structural phases of alkanethiolate self-assembled 1-12 ...public jan-willem j. clerix,a,b a....
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![Page 1: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/1.jpg)
PUBLIC
Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b
a Dep. of chem., KU Leuven, Leuvenb imec, Leuven
Structural phases of alkanethiolate self-assembled
monolayers (C1-12) on Cu by density functional theory
![Page 2: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/2.jpg)
2
ASD through SAMs, from model to method
⊖S(CH2)5CH3
Cu SiO2
![Page 3: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/3.jpg)
ASD through SAMs, from model to method
3
Structure at the interface
SAM structure: density, phase
Reactivity SAM-surface
![Page 4: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/4.jpg)
ASD through SAMs, from model to method
4
Structure at the interface
Reactivity SAM-surface
SAM structure: density, phase
![Page 5: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/5.jpg)
Generic model of SAM formation
5
Lying-down phases
Standing-up phases
«
«
Schwartz, D. K. An. Rev. Phys. Chem. 2001, 52.
![Page 6: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/6.jpg)
Density functional theory, chain length and coverage
Periodic, dispersion corrected density functional theory*
6
![Page 7: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/7.jpg)
Density functional theory, chain length and coverage
Periodic, dispersion corrected density functional theory*
7
![Page 8: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/8.jpg)
Density functional theory, chain length and coverage
Periodic, dispersion corrected density functional theory*
8
thiolates∙cm-22.08∙10141.04∙1014 4.16∙1014 5.49∙1014 8.32∙1014
(4x4)
c(4x4)
(2x2) c(2x2)
c(2x6)Cu[100]: 16.64 1014 atcm-2
Yang, Y. C. Langmuir 2012, 28.
Driver, S. M. Surf. Sci. 2001, 488.
Vollmer, S. Langmuir 2001, 17.
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Relative stability as a guide to phase behavior
9
Cu[100] + y HSR → Cu[100][−SR]x+ y−x HSR+ ൗx 2 H2*
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Short thiolates show linear adsorption
10
0.3 nm
thiolates∙cm-22.08∙10141.04∙1014 4.16∙1014 5.49∙1014 8.32∙1014
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Short thiolates show linear adsorption
11
![Page 12: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/12.jpg)
Short thiolates show linear adsorption
12
-168 kJ/mol
-17 kJ/mol
-141 kJ/mol
-176 kJ/mol
-168 kJ/mol
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Hexanethiolate shows the onset of phase behavior
13
0.8 nm
thiolates∙cm-22.08∙10141.04∙1014 4.16∙1014 5.49∙1014 8.32∙1014
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Hexanethiolate shows the onset of phase behavior
14
0.8 nm
thiolates∙cm-22.08∙10141.04∙1014 4.16∙1014 5.49∙1014 8.32∙1014
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Hexanethiolate shows the onset of phase behavior
15
![Page 16: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/16.jpg)
Hexanethiolate shows the onset of phase behavior
16
+36 kJ/mol
-198 kJ/mol
-165 kJ/mol
-199 kJ/mol
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Dodecanethiolate displays rich phase behavior
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![Page 18: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/18.jpg)
Dodecanethiolate displays rich phase behavior
18
-310 kJ/mol
-127 kJ/mol
-206 kJ/mol
-289 kJ/mol
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Dodecanethiolate displays rich phase behavior
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Chain length determines structural phase
The short thiolates
Linear adsorption behavior, saturate at 8.32∙1014 th/cm2
The intermediate thiolate
Transition from lying-down to standing-up between 2.08 and
4.16∙1014 th/cm2, saturate at 5.49∙1014 th/cm2
The long thiolate
Transition from lying-down to standing-up between 1.04 and
2.08∙1014 th/cm2, saturate at 5.49∙1014 th/cm2
20
![Page 21: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/21.jpg)
Chain length determines structural phase
The short thiolates
Linear adsorption behavior, saturate at 8.32∙1014 th/cm2
The intermediate thiolate
Transition from lying-down to standing-up between 2.08 and
4.16∙1014 th/cm2, saturate at 5.49∙1014 th/cm2
The long thiolate
Transition from lying-down to standing-up between 1.04 and
2.08∙1014 th/cm2, saturate at 5.49∙1014 th/cm2
21
![Page 22: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/22.jpg)
Chain length determines structural phase
The short thiolates
Linear adsorption behavior, saturate at 8.32∙1014 th/cm2
The intermediate thiolate
Transition from lying-down to standing-up between 2.08 and
4.16∙1014 th/cm2, saturate at 5.49∙1014 th/cm2
The long thiolate
Transition from lying-down to standing-up between 1.04 and
2.08∙1014 th/cm2, saturate at 5.49∙1014 th/cm2
22
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23
Saturation content and phase transitions depend on chain length
regime
Optimal passivation for ASD is a compromise between chain length
and surface content
Long thiolates are computationally too demanding, short thiolates
are not accurate enough
Intermediate thiolates approximate long thiolate behavior sufficiently
sufficiently
Conclusions
![Page 24: Structural phases of alkanethiolate self-assembled 1-12 ...PUBLIC Jan-Willem J. Clerix,a,b A. Sanz-Matias,a S. Armini,b J. N. Harvey,a A. Delabiea,b a Dep. of chem., KU Leuven, Leuven](https://reader033.vdocument.in/reader033/viewer/2022060504/5f1d6b92178b777a9a69ba43/html5/thumbnails/24.jpg)
24
Saturation content and phase transitions depend on chain length
regime
Optimal passivation for ASD is a compromise between chain length
and surface content
Long thiolates are computationally too demanding, short thiolates
are not accurate enough
Intermediate thiolates approximate long thiolate behavior sufficiently
sufficiently
Conclusions
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ASD through SAMs, from model to method
25
Structure at the interface
SAM structure: density, phase
Reactivity SAM-surface
✓
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ASD through SAMs, from model to method
26
Reactivity SAM-surface
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