Abstract

Schottky barrier diodes (SBDs) were fabricated by depositing Pd, Pt or Ni on single crystal, conductive n-type rutile TiO2 using e-beam evaporation. As-grown and nominally undoped rutile TiO2 single crystals are semi-insulating, and were heat-treated in forming gas flow, N2 flow or H2 gas to obtain conductive n-type crystals displaying electrical conductivities in the range of . Additionally, SBDs were deposited on Nb-doped conductive n-type rutile TiO2 with a conductivity of around . Generally, SBDs displaying a rectification of up to eight orders of magnitude were obtained, when comparing the current under reverse and forward bias. The extracted ideality factors were in the range of . From Capacitance-Voltage measurements, the built-in voltage was derived to be around , depending on the doping concentration of the specific TiO2 single crystal. Series resistances as low as were achieved. A considerable variation in the electrical characteristics of different SBDs deposited on the same crystal was found, regardless of the metal or doping strategy used. Moreover, the SBD characteristics change over time, particularly seen as a degradation in rectification, mainly related to an increase in the current under reverse bias. Additional surface treatments such as boiling in H2O2 and etching in HF do not have a significant effect on the quality of the SBDs. Clear indications for poor adhesion between TiO2 and Pd are shown. In conclusion, we demonstrate the fabrication of SBDs which are suitable for studying the fundamental properties of metal/TiO2 junctions and the characteristics of electrically-active defects in TiO2 using space-charge spectroscopy.

Highlights

  • Rutile titanium dioxide (TiO2) is a wide-bandgap semiconductor (Eg = 3.2 eV [1,2,3,4]) well-known for its photocatalytic properties [5, 6], rendering TiO2 a promising material for photo-catalytic water-splitting as well as photo-catalytic water purification [6,7,8,9,10]

  • We have studied the formation of metal/TiO2 junctions comprising Pd, Pt, Ni and Al

  • A large spread in electrical characteristics is found for Schottky barrier diodes (SBDs) fabricated on the same TiO2 crystal regardless of the doping strategy or the surface orientation

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Summary

Introduction

In applications for photo-catalysis, systems consisting of TiO2 and noble metals, such as Pd, Pt, Au or Ag, display a better performance compared to just TiO2 [29,30,31,32,33] This is believed to be due to an improved charge transfer at the interface between the metal and TiO2 due to the formation of a rectifying junction [34]. The fabrication of Schottky barrier diodes (SBDs) involving conductive TiO2 single crystals obtained by employing different doping strategies paves the way for systematic defect studies in such material as well as enables investigations of the fundamental properties of the corresponding metal/TiO2 junctions. The fabricated Pd/TiO2 junctions are found to exhibit suitable electrical characteristics for studying fundamental junction properties and the characteristics of electrically-active defects in TiO2 using space-charge spectroscopy

Experimental
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