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Electrochemical Passivation and Modification of c-Si surfaces

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Physics and Technology of Amorphous-Crystalline Heterostructure Silicon Solar Cells

Part of the book series: Engineering Materials ((ENG.MAT.,volume 0))

Abstract

This chapter addresses the electrochemical passivation of Si surfaces by hydrogen, small organic molecules and ultra-thin polymeric layers which is not yet a standard technique in Si solar cell preparation. The electrochemical surface conditioning leads to different surface structures compared to the wet-chemical techniques (Chapter 3). The electronic properties of the interface depend strongly on these surface morphologies and consequently it is important to measure and control their changes during the electrochemical processing. Therefore, pulsed photoluminescence (PL) spectroscopy is applied as fast and non-destructive method to monitor in-situ and ex-situ the electronic surface properties during electrochemical oxidation, hydrogenation, and grafting of organic molecules and ultra-thin polymeric layers. The additionally used in-situ surface photovoltage (SPV) provides information on the surface charge during the wet-chemical and electrochemical processing. Unusual low concentration of recombination active defects at Si:H surfaces, Si(111) and Si(100), can be obtained after electropolishing in the current oscillating regime in diluted HF solutions. The passivation by hydrogen is influenced by the applied potential, the current flow, the temperature and the solution composition, where nitrogen bubbling of the solution is an important step to enhance the surface passivation.

PL investigations of the organically modified surfaces show that a slightly higher defect concentration at the interface (typical by a factor of 2) is usually observed. However, organically modified Si surfaces have extremely long time stability versus oxidation in ambient air, especially after grafting of 10-carboxydecyl groups via hydrosilylation which shows an ideal Si surface passivation with respect to interface recombination losses.

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References

  1. Yablonovich, E., Allara, D.L., Chang, C.C., Gmitter, T., Bright, T.B.: Unusually low surface-recombination velocity on silicon and germanium surfaces. Phys. Rev. Lett. 57, 249–252 (1986)

    Article  Google Scholar 

  2. Angermann, H., Henrion, W., Rebien, M., Zettler, J.-T., Röseler, A.: Characterization of chemically prepared Si-surfaces by uv-vis and IR spectroscopic ellipsometry and surface photovoltage. Surf. Sci. 388, 15–23 (1997)

    Article  CAS  Google Scholar 

  3. Angermann, H., Kliefoth, K., Flietner, H.: Preparation of H-terminated Si surfaces and their characterisation by measuring the surface state density. Appl. Surf. Sci. 104-105, 107–112 (1996)

    Google Scholar 

  4. Rappich, J., Timoshenko, V.Y., Dittrich, T.: In Situ Monitoring of Electrochemical Processes at the (100) p-Si/Aqueous NH4F Electrolyte Interface by Photoluminescence. J. Electrochem. Soc. 144, 493–496 (1997)

    Article  CAS  Google Scholar 

  5. Timoshenko, V.Y., Petrenko, A.B., Stolyarov, M.N., Dittrich, T., Fuessel, W., Rappich, J.: Quantitative analysis of room temperature photoluminescence of c-Si wafers excited by short laser pulses. J. Appl. Phys. 85, 4171–4175 (1999)

    Article  CAS  Google Scholar 

  6. Dittrich, T., Burke, T., Koch, F., Rappich, J.: Passivation of an anodic oxide / p-Si interface stimulated by electron injection. J. Appl. Phys. 89, 4636–4642 (2001)

    Article  CAS  Google Scholar 

  7. Rappich, J., Dittrich, T.: Electrochemical passivation of Si and SiGe. In: Nalwa, H.S. (ed.) Handbook of Thin Film Materials, pp. 1–56. Academic Press, New York (2002)

    Google Scholar 

  8. Turner, D.R.: Electropolishing silicon in hydrofluoric acid solution. J. Electrochem. Soc. 105, 402 (1958)

    Article  CAS  Google Scholar 

  9. Ozanam, F., Chazaviel, J.-N., Radi, A., Etman, M.: Current oszillation in the anodic dissolution of silicon in flouride electrolytes. Ber. Bunsenges. Phys. Chem. 95, 98–101 (1991)

    CAS  Google Scholar 

  10. Rappich, J., Aggour, M., Rauscher, S., Lewerenz, H.J., Jungblut, H.: Electrochemical surface conditioning of n-Si(111). Surf. Sci. 335, 160–165 (1995)

    Article  CAS  Google Scholar 

  11. Rauscher, S., Dittrich, T., Aggour, M., Rappich, J., Flietner, H., Lewerenz, H.J.: Reduced interface state density after photocurrent oscillations and electrochemical hydrogenation of n-Si(111): A surface photovoltage investigation. Appl. Phys. Lett. 66, 3018–3020 (1995)

    Article  CAS  Google Scholar 

  12. Timoshenko, V.Y., Petrenko, A.B., Dittrich, T., Füssel, W., Rappich, J.: Photoluminescence characterization of non-radiative defect density on silicon surfaces and interfaces at room temperature. Thin Solid Films 364, 196–199 (2000)

    Article  CAS  Google Scholar 

  13. Timoshenko, V.Y., Rappich, J., Dittrich, T.: In Situ Photoluminescence Analysis of Nonradiative Recombination on Silicon Surfaces Treated in Fluoride Solution. Jpn. J. Appl. Phys. 36, L58–L60 (1997)

    Google Scholar 

  14. Rappich, J., Timoshenko, V.Y., Dittrich, T.: Correlation between Surface Non-Radiative Recombination and Current Oscillations at p-Si(100) during Electropolishing in Fluoride Solution. Ber. Bunsenges. Phys. Chem. 101, 139 (1997)

    CAS  Google Scholar 

  15. Rappich, J., Timoshenko, V.Y., Würz, R., Dittrich, T.: Is there a Limit for the Passivation of Si Surfaces during Anodic Oxidation in Acidic NH4F Solutions? Electrochim. Acta 45, 4629–4633 (2000)

    Article  CAS  Google Scholar 

  16. Rappich, J.H., Hartig, P., Nickel, N.H., Sieber, I., Schulze, S., Dittrich, T.: Stable electrochemically passivated Si surfaces by ultra-thin benzene-type layers. Microelec. Engin. 80, 62–65 (2005)

    Article  CAS  Google Scholar 

  17. Rappich, J., Zhang, X., Rosu, D.M., Schade, U., Hinrichs, K.: Passivation of Si surfaces investigated by in-situ photoluminescence techniques. Solid State Phenomena 156-158, 363–368 (2010)

    Google Scholar 

  18. Timoshenko, V.Y., Rappich, J., Dittrich, T.: Express characterization of indirect semiconductors by in-situ photoluminescence during chemical and electrochemical treatments. Appl. Surf. Sci. 123/124, 111–114 (1998)

    Article  CAS  Google Scholar 

  19. Higashi, G.S., Chabal, Y.J., Trucks, G.W., Raghavachari, K.: Ideal hydrogen termination of Si(111) surface. App. Phys. Lett. 56, 656–658 (1990)

    Article  CAS  Google Scholar 

  20. Kern, W.: Si Cleaning. Semiconductor International 94 (1984)

    Google Scholar 

  21. Kern, W.: The Evolution of Silicon Wafer Cleaning Technology. J. Electrochem. Soc. 137, 1887 (1990)

    Article  CAS  Google Scholar 

  22. Jakob, P., Chabal, Y.J.: Chemical etching of vicinal Si(111): Dependence of the surface structure and the hydrogen termination on the pH of the etching solutions. J. Phys. Chem. 95, 2897–2909 (1991)

    Article  CAS  Google Scholar 

  23. Lewerenz, H., Blitzer, T., Gruyters, M., Jacobi, K.: Electrolytic Hydrogenation of Silicon. J. Electrochem. Soc. 140, L44–L46 (1993)

    Google Scholar 

  24. Rappich, J., Lewerenz, H.: In Situ Fourier Transform Infrared Investigation on the Electrolytic Hydrogenation of n-Silicon (111). J. Electrochem. Soc. 142, 1233–1237 (1995)

    Article  CAS  Google Scholar 

  25. Cullis, A.G., Canham, L.T.: Visible light emission due to quantum size effects in highly porous crystalline silicon. Nature 353, 335 (1991)

    Article  CAS  Google Scholar 

  26. Chabal, Y.J., Higashi, G.S., Raghavachari, K., Burrows, V.A.: Infrared spectroscopy of Si(111) and Si(100) surfaces after HF treatment: Hydrogen termination and surface morphology. J. Vac. Sci. Technol. A 7, 2104–2109 (1989)

    Article  CAS  Google Scholar 

  27. Peter, L.M., Blackwood, D.J., Pons, S.: In situ characterizazion of the illuminated Silicon-electrolyte interface by Fourier-Transform Infrared Spectroscopy. Phys. Rev. Lett. 62, 308–311 (1989)

    Article  CAS  Google Scholar 

  28. Venkateswara Rao, A., Chazaviel, J.-N.: Chemical trends in the electromodulated infrared vibrational spectroscopy of various silicon/electrolyte interfaces. J. Electrochem. Soc. 134, 2777–2783 (1987)

    Article  Google Scholar 

  29. Morita, Y., Tokumoto, H.: Ideal Hydrogen Termination Of Si(001) Surface By Wet-Chemical Preparation. Appl. Phys. Lett. 67, 2654–2656 (1995)

    Article  CAS  Google Scholar 

  30. Grundner, M., Schulz, R.: The surface state of silicon (100) and (111) wafers after treatment with hydrofluoric acid. In: AIP Conf. Proc., vol. 167, p. 329 (1988)

    Google Scholar 

  31. Dumas, P., Chabal, Y.J.: Electron-energy-loss characterization of the H-terminated Si (111) and Si (100) surfaces obtained by etching in NH4F. Chem. Phys. Lett. 181, 537 (1991)

    Article  CAS  Google Scholar 

  32. Stuhlmann, C., Bogdány, G., Ibach, H.: Surface phonons of the hydrogen-terminated Si(111) (1x1) surface. Phys. Rev. B 45, 6786–6792 (1992)

    Article  CAS  Google Scholar 

  33. Lewerenz, H.J., Bitzer, T., Gruyters, M., Jacobi, K.: Electrolytic Hydrogenation of Silicon: A High Resolution Electron Energy Loss Spectroscopy Investigation. J. Electrochem. Soc. 140, L44–L46 (1993)

    Google Scholar 

  34. Grundner, M., Jacob, H.: Investigations on hydrophilic and hydrophobic silicon (100) wafer surfaces by X-ray photoelectron and high-resolution electron energy loss-spectroscopy. Appl. Phys. A 39, 73 (1986)

    Article  Google Scholar 

  35. Maruno, S., Iwasaki, H., Horioka, K., Li, S.-T., Nakamura, S.: Electronic structures of monohydride (2x1):H and the dihydride (1x1):2H Si(001) surfaces studied by angle-resolved electron-energy-loss spectroscopy. Phys. Rev. B 27, 4110–4116 (1983)

    Article  CAS  Google Scholar 

  36. Zaima, S., Kojima, J., Hayashi, M., Ikeda, H., Iwano, H., Yasuda, Y.: Improvements of Electrical Characteristics of Hf/p-Si(100) Interfaces by H-Termination. Jpn. J. Appl. Phys. 34, 741–745 (1995)

    Article  CAS  Google Scholar 

  37. Bitzer, T., Gruyters, M., Lewerenz, H.J., Jacobi, K.: Electrochemically prepared Si(111) 1x1-H surface. Appl. Phys. Lett. 63, 397 (1993)

    Article  CAS  Google Scholar 

  38. Harrick, N.J.: Internal Reflection Spectroscopy. Wiley Interscience, New York (1967)

    Google Scholar 

  39. Rappich, J., Jungblut, H., Aggour, M., Lewerenz, H.: Electrochemical smoothing of silicon (111). J. Electrochem. Soc. 141, L99–L102 (1994)

    Google Scholar 

  40. Ozanam, F., Chazalviel, J.-N.: In-situ infrared characterization of the electrochemical dissolution of silicon in a fluoride electrolyte. J. Electron Spec. Rel. Phenom. 64/65, 395 (1993)

    Article  Google Scholar 

  41. Lewerenz, H.J., Aggour, M.: On the origin of photocurrent oscillation at Si electrodes. J. Electroanal. Chem. 351, 159–168 (1993)

    Article  CAS  Google Scholar 

  42. Aggour, M., Giersig, M., Lewerenz, H.J.: Interface condition of n-Si(111) during photocurrent oscillations in NH4F solutions. J. Electroanal. Chem. 383, 67 (1995)

    Article  Google Scholar 

  43. Yang, F., Roodenko, K., Hinrichs, K., Rappich, J.: Electronic and surface properties during the etch-back of anodic oxides on Si(111) surfaces in 40% NH4F solution. J. Micromech. Microeng. 17, S56–S70 (2007)

    Article  Google Scholar 

  44. Uhlig, H.H., King, P.F.: The Flade Potential of Iron Passivated by Various Inorganic Corrosion Inhibitors. J. Electrochem. Soc. 106, 1–7 (1959)

    Article  CAS  Google Scholar 

  45. Gouy, G.: Sur la constitution de la charge electrique á la surface d’un electrolyte. Compt. Rend. 149, 654–657 (1909)

    CAS  Google Scholar 

  46. Chabal, Y.J.: Surface infrared spectroscopy. Surf. Sci. Rep. 8, 211 (1988)

    Article  CAS  Google Scholar 

  47. Emoto, T., Akimoto, K., Ishikawa, Y., Ichimiya, A., Tanikawa, A.: Strain near SiO2-Si interface revealed by X-ray diffraction intensity enhancement. Thin Solid Films 369, 281–284 (2000)

    Article  CAS  Google Scholar 

  48. Imai, T., Fujimoto, A., Okuyama, M., Hamakawa, Y.: Characterization of Surface Potential and Strain at Ultrathin Oxide/Silicon Interface by photoreflectance Spectroscopy. Jpn. J. Appl. Phys. 35, 1073–1076 (1996)

    Article  CAS  Google Scholar 

  49. Neaton, J.B., Muller, D.A., Ashcroft, N.W.: Electronic Properties of the Si/SiO2 Interface from First Principles. Phys. Rev. Lett. 85, 1298–1301 (2000)

    Article  CAS  Google Scholar 

  50. Nouwen, B., Stesmans, A.: Dependence of strain at the (111)Si/SiO2 interface on interfacial Si dangling-bond concentration. Mat. Sci. and Engin. A 288, 239–243 (2000)

    Article  Google Scholar 

  51. Stefanov, B.B., Gurevich, A.B., Weldon, M.K., Raghavachari, K., Chabal, Y.J.: Silicon Epoxide: Unexpected Intermediate during Silicon Oxide Formation. Phys. Rev. Lett. 81, 3908–3911 (1998)

    Article  CAS  Google Scholar 

  52. Chabal, Y.J., Dumas, P., Guyot-Sionnest, P., Higashi, G.S.: Vibrational dynamics of the ideally H-terminated Si(111) surface. Surf. Sci. 242, 524–530 (1991)

    Article  CAS  Google Scholar 

  53. Dumas, P., Chabal, Y.J., Jakob, P.: Morphology of hydrogen-terminated Si(111) and Si(100) surfaces upon etching in HF and buffered-HF solutions. Surf. Sci. 269/270, 867 (1992)

    Article  Google Scholar 

  54. Nakamura, M., Song, M.-B., Ito, M.: Etching processing of Si(111) and Si(100) surfaces in an ammonium fluoride solution investigated by in situ ATR-IR. Electrochim. Acta 41, 681–686 (1996)

    Article  CAS  Google Scholar 

  55. Bender, H., Verhaverbeke, S., Caymax, M., Vatel, O., Heyns, M.M.: Surface reconstruction of hydrogen annealed (100) silicon. J. Appl. Phys. 75, 1207 (1994)

    Article  CAS  Google Scholar 

  56. Chabal, Y.J., Rafghavachari, K.: Surface infrared study of Si(100)-(2X1)H. Phys. Rev. Lett. 53, 282–285 (1984)

    Article  CAS  Google Scholar 

  57. de Mierry, P., Etcheberry, A., Rizk, R., Etchegoin, P., Aucouturier, M.: Defects lnduced in p-Type Silicon by Photocathodic Charging of Hydrogen. J. Electrochem. Soc. 141, 1539–1546 (1994)

    Article  Google Scholar 

  58. Rappich, J., Dittrich, T., Timoshenko, Y., Beckers, I., Fuhs, W.: Influence of hydrogen incorporation into Silicon on the room-temperature photoluminescence. In: Mat. Res. Soc. Symp. Proc., vol. 452, pp. 797–802 (1997)

    Google Scholar 

  59. Allongue, P., Delamar, M., Desbat, B., Fagebaume, O., Hitmi, R., Pinson, J., Saveant, J.-M.: Covalent Modification of Carbon Surfaces by Aryl Radicals Generated from the Electrochemical Reduction of Diazonium Salts. J. Am. Chem. Soc. 119, 201–207 (1997)

    Article  CAS  Google Scholar 

  60. Allongue, P., de Villeneuve, C.H., Pinson, J., Ozanam, F., Chazalviel, J.N., Wallart, X.: Organic monolayers on Si(111) by electrochemical method. Electrochim. Acta 43, 2791 (1998)

    Article  CAS  Google Scholar 

  61. Hartig, P., Rappich, J., Dittrich, T.: Engineering of Si surfaces by electrochemical grafting of p-nitrobenzene molecules. Appl. Phys. Lett. 80, 67–69 (2002)

    Article  CAS  Google Scholar 

  62. Teyssot, A., Fidèlis, A., Fellah, S., Ozanam, F., Chazalviel, J.-N.: Anodic grafting of organic groups on the silicon surface. Electrochim. Acta 47, 2565–2571 (2002)

    Article  CAS  Google Scholar 

  63. Yang, F., Hunger, R., Roodenko, K., Hinrichs, K., Rademann, K., Rappich, J.: Vibrational and Electronic Characterization of Ethynyl Derivatives Grafted onto Hydrogenated Si(111) Surfaces. Langmuir 25, 9313–9318 (2009)

    Article  CAS  Google Scholar 

  64. Linford, M.R., Chidsey, C.E.D.: Alkyl monolayers covalently bonded to silicon surfaces. J. Am. Chem. Soc. 115, 12631–12632 (1993)

    Article  CAS  Google Scholar 

  65. Rappich, J., Hinrichs, K.: In situ study of nitrobenzene grafting on Si(1 1 1)-H surfaces by infrared spectroscopic ellipsometry. Electrochem. Commun. 11, 2316–2319 (2009)

    Article  CAS  Google Scholar 

  66. Allongue, P., de Villeneuve, C.H., Cherouvrier, G., Cortés, R., Bernard, M.-C.: Phenyl layers on H/Si(111) by electrochemical reduction of diazonium salts: monolayer versus multilayer formation. J. Electroanal. Chem. 550/551, 161–174 (2003)

    Article  Google Scholar 

  67. Rappich, J., Merson, A., Roodenko, K., Dittrich, T., Gensch, M., Hinrichs, K., Shapira, Y.: Electronic properties of Si surfaces and side reactions during electrochemical grafting of phenyl layers. J. Phys. Chem. B 110, 1332–1337 (2006)

    Article  CAS  Google Scholar 

  68. Intelmann, C.M., Hinrichs, K., Syritski, V., Yang, F., Rappich, J.: Recombination behaviour at the ultrathin polypyrrole film/silicon interface investigated by in-situ pulsed photoluminescence. Jap. J. Appl. Phys. Part I 47, 554–557 (2008)

    Article  CAS  Google Scholar 

  69. Aureau, D., Rappich, J., Moraillon, A., Allongue, P., Ozanam, F., Chazalviel, J.-N.: In situ monitoring of the electronic properties and the pH stability of grafted Si(111). J. Electroanal. Chem. 646, 33–42 (2010)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Institut für Silizium-Photovoltaik, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Kekuléstraße 5, D-12489, Berlin, Germany

    Jörg Rappich

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  1. Jörg Rappich
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Editors and Affiliations

  1. Copernicus Institute Science Technology and Society, Utrecht University, Budapestlaan 6, 3584 CD, Utrecht, The Netherlands

    Wilfried G. J. H. M. van Sark

  2. Inst. Silizium-Photovoltaik, Helmholtz-Zentrum Berlin für Materialien und Energie, Kekuléstraße 5, 12489, Berlin, Germany

    Lars Korte

  3. ENEA - Agenzia Nazionale per le Nuove Tecnologie, l’Energia e lo Sviluppo Economico Sostenibile, Unità Tecnologie Portici, Localitá Granatello P. le E. Fermi, Portici, 80055, Napoli, Italy

    Francesco Roca

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Rappich, J. (2012). Electrochemical Passivation and Modification of c-Si surfaces. In: van Sark, W.G.J.H.M., Korte, L., Roca, F. (eds) Physics and Technology of Amorphous-Crystalline Heterostructure Silicon Solar Cells. Engineering Materials, vol 0. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-22275-7_4

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