Skip to main content
SpringerLink
Log in

Nanoscale Electrodeposition of Metals and Semiconductors from Ionic Liquids Probed by Scanning Tunneling Microscopy

  • Living reference work entry
  • First Online:
Handbook of Nanoelectrochemistry

  • 404 Accesses

Abstract

In this chapter, we have reviewed the current state of the knowledge of the nanoscale electrodeposition of metals and semiconductors on single-crystal electrodes from ionic liquids (ILs), which might be vital for both basic and applied researches. Emphasis has been placed on the atomic- or submolecular-level characterization of the respective nucleation and growth by in situ scanning tunneling microscopy (STM), whose studies are still in its infancy. Firstly, technological point of STM for ILs has been briefly discussed as well as the adsorption behavior of anions and cations of ILs. Secondly, in situ STM studies on the metal electrodeposition in ILs are reviewed. For simplicity, the discussion will be categorized into reactive (e.g., Al, Zn, Li), magnetic (e.g., Fe, Co, Ni), semimetal (e.g., Sb, Bi), coinage (e.g., Cu, Ag, Au), and rare metals (e.g., Ga, Ti, Ta). Thirdly, in situ STM studies on the electrocrystallization of elemental (e.g., Si, Ge) and compound semiconductors (e.g., AlSb, ZnSb) are briefly reviewed. We conclude this chapter with our personal perspectives on future research in this field.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution

Institutional subscriptions

References

  1. Hapiot P, Lagrost C (2008) Electrochemical reactivity in room-temperature ionic liquids. Chem Rev 108:2238–2264

    Article  CAS  Google Scholar 

  2. Dean PM, Pringle JM, MacFarlane DR (2010) Structural analysis of low melting organic salts: perspectives on ionic liquids. Phys Chem Chem Phys 12:9144–9153

    Article  CAS  Google Scholar 

  3. Ma Z, Yu JH, Dai S (2010) Preparation of inorganic materials using ionic liquids. Adv Mater 22:261–285

    Article  CAS  Google Scholar 

  4. Hayes R, Warr GG, Atkin R (2010) At the interface: solvation and designing ionic liquids. Phys Chem Chem Phys 12:1709–1723

    Article  CAS  Google Scholar 

  5. Torimoto T, Tsuda T, Okazaki KI, Kuwabata S (2010) New frontiers in materials science opened by ionic liquids. Adv Mater 22:1196–1221

    Article  CAS  Google Scholar 

  6. Fujita K, Murata K, Masuda M, Nakamura N, Ohno H (2012) Ionic liquids designed for advanced applications in bioelectrochemistry. RSC Adv 2:4018–4030

    Article  CAS  Google Scholar 

  7. He P, Liu HT, Li ZY, Liu Y, Xu XD, Li JH (2004) Electrochemical deposition of silver in room-temperature ionic liquids and its surface-enhanced raman scattering effect. Langmuir 20:10260–10267

    Article  CAS  Google Scholar 

  8. Abbott AP, Mckenzie KJ (2006) Application of ionic liquids to the electrodeposition of metals. Phys Chem Chem Phys 8:4265–4279

    Article  CAS  Google Scholar 

  9. Armand M, Endres F, MacFarlane DR, Ohno H, Scrosati B (2009) Ionic-liquid materials for the electrochemical challenges of the future. Nat Mater 8:621–629.

    Google Scholar 

  10. Su YZ, Fu YC, Wei YM, Yan JW, Mao BW (2010) The electrode/ionic liquid interface electric double layer and metal electrodeposition. ChemPhysChem 11:2764–2778

    Article  CAS  Google Scholar 

  11. Abedin SZE, Endres F (2006) Electrodeposition of metals and semiconductors in air- and water-stable ionic liquids. ChemPhysChem 7:58–61

    Article  Google Scholar 

  12. Binnig G, Rohrer H, Gerber C, Weibel E (1982) Tunneling through a controllable vacuum gap. Appl Phys Lett 40:178–180

    Article  CAS  Google Scholar 

  13. Enderes F (2002) Ionic liquids: Solvents for the electrodeposition of metals and semiconductors. ChemPhysChem 3:144–154

    Article  Google Scholar 

  14. Kolb DM (2001) Electrochemical surface science. Angew Chem Int Ed 40:1162–1181

    Article  CAS  Google Scholar 

  15. Endres F, Freyland W, Gilbert B (1997) Electrochemical scanning tunnelling microscopy (ECSTM) study of silver electrodeposition from a room temperature molten salt. Ber Bunsen-Ges 101:1075–1077

    Article  CAS  Google Scholar 

  16. Lin LG, Wang Y, Yan JW, Yuan YZ, Xiang J, Mao BW (2003) An in situ STM study on the long-range surface restructuring of Au (111) in a non-chloroaluminumated ionic liquid. Electrochem Commun 5:995–999

    Article  CAS  Google Scholar 

  17. Pan GB, Freyland W (2006) 2D phase transition of PF6 adlayers at the electrified ionic liquid/Au (111) interface. Chem Phys Lett 427:96–100

    Article  CAS  Google Scholar 

  18. Gnahm M, Pajkossy T, Kolb DM (2010) The interface between Au (111) and an ionic liquid. Electrochim Acta 55:6212–6217

    Article  CAS  Google Scholar 

  19. Su YZ, Fu YC, Yan JW, Chen ZB, Mao BW (2009) Double layer of Au (100)/ionic liquid interface and its stability in imidazolium-based ionic liquids. Angew Chem Int Ed 48:5148–5151

    Article  CAS  Google Scholar 

  20. Borissov D, Aravinda CL, Freyland W, (2005) Comparative investigation of underpotential deposition of Ag from aqueous and ionic electrolytes: an electrochemical and in situ STM study. J Phys Chem B 109:11606–11615

    Article  CAS  Google Scholar 

  21. Mann O, Freyland W (2007) Mechanism of formation and electronic structure of semiconducting ZnSb nanoclusters electrodeposited from an ionic liquid. Electrochim Acta 53:518–524

    Article  CAS  Google Scholar 

  22. Pan GB, Mann O, Freyland W, Phys J (2011) Nanoscale electrodeposition of Ga on Au (111) from ionic liquids. Chem C 115:7656–7659

    CAS  Google Scholar 

  23. Gnahm M, Müller C, Répánszki R, Pajkossy T, Kolb DM (2011) The interface between Au (100) and 1-butyl-3-methyl-imidazolium-hexafluorophosphate. Phys Chem Chem Phys 13:11627–11633

    Article  CAS  Google Scholar 

  24. Gnahm M, Berger C, Arkhipova M, Kunkel H, Pajkossy T, Maas G, Kolb DM (2012) The interfaces of Au (111) and Au (100) in a hexaalkyl-substituted guanidinium ionic liquid: an electrochemical and in situ STM study. Phys Chem Chem Phys 14:10647–10652

    Article  CAS  Google Scholar 

  25. Simka W, Puszczyk D, Nawrat G (2009) Electrodeposition of metals from non-aqueous solutions. Electrochim Acta 54:5307–5319

    Article  CAS  Google Scholar 

  26. Aravinda CL, Mukhopadhyay I, Freyland W (2004) Electrochemical in situ STM study of Al and Ti–Al alloy electrodeposition on Au (111) from a room temperature molten salt electrolyte. Phys Chem Chem Phys 6:5225–5231

    Article  CAS  Google Scholar 

  27. Aravinda CL, Burger B, Freyland W (2007) Nanoscale electrodeposition of Al on n-Si (111): H from an ionic liquid. Chem Phys Lett 434:271–275

    Article  CAS  Google Scholar 

  28. Moustafa EM, El Abedin SZ, Shkurankov A, Zschippang E, Saad AY, Bund A, Endres F, (2007) Electrodeposition of Al in 1-butyl-1-methylpyrrolidinium- bis(trifluoromethylsulfonyl)amide and 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide Ionic Liquids: in situ STM and EQCM studies. J Phys Chem B 111:4693–4704

    Article  CAS  Google Scholar 

  29. Dogel J, Freyland W (2003) Layer-by-layer growth of zinc during electrodeposition on Au (111) from a room temperature molten salt. Phys Chem Chem Phys 5:2484–2487

    Article  CAS  Google Scholar 

  30. Dogel J, Tsekov R, Freyland W (2005) Two-dimensional connective nanostructures of electrodeposited Zn on Au (111) induced by spinodal decomposition. J Chem Phys 122:094703

    Article  CAS  Google Scholar 

  31. Wang JG, Tang J, Fu YC, Wei YM, Chen ZB, Mao BW (2007) STM tip-induced nanostructuring of Zn in an ionic liquid on Au (111) electrode surfaces. Electrochem Commun 9:633–638

    Article  CAS  Google Scholar 

  32. Gasparotto LHS, Borisenko N, Bocchi N, El Abedinab SZ, Endres F (2009) 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. Phys Chem Chem Phys 11:11140–11145

    Article  CAS  Google Scholar 

  33. Endres F, El Abedin SZ, Borissenko N (2006) Probing lithium and alumina impurities in air- and water stable ionic liquids by cyclic voltammetry and in situ scanning tunneling microscopy. Z Phys Chem 220:1377–1394

    Article  CAS  Google Scholar 

  34. Aravinda CL, Freyland W (2004) Electrodeposition of monodispersed Fe nanocrystals from an ionic liquid. Chem Commun 2754–2755

    Google Scholar 

  35. dos Santos MC, Geshev J, Silva DK, Schmidt JE, Pereira LG, Huber R, Allongue P (2003) Strong dependence of the Fe thin-film magnetic anisotropy on the Si (111) substrate preparation. J Appl Phys 23:1490–1494

    Article  Google Scholar 

  36. Wei YM, Fu YC, Yan JW, Sun CF, Shi Z, Xie ZX, Wu DY, Mao BW (2010) Growth and shape-ordering of iron nanostructures on Au single crystalline electrodes in an ionic liquid: a paradigm of magnetostatic coupling. J Am Chem Soc 132:8152–8157

    Article  CAS  Google Scholar 

  37. Wei YM, Zhou XS, Wang JG, Tang J, Mao BW, Kolb DM (2008) The creation of nanostructures on an Au (111) electrode by tip-induced iron deposition from an ionic liquid. Small 4:1355–1358

    Article  CAS  Google Scholar 

  38. Zell CA, Freyland W (2003) In situ STM and STS study of Co and Co-Al alloy electrodeposition from an ionic liquid. Langmuir 19:7445–7450

    Article  CAS  Google Scholar 

  39. Lin LG, Yan JW, Wang Y, Fu YC, Mao BW (2006) An in situ STM study of cobalt electrodeposition on Au (111) in BMIBF4 ionic liquid. J Exp Nanosci 1:269–278

    Article  CAS  Google Scholar 

  40. Zell CA, Freyland W (2002) STM study of 2D and 3D phase formation of Ni and Ni-Al-Alloys during electrodepostion from a chloroaluminate molten salt. Molten Salts XIII 19:660–670

    Google Scholar 

  41. Mann O, Freyland W, Phys J (2007) Electrocrystallization of distinct Ni nanostructures at the ionic liquid/Au (111) interface: An electrochemical and in-situ STM investigation. Chem C 111:9832–9838

    CAS  Google Scholar 

  42. Fu YC, Yan JW, Wang Y, Tian JH, Zhang HM, Xie ZX, Mao BW, (2007) In situ STM studies on the underpotential deposition of antimony on Au (111) and Au (100) in a BMIBF4 ionic liquid. J Phys Chem C 111:10467–10477

    Article  CAS  Google Scholar 

  43. Wang FX, Pan GB, Liu YD, Xiao Y, (2010) Electrodeposition of Sb on Au (111) from an acidic chloroaluminate ionic liquid: an in situ STM study. J Phys Chem C 114:4576–4579

    Article  CAS  Google Scholar 

  44. Aravinda CL, Freyland W (1703–1705) Nanoscale electrocrystallisation of Sb and the compound semiconductor AlSb from an ionic liquid. Chem Commun 2006

    Google Scholar 

  45. Mann O, Aravinda CL, Freyland W, (2006) Microscopic and electronic structure of semimetallic Sb and semiconducting AlSb fabricated by nanoscale electrodeposition: An in situ scanning probe investigation. J Phys Chem B 110:21521–21527

    Article  CAS  Google Scholar 

  46. Pan GB, Freyland W (2007) Electrocrystallization of Bi on Au (111) in an acidic chloroaluminate ionic liquid. Electrochim Acta 52:7254–7261

    Article  CAS  Google Scholar 

  47. Endres F, Schweizer A (2000) The electrodeposition of copper on Au(111) and on HOPG from the 66/34 mol% aluminium chloride/1-butyl-3-methylimidazolium chloride room temperature molten salt: an EC-STM study. Phys Chem Chem Phys 2:5455–5462

    Article  CAS  Google Scholar 

  48. Toney MF, Howard JN, Richer J, Borges GL, Gordon JG, Melroy OR, Yee D, Sorensen LB (1995) Electrochemical deposition of copper on a gold electrode in sulfuric acid: resolution of the interfacial structure. Phys Rev Lett 75:4472–4475

    Article  CAS  Google Scholar 

  49. Endres F, Freyland W, (1998) Electrochemical scanning tunneling microscopy investigation of HOPG and silver electrodeposition on HOPG from the acid room-temperature molten salt aluminum chloride−1-methyl-3-butyl-imidazolium chloride. J Phys Chem B 102:10229–10233

    Article  CAS  Google Scholar 

  50. Zell CA, Endres F, Freyland W (1999). Electrochemical in situ STM study of phase formation during Ag and Al electrodeposition on Au (111) from a room temperature molten salt. Phys Chem Chem Phys 1:697–704

    Article  CAS  Google Scholar 

  51. Mann O, Freyland W, Raz O, Ein-Eli Y (2008) Electrochemical deposition of ultrathin ruthenium films on Au (111) from an ionic liquid. Chem Phys Lett 460:178–181

    Article  CAS  Google Scholar 

  52. Gasparotto LHS, Borisenko N, Höfft O, Al-Salman R, Maus-Friedrichs W, Bocchi N, Zein El Abedin S, Endres F (2009) In situ STM studies of Ga electrodeposition from GaCl3 in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide. Electrochim Acta 55:218–226

    Article  CAS  Google Scholar 

  53. Mukhopadhyay I, Freyland W (2003) Electrodeposition of Ti nanowires on highly oriented pyrolytic graphite from an ionic liquid at room temperature. Langmuir 19:1951–1953

    Article  CAS  Google Scholar 

  54. Mukhopadhyay I, Aravinda CL, Borissov D, Freyland W (2005) Electrodeposition of Ti from TiCl4 in the ionic liquid l-methyl-3-butyl-imidazolium bis (trifluoro methyl sulfone) imide at room temperature: study on phase formation by in situ electrochemical scanning tunneling microscopy. Electrochim Acta 50:1275–1281

    Article  CAS  Google Scholar 

  55. Endres F, El Abedin SZ, Saad AY, Moustafa EM, Borissenko N, Price WE, Wallace GG, MacFarlane DR, Newmanc PJ, Bundd A (2008) On the electrodeposition of titanium in ionic liquids. Phys Chem Chem Phys 10:2189–2199

    Article  CAS  Google Scholar 

  56. El Abedin SZ, Farag HK, Moustafa EM, Welz-Biermanny U, Endres F (2005) Electroreduction of tantalum fluoride in a room temperature ionic liquid at variable temperatures. Phys Chem Chem Phys 7:2333–2339

    Article  Google Scholar 

  57. Borisenko N, Ispas A, Zschippang E, Liu Q, Zein El Abedin S, Bund A, Endres F (2009) In situ STM and EQCM studies of tantalum electrodeposition from TaF5 in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide. Electrochim Acta 54:519–528

    Article  Google Scholar 

  58. Pan G-B, Freyland W (2007) In situ STM investigation of spinodal decomposition and surface alloying during underpotential deposition of Cd on Au (111) from an ionic liquid. Phys Chem Chem Phys 9:3286–3290

    Article  CAS  Google Scholar 

  59. Wang FX, Pan GB, Liu YD, Xiao Y (2010) Pb deposition onto Au (111) from acidic chloroaluminate ionic liquid. Chem Phys Lett 488:112–115

    Article  CAS  Google Scholar 

  60. Endres F, Schrodt C (2000) In situ STM studies on germanium tetraiodide electroreduction on Au (111) in the room temperature molten salt 1-butyl-3-methylimidazolium hexafluorophosphate. Phys Chem Chem Phys 2:5517–5520

    Article  CAS  Google Scholar 

  61. Endres F, El Abedin SZ (2002) Nanoscale electrodeposition of germanium on Au(111) from an ionic liquid: an in situ STM study of phase formation Part I. Phys Chem Chem Phys 4:1640–1648

    Article  CAS  Google Scholar 

  62. Endres F, El Abedin SZ (2002) Nanoscale electrodeposition of germanium on Au(111) from an ionic liquid: an in situ STM study of phase formation Part II. Phys Chem Chem Phys 4:1649–1657

    Article  CAS  Google Scholar 

  63. El Abedin SZ, Borissenko N, Endres F (2004) Electrodeposition of nanoscale silicon in a room temperature ionic liquid. Electrochem Commun 6:510–514

    Article  Google Scholar 

  64. Borisenko N, El Abedin SZ (2006) Endres F In situ STM investigation of gold reconstruction and of silicon electrodeposition on Au(111) in the room temperature ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. J Phys Chem B 110:6250–6256

    Article  CAS  Google Scholar 

  65. Al-Salman R, El Abedin SZ, Endres F (2008) Electrodeposition of Ge, Si and SixGe1−x from an air- and water-stable ionic liquid. Phys Chem Chem Phys 10:4650–4657

    Article  CAS  Google Scholar 

  66. Mann O, Pan GB, Freyland W (2009) Nanoscale electrodeposition of metals and compound semiconductors from ionic liquids. Electrochim Acta 54:2487–2490

    Article  CAS  Google Scholar 

Download references

Acknowledgment

This work was financially supported by the National Basic Research Program of China (No. 2010CB934100), the National Natural Science Foundation of China (No. 21273272), and the Chinese Academy of Sciences.

Author information

Authors and Affiliations

  1. Division of Interdisciplinary Research, Suzhou Institute of Nano-tech and Nano-bionics (sinano), Chinese Academy of Sciences, 398 Ruoshui Road, SEID, Suzhou, 215123, China

    Hong-Dan Peng, Yu Zhao & Ge-Bo Pan

Authors
  1. Hong-Dan Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yu Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ge-Bo Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ge-Bo Pan .

Editor information

Editors and Affiliations

  1. Materials Engineering, Tarbiat Modares University, Tehran, Iran

    Mahmood Aliofkhazraei

  2. Department of Surface Engineering, Central of Metallurgical Research and Development Institute, Cairo, Egypt

    Abdel Salam Hamdy Makhlouf

Rights and permissions

Reprints and permissions

Copyright information

© 2015 Springer International Publishing Switzerland

About this entry

Cite this entry

Peng, HD., Zhao, Y., Pan, GB. (2015). Nanoscale Electrodeposition of Metals and Semiconductors from Ionic Liquids Probed by Scanning Tunneling Microscopy. In: Aliofkhazraei, M., Makhlouf, A. (eds) Handbook of Nanoelectrochemistry. Springer, Cham. https://doi.org/10.1007/978-3-319-15207-3_21-1

Download citation

  • DOI: https://doi.org/10.1007/978-3-319-15207-3_21-1

  • Received:

  • Accepted:

  • Published:

  • Publisher Name: Springer, Cham

  • Online ISBN: 978-3-319-15207-3

  • eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics

Publish with us

Policies and ethics

Search

Navigation