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KGaA,69469Weinheim,Germany,2011

SupportingInformation

for Adv. Mater., DOI: 10.1002/adma.201101115 Fabrication and Characterization of MIM Diodes Based on Nb/Nb 2 O 5 Via a Rapid Screening Technique Prakash Periasamy, Joseph J. Berry, Arrelaine A. Dameron, Jeremy D. Bergeson, David S. Ginley, Ryan P. OHayre, and Philip A. Parilla*

Submitted to DOI: 10.1002/adma.201101115 Fabrication and characterization of MIM diodes based on Nb/Nb2O5 via a rapid screening technique By Prakash Periasamy, Joseph J. Berry, Arrelaine A. Dameron, Jeremy D. Bergeson, David S. Ginley, Ryan P. OHayre, and Philip A. Parilla* E-mail: philip.parilla@nrel.gov, Phone: 303-384-6506, Fax: 303-384-6564 National Renewable Energy Laboratory, Golden, CO 80401 (USA)

Supporting Information
Table of Contents
S.No. 1 2 3 4 Description Plot of Nb2O5 thickness as a function of anodization voltage. XPS spectrum of Nb2O5 surface in the Nb/Nb2O5 bilayer. Photograph of the custom I-V station built specifically to test bent-wire pointcontact MIM devices. Note on statistical analysis done to calculate the asymmetry (fASYM) and nonlinearity (fNL) reported in Figs 3(a) and (b) in the main text. Page No. 2 3 4 5

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1. Plot of Nb2O5 thickness as a function of anodization voltage.

Figure S1. Plot of thickness of anodized Nb2O5 layer as a function of anodization voltage. Thickness was measured via x-ray reflectivity (XRR). A Philips XPert five-circle diffractometer was used for XRR measurements. Anodization of Nb metal film to Nb2O5 was done in a 1M H2SO4 electrolyte solution at atmosphere conditions for an anodization time of 60 seconds. Fresh H2SO4 solution was used for each data point. The growth coefficient (thickness/anodization voltage) is estimated to be 2.7 nm/V. Very similar growth coefficient was also obtained for longer anodization time. Under similar conditions, the variation in thickness is found to be less than 1 nm.

Submitted to 2. XPS spectrum of Nb2O5 surface in the Nb/Nb2O5 bilayer. XPS analysis was carried out on the anodized surface to ascertain the oxidation state of the anodized layer. Figure S2 shows the high-resolution XPS spectrum of the Nb 3d region. A survey scan was also taken (not shown here) that identified peaks of Nb and O in addition to trace impurities of C. Peak positions of the Nb 3d5/2 and Nb 3d 3/2 after corrections for the peak shift (0.7 eV based on C 1S peak) are 207.3 and 210 eV, respectively. These peak positions match very well with the reported (listed below) Nb 3d peak for Nb2O5. The range for Nb 3d5/2 peak of Nb2O5 is between 207-208 eV. [Supp. Ref. 1] Ozer et al., [Supp. Ref. 2] reported that the peak positions of Nb 3d5/2 and Nb 3d3/2 of Nb2O5 films (prepared by sol-gel, RF magnetron sputtering) close to 207.2 and 210.1 eV, respectively.

Figure S2. High-resolution XPS spectrum showing the Nb 3d region of the anodized niobium oxide surface. Peak positions of the Nb 3d5/2 and Nb 3d 3/2 after corrections for the peak shift (0.679 eV based on C 1S peak) are 207.271 and 210.018 eV, respectively. These peak positions matches very well with the reported Nb 3d peak for Nb2O5.
Supplemental Reference (Supp. Ref.) [1] W. F. S. John F.Moulder, Peter E. Sobol and Kenneth D. Bomben, Ed. Handbook of X-ray Photoelectron Spectroscopy, Physical Electronics, Minnesota 1995. [2] N. Ozer, D. G. Chen, C. M. Lampert, Thin Solid Films 1996, 277, 162.

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3. Photograph of the custom I-V station built specifically to test bent-wire point-contact MIM devices.

Figure S3. Photograph of the custom I-V station for characterizing bent-wire point-contact MIM devices. The metal 1 (M1)/insulator (I) bilayer on a silicon substrate (with native oxide) was mounted to the supporting post. The metal 2 (M2) bent-wire was contacted to the M1/I bilayer using a differential micrometer. In this study Nb/Nb2O5 is used as the M1/I bilayer. Pressed indium wire was used to glue the copper wire contact to the un-anodized M1 surface. DC bias is applied between M1 and M2 bent-wire and the resulting current is measured using a Keithley 2636 source measure unit. Current-Voltage data were recorded in a computer via LabTracer 2.0 software provided by Keithley.

Submitted to 5. Note on statistical analysis done to calculate the asymmetry (fASYM) and nonlinearity (fNL) reported in Figs 3(a) and (b) in the main paper. For each MIM configuration, thirty I-V curves were collected by positioning the metal 2 wire (M2) in (at least) three different locations on the Nb2O5 surface. fASYM and fNL were calculated from the individual I-V data. As expected, fASYM was found to be dependent on the bias voltage, whereas fNL was nearly independent on the bias voltage above the turn-on voltage (TOV). TOV is defined as the knee of the I-V curve [Reference [3] in the main paper]. fASYM reported in Fig 3(a) (see main paper) is the average of thirty asymmetry values calculated for each MIM configuration at 0.5V bias voltage. Very similar trends were seen for other bias voltages. Error bars indicate the standard deviation in the distribution of fASYM at a bias of 0.5V. Outliers were determined by evaluating the 25th and 75th quartiles after which the average asymmetry values are calculated. Since fNL is independent on bias voltage above the TOV, all the fNL values beyond TOV are included for the calculations in each of the thirty I-V curves for every MIM configuration. The TOV values for all the MIM configurations studied range from 0.1 to 0.25 V. To ensure that only points beyond TOV were evaluated, the fNL values for each of the MIM configurations were taken between 0.3 to 0.5 V for the calculations. For the example of the Nb/Nb2O5/Cu MIM configuration, 30 I-V curves are collected. In each of the 30 I-V curves, 20 fNL values between 0.3 and 0.5V are considered. Hence the total number of fNL data points for the Nb/Nb2O5/Cu configuration is 600 (30 X 20). Histograms are plotted using the data population (600 points) of fNL values for each MIM configuration were used to analyze the distribution of the data. A typical histogram plot is shown in Figure S4 for the fNL values of Nb/Nb2O5/Cu. Figure S4 indicates a typical histogram and fit to a normal distribution. This approach was applied to the other MIM configurations. Using this analysis the box and whisker plot of fNL values for each of the MIM configuration was constructed based on the values obtained fitting the normal distribution to the histograms.

Figure S4. Histogram plot of fNL values of Nb/Nb2O5/Cu. A normal distribution fit is also shown. 5