Influence of an Atom in EGaIn/Ga2O3 Tunneling Junctions Comprising Self-Assembled Monolayers
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Abstract
We compared the electrical properties of self-assembled monolayers (SAMs) formed on template-stripped Au from two homologous series of five different oligo-(phenylene)s bearing alkane thiol tails. The terminal phenyl ring is substituted by a 4-pyridyl ring in one series, thus the two differ only by the substitution of C-H for N. We formed tunneling junctions using the liquid metal eutectic Ga-In (EGaIn) as a nondamaging, conformal top contact that is insensitive to functional groups and measured the current-density, J, tunneling decay constants, β, and transition voltages, Vtrans. Conductance measurements alone did not sufficiently differentiate the two series of molecules. The length dependences of the two series of SAMs produced values of β of 0.44 and 0.42 Å-1 for pyridyl- and phenyl-terminated SAMs, respectively, which lie between the expected values for alkanethiolates and oligo(phenylene)s. The values of Vtrans were ∼0.3 V larger for the phenyl-terminated SAMs than for the pyridyl-terminated SAMs. A comparison of the values of J to highest occupied molecular orbital (HOMO) levels determined by density functional theory (DFT) calculations revealed an odd-even effect for the phenyl-terminated SAMs but not the pyridyl-terminated SAMs. Plots of Vtrans versus the measured shift in work function, measured with a Kelvin probe, reveal a roughly linear trend. Plots of the difference between HOMO and Fermi energies reveal a strong linear trend with two distinct series that clearly differentiate the two series of SAMs, even between SAMs with nearly identical HOMO levels, but only when the dipole-induced shift in vacuum level is considered. The influence of the electronic properties of the SAMs is clearly evident in the conductance data and highlights the importance of molecular dipoles in tunneling junctions comprising SAMs. Taken together, the data show that tunneling junctions incorporating EGaIn as a top contact are sensitive enough to differentiate SAMs that differ by the substitution of a single atom.
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en" level="a">Influence of an Atom in EGaIn/Ga<sub>2</sub>O<sub>3</sub> Tunneling Junctions Comprising Self-Assembled Monolayers</title><author><name sortKey="Fracasso, Davide" uniqKey="Fracasso D">Davide Fracasso</name><affiliation wicri:level="4"><inist:fA14 i1="01"><s1>Stratingh Institute for Chemistry and Zemike Institute for Advanced Materials, University of Groningen, Nijenborgh 4</s1><s2>9747 AG Groningen</s2><s3>NLD</s3><sZ>1 aut.</sZ><sZ>5 aut.</sZ></inist:fA14><country>Pays-Bas</country><wicri:noRegion>9747 AG Groningen</wicri:noRegion><orgName type="university">Université de Groningue</orgName><placeName><settlement type="city">Groningue (ville)</settlement><region>Groningue (province)</region></placeName></affiliation></author><author><name sortKey="Muglali, Mutlu Iskender" uniqKey="Muglali M">Mutlu Iskender Muglali</name><affiliation wicri:level="1"><inist:fA14 i1="02"><s1>Max-Planck-Institut für Einsenforschung GmbH, Max-Planck-Strasse 1</s1><s2>40237 Düsseldorf</s2><s3>DEU</s3><sZ>2 aut.</sZ><sZ>3 aut.</sZ></inist:fA14><country>Allemagne</country><wicri:noRegion>40237 Düsseldorf</wicri:noRegion><wicri:noRegion>Max-Planck-Strasse 1</wicri:noRegion><wicri:noRegion>40237 Düsseldorf</wicri:noRegion></affiliation></author><author><name sortKey="Rohwerder, Michael" uniqKey="Rohwerder M">Michael Rohwerder</name><affiliation wicri:level="1"><inist:fA14 i1="02"><s1>Max-Planck-Institut für Einsenforschung GmbH, Max-Planck-Strasse 1</s1><s2>40237 Düsseldorf</s2><s3>DEU</s3><sZ>2 aut.</sZ><sZ>3 aut.</sZ></inist:fA14><country>Allemagne</country><wicri:noRegion>40237 Düsseldorf</wicri:noRegion><wicri:noRegion>Max-Planck-Strasse 1</wicri:noRegion><wicri:noRegion>40237 Düsseldorf</wicri:noRegion></affiliation></author><author><name sortKey="Terfort, Andreas" uniqKey="Terfort A">Andreas Terfort</name><affiliation wicri:level="1"><inist:fA14 i1="03"><s1>Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7</s1><s2>60438 Frankfurt</s2><s3>DEU</s3><sZ>4 aut.</sZ></inist:fA14><country>Allemagne</country><wicri:noRegion>60438 Frankfurt</wicri:noRegion><wicri:noRegion>Max-von-Laue-Strasse 7</wicri:noRegion><wicri:noRegion>60438 Frankfurt</wicri:noRegion></affiliation></author><author><name sortKey="Chiechi, Ryan C" uniqKey="Chiechi R">Ryan C. Chiechi</name><affiliation wicri:level="4"><inist:fA14 i1="01"><s1>Stratingh Institute for Chemistry and Zemike Institute for Advanced Materials, University of Groningen, Nijenborgh 4</s1><s2>9747 AG Groningen</s2><s3>NLD</s3><sZ>1 aut.</sZ><sZ>5 aut.</sZ></inist:fA14><country>Pays-Bas</country><wicri:noRegion>9747 AG Groningen</wicri:noRegion><orgName type="university">Université de Groningue</orgName><placeName><settlement type="city">Groningue (ville)</settlement><region>Groningue (province)</region></placeName></affiliation></author></titleStmt><publicationStmt><idno type="inist">13-0316388</idno><date when="2013">2013</date><idno type="stanalyst">PASCAL 13-0316388 INIST</idno><idno type="RBID">Pascal:13-0316388</idno><idno type="wicri:Area/Main/Corpus">000687</idno><idno type="wicri:Area/Main/Repository">000A54</idno></publicationStmt><seriesStmt><idno type="ISSN">1932-7447</idno><title level="j" type="abbreviated">J. phys. chem., C</title><title level="j" type="main">Journal of physical chemistry. C</title></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Density functional method</term><term>Electronic structure</term><term>Fermi level</term><term>Frontier orbital</term><term>Gallium alloys</term><term>Gallium oxide</term><term>Indium alloys</term><term>Self-assembled layers</term><term>Tunnel effect</term><term>Tunnel junction</term><term>Work functions</term></keywords><keywords scheme="Pascal" xml:lang="fr"><term>Effet tunnel</term><term>Orbitale frontière</term><term>Méthode fonctionnelle densité</term><term>Travail sortie</term><term>Niveau Fermi</term><term>Structure électronique</term><term>Oxyde de gallium</term><term>Jonction tunnel</term><term>Couche autoassemblée</term><term>Gallium alliage</term><term>Indium alliage</term><term>Ga2O3</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">We compared the electrical properties of self-assembled monolayers (SAMs) formed on template-stripped Au from two homologous series of five different oligo-(phenylene)s bearing alkane thiol tails. The terminal phenyl ring is substituted by a 4-pyridyl ring in one series, thus the two differ only by the substitution of C-H for N. We formed tunneling junctions using the liquid metal eutectic Ga-In (EGaIn) as a nondamaging, conformal top contact that is insensitive to functional groups and measured the current-density, J, tunneling decay constants, β, and transition voltages, V<sub>trans</sub>. Conductance measurements alone did not sufficiently differentiate the two series of molecules. The length dependences of the two series of SAMs produced values of β of 0.44 and 0.42 Å<sup>-1</sup> for pyridyl- and phenyl-terminated SAMs, respectively, which lie between the expected values for alkanethiolates and oligo(phenylene)s. The values of V<sub>trans</sub> were ∼0.3 V larger for the phenyl-terminated SAMs than for the pyridyl-terminated SAMs. A comparison of the values of J to highest occupied molecular orbital (HOMO) levels determined by density functional theory (DFT) calculations revealed an odd-even effect for the phenyl-terminated SAMs but not the pyridyl-terminated SAMs. Plots of V<sub>trans</sub> versus the measured shift in work function, measured with a Kelvin probe, reveal a roughly linear trend. Plots of the difference between HOMO and Fermi energies reveal a strong linear trend with two distinct series that clearly differentiate the two series of SAMs, even between SAMs with nearly identical HOMO levels, but only when the dipole-induced shift in vacuum level is considered. The influence of the electronic properties of the SAMs is clearly evident in the conductance data and highlights the importance of molecular dipoles in tunneling junctions comprising SAMs. Taken together, the data show that tunneling junctions incorporating EGaIn as a top contact are sensitive enough to differentiate SAMs that differ by the substitution of a single atom.</div></front></TEI><inist><standard h6="B"><pA><fA01 i1="01" i2="1"><s0>1932-7447</s0></fA01><fA03 i2="1"><s0>J. phys. chem., C</s0></fA03><fA05><s2>117</s2></fA05><fA06><s2>21</s2></fA06><fA08 i1="01" i2="1" l="ENG"><s1>Influence of an Atom in EGaIn/Ga<sub>2</sub>O<sub>3</sub> Tunneling Junctions Comprising Self-Assembled Monolayers</s1></fA08><fA11 i1="01" i2="1"><s1>FRACASSO (Davide)</s1></fA11><fA11 i1="02" i2="1"><s1>MUGLALI (Mutlu Iskender)</s1></fA11><fA11 i1="03" i2="1"><s1>ROHWERDER (Michael)</s1></fA11><fA11 i1="04" i2="1"><s1>TERFORT (Andreas)</s1></fA11><fA11 i1="05" i2="1"><s1>CHIECHI (Ryan C.)</s1></fA11><fA14 i1="01"><s1>Stratingh Institute for Chemistry and Zemike Institute for Advanced Materials, University of Groningen, Nijenborgh 4</s1><s2>9747 AG Groningen</s2><s3>NLD</s3><sZ>1 aut.</sZ><sZ>5 aut.</sZ></fA14><fA14 i1="02"><s1>Max-Planck-Institut für Einsenforschung GmbH, Max-Planck-Strasse 1</s1><s2>40237 Düsseldorf</s2><s3>DEU</s3><sZ>2 aut.</sZ><sZ>3 aut.</sZ></fA14><fA14 i1="03"><s1>Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7</s1><s2>60438 Frankfurt</s2><s3>DEU</s3><sZ>4 aut.</sZ></fA14><fA20><s1>11367-11376</s1></fA20><fA21><s1>2013</s1></fA21><fA23 i1="01"><s0>ENG</s0></fA23><fA43 i1="01"><s1>INIST</s1><s2>549C</s2><s5>354000504199290540</s5></fA43><fA44><s0>0000</s0><s1>© 2013 INIST-CNRS. All rights reserved.</s1></fA44><fA45><s0>62 ref.</s0></fA45><fA47 i1="01" i2="1"><s0>13-0316388</s0></fA47><fA60><s1>P</s1></fA60><fA61><s0>A</s0></fA61><fA64 i1="01" i2="1"><s0>Journal of physical chemistry. C</s0></fA64><fA66 i1="01"><s0>USA</s0></fA66><fC01 i1="01" l="ENG"><s0>We compared the electrical properties of self-assembled monolayers (SAMs) formed on template-stripped Au from two homologous series of five different oligo-(phenylene)s bearing alkane thiol tails. The terminal phenyl ring is substituted by a 4-pyridyl ring in one series, thus the two differ only by the substitution of C-H for N. We formed tunneling junctions using the liquid metal eutectic Ga-In (EGaIn) as a nondamaging, conformal top contact that is insensitive to functional groups and measured the current-density, J, tunneling decay constants, β, and transition voltages, V<sub>trans</sub>. Conductance measurements alone did not sufficiently differentiate the two series of molecules. The length dependences of the two series of SAMs produced values of β of 0.44 and 0.42 Å<sup>-1</sup> for pyridyl- and phenyl-terminated SAMs, respectively, which lie between the expected values for alkanethiolates and oligo(phenylene)s. The values of V<sub>trans</sub> were ∼0.3 V larger for the phenyl-terminated SAMs than for the pyridyl-terminated SAMs. A comparison of the values of J to highest occupied molecular orbital (HOMO) levels determined by density functional theory (DFT) calculations revealed an odd-even effect for the phenyl-terminated SAMs but not the pyridyl-terminated SAMs. Plots of V<sub>trans</sub> versus the measured shift in work function, measured with a Kelvin probe, reveal a roughly linear trend. Plots of the difference between HOMO and Fermi energies reveal a strong linear trend with two distinct series that clearly differentiate the two series of SAMs, even between SAMs with nearly identical HOMO levels, but only when the dipole-induced shift in vacuum level is considered. The influence of the electronic properties of the SAMs is clearly evident in the conductance data and highlights the importance of molecular dipoles in tunneling junctions comprising SAMs. Taken together, the data show that tunneling junctions incorporating EGaIn as a top contact are sensitive enough to differentiate SAMs that differ by the substitution of a single atom.</s0></fC01><fC02 i1="01" i2="3"><s0>001B70C30</s0></fC02><fC02 i1="02" i2="3"><s0>001B70C50G</s0></fC02><fC03 i1="01" i2="3" l="FRE"><s0>Effet tunnel</s0><s5>03</s5></fC03><fC03 i1="01" i2="3" l="ENG"><s0>Tunnel effect</s0><s5>03</s5></fC03><fC03 i1="02" i2="X" l="FRE"><s0>Orbitale frontière</s0><s5>05</s5></fC03><fC03 i1="02" i2="X" l="ENG"><s0>Frontier orbital</s0><s5>05</s5></fC03><fC03 i1="02" i2="X" l="SPA"><s0>Orbital frontera</s0><s5>05</s5></fC03><fC03 i1="03" i2="3" l="FRE"><s0>Méthode fonctionnelle densité</s0><s5>06</s5></fC03><fC03 i1="03" i2="3" l="ENG"><s0>Density functional method</s0><s5>06</s5></fC03><fC03 i1="04" i2="3" l="FRE"><s0>Travail sortie</s0><s5>07</s5></fC03><fC03 i1="04" i2="3" l="ENG"><s0>Work functions</s0><s5>07</s5></fC03><fC03 i1="05" i2="3" l="FRE"><s0>Niveau Fermi</s0><s5>09</s5></fC03><fC03 i1="05" i2="3" l="ENG"><s0>Fermi level</s0><s5>09</s5></fC03><fC03 i1="06" i2="3" l="FRE"><s0>Structure électronique</s0><s5>10</s5></fC03><fC03 i1="06" i2="3" l="ENG"><s0>Electronic structure</s0><s5>10</s5></fC03><fC03 i1="07" i2="X" l="FRE"><s0>Oxyde de gallium</s0><s5>15</s5></fC03><fC03 i1="07" i2="X" l="ENG"><s0>Gallium oxide</s0><s5>15</s5></fC03><fC03 i1="07" i2="X" l="SPA"><s0>Galio óxido</s0><s5>15</s5></fC03><fC03 i1="08" i2="X" l="FRE"><s0>Jonction tunnel</s0><s5>16</s5></fC03><fC03 i1="08" i2="X" l="ENG"><s0>Tunnel junction</s0><s5>16</s5></fC03><fC03 i1="08" i2="X" l="SPA"><s0>Unión túnel</s0><s5>16</s5></fC03><fC03 i1="09" i2="3" l="FRE"><s0>Couche autoassemblée</s0><s5>17</s5></fC03><fC03 i1="09" i2="3" l="ENG"><s0>Self-assembled layers</s0><s5>17</s5></fC03><fC03 i1="10" i2="3" l="FRE"><s0>Gallium alliage</s0><s5>18</s5></fC03><fC03 i1="10" i2="3" l="ENG"><s0>Gallium alloys</s0><s5>18</s5></fC03><fC03 i1="11" i2="3" l="FRE"><s0>Indium alliage</s0><s5>19</s5></fC03><fC03 i1="11" i2="3" l="ENG"><s0>Indium alloys</s0><s5>19</s5></fC03><fC03 i1="12" i2="3" l="FRE"><s0>Ga2O3</s0><s4>INC</s4><s5>52</s5></fC03><fN21><s1>301</s1></fN21></pA></standard></inist></record>Pour manipuler ce document sous Unix (Dilib)
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