Metal-molecule-metal junctions based on alkane thiol (C n T) and oligophenylene thiol (OPT n ) self-assembled monolayers (SAMs) and Au electrodes are expected to exhibit similar electrical asymmetry, as both junctions have one chemisorbed Au–S contact and one physisorbed, van der Waals contact. Asymmetry is quantified by the current rectification ratio RR apparent in the current–voltage ( I – V ) characteristics. Here we show that RR < 1 for C n T and RR > 1 for OPT n junctions, in contrast to expectation, and further, that RR behaves very differently for C n T and OPT n junctions under mechanical extension using the conducting probe atomic force microscopy (CP-AFM) testbed. The analysis presented in this paper, which leverages results from the previously validated single level model and ab initio quantum chemical calculations, allows us to explain the puzzling experimental findings for C n T and OPT n in terms of different current rectification mechanisms. Specifically, in C n T-based junctions the Stark effect creates the HOMO level shifting necessary for rectification, while for OPT n junctions the level shift arises from position-dependent coupling of the HOMO wavefunction with the junction electrostatic potential profile. On the basis of these mechanisms, our quantum chemical calculations allow quantitative description of the impact of mechanical deformation on the measured current rectification. Additionally, our analysis, matched to experiment, facilitates direct estimation of the impact of intramolecular electrostatic screening on the junction potential profile. Overall, our examination of current rectification in benchmark molecular tunnel junctions illuminates key physical mechanisms at play in single step tunneling through molecules, and demonstrates the quantitative agreement that can be obtained between experiment and theory in these systems.
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Work function and temperature dependence of electron tunneling through an N-type perylene diimide molecular junction with isocyanide surface linkers
Conducting probe atomic force microscopy (CP-AFM) was employed to examine electron tunneling in self-assembled monolayer (SAM) junctions. A 2.3 nm long perylene tetracarboxylic acid diimide (PDI) acceptor molecule equipped with isocyanide linker groups was synthesized, adsorbed onto Ag, Au and Pt substrates, and the current–voltage ( I – V ) properties were measured by CP-AFM. The dependence of the low-bias resistance ( R ) on contact work function indicates that transport is LUMO-assisted (‘n-type behavior’). A single-level tunneling model combined with transition voltage spectroscopy (TVS) was employed to analyze the experimental I – V curves and to extract the effective LUMO position ε l = E LUMO − E F and the effective electronic coupling ( Γ ) between the PDI redox core and the contacts. This analysis revealed a strong Fermi level ( E F ) pinning effect in all the junctions, likely due to interface dipoles that significantly increased with increasing contact work function, as revealed by scanning Kelvin probe microscopy (SKPM). Furthermore, the temperature ( T ) dependence of R was found to be substantial. For Pt/Pt junctions, R varied more than two orders of magnitude in the range 248 K < T < 338 K. Importantly, the R ( T ) data are consistent with a single step electron tunneling mechanism and allow independent determination of ε l , giving values compatible with estimates of ε l based on analysis of the full I – V data. Theoretical analysis revealed a general criterion to unambiguously rule out a two-step transport mechanism: namely, if measured resistance data exhibit a pronounced Arrhenius-type temperature dependence, a two-step electron transfer scenario should be excluded in cases where the activation energy depends on contact metallurgy. Overall, our results indicate (1) the generality of the Fermi level pinning phenomenon in molecular junctions, (2) the utility of employing the single level tunneling model for determining essential electronic structure parameters ( ε l and Γ ), and (3) the importance of changing the nature of the contacts to verify transport mechanisms.
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- Award ID(s):
- 1708173
- NSF-PAR ID:
- 10060876
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 10
- Issue:
- 3
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 964 to 975
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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null (Ed.)This paper addresses the mechanism for rectification in molecular tunneling junctions based on alkanethiolates terminated by a bipyridine group complexed with a metal ion, that is, having the structure AuTS-S(CH2)11BIPY-MCl2 (where M = Co or Cu) with a eutectic indium–gallium alloy top contact (EGaIn, 75.5% Ga 24.5% In). Here, AuTS-S(CH2)11BIPY is a self-assembled monolayer (SAM) of an alkanethiolate with 4-methyl-2,2′-bipyridine (BIPY) head groups, on template-stripped gold (AuTS). When the SAM is exposed to cobalt(II) chloride, SAMs of the form AuTS-S(CH2)11BIPY-CoCl2 rectify current with a rectification ratio of r+ = 82.0 at ±1.0 V. The rectification, however, disappears (r+ = 1.0) when the SAM is exposed to copper(II) chloride instead of cobalt. We draw the following conclusions from our experimental results: (i) AuTS-S(CH2)11BIPY-CoCl2 junctions rectify current because only at positive bias (+1.0 V) is there an accessible molecular orbital (the LUMO) on the BIPY-CoCl2 moiety, while at negative bias (−1.0 V), neither the energy level of the HOMO or the LUMO lies between the Fermi levels of the electrodes. (ii) AuTS-S(CH2)11BIPY-CuCl2 junctions do not rectify current because there is an accessible molecular orbital on the BIPY-CuCl2 moiety at both negative and positive bias (the HOMO is accessible at negative bias, and the LUMO is accessible at positive bias). The difference in accessibility of the HOMO levels at −1.0 V causes charge transfer—at negative bias—to take place via Fowler–Nordheim tunneling in BIPY-CoCl2 junctions, and via direct tunneling in BIPY-CuCl2 junctions. This difference in tunneling mechanism at negative bias is the origin of the difference in rectification ratio between BIPY-CoCl2 and BIPY-CuCl2 junctions.more » « less
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Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K. The spectral peaks for VB = 2.8 and 3.0 V both occur around = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). 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And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018).more » « less
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We report on growth and electrical properties of α-Ga2O3films prepared by halide vapor phase epitaxy (HVPE) at 500 °C on α-Cr2O3buffers predeposited on sapphire by magnetron sputtering. The α-Cr2O3buffers showed a wide microcathodoluminescence (MCL) peak near 350 nm corresponding to the α-Cr2O3bandgap and a sharp MCL line near 700 nm due to the Cr+intracenter transition. Ohmic contacts to Cr2O3were made with both Ti/Au or Ni, producing linear current–voltage ( I– V) characteristics over a wide temperature range with an activation energy of conductivity of ∼75 meV. The sign of thermoelectric power indicated p-type conductivity of the buffers. Sn-doped, 2- μm-thick α-Ga2O3films prepared on this buffer by HVPE showed donor ionization energies of 0.2–0.25 eV, while undoped films were resistive with the Fermi level pinned at ECof 0.3 eV. The I– V and capacitance–voltage ( C– V) characteristics of Ni Schottky diodes on Sn-doped samples using a Cr2O3buffer indicated the presence of two face-to-face junctions, one between n-Ga2O3and p-Cr2O3, the other due to the Ni Schottky diode with n-Ga2O3. The spectral dependence of the photocurrent measured on the structure showed the presence of three major deep traps with optical ionization thresholds near 1.3, 2, and 2.8 eV. Photoinduced current transient spectroscopy spectra of the structures were dominated by deep traps with an ionization energy of 0.95 eV. These experiments suggest another pathway to obtain p–n heterojunctions in the α-Ga2O3system.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C7NR06461F
