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1. N. F. Mott and R. W. Gurney, Electronic Processes in Ionic Crystals. (Oxford University Press, London, 1948).
2. W. G. Spitzer and C. A. Mead, Barrier Height Studies on Metal-Semiconductor Systems. J. Appl. Phys. 34, 3061 (1963).
3. C. R. Crowell, H. B. Shore, and E. E. LaBate, Surface-State and Interface Effects in Schottky Barriers at n-Type Silicon Surfaces. J. Appl. Phys. 36, 3843 (1965).
4. L. J. Brillson, Transition in Schottky Barrier Formation with Chemical Reactivity. Phys. Rev. Lett. 40, 260 (1978).
5. S. M. Sze and K. K. Ng, Physics of Semiconductor Devices. (Wiley-Interscience, New York, 2007).
6. J. Bardeen, Surface States and Rectification at a Metal Semi-Conductor Contact. Phys. Rev. 71, 717 (1947).
7. A. M. Cowley and S. M. Sze, Surface States and Barrier Height of Metal-Semiconductor Systems. J. Appl. Phys. 36, 3212 (1965).
8. To some extent, this value can vary for different semiconductors and different doping concentrations.
9. S. Kurtin, T. C. McGill, and C. A. Mead, Fundamental Transition in the electronic Nature of Solids. Phys. Rev. Lett. 22, 1433 (1969).
10. V. Heine, Theory of Surface States. Phys. Rev. 138, A1689 (1965).
11. W. E. Spicer, Unified defect model and beyond. J. Vac. Sci. Technol. 17, 1019 (1980).
12. J. L. Freeouf and J. M. Woodall, Schottky barriers: An effective work function model. Appl. Phys. Lett. 39, 727 (1981).
13. R. T. Tung, Chemical Bonding and Fermi Level Pinning at Metal-Semiconductor Interfaces. Phys. Rev. Lett. 84, 6078 (2000).
14. D. M. Alloway, M. Hofmann, D. L. Smith, N. E. Gruhn, A. L. Graham et al., Interface Dipoles Arising from Self-Assembled Monolayers on Gold: UV-Photoemission Studies of Alkanethiols and Partially Fluorinated Alkanethiols. J. Phys. Chem. B 107, 11690 (2003).
15. Y. Selzer and D. Cahen, Fine Tuning of Au/SiO2/Si Diodes by Varying Interfacial Dipoles Using Molecular Monolayers. Adv. Mater. 13, 508 (2001).<508::AID-ADMA508>3.0.CO;2-8
16. A. Vilan and D. Cahen, How organic molecules can control electronic devices. Trends Biotechnol 20, 22 (2002).
17. R. Cohen, L. Kronik, A. Shanzer, D. Cahen, A. Liu et al., Molecular Control over Semiconductor Surface Electronic Properties: Dicarboxylic Acids on CdTe, CdSe, GaAs, and InP. J. Am. Chem. Soc. 121, 10545 (1999).
18. R. Hunger, R. Fritsche, B. Jaeckel, W. Jaegermann, L. J. Webb et al., Chemical and electronic characterization of methyl-terminated Si(111) surfaces by high-resolution synchrotron photoelectron spectroscopy. Phys. Rev. B 72, 045317 (2005).
19. D. Aureau, A. Moraillon, C. Henry de Villeneuve, F. Ozanam, P. Allongue et al., Electronic Properties and pH Stability of Si(111)/Alkyl Monolayers. ECS Trans. 19, 373 (2009).
20. A. Vilan, J. Ghabboun, and D. Cahen, Molecule−Metal Polarization at Rectifying GaAs Interfaces. J. Phys. Chem. B 107, 6360 (2003).
21. H. Takato, I. Sakata, and R. Shimokawa, Quinhydrone/methanol treatment for the measurement of carrier lifetime in silicon substrates. Jpn. J. Appl. Phys. 2 41, L870 (2002).
22. The treatment was reported originally with quinhydrone (QH), a charge transfer complex of p-benzoquinone (p-BQ) and hydroquinone (HQ). In our hands, using p-BQ or HQ solution, instead of QH, produces the same results in terms of surface dipole and passivation, as will be discussed below. We ascribe this equivalence to cross contamination of p-BQ in the HQ and vice versa.
23. See supplementary material at for XPS results indicating that the surface is mostly methoxy-terminated, for the C-V measurements and their comparison to SBH extracted from J-V, for the BE of Si2p as measured by XPS for H-terminated and HQ-MeOH treated n-Si(100), for the XPS C1s line, for the junction band diagram, and for the full statistics of the J-V measurements. [Supplementary Material]
24. A. B. Sieval, C. L. Huisman, A. Schonecker, F. M. Schuurmans, A. S. H. van der Heide et al., Silicon Surface Passivation by Organic Monolayers: Minority Charge Carrier Lifetime Measurements and Kelvin Probe Investigations. J. Phys. Chem. B 107, 6846 (2003).
25. S. Avasthi, Y. Qi, G. K. Vertelov, J. Schwartz, A. Kahn et al., Silicon surface passivation by an organic overlayer of 9,10-phenanthrenequinone. Appl. Phys. Lett. 96, 222109 (2010).
26. E. J. Nemanick, P. T. Hurley, B. S. Brunschwig, and N. S. Lewis, Chemical and Electrical Passivation of Silicon (111) Surfaces through Functionalization with Sterically Hindered Alkyl Groups. J. Phys. Chem. B 110, 14800 (2006).
27. A. Salomon, D. Berkovich, and D. Cahen, Molecular modification of an ionic semiconductor–metal interface: ZnO/molecule/Au diodes. Appl. Phys. Lett. 82, 1051 (2003).
28. L. Kronik and Y. Shapira Surface photovoltage phenomena: theory, experiment, and applications. Surf. Sci. rep. 37, 1 (1999).
29. To translate relative CPD values into WF the Kelvin probe reference electrode was calibrated against that of highly oriented freshly peeled pyrolytic graphite (HOPG), with a known WF of 4.6 eV.
30. H. Haick, M. Ambrico, T. Ligonzo, and D. Cahen, Discontinuous molecular films can control metal/semiconductor junctions. Adv. Mater. 16, 2145 (2004).
31. Another possible explanation is that with longer alcohols as solvent the competition between hydroquinone and alkoxy species shifts towards the alkoxy, which has a lower dipole on Si than the quinone. This, though, is less likely, because even for methanol, HQ was found to bind only to a small fraction of the surface.
32. B. Chhabra, S. Suzer, R. L. Opila, and C. B. Honsberg, Electrical and chemical characterization of chemically passivated silicon surfaces. Photovoltaic Specialists Conference, 2008. PVSC '08. 33rd IEEE 14 (2008).
33. We have chosen curves for which we have C-V measurement taken immediately afterwards, but as can be seen in the supporting information they fit well in the dispersion of their families.
34. Y. Liu and H. Yu, Alkyl Monolayer-Passivated Metal–Semiconductor Diodes: Molecular Tunability and Electron Transport. ChemPhysChem 3, 799 (2002).<799::AID-CPHC799>3.0.CO;2-V
35. We added this value, although physically incorrect, for the sake of comparison with current and older data published for Si/metal junctions.
36. G. Ashkenasy, D. Cahen, R. Cohen, A. Shanzer, and A. Vilan, Molecular engineering of semiconductor surfaces and devices. Acc. Chem. Res. 35, 121 (2002).
37. A. Salomon, T. Boecking, C. K. Chan, F. Amy, O. Girshevitz et al., How Do Electronic Carriers Cross Si-Bound Alkyl Monolayers? Phys. Rev. Lett. 95, 266807 (2005).
38. H. Takato, I. Sakata, and R. Shimokawa, Surface passivation of silicon substrates using quinhydrone/methanol treatment. Photovoltaic Energy Conversion, 2003. Proceedings of 3rd World Conference on 2, 1108 (2003).
39. H. Cohen, Chemically resolved electrical measurements using x-ray photoelectron spectroscopy. Appl. Phys. Lett. 85, 1271 (2004).
40. H. Cohen, C. Nogues, I. Zon, and I. Lubomirsky, e-beam-referenced work-function evaluation in an x-ray photoelectron spectrometer. J. Appl. Phys. 97, 113701 (2005).
41. O. Yaffe, L. Scheres, S. R. Puniredd, N. Stein, A. Biller et al., Molecular Electronics at Metal/Semiconductor Junctions. Si Inversion by Sub-Nanometer Molecular Films. Nano Letters 9, 2390 (2009).
42. J. Schmidt and A. G. Aberle, Accurate method for the determination of bulk minority-carrier lifetimes of mono- and multicrystalline silicon wafers. J. Appl. Phys. 81, 6186 (1997).
43. M. B. Prince, Drift Mobilities in Semiconductors. II. Silicon. Phys. Rev. 93, 1204 (1954).
44. The molecular surface dipole for those monolayers, as well as for other high quality SAMs on oxide-free Si we have measured, is not completely independent on the substrate type and doping. A report on that finding is to be published soon.
45. R. B. Godfrey and M. A. Green, 655 mV open-circuit voltage, 17.6% efficient silicon MIS solar cells. Appl. Phys. Lett. 34, 790 (1979).
46. R. J. Stirn and Y. C. M. Yeh, A 15% efficient antireflection-coated metal-oxide-semiconductor solar cell. Appl. Phys. Lett. 27, 95 (1975).
47. M. A. Green, F. D. King, and J. Shewchun, Minority-carrier MIS tunnel-diodes and their application to electron-voltaic and photo-voltaic energy-conversion .1. Theory. Solid State Electron. 17, 551 (1974).
48. P. Chattopadhyay, Functional dependence of open-circuit voltage on interface parameters and doping concentration of MIS solar cells. physica status solidi (a) 140, 587 (1993).
49. M. Wittmer and J. L. Freeouf, Ideal Schottky diodes on passivated silicon. Phys. Rev. Lett. 69, 2701 (1992).
50. H. Haick, M. Ambrico, T. Ligonzo, R. T. Tung, and D. Cahen, Controlling Semiconductor/Metal Junction Barriers by Incomplete, Nonideal Molecular Monolayers. J. Am. Chem. Soc. 128, 6854 (2006).
51. J. Shewchun, M. A. Green, and F. D. King, Minority-carrier MIS tunnel-diodes and their application to electron-voltaic and photo-voltaic energy-conversion .2. Experiment. Solid State Electron. 17, 563 (1974).
52. S. J. Fonash, The role of the interfacial layer in metal−semiconductor solar cells. J. Appl. Phys. 46, 1286 (1975).
53. N. G. Tarr, D. L. Pulfrey, and D. S. Camporese, An analytic model for the MIS tunnel junction. IEEE T. Electron. Dev. 30, 1760 (1983).
54. B. Chhabra, S. Bowden, R. L. Opila, and C. B. Honsberg, High effective minority carrier lifetime on silicon substrates using quinhydrone-methanol passivation. Appl. Phys. Lett. 96, 063502 (2010).
55. C. Sommerhalter, T. W. Matthes, T. Glatzel, A. Jäger-Waldau, and M. C. Lux-Steiner, High-sensitivity quantitative Kelvin probe microscopy by noncontact ultra-high-vacuum atomic force microscopy. Appl. Phys. Lett. 75, 286 (1999).

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We report near-perfect transfer of the electrical properties of oxide-free Si surface , modified by a molecular monolayer, to the interface of a junction made with that modified Si surface. Such behavior is highly unusual for a covalent, narrow bandgap semiconductor, such as Si. Short, ambient atmosphere, room temperature treatment of oxide-free Si(100) in hydroquinone (HQ)/alkyl alcohol solutions, fully passivates the Si surface, while allowing controlled change of the resulting surface potential. The junctions formed, upon contacting such surfaces with Hg, a metal that does not chemically interact with Si, follow the Schottky-Mott model for metal-semiconductor junctions closer than ever for Si-based junctions. Two examples of such ideal behavior are demonstrated: a) Tuning the molecular surface dipole over 400 mV, with only negligible band bending, by changing the alkyl chain length. Because of the excellent passivation this yields junctions with Hg with barrier heights that follow the change in the Si effective electron affinity nearly ideally. b) HQ/ methanol passivation of Si is accompanied by a large surface dipole, which suffices, as interface dipole, to drive the Si into strong inversion as shown experimentally via its photovoltaic effect. With only ∼0.3 nm molecular interlayer between the metal and the Si, our results proves that it is passivation and prevention of metal-semiconductor interactions that allow ideal metal-semiconductor junction behavior, rather than an insulating transport barrier.


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