc., 2007: 1.

[3] Tompkins H G, Irene E A. Handbook of ellipsometry[M]. New York: William Andrew, Inc., 2005: 1.

[4] Huang Z Q(黄宗卿), Zhang S T(张胜涛), Xie S F(谢上芬), et al. Spectroellipsometric studies on electrochemistry and its application[J]. Journal of Electrochemistry (电化学), 1999, 5(3): 247-253.

[5] Tronstad L. The validity of Drude's optical method of investigating transparent films on metals[J]. Transactions of the Faraday Society, 1935, 31(2): 1151-1158.

[6] Sayder P G, Rost M C, Buabbud G H, et al. Variable angle of incidence spectroscopic ellipsometry-application to GAAS-ALXGA1-XAS multiple heterostructures[J]. Journal of Applied Physics, 1986, 60(9): 3293-3302.

[7] Okabe H, Hayakawa M, Matoba J, et al. Error-reduced channeled spectroscopic ellipsometer with palm-size sensing head[J]. Review of Scientific Instruments, 2009, 80(8): 0831041.

[8] Schaftinghen T V, Joiret S, Deslouis C, et al. In situ Raman spectroscopy and spectroscopic ellipsometry analysis of the iron/polypyrrole interface[J]. The Journal of Physical Chemistry C, 2007, 111(39): 14400-14409

[9] Li L J(李凌杰), Lei J L(雷惊雷), He D H(贺东海), et al. Study on corrosion of magnesium alloy in simulated cooling water with in situ spectroscopic ellipsometry[J]. Corrosion Science and Protection Technology (腐蚀科学与防护技术), 2009, 21(3): 236-238.

[10] Lei J L(雷惊雷), Zhang L N(张李娜), Li L J(李凌杰), et al. In situ ellipsometric study on initial stages of porous anodization of aluminum[J]. Acta Physico-Chimica Sinica(物理化学学报), 2010, 26(9): 2392-2396.

[11] Li L J, Lei J L, Yu S H, et al. In situ ellipsometric studies of formation kinetics of rare earth metal conversion coatings on magnesium alloy[J]. Physica Status Solidi C Conferences, 2008, 5(5): 1308-1311.

[12] Meuse C W. Infrared spectroscopic ellipsometry of self-assembled monolayers[J]. Langmuir, 2000, 16(24): 9483-9487.

[13] Sun G G, Hovest?dt M, Zhang X, et al. Infrared spectroscopic ellipsometry (IRSE) and X-ray photoelectron spectroscopy (XPS) monitoring the preparation of maleimide-functionalized surfaces: From Au towards Si(111)[J]. Surface and Interface Analysis, 2011, 43(9): 1203-1210.

[14] Campestrini P, Bohm S, Schram T, et al. Study of the formation of chromate conversion coatings on Alclad 2024 aluminum alloy using spectroscopic ellipsometry[J]. Thin Solid Films, 2002, 410(1/2): 76-85.

[15] Franquet A, Terryn H, Vereecken J. Composition and thickness of non-functional organosilane films coated on aluminium studied by means of infra-red spectroscopic ellipsometry[J]. Thin Solid Films, 2003, 441(1/2): 76.

[16] Balevicius Z, Vaicikauskas V, Babonas G J. The role of surface roughness in total internal reflection ellipsometry of hybrid systems[J]. Applied Surface Science, 2009, 256(3): 640-644.

[17] Poksinski M, Dzuho H, Arwin H. Copper corrosion monitoring with total internal re?ection ellipsometry[J]. Journal of the Electrochemical Society, 2003, 150(11): B536-B539.

[18] Asinovski L, Beaglehole D, Clarkson M T. Imaging ellipsometry: Quantitative analysis[J]. Physica Status Solidi A, 2008, 205(4): 764-771.

[19] Wurstbauer U, R?ling C, Wurstba U, et al. Imaging ellipsometry of grapheme[J]. Applied Physics Letters, 2010, 97(23): 231901.

[20] Zhan Q W, Leger J R. High-resolution imaging ellipsometer[J]. Applied Optics, 2002, 41(22): 4443-4450.

[21] Ratcliff E L, Hillier A C. Directed electrodeposition of polymer films using spatially controllable electric field gradients[J]. Langmuir, 2007, 23(19), 9905-9910.

[22] Li W(李威), Jin C Y(金承钰). Analytical approach and methods for ellipsommetry on thin film[J]. Chinese Journal of Spectroscopy Laboratory(光谱实验室), 2010, 27 (1): 66-76.

[23] McLaughlin D V P, Pearce J M. Analytical model for the optical functions of indium gallium nitride with application to thin film solar photovoltaic cells[J]. Materials Science and Engineering B, 2012, 177(2): 239-244.

[24] Feng X S(封雪松), Lei J L(雷惊雷), Chen A X(陈爱祥), et al. Ellipsometric study on colored electroplating of cuprous oxide on Ni substrate[J]. Journal of Electrochemistry (电化学) 2009, 15(3): 310-314.

[25] Hauffman T, Lokeren L V, Willem R, et al. In situ study of the deposition of (ultra)thin organic phosphonic acid layers on the oxide of aluminum[J]. Langmuir, 2012, 28(6): 3167-3173.

[26] Kostecki R, Kong F P, Matsuo Y, et al. Interfacial studies of a thin-film Li2Mn4O9 electrode[J]. Electrochimica Acta, 1999, 45(1/2): 225-233.

[27] Bard A J, Faulkner L R. Electrochemical methods: Fundamentals and applications[M]. 2nd Ed. New York: John Wiley & Sons, Inc., 2001: 684.

[28] Kato T, Sago Y, Fujiwara H. Optoelectronic properties of Mg2Si semiconducting layers with high absorption coefficients[J]. Journal of Applied Physics, 2011, 110(6): 063723.

[29] Akagawa M, Fujiwara H. High-precision characterization of textured a-Si:H/ SnO2:F structures by spectroscopic ellipsometry[J]. Journal of Applied Physics, 2011, 110(7): 073518.

[30] Yoon J H, Cho S, Kim W M, et al. Optical analysis of the microstructure of a Mo back contact for Cu(In,Ga)Se2 solar cells and its effects on Mo film properties and Na diffusivity[J]. Solar Energy Materials and Solar Cells, 2011, 95(11): 2959-2964.

[31] Kong F, Kostecki R, Nadeau G, et al. In situ studies of SEI formation[J]. Journal of Power Sources. 2001, 97-98(1): 58-66.

[32] Lei J L, Li L J, Kostecki R, et al. Characterization of SEI layers on LiMn2O4 cathodes with in situ spectroscopic ellipsometry[J]. Journal of the Electrochemical Society, 2005, 152(4): A774-A777.

[33] McArthur M A, Trussler S, Dahn J R. In situ investigations of SEI layer growth on electrode materials for lithium-ion batteries using spectroscopic ellipsometry[J]. Journal of the Electrochemical Society, 2012, 159(3): A198-A207.

[34] Lux S F, Lucas I T, Pollak E, et al. The mechanism of HF formation in LiPF6 based organic carbonate electrolytes[J]. Electrochemistry Communications, 2012, 14(1): 47-50

[35] Bass J D, Grosso D, Boissiere C, et al. Pyrolysis, crystallization, and sintering of mesostructured titania thin films assessed by in situ thermal ellipsometry[J]. Journal of the American Chemical Society, 2008, 130(25), 7882-7897.

[36] Krins N, Bass John, Grosso D, et al. NbVO5 mesoporous thin films by evaporation induced micelles packing: Pore size dependence of the mechanical stability upon thermal treatment and Li insertion/extraction[J]. Chemistry of Materials, 2011, 23(18): 4124-4131.

[37] Thery J, Martin S, Faucheux V, et al. Fluorinated carboxylic membranes deposited by plasma enhanced chemical vapour deposition for fuel cell applications[J]. Journal of Power Sources, 2010, 195(17): 5573-5580.

[38] Kong F, Kostecki R, McLarnon F, et al. Spectroscopic ellipsometry of electrochemical precipitation and oxidation of nickel hydroxide films[J]. Thin Solid Films, 1998, 313-314(1): 775-780.

[39] Zhang S T(张胜涛), Huang Z Q(黄宗卿). Study on transformation between Ni(OH)2 and NiOOH by ellipsometric spectrometry with wavelength sweep[J]. Chinese Journal of Analytical Chemistry (分析化学), 1994, 22(12): 1193-1196.

[40] Zhang S T(张胜涛), Huang Z Q(黄宗卿). Effect of cobalt ion implantation on behavior of Ni(OH)2/NiOOH electrode[J]. Journal of Chongqing University(Natural Science Edition), (重庆大学学报, 自然科学版), 1994, 17(6): 74-77.

[41] Li N B(李念兵), Tang C Y(陶长元), Zhang S T(张胜涛), et al. Study on properties of surface solution layer of K4[Fe(CN)6]/K3[Fe(CN)6] with graze ellipsometry[J]. Acta Physico-Chimica Sinica(物理化学学报), 1998, 14(7): 654-658.

[42] Li L J(李凌杰), Zhang S T(张胜涛), Li D(李荻), et al. Study on electrochemical performance of zinc-plated foam nickel electrode in alkaline solution[J]. Chinese Journal of Power Sources (电源技术), 2000, 24(6): 330-332.
[43] Dardona S, Chen L, Kryzman M, et al. Polarization controlled kinetics and composition of trivalent chromium coatings on aluminum[J]. Analytical Chemistry, 2011, 83(16): 6127-6131.
[44] Lei J L(雷惊雷), Zheng S(郑莎), Li L J(李凌杰), et al. Applications of ellipsometry in corrosion and protection of metals[J]. Corrosion Science and Protection Technology (腐蚀科学与防护技术), 2012, 24(2): 91-94.
[45] Ohtsuka T, Hyono A, Sasaki Y. Potential modulation reflectance of passivated type 304 stainless steel in sulfuric acid solution[J]. Electrochimica Acta, 2012, 60(1): 384-391.
[46] Keller F, Hunter M S, Robinson D L. Structural features of oxide coating on aluminum[J]. Journal of the Electrochemical Society, 1953, 100(9): 411-419.
[47] Masuda H, Fukuda K. Ordered metal nanohole arrays made by a two-step replication of honeycomb structures of anodic alumina[J]. Science, 1995, 268(5216): 1466-1468.
[48] Dell’Oca C J, Fleming P J. Initial stages of oxide growth and pore initiation in the porous anodization of aluminum[J]. Journal of the Electrochemical Society, 1976, 123(10): 1487-1493.
[49] Schnyder B, K?tz, R. Spectroscopic ellipsometry and XPS studies of anodic aluminum oxide formation in sulfuric acid[J]. Journal of Electroanalytical Chemistry, 1992, 339(1/2): 167-185.
[50] Huang Z Q(黄宗卿). Application of ellipsometry to the study of corrosion of metals[J]. Journal of Chongqing University, Natural Science Ed.(重庆大学学报,自然科学版), 1980, 3(2): 72.
[51] Chen S P(陈声培). Investigation of growth of anodic alumina film with in situ ellipsometry[J]. University Chemistry(大学化学), 1996, 11(5):42-44.
[52] Chen X P(陈小平), Li H Q(李辉勤), Guo J J(过家驹). The application of ellipsometry to the study of the metallic corrosion[J]. Journal of Beijing University of Iron and Steel Technology(北京钢铁学院学报), 1984, 6(3): 83-91.
[53] Guo J J(过家驹), Li H Q(李辉勤), Chen X P(陈小平). Microelectrochemical behaviour and change of the passive film thickness with crevice of the crevice corrosion of stainless steel[J]. Journal of Chinese Society for Corrosion and Protection(中国腐蚀与防护学报), 1985, 5(2): 92-99.
[54] Zhou Q C(周庆初), Xu N X(徐乃欣), Shi S T(石声泰). An ellipsometric study of passive films formed on duplex stainless steel in chloride solution[J]. Journal of Chinese Society for Corrosion and Protection(中国腐蚀与防护学报), 1986, 6(4): 255-263.
[55] Zhou Q C(周庆初), Xu N X(徐乃欣), Shi S T(石声泰). An ellipsometric study of passive films formed on Nickel in boric acid-borax solution[J]. Journal of Chinese Society for Corrosion and Protection(中国腐蚀与防护学报), 1990, 10(4): 287-296.
[56] Han W A(韩文安), Zou F(邹锋). Feature of multi-layer chemical conversion film on brass[J]. Acta Metallurgica Sinica(金属学报), 1993, 29(4): 148-152.
[57] Sui S F(隋森芳), Chen H M(陈鹤鸣). An ellipsometry study of the properties of very thin passive film on 1Cr18Ni9Ti steel[J]. Journal of Chinese Society for Corrosion and Protection(中国腐蚀与防护学报), 1984, 4(1): 53-60.
[58] Muller R H, Farmer J C. Macroscopic optical model for the ellipsometry of an underpotential deposit: Lead on copper and silver[J]. Surface Science, 1983, 135(1/3): 521-531.
[59] Ohtsuka T, Komori A. Study of initial layer formation of Zn-Ni alloy electrodeposition by in situ ellipsometry[J]. Electrochimica Acta, 1998, 43(21/22): 3269-3276.
[60] Huang Z Q, Ord J L. An optical study of iron electrode in alkaline electrolyte[J]. Journal of the Electrochemical Society, 1985, 132(1): 24-28.
[61] Ran Y C(冉迎春), Xie S F(谢上芬), Yang Y R(杨雨如), et al. Investigation on the ellipsometry for determination of silver in comparison with anodic stripping voltammetry[J]. Chinese Journal of Analytical Chemistry(分析化学), 1997, 25(7): 807-810.
[62] Zhu W(朱伟), Yang Y R(杨雨如), Huang Z Q(黄宗卿). Simultaneously quantitative analysis of copper and silver through electrochemical stripping ellipsometry[J]. Chemical Research and Application(化学研究与应用), 1998, 10(3): 294-297.
[63] Zhu W(朱伟), Yang Y R(杨雨如), Huang Z Q(黄宗卿). Investigation on the ellipsometry for the detection of nickel through anodic stripping voltammetry[J]. Journal of Electrochemistry(电化学), 1998, 4(1): 106-110.
[64] Dong S J(董绍俊), Che G L(车广礼), Xie Y W(谢远武). Chemically modified electrodes(化学修饰电极)[M]. 2nd Ed. Beijing: Science Press, 2003: 1.
[65] Porter M D, Bright T B, Allara D L, et al. Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry[J]. Journal of the American Chemical Society, 1987, 109(12): 3559-3568.
[66] Wasserman S R, Whitesides G M, Tidswell I M, et al. The structure of self-assembled monolayers of alkalsiloxanes on silicon: A comparison of results from ellipsometry and low-angle X-ray reflectivity[J]. Journal of the American Chemical Society, 1989, 111(15): 5852-5861.
[67] Han Y, Noguchi H, Sakaguchi K, et al. Formation process and solvent-dependent structure of a polyproline self-assembled monolayer on a gold surface[J]. Langmuir, 2011, 27(19): 11951-11957.
[68] Rodenhausen K B, Duensing B A, Kasputis T, et al. In situ monitoring of alkanethiol self-assembled monolayer chemisorption with combined spectroscopic ellipsometry and quartz crystal microbalance techniques[J]. Thin Solid Films, 2011, 519(9): 2817-2820.
[69] Xue M Y(薛茗月), Zhan Z H(湛志华), Zhang S T(张胜涛). Characterization of manganese/chromium hexacyanoferrate modified electrode with in situ ellipsometry[J]. Journal of Guilin Normal College (桂林师范高等专科学校学报), 2009, 23(1): 171-173.
[70] Cabrita J F, Viana A S, Montforts F P, et al. Mixed self-assembled monolayers of Co-porphyrin and n-alkane phosphonates on gold[J]. Surface Science, 2011, 605(15/16): 1412-1419.
[71] Pedano M L, Pietrasanta L I, Teijelo M L, et al. Characterization of DNA layers adsorbed on glassy carbon electrodes[J]. Electroanalysis, 2008, 20(7): 739-749.
[72] Thiagarajan S, Tsai T H, Chen S M. Easy modification of glassy carbon electrode for simultaneous determination of ascorbic acid, dopamine and uric acid[J]. Biosensors and Bioelectronics, 2009, 24(8):2712-2715.
[73] Deveci P, Taner B, üstünda? Z, et al. Synthesis, enhanced spectroscopic characterization and electrochemical grafting of N-(4-aminophenyl)aza-18- crown-6: Application of DEPT, HETCOR,HMBC-NMR and X-ray photoelectron spectroscopy[J]. Journal of Molecular Structure, 2010, 982(1/3): 162-168.
[74] Oztekin Y, Yazicigil Z. Surface modification and characterization of phenanthroline nanofilms on carbon substrate[J]. Surface and Interface Analysis, 2011, 43(5): 923-930.
[75] Tranchida D, Diaz J, Sch?n P, et al. Scanning near-field ellipsometry microscopy: Imaging nanomaterials with resolution below the diffraction limit[J]. Nanoscale, 2011, 3(1): 233-239.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.