Improved Pt/Au and W/Pt/Au Schottky contacts on n-type ZnO using ozone cleaning

K. Ip, B. P. Gila, A. H. Onstine, E. S. Lambers, Y. W. Heo et al. Citation: Appl. Phys. Lett. 84, 5133 (2004); doi: 10.1063/1.1764940 View online: http://dx.doi.org/10.1063/1.1764940 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v84/i25 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS

VOLUME 84, NUMBER 25

21 JUNE 2004

Improved Pt/ Au and W / Pt/ Au Schottky contacts on n-type ZnO using ozone cleaning
K. Ip, B. P. Gila, A. H. Onstine, E. S. Lambers, Y. W. Heo, K. H. Baik, D. P. Norton, and S. J. Peartona)
Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611

S. Kim, J. R LaRoche, and F. Ren

Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611

(Received 5 December 2003; accepted 28 April 2004; published online 4 June 2004) UV-ozone cleaning prior to metal deposition of either e-beam Pt contacts or sputtered W contacts on n-type single-crystal ZnO is found to signicantly improve their rectifying characteristics. Pt contacts deposited directly on the as-received ZnO surface are Ohmic but show rectifying behavior with ozone cleaning. The Schottky barrier height of these Pt contacts was 0.70 eV, with ideality factor of 1.5 and a saturation current density of 6.2 106 A cm2. In contrast, the as-deposited W contacts are Ohmic, independent of the use of ozone cleaning. Postdeposition annealing at 700 C produces rectifying behavior with Schottky barrier heights of 0.45 eV for control samples and 0.49 eV for those cleaned with ozone exposure. The improvement in rectifying properties of both the Pt and W contacts is related to removal of surface carbon contamination from the ZnO. 2004 American Institute of Physics. [DOI: 10.1063/1.1764940] ZnO is currently under development for use in UV light emitters, spin functional devices, gas sensors, transparent electronics, and surface acoustic wave devices.114 It has a direct band gap energy of 3.3 eV and large exciton binding energy of 60 meV, which makes it well-suited to developing high brightness UV light sources and transparent electronics. To realize UV light emitters/detectors or eld effect transistors, it is necessary to develop reliable, reproducible doping methods and Ohmic and rectifying contacts to this material in order to exploit these device opportunities. Previous reports have shown Au, Ag, and Pd form rectifying contacts on n-type ZnO with Schottky barrier heights in the range of 0.6 0.8 eV.1232 However, the trend in barrier heights did not correlate with the metal work functions, suggesting that either intrinsic surface states or residual surface contamination is playing a role in determining the electrical properties of the contacts. In addition, the thermal stability of Au was extremely poor, with degradation occurring even at 60 C.2327 Various surface cleaning procedures prior to depositing contacts on ZnO have been reported, such as etching in concentrated phosphoric or nitric acid or organic solvent rinsing.2333 However, in most cases the reported ideality factors are high, indicating the presence of transport mechanisms such as tunneling, the impact of interface states, or the inuence of deep recombination centers. This letter demonstrates that the UV ozone cleaning of the n-type ZnO surface prior to deposition of either e-beam Pt or sputtered W contacts produces signicant improvements in the rectifying properties of these contacts and that W contacts are stable up to 700 C. The samples were the (0001) undoped grade I quality bulk ZnO crystals from Cermet. The samples were epiready one-side-Zn-face-polished by the manufacturer. The room temperature electron concentration and mobility from van der Pauw measurements were 1017 cm3 and 190 cm2 / V s,
a)

Electronic mail: spear@mse.u.edu 5133

respectively. To study the effects of UV ozone treatment (UVOCS UV Ozone Cleaning System Model 70606B) prior to Schottky metal deposition, samples wee exposed for 30 min at room temperature and then characterized with atomic force microscopy (tapping mode, 1 m 1 m) and also x-Ray photoelectron spectroscopy XPS/ ESCA in a Perkin-Elmer PHI 5100 system. The contact study was performed by depositing a full back side Ohmic contact by e-beam evaporation, consisting of Ti/ Al/ Pt/ Au 200/ 800/ 400/ 800 . This was annealed at 200 C, 1 min, N2 ambient. The subsequent contacts were deposited either with or without 30 min UV Ozone treatments. The 50- m -diam Pt Schottky contacts were patterned by standard liftoff photolithography after e-beam evaporation of Pt/ Au 200/ 1000 . The W contacts were also patterned by standard lift-off photolithography after deposition of W / Pt/ Au 720/ 200/ 1000 by sputtering in a Kurt J. Lesker CMS-18 system. In each case the samples were characterized with an HP 4156 Semiconductor Parameter Analyzer and AES Perkin-Elmer PHI 660 Scanning Auger Microscope after postsputtering anneals up to 700 C under a N2 ambient for 1 min. The XPS data showed that the average surface concentration of C on the ZnO surface was decreased from 29.5 at. % to 5.8 at. % as a result of the ozone treatment. Depth proling showed that this effect was purely a surface phenomenon, with the C concentration below the detection limit after 100 in both as-received and ozone-cleaned samples. This reduction of C contamination by the ozone cleaning had a major effect on the electrical characteristics of the contacts deposited on these surfaces. The currentvoltage I V characteristics for the Pt metallization are shown in Fig. 1. The sample without ozone treatment resulted in the linear I V characteristics expected of Ohmic contacts. In contract, the samples treated with ozone exhibited excellent rectifying behavior. For these contacts, the Schottky barrier height was obtained by tting the forward characteristics to
2004 American Institute of Physics

0003-6951/2004/84(25)/5133/3/$20.00

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Appl. Phys. Lett., Vol. 84, No. 25, 21 June 2004

Ip et al.

FIG. 1. I V characteristics from Pt/ Au contacts on either control or ozonecleaned n-type ZnO.

the relation for thermionic emission over a barrier JF = A* T2exp eV e b exp , kT nkT 1

where J is the current density, A* is the Richardsons constant for n-ZnO, T the absolute temperature, e the electronic charge, b the barrier height, k Boltzmanns constant, n the ideality factor, and V the applied voltage. From the data, b was obtained as 0.70 eV for the as-deposited Pt on the ozone cleaned surface, with a saturation current density of 6.2 106 A cm2 The ideality factor was 1.5, suggesting transport mechanisms other than thermionic emission, such as recombination. The transition from Ohmic to rectifying behavior as a result of the ozone cleaning may be due to the removal of a defective surface layer that contains C contamination and which prevents electrical contact of the Pt with the ZnO surface. The W contacts exhibited nonrectifying behavior for assputtered, 250 and 500 C annealed conditions, independent of the use of ozone cleaning. As shown in Fig. 2, after annealing at 700 C, the contacts were rectifying in all cases with barrier heights of 0.45 eV without ozone cleaning and 0.49 eV with ozone cleaning. The ideality factors for all of these contacts was 2. The as-deposited results appear to be dominated by residual ion-induced damage from the sputtering process. The postdeposition annealing of the W / Pt/ Au metallization did not cause any detectable intermixing up to temperatures of 500 C but after 700 C anneal, the AES depth pro-

FIG. 3. AES depth proles from W / Pt/ Au contacts on ZnO after annealing at either 500 or 700 C.

les showed that Zn diffused out to the Au Pt interface (Fig. 3). This effect was independent of whether the samples had been exposed to ozone. As reported previously, the Pt contacts are less thermally stable, showing contact intermixing at temperatures as low as 350 C.33 In summary, the use of UV ozone cleaning of ZnO surfaces prior to deposition of either e-beam Pt or sputtered W contacts improves the subsequent rectifying nature of these contacts. The as-deposited Pt contacts on ozone-cleaned n-type ZnO surfaces show reasonable barrier heights and ideality factors, while the W contacts require postdeposition annealing to remove sputter-induced damage. The ozone cleaning produces clear benets in improving rectifying contacts on n-type ZnO. This research was sponsored by the Army Research Ofce under Grant No. DAAD19-01-1-0603, the Army Research Laboratory, the National Science Foundation (DMR 0400416), and the Air Force Ofce of Scientic Research.
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FIG. 2. I V characteristics from as-deposited or 700 C annealed W / Pt/ Au contacts on n-type ZnO, both for ozone-cleaning and no-cleaning cases.

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Appl. Phys. Lett., Vol. 84, No. 25, 21 June 2004

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