Online citations, reference lists, and bibliographies.
Please confirm you are human
(Sign Up for free to never see this)
← Back to Search

Maximizing The Dielectric Response Of Molecular Thin Films Via Quantum Chemical Design.

Henry M. Heitzer, T. Marks, M. Ratner
Published 2014 · Materials Science, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy
Share
Developing high-capacitance organic gate dielectrics is critical for advances in electronic circuitry based on unconventional semiconductors. While high-dielectric constant molecular substances are known, the mechanism of dielectric response and the fundamental chemical design principles are not well understood. Using a plane-wave density functional theory formalism, we show that it is possible to map the atomic-scale dielectric profiles of molecule-based materials while capturing important bulk characteristics. For molecular films, this approach reveals how basic materials properties such as surface coverage density, molecular tilt angle, and π-system planarity can dramatically influence dielectric response. Additionally, relatively modest molecular backbone and substituent variations can be employed to substantially enhance film dielectric response. For dense surface coverages and proper molecular alignment, conjugated hydrocarbon chains can achieve dielectric constants of >8.0, more than 3 times that of analogous saturated chains, ∼2.5. However, this conjugation-related dielectric enhancement depends on proper molecular orientation and planarization, with enhancements up to 60% for proper molecular alignment with the applied field and an additional 30% for conformations such as coplanarity in extended π-systems. Conjugation length is not the only determinant of dielectric response, and appended polarizable high-Z substituents can increase molecular film response more than 2-fold, affording estimated capacitances of >9.0 μF/cm2. However, in large π-systems, polar substituent effects are substantially attenuated.
This paper references
Comparison and Benchmark Database; Johnson, R
NIST Computational Chemistr (2013)
10.1021/ja809555c
Design, synthesis, and characterization of ladder-type molecules and polymers. Air-stable, solution-processable n-channel and ambipolar semiconductors for thin-film transistors via experiment and theory.
H. Usta (2009)
10.1038/nature02987
Low-voltage organic transistors with an amorphous molecular gate dielectric
M. Halik (2004)
10.1103/PHYSREVB.75.155429
Intrinsic dielectric properties of phthalocyanine crystals: An ab initio investigation
N. Shi (2007)
10.1073/pnas.1120311109
Tuning the threshold voltage in electrolyte-gated organic field-effect transistors
L. Kergoat (2012)
10.1007/s10853-012-6411-5
Dielectric permittivity of ultrathin PbTiO3 nanowires from first principles
G. Pilania (2012)
10.1063/1.2428291
Polarizability and second hyperpolarizability evaluation of long molecules by the density functional theory with long-range correction.
H. Sekino (2007)
10.1002/ADFM.200800876
The Dielectric Constant of Self-Assembled Monolayers
Lorenz Romaner (2008)
10.1063/1.356116
Mechanism of leakage current through the nanoscale SiO2 layer
S. Nagano (1994)
10.1126/SCIENCE.1081572
Electron Transport in Molecular Wire Junctions
A. Nitzan (2003)
10.1002/AENM.201200912
Domain Purity, Miscibility, and Molecular Orientation at Donor/Acceptor Interfaces in High Performance Organic Solar Cells: Paths to Further Improvement
W. Ma (2013)
10.1016/S0022-0728(97)00091-0
Electron transfer reactions in chemistry theory and experiment
R. Marcus (1997)
10.1021/ar200006r
n-Channel semiconductor materials design for organic complementary circuits.
H. Usta (2011)
10.1063/1.2339037
Dielectric properties of Cu-phthalocyanine systems from first principles
N. Shi (2006)
10.1021/ja401904d
First-principles calculation of dielectric response in molecule-based materials.
Henry M. Heitzer (2013)
10.1002/PSSB.201248143
Charge Transport Physics of High‐Mobility Molecular Semiconductors
H. Sirringhaus (2012)
10.1021/JP0122124
Twist Angles and Rotational Energy Barriers of Biphenyl and Substituted Biphenyls
F. Grein (2002)
10.1073/PNAS.0501027102
σ-π molecular dielectric multilayers for low-voltage organic thin-film transistors
M. Yoon (2005)
10.1103/PHYSREVB.80.165432
First-principles investigations of the dielectric properties of polypropylene/metal-oxide interfaces
L. Yu (2009)
10.1002/jcc.20495
Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction
S. Grimme (2006)
10.1002/jcc.540141112
General atomic and molecular electronic structure system
M. Schmidt (1993)
10.1063/1.121183
Alkanethiol self-assembled monolayers as the dielectric of capacitors with nanoscale thickness
M. A. Rampi (1998)
10.1038/nature05533
Ultralow-power organic complementary circuits
H. Klauk (2007)
10.1063/1.1871934
Longitudinal polarizability of long polymeric chains: quasi-one-dimensional electrostatics as the origin of slow convergence.
K. Kudin (2005)
10.1002/1521-3773(20010716)40:14<2574::AID-ANIE2574>3.0.CO;2-N
The Discovery of Polyacetylene Film: The Dawning of an Era of Conducting Polymers (Nobel Lecture).
H. Shirakawa (2001)
10.1021/ar2001233
Chemical and engineering approaches to enable organic field-effect transistors for electronic skin applications.
A. Sokolov (2012)
10.1557/JMR.2004.0266
Organic thin film transistors: From theory to real devices
G. Horowitz (2004)
10.1021/J100155A072
Adsorbed .omega.-hydroxy thiol monolayers on gold electrodes: evidence for electron tunneling to redox species in solution
C. Miller (1991)
10.1073/pnas.0701472104
Electron tunneling through alkanedithiol self-assembled monolayers in large-area molecular junctions
H. Akkerman (2007)
A REVIEW ON NONLINEAR OPTICAL PROPERTIES OF DONOR-ACCEPTOR DERIVATIVES OF NAPHTHALENE AND AZANAPHTHALENE
H. Alyar (2013)
10.1038/nmat2560
Solution-deposited sodium beta-alumina gate dielectrics for low-voltage and transparent field-effect transistors.
B. N. Pal (2009)
10.1063/1.448868
Relationship between band gap and bond length alternation in organic conjugated polymers
J. Brédas (1985)
10.1063/1.477731
Assessment of Conventional Density Functional Schemes for Computing the Polarizabilities and Hyperpolarizabilities of Conjugated Oligomers: An Ab Initio Investigation of Polyacetylene Chains
B. Champagne (1998)
10.1051/EPJAP:2004206
High dielectric constant oxides
J. Robertson (2004)
10.1021/la802944n
Study on the formation of self-assembled monolayers on sol-gel processed hafnium oxide as dielectric layers.
Guy G Ting (2009)
10.1063/1.338278
Space‐charge conduction and relaxation in dielectric films
H. Henisch (1987)
10.1103/PHYSREVB.73.193310
Cooperative effects and dipole formation at semiconductor and self-assembled-monolayer interfaces
A. Natan (2006)
10.1021/CM102419Z
π-Conjugated Polymers for Organic Electronics and Photovoltaic Cell Applications†
A. Facchetti (2011)
10.1021/ja807876c
Pushing and pulling a Sn ion through an adsorbed phthalocyanine molecule.
Y. Wang (2009)
10.1088/0953-8984/21/39/395502
Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
Yanli Wang (2009)
10.1002/CHIN.200926239
Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications
Amaresh Mishra (2009)
10.1021/CR0300789
Self-assembled monolayers of thiolates on metals as a form of nanotechnology.
J. Love (2005)
10.1002/ADFM.200902162
Polarizability, Susceptibility, and Dielectric Constant of Nanometer‐Scale Molecular Films: A Microscopic View
A. Natan (2010)
10.1021/JA063290D
Gate dielectric chemical structure-organic field-effect transistor performance correlations for electron, hole, and ambipolar organic semiconductors.
M. Yoon (2006)
10.1021/cr9001275
High-k organic, inorganic, and hybrid dielectrics for low-voltage organic field-effect transistors.
R. Ponce Ortiz (2010)
10.1016/S0040-4020(98)00814-X
Barriers to rotation about the chiral axis of tertiary aromatic amides
A. Ahmed (1998)
10.1038/srep01705
Molecular distortion and charge transfer effects in ZnPc/Cu(111)
B. Amin (2013)
10.1103/PHYSREVB.74.045318
Atomic-scale dielectric permittivity profiles in slabs and multilayers
N. Shi (2006)
10.1364/OE.16.019770
Kramers-Kronig-consistent optical functions of anisotropic crystals: generalized spectroscopic ellipsometry on pentacene.
M. Dressel (2008)
10.1002/PSSB.201046303
Accurate treatment of solids with the HSE screened hybrid
T. M. Henderson (2011)
10.1038/ncomms5845
Rational design of all organic polymer dielectrics.
Vinit Sharma (2014)
10.1109/VLSIT.1998.689265
Ultra-thin, 1.0-3.0 nm, gate oxides for high performance sub-100 nm technology
T. Sorsch (1998)
10.1103/PHYSREVLETT.83.694
Electric field dependence of the exchange-correlation potential in molecular chains
S. V. Gisbergen (1999)
10.1109/JPROC.2009.2021680
Materials and Applications for Solution-Processed Organic Field-Effect Transistors
H. Sirringhaus (2009)
10.1021/CR9502357
Formation and Structure of Self-Assembled Monolayers.
A. Ulman (1996)
10.1116/1.588404
Scanning tunneling microscope investigations of lead–phthalocyanine on MoS2
R. Strohmaier (1996)
10.1103/PHYSREVB.41.7892
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism.
Vanderbilt (1990)
10.1021/jp061759l
Charge transport through polyene self-assembled monolayers from multiscale computer simulations.
C. George (2008)
10.1002/adma.200903697
Polymer-fullerene bulk-heterojunction solar cells.
C. Brabec (2010)
10.1002/CHIN.200830274
Organic Semiconductors for Solution-Processable Field-Effect Transistors (OFETs)
S. Allard (2008)
10.1063/1.2748841
Large-area patterning of a solution-processable organic semiconductor to reduce parasitic leakage and off currents in thin-film transistors
Kimberly C. Dickey (2007)
10.1021/ja077933g
Variable density effect of self-assembled polarizable monolayers on the electronic properties of silicon.
Naama Peor (2008)
10.1063/1.3589145
Comparing modern density functionals for conjugated polymer band structures: screened hybrid, Minnesota, and Rung 3.5 approximations.
Benjamin G. Janesko (2011)
10.1021/ja3050713
Solar cell efficiency, self-assembly, and dipole-dipole interactions of isomorphic narrow-band-gap molecules.
C. Takacs (2012)
10.1126/science.243.4899.1674
Polar Solvent Dynamics and Electron-Transfer Reactions
M. Maroncelli (1989)
10.1126/science.251.4996.919
Free Energy and Temperature Dependence of Electron Transfer at the Metal-Electrolyte Interface
C. Chidsey (1991)
10.1021/ja4019429
Ambient-processable high capacitance hafnia-organic self-assembled nanodielectrics.
K. Everaerts (2013)
10.1021/JA971921L
Through-Bond and Chain-to-Chain Coupling. Two Pathways in Electron Tunneling through Liquid Alkanethiol Monolayers on Mercury Electrodes
K. Slowinski (1997)
10.1016/0009-2614(95)00076-G
Molecular polarisabilities - a comparison of density functional theory with standard ab initio methods
S. McDowell (1995)
10.1002/(SICI)1521-4095(199803)10:5<365::AID-ADMA365>3.0.CO;2-U
Organic Field‐Effect Transistors
G. Horowitz (1998)
10.1063/1.1924693
Packing density and structure effects on energy-transfer dynamics in argon collisions with organic monolayers.
B. Day (2005)
10.1039/B706122F
Electron and energy transfer in donor-acceptor systems with conjugated molecular bridges.
B. Albinsson (2007)
10.1021/la300975s
Influence of dipole-dipole interactions on coverage-dependent adsorption: CO and NO on Pt(111).
P. Deshlahra (2012)
10.1021/ja9013166
Charge conduction and breakdown mechanisms in self-assembled nanodielectrics.
Sara A Dibenedetto (2009)
10.1038/35104535
Smart single-chip gas sensor microsystem
C. Hagleitner (2001)
10.1063/1.2948862
Bending-stress-driven phase transitions in pentacene thin films for flexible organic field-effect transistors
Chanwoo Yang (2008)
10.1002/CHIN.201015266
Molecular Understanding of Organic Solar Cells: The Challenges
J. Brédas (2010)
10.1103/PHYSREVB.72.052107
Dielectric properties of nanoscale Hf O 2 slabs
R. Ramprasad (2005)
10.1021/NL0515753
Localized surface plasmon resonance spectroscopy of single silver nanocubes.
L. J. Sherry (2005)
10.1021/cr900150b
Materials and applications for large area electronics: solution-based approaches.
A. C. Arias (2010)
AmbientProcessable High Capacitance Hafnia-Organic SelfAssembled Nanodielectrics
K. Everaerts (2013)
10.1039/b614393h
Novel small molecules for organic field-effect transistors: towards processability and high performance.
M. Mas-Torrent (2008)
10.1063/1.2209197
Polarizability of phthalocyanine based molecular systems : A first-principles electronic structure study
R. Ramprasad (2006)
10.1103/PHYSREVB.71.144104
Theory of atomic-scale dielectric permittivity at insulator interfaces
F. Giustino (2005)
10.1002/adma.200901454
Recent progress in n-channel organic thin-film transistors.
Yugeng Wen (2010)
10.1002/ADFM.201101418
Mechanistic Considerations of Bending‐Strain Effects within Organic Semiconductors on Polymer Dielectrics
A. Sokolov (2012)
10.1038/NMAT1061
Flexible active-matrix displays and shift registers based on solution-processed organic transistors
G. Gelinck (2004)
10.1063/1.97417
Macromolecular electronic device: Field-effect transistor with a polythiophene thin film
A. Tsumura (1986)
10.1002/ADMA.200802733
High-Performance Organic Field-Effect Transistors
D. Braga (2009)
10.1103/PHYSREVLETT.89.117601
Dielectric constants of Zr silicates: a first-principles study.
G. Rignanese (2002)
10.1038/nmat2834
Highly sensitive flexible pressure sensors with microstructured rubber dielectric layers.
S. Mannsfeld (2010)
10.1038/ncomms2707
Design principle for increasing charge mobility of π-conjugated polymers using regularly localized molecular orbitals
J. Terao (2013)
10.1002/ADMA.200803267
Molecular self-assembled monolayers and multilayers for organic and unconventional inorganic thin-film transistor applications
Sara A Dibenedetto (2009)
10.1021/ja902751e
Structure-performance correlations in vapor phase deposited self-assembled nanodielectrics for organic field-effect transistors.
Sara A Dibenedetto (2009)
10.1038/nchem.1362
Single solvent molecules can affect the dynamics of substitution reactions.
R. Otto (2012)
10.1016/J.INFRARED.2006.04.001
Energy gap refractive index relations in semiconductors An overview
N. Ravindra (2007)
10.1002/CHIN.198741056
Spontaneously Organized Molecular Assemblies. Part 4. Structural Characterization of n‐Alkyl Thiol Monolayers on Gold by Optical Ellipsometry, IR Spectroscopy, and Electrochemistry.
M. Porter (1987)
10.1002/adma.200903628
n-Type organic semiconductors in organic electronics.
J. Anthony (2010)
10.1002/CHIN.200827240
Novel Small Molecules for Organic Field-Effect Transistors: Towards Processability and High Performance
M. Mas-Torrent (2008)
10.1039/b902589h
A new generalized Kohn-Sham method for fundamental band-gaps in solids.
Helen R. Eisenberg (2009)
10.1074/jbc.M110.136200
Analysis of the Conformational Stability and Activity of Candida antarctica Lipase B in Organic Solvents
C. Li (2010)
10.1021/ar4002262
Hybrid gate dielectric materials for unconventional electronic circuitry.
Y. Ha (2014)
10.1103/PHYSREVLETT.77.3865
Generalized Gradient Approximation Made Simple.
Perdew (1996)
10.1063/1.2834918
Systematic optimization of long-range corrected hybrid density functionals.
Jeng-Da Chai (2008)
10.1021/ct800182e
Torsional Barriers and Equilibrium Angle of Biphenyl: Reconciling Theory with Experiment.
M. P. Johansson (2008)
Tunneling Gate Oxide A RTIC LE HEITZER
H. S. Momose (2014)
10.1109/MEI.2007.288472
Electrical Properties of Polymers, 2nd edition [Book Review]
J. Shea (2007)
10.1021/JA00242A020
Spontaneously organized molecular assemblies. 3. Preparation and properties of solution adsorbed monolayers of organic disulfides on gold surfaces
R. Nuzzo (1987)
10.1016/S1567-1739(01)00052-9
The discovery of polyacetylene film – the dawning of an era of conducting polymers
H. Shirakawa (2001)
10.1002/CHIN.200544296
Toward the Ideal Organic Light-Emitting Diode. The Versatility and Utility of Interfacial Tailoring by Cross-Linked Siloxane Interlayers
J. Veinot (2005)



This paper is referenced by
10.1021/acsnano.8b05490
Large-Area All-Carbon Nanocapacitors from Graphene and Carbon Nanomembranes.
Xianghui Zhang (2018)
10.1021/ACS.JPCC.7B08053
Odd-Even Effects in Electroactive Self-Assembled Monolayers Investigated by Electrochemical Surface Plasmon Resonance and Impedance Spectroscopy
Y. Feng (2017)
10.12677/JAPC.2015.42009
酞菁铜(CuPc)分子有序纳米结构的自组织生长
宋欢欢 (2015)
10.1139/cjc-2020-0005
An electrochemical immittance analysis of the dielectric properties of self-assembled monolayers
Eric R Dionne (2020)
10.1016/j.jphotochem.2020.112756
The effect of a two-dimensional structure on the dielectric constant and photovoltaic characteristics
K. Mishima (2020)
10.1021/jacs.5b03301
Molecular Donor-Bridge-Acceptor Strategies for High-Capacitance Organic Dielectric Materials.
Henry M. Heitzer (2015)
10.1021/acs.jpca.8b01348
Can the Dielectric Constant of Fullerene Derivatives Be Enhanced by Side-Chain Manipulation? A Predictive First-Principles Computational Study
Selim Sami (2018)
10.1021/ACS.JPCC.6B12949
Supramolecular Structure of the Monolayer Triggers Odd–Even Effects in the Tunneling Rates across Noncovalent Junctions on Graphene
P. Song (2017)
10.1021/jacs.5b05761
The Origin of the Odd-Even Effect in the Tunneling Rates across EGaIn Junctions with Self-Assembled Monolayers (SAMs) of n-Alkanethiolates.
L. Jiang (2015)
10.1021/jacs.6b02039
Comparison of DC and AC Transport in 1.5-7.5 nm Oligophenylene Imine Molecular Wires across Two Junction Platforms: Eutectic Ga-In versus Conducting Probe Atomic Force Microscope Junctions.
C. S. S. Sangeeth (2016)
10.1039/C7TC00893G
Engineering dielectric constants in organic semiconductors
A. Armin (2017)
10.1021/acsnano.7b01807
Chain Length Dependence of the Dielectric Constant and Polarizability in Conjugated Organic Thin Films.
C. Van Dyck (2017)
10.1002/cssc.201500950
Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air-Insensitive Electron Acceptors for Artificial Photosynthesis
H. Chen (2015)
Molecular Models for Conductance in Junctions and Electrochemical Electron Transfer
Shobeir Mazinani (2015)
10.1021/acs.accounts.6b00173
Computation of Dielectric Response in Molecular Solids for High Capacitance Organic Dielectrics.
Henry M. Heitzer (2016)
10.1002/adma.201502968
Tuning the Tunneling Rate and Dielectric Response of SAM-Based Junctions via a Single Polarizable Atom.
Dandan Wang (2015)
Semantic Scholar Logo Some data provided by SemanticScholar