Charge Transport and Thermoelectric Properties of Carbon-Sulfide

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Charge Transport and Thermoelectric Properties of Carbon-Sulfide Nanobelts in Single-Molecule Sensors Leighton O. Jones, Martin A. Mosquera, George C. Schatz, and Mark A. Ratner Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.8b05119 • Publication Date (Web): 05 Feb 2019 Downloaded from http://pubs.acs.org on February 7, 2019

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is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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Chemistry of Materials

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ACS Paragon Plus Environment


Figure 1. (A) Illustration of the carbon (●) sulfide (●) nanobelts in increasing diameter: S3 (0.56 nm), S4 (0.70 nm) and S5 (0.82 nm) and their lengths remain largely the same ~ 0.83 nm; the numbers 3-5 represent the number of S atoms on one end, see ref. 56; (B) cut-open structures of the nanobelts; (C) An isometric view of a typical junction set up for S5 showing the central scatter region and the semi-infinite bulk electrodes; the number of gold layers (111) is denoted in superscript. Full details in methods section.

40

S3 S4 S5

30 20

Current (A)

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10 0 -10 -20 -30 -40 -2

-1.5

-1

-0.50

0

0.50

1

1.5

2

Voltage Bias (V) Figure 2. Calculated J-V curves between -2 to 2 V for single-molecule junctions with the nanobelts S3-S5; the dashed lines are to guide the eye only and the diagonal line represents an ideal Ohmic metal.


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Figure 3. (A) Transmission function at zero voltage bias [0 V] plotted logarithmically vs the eigenchannel and referenced to the Fermi energy (E-Ef); (B) the projected density of states (PDOS) of the carbon (●) and sulfur (●) combined s and p orbital contributions for each nanobelt S3-S5. The Fermi energies for both A and B are shown with a vertical blue dashed line.

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10

1

-2.0 V -1.8 V -1.6 V -1.4 V -1.2 V -1.0 V

0.1

-0.8 V -0.6 V -0.4 V -0.2 V 0V

0.01 -2

-1

0

1

1

0V 0.2 V 0.4 V 0.6 V 0.8 V 1.0 V

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-2

-1

0

0.1

0.01 1

1

0.1

2

-1

0

1

-2

0.01

0

1

2

1

2

1

2

10

1

0.1

0.01 0

-1

E-Ef (eV)

Transmission Ef

Transmission Ef

0.1

2

0.1

E-Ef (eV)

1

1

1

2

10

-1

0

1.0 V 1.2 V 1.4 V 1.6 V 1.8 V 2.0 V

0.01

-2

10

-0.2 V 0V 0.2 V 0.4 V 0.6 V 0.8 V

10

E-Ef (eV)

-2

-1

-1.2 V -1.0 V -0.8 V -0.6 V -0.4 V

E-Ef (EV)

0.01 0

-2.0 V -1.8 V -1.6 V -1.4 V

-2

2

Transmission Ef

Transmission Ef

1

-1

0.1

0.01

1

10

-2

1

E-Ef (EV)

10

Transmission Ef

1.2 V 1.4 V 1.6 V 1.8 V 2.0 V

0.01

2

E-Ef (EV)

Transmission Ef

10

Transmission Ef

Transmission Ef

Transmission Ef

10

-2

-1

E-Ef (eV)

0

1

1

0.1

0.01

2

-2

-1

0

E-Ef (eV)

E-Ef (eV)

Figure 4. Transmission function of the nanobelts plotted logarithmically against the eigenchannel with respect to the Fermi level (E-Ef / eV) as a function of applied voltage bias between -2 to 0 V (left hand panels, 0 to 2 V (central panels) and between -2 and 2 V (right hand panels).

Conductance GEf[0V] / S

0.5

0.4

0.3

0.2

0.1

0.0 -2

-1

0

1

Voltage Bias (V)

2

C

45

Thermopower S / V K-1

B

A Transmission Ef

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40 35 30 25 20 15 10 5 0 50

100

150

200

250

300

Temperature / K

10 0 -10 -20 -30 -40 -50 -60 -70 -2

-1.5

-1

-0.50

0

0.50

1

1.5

2

Voltage Bias (V)

Figure 5. (A) Transmission function at the Fermi energy Ef vs voltage bias (V); (B) electrical conductance (G)84 as a function of temperature (K) at zero voltage bias.; (C) thermopower S (V K-1) as a function of voltage bias (V), the dashed lines are to guide the eye only; (S3, □), (S4, △), (S5, 〇).


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Figure 6. Cartoon of the eigenvalue alignment of the nanobelts isolated (left) and in contact either side of each nanobelt with one layer of the gold surface (right) in a molecular junction.

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Figure 7. An isometric view of the frontier molecular orbitals ±1 in the device scatter region with zero bias for S3, S4 and S5.

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Figure 8. Van der Waals representation of the gases which have adsorbed or functionalized the surface of the S3 nanobelt junction.


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A

80

Conductance GEf[0V] / S

70 60 50 40 30 20 10 7

S3 @

C

O

O

2

6

N

N

5

S3 @

2

4

O

F

S3 @

S3 @

H

S3 @

B

3

S3 @

2

F

1

2

0

S3

Figure 9. (A) Transmission function ([0 V)) plotted logarithmically against the eigenchannel and referenced to the Fermi energy (E-Ef / eV) at zero voltage bias; (B) the projected Density of States (DOS) of the combined s and p orbitals for the S3 nanobelt junction with the diatomic gas adsorptions: CO, HF, N2, NO, F2 and O2 with their atomic contributions in color; the Fermi energy is shown with a dotted blue line.

Thermopower S / V K-1

20 0 -20 -40 -60 -80 -100

S3 @ O S3 2 @ N S3 2 @ N O S3 @ C O

2

F S3 @

S3 @ H

F

-120

S3

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Figure 10. (A) Histogram plot of the conduction (GEf[0 V] / S) and (B) the thermopower function (S / V K-1) for the S3 and gas junctions S3@XZ around the Fermi energy at zero voltage bias.



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𝐼(𝑉) =

2𝑒 ℎ

∞

∫−∞ 𝑑𝐸[𝑓𝐿 (𝐸, 𝑉) − 𝑓𝑅 (𝐸, 𝑉)] 𝑇(𝐸, 𝑉)

 



±1

𝐸𝐵 = 𝐸𝑆𝑊𝐻𝑁𝐵@𝐺𝐴𝑆 − (𝐸𝑆𝑊𝐻𝑁𝐵 + 𝐸𝐺𝐴𝑆 )




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Charge Transport and Thermoelectric Properties of Carbon-Sulfide

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