U.S. patent application number 15/449587 was filed with the patent office on 2017-10-19 for electro-polarizable compound and capacitor.
This patent application is currently assigned to Capacitor Sciences Incorporated. The applicant listed for this patent is Capacitor Sciences Incorporated. Invention is credited to Paul T. Furuta, Pavel Ivan Lazarev, Yan Li, Barry K. Sharp.
Application Number | 20170301477 15/449587 |
Document ID | / |
Family ID | 60001438 |
Filed Date | 2017-10-19 |
United States Patent
Application |
20170301477 |
Kind Code |
A1 |
Lazarev; Pavel Ivan ; et
al. |
October 19, 2017 |
ELECTRO-POLARIZABLE COMPOUND AND CAPACITOR
Abstract
A composite oligomeric material includes one or more repeating
backbone units; one or more polarizable units incorporated into or
connected to one or more of the one or more repeating backbone
units; and one or more resistive tails connected to one or more of
the repeating backbone units or to the one or more polarizable
units as a side chain on the polarizable unit, on a handle linking
a polarizable unit to a backbone unit, or directly attached to a
backbone unit. The composite oligomer material may be polymerized
to form a metadielectric, which may be sandwiched between to
electrodes to form a metacapacitor.
Inventors: |
Lazarev; Pavel Ivan; (Menlo
Park, CA) ; Furuta; Paul T.; (Sunnyvale, CA) ;
Sharp; Barry K.; (Redwood City, CA) ; Li; Yan;
(Fremont, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Capacitor Sciences Incorporated |
Menlo Park |
CA |
US |
|
|
Assignee: |
Capacitor Sciences
Incorporated
Menlo Park
CA
|
Family ID: |
60001438 |
Appl. No.: |
15/449587 |
Filed: |
March 3, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62318134 |
Apr 4, 2016 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 73/024 20130101;
H01G 9/07 20130101; C08F 20/36 20130101; H01G 4/18 20130101; C08F
220/36 20130101; H01G 9/04 20130101; C08F 220/1818 20200201 |
International
Class: |
H01G 9/07 20060101
H01G009/07; C08F 20/36 20060101 C08F020/36; C08G 73/02 20060101
C08G073/02; H01G 9/04 20060101 H01G009/04 |
Claims
1. A composite oligomeric material comprising: one or more
repeating backbone units one or more polarizable units incorporated
into or connected to one or more of the one or more repeating
backbone units, and one or more resistive tails connected to one or
more of the repeating backbone units or to the one or more
polarizable units as a side chain on the polarizable unit, on a
handle linking a polarizable unit to a backbone unit, or directly
attached to a backbone unit.
2. A composite oligomeric material as in claim 1, wherein the at
least one polarizable unit is attached to a repeating backbone unit
via a handle, as partially incorporated into said repeating
backbone unit, or fully part of the repeating backbone unit.
3. A composite oligomeric material as in claim 2, wherein the
general structure of said composite oligomeric material is selected
from the list: ##STR00038## wherein "Monomer", Mono 1 and Mono2
each represent a backbone unit; "Tail" is the resistive tail;
"Polar Unit" is the polarizable unit; "Linker" is the handle or a
connecting group; "m1", "m2", "p" and "t" represent an integer
indicating the number of occurrences of mono1, mono2, Polar Unit,
and Tail respectively; and "1" is equal to 0 or 1; "n" is an
integer greater than or equal to 1 representing the number of
repeat units of the composite oligomeric material.
4. A composite oligomeric material as in claim 1, wherein the
polarizable unit comprises a rylene fragment doped with at least
one electron donor and at least one electron acceptor.
5. A capacitor as in claim 3 wherein the polarizable unit is
described by any of the following formulae: ##STR00039##
##STR00040## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4
substituents are independently selected in each occurrence from the
group comprised of hydrogen, an electron donor, an electron
acceptor, and a resistive tail; R.sub.A.sup.1, R.sub.A'.sup.1,
R.sub.A''.sup.1, R.sub.A'''.sup.1, R.sub.A''''.sup.1, and
R.sub.A'''''.sup.1 are each independently selected from the group
comprised of hydrogen, a resistive tail, an electron donor, and an
electron acceptor, and n.sub.1, n.sub.2, and n.sub.3 can be any
integer between 0 and 8 with the provision that not all n.sub.1,
n.sub.2, and n.sub.3 values can equal 0.
6. A composite oligomeric material as in claim 1, wherein the
polarizable unit comprises an electron donor, a conjugated bridge
and an electron acceptor.
7. A composite oligomeric material as in claim 6 wherein the
polarizable unit is at least one chromophore.
8. A composite oligomeric material as in claim 7, wherein the at
least one chromophore consists of dopant groups that enhance the
polarizability of the chromophore.
9. A composite oligomeric material as in claim 8, wherein the
dopant groups are independently selected from the group consisting
of electron donor and electron acceptor groups; and wherein the
electron donor groups are selected from amine and alkoxy
groups.
10. A composite oligomeric material as in claim 9, wherein the
amine groups of the type R--N--R' or R--N--R where R and R' are
independently selected from the group consisting of hydrogen,
resistive tails, linker groups connected to resistive tails, linker
groups connected to the one or more repeating backbone units, and
the one or more repeating backbone units.
11. A composite oligomeric material as in claim 1, wherein the
resistive tails are alkyl chains.
12. A composite oligomeric material as in claim 1, wherein the
resistive tails are rigid.
13. A composite oligomeric material as in claim 12, wherein the
rigid resistive tails are selected from the group comprised of
unsubstituted saturated cycloalkyl, substituted saturated
cycloalkyl, unsubstituted saturated cyclic hydrocarbon wherein the
hydrocarbon chain may be interrupted by an element from the list of
O, S, N, and P, and substituted saturated cyclic hydrocarbon
wherein the hydrocarbon chain may be interrupted by an element from
the list of O, S, N, and P.
14. A composite oligomeric material as in claim 7, wherein the
resistive tails are covalently attached to the chromophore.
15. A composite oligomeric material as in claim 7, wherein the
resistive tails are covalently attached to an oligomeric repeating
backbone.
16. A composite oligomeric material in claim 15, wherein the
chromophore possesses a NRR' group where R and R' are the resistive
tails and are independently selected from the list consisting of
hydrogen, unsubsituted alkyl, substituted alkyl, unsubstituted
cycloalkyl, substituted cycloalkyl, unsubstituted heterocyclic,
substituted heterocyclic.
17. A composite oligomeric material as in claim 1 wherein the
repeating backbone unit belongs to one of the groups selected from
(meth)acrylates, polyvinyl, peptides, peptoids, and polyimides.
18. A composite oligomeric material as in claim 7, wherein the
chromophores are azo-dye chromophores.
19. A composite oligomeric material as in claim 18 wherein the
azo-dye chromophores are selected from Disperse Red-1 and Black
Hole Quencher-2 and oligomers thereof
20. A metadielectric material comprising a structured arrangement
of composite oligomeric materials according to claim 1, and having
a resistivity greater than or equal to about 10.sup.16 Ohm-cm and a
relative permittivity greater than or equal to about 1000.
21. A metadielectric material as in claim 20, wherein the
structured arrangement of composite oligomeric materials is a
crystalline structured arrangement.
22. The metadielectric material as in claim 21, wherein the
crystalline structured arrangement of the composite oligomeric
materials includes crystalline ordered arrangements selected from
the list of thermotropic and isotropic crystal ordering.
23. A metadielectric material as in claim 20, wherein the
structured arrangement of composite oligomeric materials includes
lamella or lamella-like structures.
24. A capacitor comprising a first conductive layer, a second
conductive layer, and a dielectric layer sandwiched between the
first and second conductive layers; wherein the dielectric layer is
a film comprised of a metadielectric material that has a
resistivity greater than or equal to about 10.sup.16 Ohm-cm, a
relative permittivity greater than or equal to about 1000, wherein
the metadielectric material includes a composite oligomeric
material comprising: one or more repeating backbone units one or
more polarizable units incorporated into or connected to one or
more of the one or more repeating backbone units, and one or more
resistive tails connected to one or more of the repeating backbone
units or to the one or more polarizable units as a side chain on
the polarizable unit, on a handle linking a polarizable unit to a
repeating backbone unit, or directly attached to a repeating
backbone unit.
25. A capacitor as in claim 24, further comprising an insulating
layer, wherein the dielectric layer is a thin film, the first and
second conductive layers are metal, and the insulating layer is
independently selected from a list including a metadielectric
material, polypropylene (PP), polyethylene terephthalate polyester
(PET), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN),
polycarbonate (PP), polystyrene (PS), and polytetrafluoroethylene
(PTFE).
26. A capacitor as in claim 24 wherein the dielectric layer
includes a polymer with the metadielectric material suspended as a
guest in a guest-host system.
27. A capacitor as in claim 26 where in the host polymer is
selected from poly(methyl methacrylate), polyimides,
polycarbonates, and poly(.epsilon.-caprolactone).
28. A capacitor as in claim 24 wherein the metadielectric material
is incorporated into a larger polymer matrix wherein the polymer
matrix may possess the same or different repeating backbone unit as
the metadielectric material.
29. A capacitor as in claim 24 wherein the composite oligomeric
material is capable of forming structures selected from the list of
lyotropic crystal structures, thermotropic crystal structures,
lamella structures, and lamella-like structures.
Description
CLAIM OF PRIORITY
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/318,134 filed Apr. 4, 2016, which is hereby
incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present disclosure relates generally to passive
components of electrical circuit and more particularly to a
composite organic compound and capacitor based on this material and
intended for energy storage. A capacitor is an energy storage
device that stores an applied electrical charge for a period of
time and then discharges it. It is charged by applying a voltage
across two electrodes and discharged by shorting the two
electrodes. A voltage is maintained until discharge even when the
charging source is removed. A capacitor blocks the flow of direct
current and permits the flow of alternating current. The energy
density of a capacitor is usually less than for a battery, but the
power output of a capacitor is usually higher than for a battery.
Capacitors are often used for various purposes including timing,
power supply smoothing, coupling, filtering, tuning and energy
storage. Batteries and capacitors are often used in tandem such as
in a camera with a flash. The battery charges the capacitor that
then provides the high power needed for a flash. The same idea
works in electric and hybrid vehicles where batteries provide
energy and capacitors provide power for starting and
acceleration.
BACKGROUND
[0003] A capacitor is a passive electronic component that is used
to store energy in the form of an electrostatic field, and
comprises a pair of electrodes separated by a dielectric layer.
When a potential difference exists between the two electrodes, an
electric field is present in the dielectric layer. An ideal
capacitor is characterized by a single constant value of
capacitance, which is a ratio of the electric charge on each
electrode to the potential difference between them. For high
voltage applications, much larger capacitors have to be used.
[0004] One important characteristic of a dielectric material is its
breakdown field. This corresponds to the value of electric field
strength at which the material suffers a catastrophic failure and
conducts electricity between the electrodes. For most capacitor
geometries, the electric field in the dielectric can be
approximated by the voltage between the two electrodes divided by
the spacing between the electrodes, which is usually the thickness
of the dielectric layer. Since the thickness is usually constant it
is more common to refer to a breakdown voltage, rather than a
breakdown field. There are a number of factors that can
dramatically reduce the breakdown voltage. In particular, the
geometry of the conductive electrodes is important factor affecting
breakdown voltage for capacitor applications. In particular, sharp
edges or points hugely increase the electric field strength locally
and can lead to a local breakdown. Once a local breakdown starts at
any point, the breakdown will quickly "trace" through the
dielectric layer until it reaches the opposite electrode and causes
a short circuit.
[0005] Breakdown of the dielectric layer usually occurs as follows.
Intensity of an electric field becomes high enough to "pull"
electrons from atoms of the dielectric material and makes them
conduct an electric current from one electrode to another. Presence
of impurities in the dielectric or imperfections of the crystal
structure can result in an avalanche breakdown as observed in
semiconductor devices.
[0006] Another important characteristic of a dielectric material is
its dielectric permittivity. Different types of dielectric
materials are used for capacitors and include ceramics, polymer
film, paper, and electrolytic capacitors of different kinds. The
most widely used polymer film materials are polypropylene and
polyester. Increasing dielectric permittivity allows for increasing
volumetric energy density, which makes it an important technical
task.
[0007] One method for creating dielectrics with high permittivity
is to use highly polarizable materials which when placed in between
two electrodes and subjected to an electric field can more easily
absorb more electrons due to polarized ends of the molecule
orienting toward oppositely charged electrodes. U.S. patent
application Ser. No. 15/043,186 (Attorney Docket No. CSI-019A)
demonstrates a method of incorporating highly polarizable molecules
into an oligomer to create such a dielectric material and is hereby
incorporated in its entirety by reference.
[0008] The article "Synthesis and spectroscopic characterization of
an alkoxysilane dye containing C. I. Disperse Red 1" (Yuanjing Cui,
Minquan Wang, Lujian Chen, Guodong Qian, Dyes and Pigments, 62
(2004) pp. 43-47) describe the synthesis of an alkoxysilane dye
(ICTES-DR1) which was copolymerized by sol-gel processing to yield
organic-inorganic hybrid materials for use as second-order
nonlinear optical (NLO) effect. C. I. Disperse Red 1 (DR1) was
attached to Si atoms by a carbamate linkage to provide the
functionalized silane via the nucleophilic addition reaction of
3-isocyanatopropyl triethoxysilane (ICTES) with DR1 using
triethylamine as catalyst. The authors found that triethylamine and
dibutyltin dilaurate were almost equally effective as catalysts.
The physical properties and structure of ICTES-DR1 were
characterized using elemental analysis, mass spectra, 1 H-NMR,
FTIR, UV-visible spectra and differential scanning calorimetry
(DSC). ICTES-DR1 displays excellent solubility in common organic
solvents.
[0009] Second-order nonlinear optical (NLO) effects of organic
molecules have been extensively investigated for their advantages
over inorganic crystals. Properties studied, for example, include
their large optical non-linearity, ultra fast response speed, high
damage thresholds and low absorption loss, etc. Particularly,
organic thin films with excellent optical properties have
tremendous potential in integrated optics such as optical
switching, data manipulation and information processing. Among
organic NLO molecules, azo-dye chromophores have been a special
interest to many investigators because of their relatively large
molecular hyper-polarizability (b) due to delocalization of the
p-electronic clouds. They were most frequently either incorporated
as a guest in the polymeric matrix (guest--host polymers) or
grafted into the polymeric matrix (functionalized polymers) over
the past decade.
[0010] Chromophoric orientation is obtained by applying a static
electric field or by optical poling. Whatever the poling process,
poled-order decay is an irreversible process which tends to
annihilate the NLO response of the materials and this process is
accelerated at higher temperature. For device applications, the
most probable candidate must exhibit inherent properties that
include: (i) high thermal stability to withstand heating during
poling; (ii) high glass transition temperature (T.sub.g) to lock
the chromophores in their acentric order after poling.
[0011] Most of the polymers, however, have either low T.sub.g or
poor thermal stability which makes them unsuitable for direct use.
To overcome these problems, one attractive approach is
incorporating the nonlinear optical active chromophore into a
polymerizable silane by covalent bond to yield an alkoxysilane dye
which can be copolymerized via sol-gel processing to form
organic-inorganic hybrid materials. The hydrolysis and condensation
of functionalized silicon alkoxydes can yield a rigid amorphous
three-dimensional network which leads to slower relaxation of NLO
chromophores. Therefore, sol-gel hybrid nonlinear optical materials
have received significant attention and exhibited the desired
properties. In this strategy, the design and synthesis of new
network-forming alkoxysilane dye are of paramount importance and
detailed investigation of them will offer great promise in the
fabrication of new materials for second-order nonlinear optics that
will eventually meet the basic requirements in building photonic
devices.
[0012] In the article "Design and Characterization of Molecular
Nonlinear Optical Switches" (Frederic Castet et. al., ACCOUNTS OF
CHEMICAL RESEARCH, pp. 2656-2665, (2013), Vol. 46, No. 11), Castet
et. al. illustrate the similarities of the experimental and
theoretical tools to design and characterize highly efficient NLO
switches but also the difficulties in comparing them. After
providing a critical overview of the different theoretical
approaches used for evaluating the first hyperpolarizabilities,
Castet et. al. reported two case studies in which theoretical
simulations have provided guidelines to design NLO switches with
improved efficiencies. The first example presents the joint
theoretical/experimental characterization of a new family of
multi-addressable NLO switches based on benzazolo-oxazolidine
derivatives. The second focuses on the photoinduced commutation in
merocyanine-spiropyran systems, where the significant NLO contrast
could be exploited for metal cation identification in a new
generation of multiusage sensing devices. Finally, Castet et. al.
illustrated the impact of environment on the NLO switching
properties, with examples based on the keto-enol equilibrium in
aniline derivatives. Through these representative examples, Castet
et. al. demonstrated that the rational design of molecular NLO
switches, which combines experimental and theoretical approaches,
has reached maturity. Future challenges consist in extending the
investigated objects to supramolecular architectures involving
several NLO-responsive units, in order to exploit their cooperative
effects for enhancing the NLO responses and contrasts.
[0013] Two copolymers of 3-alkylthiophene (alkyl=hexyl, octyl) and
a thiophene functionalized with Disperse Red 19 (TDR19) as
chromophore side chain were synthesized by oxidative polymerization
by Maril Chavez-Castillo et. al. ("Third-Order Nonlinear Optical
Behavior of Novel Polythiophene Derivatives Functionalized with
Disperse Red 19 Chromophore", Hindawi Publishing Corporation
International Journal of Polymer Science, Volume 2015, Article ID
219361, 10 pages, http://dx.doi.org/10.1155/2015/219361). The
synthetic procedure was easy to perform, cost-effective, and highly
versatile. The molecular structure, molecular weight distribution,
film morphology, and optical and thermal properties of these
polythiophene derivatives were determined by NMR, FT-IR, UV-Vis
GPC, DSC-TGA, and AFM. The third-order nonlinear optical response
of these materials was performed with nanosecond and femtosecond
laser pulses by using the third-harmonic generation (THG) and
Z-scan techniques at infrared wavelengths of 1300 and 800 nm,
respectively. From these experiments it was observed that although
the TRD19 incorporation into the side chain of the copolymers was
lower than 5%, it was sufficient to increase their nonlinear
response in solid state. For instance, the third-order nonlinear
electric susceptibility of solid thin films made of these
copolymers exhibited an increment of nearly 60% when TDR19
incorporation increased from 3% to 5%. In solution, the copolymers
exhibited similar two-photon absorption cross sections
.sigma..sub.2PA with a maximum value of 8545 GM and 233 GM (1
GM=10.sup.-50 cm.sup.4 s) per repeated monomeric unit.
[0014] The theory of molecular nonlinear optics based on the
sum-over-states (SOS) model was reviewed by Mark G. Kuzyk et. al.
("Theory of Molecular Nonlinear Optics", Advances in Optics and
Photonics 5, 4-82 (2013) doi: 10.1364/AOP .5.000004). The
interaction of radiation with a single wtp-isolated molecule was
treated by first-order perturbation theory, and expressions were
derived for the linear (.alpha..sub.ij) polarizability and
nonlinear (.beta..sub.ijk, .gamma..sub.ijkl) molecular
hyperpolarizabilities in terms of the properties of the molecular
states and the electric dipole transition moments for light-induced
transitions between them. Scale invariance was used to estimate
fundamental limits for these polarizabilities. The crucial role of
the spatial symmetry of both the single molecules and their
ordering in dense media, and the transition from the single
molecule to the dense medium case (susceptibilities
.chi..sup.(1).sub.ij, .chi..sup.(2).sub.ijk,
.chi..sup.(3).sub.ijkl), is discussed. For example, for
.beta..sub.ijk, symmetry determines whether a molecule can support
second-order nonlinear processes or not. For non-centrosymmetric
molecules, examples of the frequency dispersion based on a
two-level model (ground state and one excited state) are the
simplest possible for .beta..sub.ijk and examples of the resulting
frequency dispersion were given. The third-order susceptibility is
too complicated to yield simple results in terms of symmetry
properties. It will be shown that whereas a two-level model
suffices for non-centrosymmetric molecules, symmetric molecules
require a minimum of three levels in order to describe effects such
as two-photon absorption. The frequency dispersion of the
third-order susceptibility will be shown and the importance of one
and two-photon transitions will be discussed.
[0015] The promising class of (polypyridine-ruthenium)-nitrosyl
complexes capable of high yield Ru--NO/Ru--ON isomerization has
been targeted as a potential molecular device for the achievement
of complete NLO switches in the solid state by Joelle Akl, Chelmia
Billot et. al. ("Molecular materials for switchable nonlinear
optics in the solid state, based on ruthenium-nitrosyl complexes",
New J. Chem., 2013, 37, 3518-3527). A computational investigation
conducted at the PBEO/6-31+G** DFT level for benchmark systems of
general formula [R-terpyridine-Ru.sup.IICl.sub.2(NO)](PF.sub.6) (R
being a substituent with various donating or withdrawing
capabilities) lead to the suggestion that an isomerization could
produce a convincing NLO switch (large value of the
.beta..sub.ON/.beta..sub.OFF ratio) for R substituents of weak
donating capabilities. Four new molecules were obtained in order to
test the synthetic feasibility of this class of materials with
R=4'-p-bromophenyl, 4'-p-methoxyphenyl, 4'-p-diethylaminophenyl,
and 4'-p-nitrophenyl. The different cis-(Cl,Cl) and trans-(Cl,Cl)
isomers can be separated by HPLC, and identified by NMR and X-ray
crystallographic studies.
[0016] Single crystals of doped aniline oligomers can be produced
via a simple solution-based self-assembly method (see Yue Wang et.
al., "Morphological and Dimensional Control via Hierarchical
Assembly of Doped Oligoaniline Single Crystals", J. Am. Chem. Soc.
2012, v. 134, pp. 9251-9262). Detailed mechanistic studies reveal
that crystals of different morphologies and dimensions can be
produced by a "bottom-up" hierarchical assembly where structures
such as one-dimensional (1-D) nanofibers can be aggregated into
higher order architectures. A large variety of crystalline
nanostructures including 1-D nanofibers and nanowires, 2-D
nanoribbons and nanosheets, 3-D nanoplates, stacked sheets,
nanoflowers, porous networks, hollow spheres, and twisted coils can
be obtained by controlling the nucleation of the crystals and the
non-covalent interactions between the doped oligomers. These
nanoscale crystals exhibit enhanced conductivity compared to their
bulk counterparts as well as interesting structure--property
relationships such as shape--dependent crystallinity. Further, the
morphology and dimension of these structures can be largely
rationalized and predicted by monitoring molecule--solvent
interactions via absorption studies. Using doped tetraaniline as a
model system, the results and strategies presented by Yue Wang et.
al. provide insight into the general scheme of shape and size
control for organic materials.
[0017] Hu Kang et. al. detail the synthesis and chemical/physical
characterization of a series of unconventional twisted
.pi.-electron system electro-optic (EO) chromophores ("Ultralarge
Hyperpolarizability Twisted .pi.-Electron System Electro-Optic
Chromophores: Synthesis, Solid-State and Solution-Phase Structural
Characteristics, Electronic Structures, Linear and Nonlinear
Optical Properties, and Computational Studies", J. AM. CHEM. SOC.
2007, vol. 129, pp. 3267-3286). Crystallographic analysis of these
chromophores reveals large ring-ring dihedral twist angles
(80-89.degree.) and a highly charge-separated zwitterionic
structure dominating the ground state. NOE NMR measurements of the
twist angle in solution confirm that the solid-state twisting
persists essentially unchanged in solution. Optical, IR, and NMR
spectroscopic studies in both the solution phase and solid state
further substantiate that the solid-state structural
characteristics persist in solution. The aggregation of these
highly polar zwitterions is investigated using several experimental
techniques, including concentration-dependent optical and
fluorescence spectroscopy and pulsed field gradient spin-echo
(PGSE) NMR spectroscopy in combination with solid-state data. These
studies reveal clear evidence of the formation of centrosymmetric
aggregates in concentrated solutions and in the solid state and
provide quantitative information on the extent of aggregation.
Solution-phase DC electric-field-induced second-harmonic generation
(EFISH) measurements reveal unprecedented hyperpolarizabilities
(nonresonant .mu..beta. as high as -488,000.times.10.sup.-48 esu at
1907 nm). Incorporation of these chromophores into guest-host poled
polyvinylphenol films provides very large electro-optic
coefficients (r.sub.33) of .about.330 .mu.m/V at 1310 nm. The
aggregation and structure-property effects on the observed
linear/nonlinear optical properties were discussed. High-level
computations based on state-averaged complete active space
self-consistent field (SA-CASSCF) methods provide a new rationale
for these exceptional hyperpolarizabilities and demonstrate
significant solvation effects on hyperpolarizabilities, in good
agreement with experiment. As such, this work suggests new
paradigms for molecular hyperpolarizabilities and
electro-optics.
[0018] U.S. Pat. No. 5,395,556 (Tricyanovinyl Substitution Process
for NLO Polymers) demonstrate NLO effect of polymers that specifies
a low dielectric constant. U.S. patent application Ser. No.
11/428,395 (High Dielectric, Non-Linear Capacitor) develops high
dielectric materials with non-linear effects. It appears to be an
advance in the art to achieve non-linear effects through
supramolecular chromophore structures that are insulated from each
other that include doping properties in the connecting insulating
or resistive elements to the composite organic compound. It further
appears to be an advance in the art to combine composite organic
compounds with non-linear effects that form ordered structures in a
film and are insulated from each other and do not rely on forming
self-assembled monolayers on a substrate electrode.
[0019] The production and use of oligomers of azo-dye chromophores
with resistive tails is described in U.S. Patent Application
62/318,134 (Attorney Docket No. CSI-050) which is hereby
incorporated in its entirety by reference.
[0020] Capacitors as energy storage device have well-known
advantages versus electrochemical energy storage, e.g. a battery.
Compared to batteries, capacitors are able to store energy with
very high power density, i.e. charge/recharge rates, have long
shelf life with little degradation, and can be charged and
discharged (cycled) hundreds of thousands or millions of times.
However, capacitors often do not store energy in small volume or
weight as in case of a battery, or at low energy storage cost,
which makes capacitors impractical for some applications, for
example electric vehicles. Accordingly, it may be an advance in
energy storage technology to provide capacitors of higher
volumetric and mass energy storage density and lower cost.
[0021] A need exists to improve the energy density of capacitors
while maintaining the existing power output. There exists a further
need to provide a capacitor featuring a high dielectric constant
sustainable to high frequencies where the capacitance is voltage
dependent. Such a capacitor is the subject of the present
disclosure. The capacitor of the present disclosure builds on past
work on non-linear optical chromophores and non-linear capacitors
comprising said chromophores.
[0022] In high frequency applications, it is often important that
the capacitors used do not have high dielectric losses. In the case
of ferroelectric ceramic capacitors with a high dielectric
constant, the presence of domain boundaries and electrostriction
provide loss mechanisms that are significant. In contrast, the high
dielectric mechanism disclosed in this disclosure involves the
movement of an electron in a long molecule and its fixed donor.
This occurs extremely rapidly so that losses even at gigahertz
frequencies are small.
[0023] A second very useful property of the type of capacitor
disclosed in the disclosure is its non-linearity. In many
applications, it is desirable to have a voltage sensitive
capacitance to tune circuits and adjust filters. The disclosed
capacitors have such a property; as the mobile electron moves to
the far end of the chromophore as the voltage increases, its motion
is stopped so that with additional voltage little change in
position occurs. As a consequence, the increase in the electric
moment of the dielectric is reduced resulting in a diminished
dielectric constant.
[0024] A third useful property of the type of capacitor disclosed
in the disclosure is its resistivity due to ordered resistive tails
covalently bonded to the composite organic compound. In many
instances, electron mobility is hindered by a matrix of resistive
materials. Ordered resistive tails can enhance the energy density
of capacitors by increasing the density of polarization units in
organized structures such as lamella or lamella-like or micelle
structures, while also limiting mobility of electrons on the
chromophores. The ordered resistive tails may also crosslink to
further enhance the structure of the dielectric film which can
reduce localized film defects and enhance the film's breakdown
voltage or field. Further, ordered resistive tails can improve
solubility of the composite compound in organic solvents. Still
further, the ordered resistive tails act to hinder electro-polar
interactions between supramolecular structures formed from pi-pi
stacking of the optionally attached polycyclic conjugated
molecule.
[0025] If the resistive tails may be rigid in structure, thereby
stabilizing pi-pi stacking by holding the individual ring system in
place and stabilizing the overall material by preventing the
presence of voids due to coiling of alkyl chains. This is described
in greater detail in U.S. patent application Ser. No. 15/043,247
(Attorney Docket No. CS1-51B), which is incorporated herein in its
entirety by reference.
[0026] A fourth very useful property of the type of capacitor
disclosed in the disclosure is enhancing the non-linear response of
the chromophores by using non-ionic dopant groups to change
electron density of the chromophores. Manipulation of the electron
density of the chromophores can significantly increase the
non-linear response which is useful for increasing the
polarizability and the type of dopant groups on chromophores is
also important to achieving enhanced non-linear polarization versus
a neutral or deleterious effect on the non-linearity of the
chromophore.
[0027] A fifth very useful property of the type of capacitor
disclosed in the disclosure is enhancing the non-linear response of
the chromophores by using non-ionic dopant connecting groups to
change electron density of the chromophores. Manipulation of the
electron density of the chromophores can significantly increase the
non-linear response which is useful for increasing the polarization
of the capacitor and thus energy density of said capacitor.
However, placement and type of dopant connecting groups on
chromophores is also important to achieving enhanced non-linear
polarization versus a neutral or deleterious effect on the
non-linearity of the chromophore.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0028] FIG. 1 shows a metacapacitor with two electrodes and a
metadielectric according to aspects of the present disclosure.
[0029] FIG. 2A shows a formation of two metal strips on top and
bottom surfaces of the plastic layer for a coiled metacapacitor
according to an aspect of the present disclosure.
[0030] FIG. 2B shows a winding of the multilayered tape for a
coiled metacapacitor according to an aspect of the present
disclosure.
[0031] FIG. 3 shows a coiled film metacapacitor according to an
aspect of the present disclosure.
[0032] FIG. 4 shows an example of a chemical structure of a YanLi
material that may be used to form a metadielectric for a
metacapacitor according to aspects of the present disclosure.
SUMMARY
[0033] Aspects of the present disclosure include a class of
materials referred to herein as YanLi materials and YanLi
oligomers. In general, a YanLi material is a composite oligomeric
material comprised of monomers that have polarizable and insulating
components. The monomers may include a polarizable unit having a
non-linear polarizable core that includes a conjugated ring system
and at least one dopant group. The monomers also include an
insulating tail as a side chain on the polarizable unit, on the
handle linking a polarizable unit to the monomer backbone, or
directly attached to the monomer backbone. Additionally, the
polarizable unit may be partially or fully incorporated into the
monomer backbone. A particular subclass of YanLi materials are
referred to herein as YanLi dielectrics, which are polymers of one
or more YanLi materials.
[0034] One aspect of the present disclosure is to provide a
capacitor with a high power output. A further aspect of the present
disclosure is to provide a capacitor featuring a high dielectric
constant sustainable to high voltage. A still further aspect of the
present disclosure is to provide a capacitor featuring voltage
dependent capacitance. In yet another aspect of the present
disclosure, a method to make such a capacitor is provided.
[0035] The capacitor, in its simplest form, comprises a first
electrode, a second electrode and a composite oligomer between the
first electrode and the second electrode. The composite oligomer
includes resistive tails and polarizable oligomer groups attached
as a pendant to a monomer backbone or incorporated in a monomer
backbone forming a composite monomer. The polarizable unitson the
monomer backbone may have dopant groups which can be independently
selected from electron acceptor and electron donor groups separated
by a conjugated ring system with or without a conjugated bridge.
The conjugated bridge comprises one or more double bonds that
alternate with single bonds in an unsaturated compound. Among the
many elements that may be present in the double bond, carbon,
nitrogen, oxygen and sulfur are the most preferred heteroatoms. The
.pi. electrons in the conjugated ring system are delocalized across
the length of the ring system. Among the many types of resistive
tails that may be present in the composite monomer, alkyl chains,
branched alkyl chains, fluorinated alkyl chains, branched
flouroalkyl chains, poly(methyl methacrylate) chains are examples.
When a bias is applied across the first and second electrodes, the
composite oligomer becomes more or less polarized with electron
density moving to compensate the field induced by the applied bias.
When the bias is removed, the original charge distribution is
restored. Typically, the capacitor comprises a plurality of YanLi
oligomers (varying in length and/or type of monomer units) as a
structured dielectric film.
DETAILED DESCRIPTION
[0036] According to aspects of the present disclosure an energy
storage device, such as a capacitor, may include first and second
electrodes selected from the group consisting of conductors and
semiconductors. Conductors include, but are not limited to, metals,
conducting polymers, carbon nano-materials, and graphite including
graphene sheets. Semiconductors include, but are not limited to,
silicon, germanium, silicon carbide, gallium arsenide and selenium.
The electrode may or may not be formed on a flat support. Flat
supports may include, but are not limited to, glass, plastic,
silicon, and metal surfaces.
[0037] The present disclosure provides a metacapacitor comprising
two metal electrodes positioned parallel to each other and which
can be rolled or flat and planar and a metadielectric layer between
said electrodes and optionally an insolation layer. The
metadielectric layer comprises the electro-polarizable compounds as
disclosed below.
[0038] A metadielectric layer may be a film made from composite
oligomers referred to herein as YanLi materials. Such a composite
oligomeric material is characterized by a chemical structure that
includes a repeating backbone unit, a polarizable unit, and a
resistive tail. The polarizable unit may be incorporated into or
connected as a pendant to the backbone unit and the resistive tail
may be connected to the backbone unit or polarizable unit or a
separate backbone unit. Nothing in the description, embodiments,
and figures herein should suggest that these features must be
separate aspects of the molecular structure. Many embodiments will
have polarizable units that are not incorporated into the backbone,
but it is indeed possible that portions or all of the backbone are
part of the polarizable unit. The polarizable unit must possess a
high degree of conjugation. Herein, we define "polarizable unit" to
mean any multicyclic arrangement where electrons are delocalized
over the entire portion of the chemical structure via conjugated
single and double bonds. Herein, anisometric is defined as the
condition of a molecule possessing charge or partial charge
asymmetry along an axis. Possible, non-limiting, forms of this
conjugation are polycyclic fused aromatic systems or a conjugated
bridge where aromatic systems are connected by alternating single
and double bonds.
[0039] Alternatively, the metadielectric layer maybe comprised of
any organic composite oligomers, compounds, or polymers as
disclosed in U.S. patent application Ser. No. 14/710,491 (attorney
docket number CSI-003) filed May 12, 2015, Ser. No. 15/043,186
(attorney docket number CSI-019A) filed Feb. 12, 2016, Ser. No.
15/043,209 (attorney docket number CSI-019B) filed Feb. 12, 2016,
Ser. No. 15/194,224 (attorney docket number CSI-044) filed Jun. 27,
2016, Ser. No. 15/043,247 (attorney docket number CSI-046) filed
Feb. 12, 2016, Ser. No. 15/090,509 (attorney docket number CSI-051)
filed Apr. 4, 2016, and Ser. No. 15/163,595 (attorney docket number
CSI-051B) filed May. 24, 2016 all of which are entirely
incorporated herein.
[0040] FIG. 1 illustrates an example of a metacapacitor having a
first electrode 1, a second electrode 2, and a metadielectric layer
3 disposed between said first and second electrodes. The electrodes
1 and 2 may be made of a metal, such as copper, zinc, or aluminum
or other conductive material such as graphite or carbon
nanomaterials and are generally planar in shape.
[0041] The electrodes 1, 2 may be flat and planar and positioned
parallel to each other. Alternatively, the electrodes may be planar
and parallel, but not necessarily flat, they may be coiled, rolled,
bent, folded, or otherwise shaped to form the capacitor. It is also
possible for the electrodes to be non-flat, non-planar, or
non-parallel or some combination of two or more of these. By way of
example and not by way of limitation, a spacing d between the
electrodes 1 and 2 may range from about 3 nm to about 100 .mu.m.
The maximum voltage V.sub.bd between the electrodes land 2 is
approximately the product of the breakdown field E.sub.bd and the
electrode spacing d. If E.sub.bd=0.1 V/nm and the spacing d between
the electrodes 1 and 2 is 100 microns (100,000 nm), the maximum
voltage V.sub.bd would be 10,000 volts.
[0042] Additionally, the metacapacitor may have an insulation layer
to insulate electrodes 1 and 2 from making ohmic contact with each
other in coiled, rolled, bent, and folded embodiments. Non-limiting
examples of the insolation layer include metadielectric material,
polypropylene (PP), polyethylene terephthalate polyester (PET),
polyphenylene sulfide (PPS), polyethylene naphthalate (PEN),
polycarbonate (PP), polystyrene (PS), and polytetrafluoroethylene
(PTFE).
[0043] The electrodes 1 and 2 may have the same shape as each
other, the same dimensions, and the same area A. By way of example,
and not by way of limitation, the area A of each electrode 1 and 2
may range from about 0.01 m.sup.2 to about 1000 m.sup.2. By way of
example and not by way of limitation for rolled capacitors,
electrodes up to, e.g., 1000 m long and 1 m wide.
[0044] These ranges are non-limiting. Other ranges of the electrode
spacing d and area A are within the scope of the aspects of the
present disclosure.
[0045] If the spacing d is small compared to the characteristic
linear dimensions of electrodes (e.g., length and/or width), the
capacitance C of the capacitor may be approximated by the
formula:
C=.epsilon..epsilon..sub.oA/d, (V)
where .epsilon..sub.o is the permittivity of free space
(8.85.times.10.sup.-12 Coulombs.sup.2/(Newtonmeter.sup.2)) and
.epsilon. is the dielectric constant of the dielectric layer. The
energy storage capacity U of the capacitor may be approximated
as:
U=1/2.epsilon..epsilon..sub.oAE.sub.bd.sup.2d (VI)
[0046] The energy storage capacity U is determined by the
dielectric constant .epsilon., the area A, the electrode spacing d,
and the breakdown field E.sub.bd. By appropriate engineering, a
capacitor or capacitor bank may be designed to have any desired
energy storage capacity U. By way of example, and not by way of
limitation, given the above ranges for the dielectric constant
.epsilon., electrode area A, and breakdown field E.sub.bd a
capacitor in accordance with aspects of the present disclosure may
have an energy storage capacity U ranging from about 500 Joules to
about 210.sup.16 Joules.
[0047] For a dielectric constant c ranging, e.g., from about 100 to
about 1,000,000 and constant breakdown field E.sub.bd between,
e.g., about 0.1 and 0.5 V/nm, a capacitor of the type described
herein may have a specific energy capacity per unit mass ranging
from about 10 Wh/kg up to about 100,000 Wh/kg, though
implementations are not so limited.
[0048] Alternatively, in some embodiments, electrodes 1 and 2 may
have different shapes from each other with the same or different
dimensions, and the same or different areas.
[0049] The present disclosure includes metacapacitors that are
coiled, e.g., as depicted in FIGS. 2A, 2B and 3. As shown in FIG.
2A, electrodes 19, 21, e.g., metal electrodes, are formed onto
opposite surfaces of a metadielectric layer 17 with margin portions
18, 20 that are free of metal located on opposite edges of the
metadielectric layer 17. In some embodiments, such a configuration
of electrodes 19, 21 and metadielectric layer 17 form a tape or a
multilayered tape. An electrically insulating layer 15, e.g., a
plastic material is formed over one of the electrodes 21 or a
plastic film is overlaid on one of the electrodes 21. The
electrically insulating layer 15 may include metadielectric
materials or common capacitor insulating materials such as PET. The
metadielectric lay 17 may be formed, e.g., by applying a solution
containing YanLi material to the electrode 19 and then drying the
applied solution to form a solid layer of the YanLi material.
[0050] Alternatively, electrodes 19 and 21 may be formed onto
opposite surfaces of an insulating layer 15 with margin portions
18, 20 that are free of electrode material located on opposite
edges of the insulating layer 15. In some embodiments, such a
configuration of electrodes 19, 21 and insulating layer 15 form a
tape or a multilayered tape. The electrically insulating layer 15
may include metadielectric materials or common capacitor insulating
materials such as PET. The metadielectric lay 17 may be formed,
e.g., by applying a solution containing YanLi material to the
electrode 19 and then drying the applied solution to form a solid
layer of the YanLi material.
[0051] In some implementations, the applied YanLi material may be a
polymerized solution of YanLi oligomers which is dried to form a
metadielectric. In some implementations, the YanLi material may be
polymerized to form a metadielectric. The thickness of the
metadielectric layer may be a relatively uniformly thick layer. The
metadielectric layer thickness may range from 0.1 .mu.m to 50 .mu.m
depending on the desired maximum capacitor voltage. In general
thicker metadielectric layers are used for higher maximum capacitor
voltages. Furthermore, with a given metacapcitor the metadielectric
layer thickness may vary due to normal manufacturing process
variations, e.g., by about 1% to 10% of a nominal thickness value.
In the example shown in FIG. 2A the first metal electrode 19 is
formed on a portion of a first surface of the metadielectric layer
17 with a first margin portion 18 that is free of metal. The second
electrode 21 is formed on a portion of a second surface of the
plastic layer with a second margin portion 20 located on an
opposite edge of the metadielectric layer 17 being free of metal.
The multilayered structure depicted in FIG. 2A may be wound into a
coil as shown in FIG. 2B. The insulating layer 15 prevents
undesired electrical shorts between the first and second electrodes
after being wound into the coil. By way of example and not by way
of limitation, the insulating layer 15 may include a metadielectric
material, polypropylene (PP), polyethylene terephthalate polyester
(PET), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN),
polycarbonate (PP), polystyrene (PS), or polytetrafluoroethylene
(PTFE).
[0052] In the example depicted in FIG. 4, a metacapacitor 22
comprises a first electrode 23, a second electrode 25, and a
metadielectric material layer 24 of the type described herein
disposed between said first and second electrodes. The electrodes
23 and 25 may be made of a metal, such as copper, zinc, or aluminum
or other conductive material such as graphite or carbon
nanomaterials and are generally planar in shape. In one
implementation, the electrodes and metadielectric material layer 24
are in the form of long strips of material that are sandwiched
together and wound into a coil along with an insulating material
26, e.g., a plastic film such as polypropylene or polyester to
prevent electrical shorting between the electrodes 23 and 25.
Alternatively, the insulating material may include a metadielectric
layer comprised of any composite oligomer or polymer formed
therefrom, as described herein below. Non-limiting examples of
suitable coiled capacitors are described in and U.S. patent
application Ser. No. 14/752,600 (Attorney Docket No. CSI-017) which
is herein incorporated by reference in their entirety. In this
aspect, the present invention provides a coiled capacitor
comprising a coil formed by a flexible multilayered tape, and a
first terminating electrode (a first contact layer) and a second
terminating electrode (a second contact layer) which are located on
butts of the coil. The flexible multilayered tape contains the
following sequence of layers: first metal layer, a layer of a
plastic, second metal layer, a layer of energy storage material.
The first metal layer forms an ohmic contact with the first
terminating electrode (the first contact layer) and the second
metal layer (the second contact layer) forms an ohmic contact with
the second terminating electrode. The layer of energy storage
material may be any oligomer or polymer described herein
[0053] FIG. 4 illustrates an example of the in the chemical
structure of a YanLi material as a monomer of a polymer, wherein
the polarizable unit is a doped chromophore 48, having an electron
donor 44, two conjugated bridges 43, an electron acceptor 42; and
where in the tail 41 is covalently bounded to the electron donor
group 44. A composite oligomer forming the polarizable unit can
have more than one electron donor 44, electron acceptor 42, and
tail 41. In some embodiments, the composite oligomer forming the
polarizable unit has an aromatic ring system in conjugation with a
conjugated bridge. In some embodiments, the aromatic ring system
consists of fused aromatic rings in conjugation. According to
aspects of the present disclosure, a composite oligomer may
comprise a mixture of molecules. A YanLi material made of monomers
of the type shown in FIG. 4 may be polymerized to form a YanLi
dielectric.
[0054] In one embodiment of the present disclosure, the layer's
relative permittivity is greater than or equal to 1000. In another
embodiment of the present disclosure, the polarization (P) of the
metadielectric layer comprises first-order (.epsilon..sub.(1)) and
second-order (.epsilon..sub.(2)) and third order
(.epsilon..sub.(3)) permittivities according to the following
formula:
P=.epsilon..sub.0(.epsilon..sub.1-1)E+.epsilon..sub.0.epsilon..sub.2E.su-
p.2+.epsilon..sub.0.epsilon..sub.3E.sup.3+ . . .
[0055] where P is the polarization of the material, which also can
be represented by the following formula:
P=NP.sub.induced
[0056] where P.sub.induced is the induced polarization which can be
expressed by the formula:
P.sub.induced=.alpha.E.sub.loc+.beta.E.sub.loc.sup.2+.gamma.E.sub.loc.su-
p.3+ . . .
[0057] where E.sub.loc is the localized field and is expressed by
the formula:
E.sub.loc=E+P/(3.epsilon..sub.0)
[0058] The real part of the relative permittivity (.epsilon.') as
can be seen from the above equations, also comprises first, second,
and third order permittivities. Further, permittivity of a
capacitor is a function of applied voltage and thickness of the
capacitor's dielectric (d). Where voltage is the DC-voltage which
is applied to the metadielectric layer, and d is the layer
thickness. In another embodiment of the present invention, the
layer's resistivity is greater than or equal to 10.sup.15 ohm cm.
In yet another embodiment of the present invention, the layer's
resistivity is between 10.sup.16 ohm cm and 10.sup.22 ohm cm.
[0059] In one embodiment, the composite oligomer comprises more
than one type of resistive tails. In another embodiment, the
composite oligomer comprises more than one type of ordered
resistive tails. In yet another embodiment, the composite oligomer
comprises at least one type of resistive tail or at least one type
of ordered resistive tails.
[0060] In order that the invention may be more readily understood,
reference is made to the following examples, which are intended to
be illustrative of the invention, but are not intended to limit the
scope.
[0061] In one embodiment, a liquid or solid composite oligomer is
placed between the first and second electrodes. A solid chromophore
is, for example, pressed into a pellet and placed between the first
electrode and the second electrode. The chromophore can be ground
into a powder before pressing.
[0062] In another embodiment, at least one type of YanLi material
or YanLi oligomer may be dissolved or suspended in a solvent. The
resultant material can be spin coated, extruded via slot die,
roll-to-roll coated, or pulled and dried to form a dielectric
film.
[0063] In another embodiment, a tailless composite oligomer may be
dissolved or suspended in a polymer. This is termed a "guest-host"
system where the oligomer is the guest and the polymer is the host.
Polymer hosts include, but are not limited to, poly(methyl
methacrylate), polyimides, polycarbonates and poly(c-caprolactone).
These systems are cross-linked or non-cross-linked.
[0064] In another embodiment, a tailless composite oligomer may be
attached to a polymer. This is termed a "side-chain polymer"
system. This system has the advantages over guest-host systems
because high composite oligomer concentrations are incorporated
into the polymer with high order and regularity and without phase
separation or concentration gradients. Side chain polymers include,
but are not limited to,
poly[4-(2,2-dicyanovinyl)-N-bis(hydroxyethyl)aniline-alt-(4,4'-methyleneb-
is(phenylisocyanate))]urethane,
poly[4-(2,2-dicyanovinyl)-N-bis(hydroxyethyl)aniline-alt-(isophoronediiso-
cyanate)]urethane, poly(9H-carbazole-9-ethyl acrylate),
poly(9H-carbazole-9-ethyl methacrylate), poly(Disperse Orange 3
acrylamide), poly(Disperse Orange 3 methacrylamide), poly(Disperse
Red 1 acrylate), poly(Disperse Red 13 acrylate), poly(Disperse Red
1 methacrylate), poly(Disperse Red 13 methacrylate), poly[(Disperse
Red 19)-alt-(1,4-diphenylmethane urethane)], poly(Disperse Red
19-p-phenylene diacrylate), poly(Disperse Yellow 7 acrylate),
poly(Disperse Yellow 7 methacrylate), poly[(methyl
methacrylate)-co-(9-H-carbazole-9-ethyl acrylate)], poly[(methyl
methacrylate)-co-(9-H-carbazole-9-ethyl methacrylate)], poly[methyl
methacrylate-co-(Disperse Orange 3 acrylamide)], poly[methyl
methacrylate-co-(Disperse Orange 3 methacrylamide)], poly[(methyl
methacrylate)-co-(Disperse Red 1 acrylate)], poly[(methyl
methacrylate)-co-(Disperse Red 1 methacrylate)], poly[(methyl
methacrylate)-co-(Disperse Red 13 acrylate)], poly[(methyl
methacrylate)-co-(Disperse Red 13 methacrylate)], poly[methyl
methacrylate-co-(Disperse Yellow 7 acrylate)], poly[methyl
methacrylate-co-(Disperse Yellow 7 methacrylate)], poly
[[(S)-1-(4-nitrophenyl)-2-pyrrolidinemethyl]acrylate],
poly[(((S)-(-)-1-(4-nitrophenyl)-2-pyrrolidinemethyl)acrylate-co-methyl
methacrylate], poly
[[((S)-1-(4-nitrophenyl)-2-pyrrolidinemethyl]methacrylate] and
poly[((S)-(-)-1-(4-nitrophenyl)-2-pyrrolidinemethyl)methacrylate-co-methy-
l methacrylate]. These systems are cross-linked or
non-cross-linked.
[0065] In another embodiment, tailless composite oligomers may be
embedded in matrices such as oxides, halides, salts and organic
glasses. An example of a matrix is inorganic glasses comprising the
oxides of aluminum, boron, silicon, titanium, vanadium and
zirconium.
[0066] According to aspects of the present disclosure, the
oligomers that make up a YanLi material may be aligned, partially
aligned or unaligned. The composite oligomer is preferably aligned
for optimal geometric configuration of polarizing units as this
results in higher capacitance values in the capacitor. One method
of alignment is to apply a DC electric field to the composite
oligomer at a temperature at which the composite oligomer can be
oriented. This method is termed "poling." Poling is generally
performed near the glass transition temperature of polymeric and
glassy systems. One possible method of poling is corona poling.
Other methods of alignment could be roll-to-roll, Meyer bar, dip,
slot die, and air knife coating of solutions and liquid crystal
solutions of said side-chain polymers or composite oligomers.
[0067] In some instances, the side-chain polymer or composite
oligomers may form liquid crystals in solution or solvent and with
or without external influence. Non-limiting examples of liquid
crystals include lyotropic and thermotropic liquid crystals.
Non-limiting examples of external influences include heat, electric
field, mechanical disturbances (e.g. vibration or sonication), and
electromagnetic radiation. Said liquid crystals are supramolecular
structures comprised of said side-chain polymers or composite
oligomer in solution or solvent and are ordered and aligned or
partially ordered or partially aligned. Such liquid crystal
materials may be coated onto a substrate, e.g., by roll-to-roll,
Meyer bar, dip, slot die, or air knife coating in a process that
includes mechanical ordering of the liquid crystals, and drying of
the liquid crystal solution or evaporation of the solvent such that
the liquid crystals form a crystalline or semi-crystalline layer or
film of metadielectric material.
[0068] By way of example, and not by way of limitations, structures
1-4 in Table 1 below are possible general structures for YanLi
materials. In Table 1, the term "Polar Unit" is equivalent to
polarizable unit as defined above, "t" is an integer representing
the number of repeat units of the oligomeric material, and "n" and
"m" are integers representing the number of subunits present in the
composite oligomeric material.
TABLE-US-00001 TABLE 1 Examples of the composite oligomeric
material general structure ##STR00001## 1 ##STR00002## 2
##STR00003## 3 ##STR00004## 4
[0069] In the case of polycyclic aromatic systems, rylene fragments
are a possible implementation of the polarizable unit. Some
non-limiting examples of the use of rylene fragments as the
polarizable unit are listed in Table 2. These polarizable units
could be incorporated as sidechains to the oligomer via a wide
variety of linkers or used as crosslinking agents to join polymers
into a polymer network. Use of rylenes in capacitors is described
in greater detail in U.S. patent application Ser. No. 14/919,337
(Attorney Docket No. CS1-022), which is incorporated herein in its
entirety by reference. Table 2 includes examples of rylene
fragments, wherein the repeat unit can range from 0 to 8
repeats.
TABLE-US-00002 TABLE 2 Examples of the polycyclic organic compound
comprising rylene fragments ##STR00005## 1 ##STR00006## 2
##STR00007## 3 ##STR00008## 4 ##STR00009## 5 ##STR00010## 6
##STR00011## 7 ##STR00012## 8 ##STR00013## 9 ##STR00014## 10
##STR00015## 11 ##STR00016## 12 ##STR00017## 13
[0070] The rylene fragments may be made further polarizable by
adding a variety of functional groups to various positions of the
structure. Incorporating electron donors and electron acceptors is
one way to enhance the polarizability. Electrophilic groups
(electron acceptors) are selected from --NO.sub.2, --NH.sub.3.sup.+
and --NR.sub.3.sup.+ (quaternary nitrogen salts), counterion
Cl.sup.-or Br.sup.-, --CHO (aldehyde), --CRO (keto group),
--SO.sub.3H (sulfonic acids), --SO.sub.3R (sulfonates),
SO.sub.2NH.sub.2 (sulfonamides), --COOH (carboxylic acid), --COOR
(esters, from carboxylic acid side), --COCl (carboxylic acid
chlorides), --CONH.sub.2 (amides, from carboxylic acid side),
--CF.sub.3, --CCl.sub.3, --CN, wherein R is radical selected from
the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl,
neopentyl, cyclohexyl etc.), allyl (--CH.sub.2--CH.dbd.CH.sub.2),
benzyl (--CH.sub.2C.sub.6H.sub.5) groups, phenyl (+substituted
phenyl) and other aryl (aromatic) groups. Nucleophilic groups
(electron donors) are selected from --O.sup.- (phenoxides, like
--ONa or --OK), --NH.sub.2, --NHR, --NR.sub.2, --NRR', --OH, OR
(ethers), --NHCOR (amides, from amine side), --OCOR (esters, from
alcohol side), alkyls, --C.sub.6H.sub.5, vinyls, wherein R and R'
are radicals independently selected from the list comprising alkyl
(methyl, ethyl, isopropyl, tent-butyl, neopentyl, cyclohexyl etc.),
allyl (--CH2-CH.dbd.CH2), benzyl (--CH2C6H5) groups, phenyl
(+substituted phenyl) and other aryl (aromatic) groups. Preferred
electron donors include, but are not limited to, amino and
phosphino groups and combinations thereof. Preferred electron
acceptors include, but are not limited to, nitro, carbonyl, oxo,
thioxo, sulfonyl, malononitrile, isoxazolone, cyano, dicyano,
tricyano, tetracycano, nitrile, dicarbonitrile, tricarbonitrile,
thioxodihydropyrimidinedione groups and combinations thereof. More
conjugated bridges include, but are not limited to,
1,2-diphenylethene, 1,2-diphenyldiazene, styrene,
hexa-1,3,5-trienylbenzene and 1,4-di(thiophen-2-yl)buta-1,3-diene,
alkenes, dienes, trienes, polyenes, diazenes and combinations
thereof.
[0071] Existence of the electrophilic groups (acceptors) and the
nucleophilic groups (donors) in the aromatic polycyclic conjugated
molecule promotes increase of electronic polarizability of these
molecules. Under the influence of external electric field electrons
are displaced across the polarizable unit to compensate the
electric field. The nucleophilic groups (donors) and the
electrophilic groups (acceptors) add to the electron density of the
polarizable unit, which increases polarizability of such molecules
and ability to form compensating electric field counter in the
presence of an electric field. Thus, a distribution of electronic
density in the molecules is non-uniform. The presence of the
polarizable unitsleads to increasing of polarization ability of the
disclosed material because of electronic conductivity of the
polarizable units. Ionic groups may increase polarization of the
disclosed YanLi material. The polarizable units can be nonlinearly
polarizable and may be comprised of an aromatic polycyclic
conjugated molecule with at least one dopant group, the polarizable
units and are placed into a resistive envelope formed by resistive
substituents. In some instances, the resistive substituents provide
solubility of the organic compound in a solvent and act to
electrically insulate supramolecular structures comprised of the
YanLi material from neighboring supramolecular structures of the
YanLi material. A non-centrosymmetric arrangement of the dopant
group(s) can lead to a strong nonlinear response of the compound's
electronic polarization in the presence of an electric field.
Additionally, an anisometric molecule or polarizing unit can lead
to a strong nonlinear response of the compound's electronic
polarization in the presence of an electric field. Resistive
substituents (e.g. resistive tails described above) increase the
electric strength of these electro-polarizable compounds and
breakdown voltage of the dielectric layers made on their basis.
[0072] An example of attachment of a rylene fragment to a polymer
chain is shown below.
##STR00018##
In the example shown above it is readily apparent that one or both
ends of the rylene fragment may be attached to a polymer chain via
T, T.sub.p, or T'.sub.p, and may be functionalized for better
polarizability at R.sub.m, R'.sub.m, R.sub.1, R.sub.2, R.sub.3, or
R.sub.4. The preferred but non-limiting range for n, n.sub.1,
n.sub.2, and n.sub.3 are between 0 and 8, with the proviso that the
rylene fragment needs at least one naphthalene unit in order to be
considered a rylene fragment and n, n.sub.1, n.sub.2, and n.sub.3
are independently selected from said range of integers.
[0073] Rylene fragments may also be fused with anthracene
structures at the nitrogen containing ends. Some non-limiting
examples are shown below. These species will similarly benefit in
polarizability by the addition of dopant groups, as illustrated in
the examples below.
##STR00019## ##STR00020##
In the above examples R.sub.1, R.sub.2, R.sub.3, and R.sub.4
substituents are independently absent, a resistive tail, or a
dopant group in each occurrence, R.sub.A.sup.1, R.sub.A'.sup.1,
R.sub.A''.sup.1, R.sub.A'''.sup.1, R.sub.A''''.sup.1, and
R.sub.A'''''.sup.1 are each independently absent, a resistive tail,
or a dopant group, and each occurrence of n.sub.1, n.sub.2, and
n.sub.3 can be any integer independently selected from 0 to 8 with
the provision that not all n.sub.1, n.sub.2, and n.sub.3 values can
equal 0.
[0074] In many implementations, but not all, the composite oligomer
may include a repeating backbone and a polarizable unit in the form
of one or more azo-dye chromophores. The azo-dye chromophores may
be phenyl groups in conjugated connection via an azo-bridge, such
that there are "n" phenyl groups and "n-1" azo-bridges where n is
an integer between 2 and 16. The repeating backbone may contain a
portion of the chromophore or possess a handle allowing the
chromophore to be present as sidechains. Sidechains may be added to
the final polymerized product or incorporated into individual
monomers that are then polymerized. If incorporated into the
backbone the chromophores may be modified such that they react with
the other segments of the backbone to form the final product or
they may be incorporated into monomers that are then
polymerized.
[0075] These chromophores impart high polarizability due to
delocalization of electrons. This polarizability may be enhanced by
dopant groups. The composite oligomer may further include resistive
tails that will provide insulation within the material. In some
embodiments, the resistive tails can be substituted or
unsubstituted carbon chains (C.sub.nX.sub.2n+1, where "X"
represents hydrogen, fluorine, chlorine, or any combination
thereof). In some embodiments, the resistive tails may be rigid
fused polycyclic aryl groups in order to limit the motion of the
sidechains, potential stabilizing van der Waals interactions
between sidechains while simultaneously making the material more
stable by eliminating voids. In some embodiments, the resistive
tails may be rigid in order to limit voids within the material.
Non-limiting examples of repeating backbones include, but are not
limited to, (meth)acrylates, polyvinyls, peptides, peptoids, and
polyimides.
[0076] Examples of reactions for synthesizing composite oligomers
of the type described herein are shown and described below.
##STR00021## ##STR00022##
No technical complications are expected in adapting these syntheses
to monomers bearing both chromophore and resistive tail, as in
formula 1 from Table 1.
##STR00023##
[0077] Examples of suitable chromophores are, but are not limited
to, Disperse Red-1, Black Hole Quencher-1, and Black Hole
Quencher-2. In many of the embodiments it may not be necessary for
all monomer units to bear a chromophore, and in some it may be
desirable to possess other side chains or sites within the
repeating backbone that impart other qualities to the material such
as stability, ease of purification, flexibility of finished film,
etc.
[0078] For embodiments where the chromophores are incorporated as
side chains, the resistive tails may be added before the sidechains
are attached to a finished oligomer, after sidechains have been
chemically added to a finished oligomer, or incorporated into the
oligomer during synthesis by incorporation into monomer units.
[0079] For embodiments where the chromophore is part of the
backbone the tails may be attached to the finished composite
oligomer or incorporated into monomer units and added during
composite synthesis.
[0080] Non-limiting examples of suitable tails are alkyl,
haloalkyl, cycloakyl, cyclohaloalkyl, and polyether.
[0081] Syntheses of the four different YanLi materials described
herein will be further explained.
##STR00024##
[0082] 2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)
diazenyl)phenyl) diazenyl)phenyl)(ethyl) amino)ethan-1-ol (1). Fast
Black K Salt (25%, 30 g) was dissolved in 250 mL acetonitrile and
250 mL NaOAc buffer solution (pH=4) and the resulting solution was
stirred for 1 hour and then sonicated for 15 min, followed by
vacuum filtration. The filtrate was dropwise added to a solution of
2-(ethyl(phenyl)amino)ethan-1-ol (4.1 g in 65 mL acetonitrile) at
0.degree. C. The resultant solution was stirred at room temperature
for 16 hours and the precipitate was filtered out and washed with
mix solvent of acetonitrile/water (1:1) and dried under vacuum. The
product was obtained as a black powder.
##STR00025##
[0083]
2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)dia-
zenyl)phenyl)(ethyl) amino)ethyl methacrylate (2). To the solution
of compound 1 (5.0 g) and triethylamine (4.4 mL) in 70 mL THF
(anhydrous) at 0.degree. C., was dropwise added a solution of
methacryloyl chloride (3.1 mL) in THF (anhydrous, 10 mL). The
resulting solution was warmed up to room temperature and was
stirred overnight at room temperature. The reaction solution was
filtered and THF was used to wash the insoluble; the filtrate was
concentrated under vacuum and diluted in dichloromethane. The
diluted solution was washed with water and the solvent was removed
under vacuum. The crude product was purified with column
chromatography and 3.2 g pure product was isolated as a black
powder.
##STR00026##
[0084] Polymer 1. Compound 2 (2.0 g), stearylmethacrylate (1.2 g)
and AIBN (160 mg) were dissolved in anhydrous toluene (12 mL) in a
sealed flask and the resulting solution was heated to 85.degree. C.
for 18 hours and then cooled to room temperature. The polymer was
obtained by precipitating in isopropanol.
##STR00027##
[0085] (E)-2-(ethyl(4-((4-nitrophenyl)diazenyl)phenyl)amino)ethyl
methacrylate (3). Compound 3 was synthesized from Desperse Red-1
and methacryloyl chloride using preparation procedure of compound
2.
##STR00028##
[0086] Polymer 2. Polymer 2 was synthesized from compound 3 and
stearylmethacrylate using preparation procedure of polymer 1.
##STR00029##
[0087]
2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)dia-
zenyl)phenyl) (ethyl)amino) ethyl nonadecanoate (4): To the
solution of compound 1 (0.5 g) and triethylamine (0.46 mL) in 15 mL
THF at 0.degree. C., was dropwise added a solution of stearoyl
chloride (1.12 mL) in THF. The resulting solution was warmed up to
room temperature and was stirred overnight at room temperature. The
reaction solution was filtered and THF was used to wash the
insoluble; the filtrate was concentrated under vacuum and residue
was taken in dichloromethane. The crude product solution was washed
with water and the solvent was removed under vacuum. The crude
product was purified with column chromatography.
##STR00030##
2-((4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diazenyl)-
phenyl)(ethyl) amino)ethyl nonadecanoate (5)
[0088] Compound 4 (1.0 g) was dissolved in dichloromethane (30 mL)
and cooled to -78.degree. C.; BBr.sub.3 (0.72 g) was slowly added
into the solution. The resulting reaction mixture was slowly warmed
to room temperature and was kept at room temperature with stirring
for 12 hours. Sodium bicarbonate aqueous solution was injected in
the reaction mixture at 0.degree. C. and diluted with
dichloromethane. The solution was washed with water and brine, and
then concentrated under vacuum. The product was purified via flash
column chromatography.
##STR00031##
2-((4-((E)-(2,5-bis(2-aminoethoxy)-4-((E)-(4-nitrophenyl)diazenyl)phenyl)-
diazenyl)phenyl) (ethyl)amino)ethyl nonadecanoate (6)
[0089] Compound 6 (0.73 g), K.sub.2CO.sub.3 (1.38 g) and tert-butyl
(2-bromoethyl)carbamate (0.44 g) were added to DMF (15 mL), and the
resulting mixture was stirred at 65.degree. C. overnight. H.sub.2O
(400 mL) was added to the reaction mixture and the aqueous layer
was extracted with EtOAc (200 mL.times.2). The combined organic
layer was washed with H.sub.2O (100 mL.times.2) and brine (50 mL),
dried over Na.sub.2SO.sub.4, filtered, and concentrated under
reduced pressure. The crude product was purified by silica column
chromatography. The pure product was dissolved in dichloromethane
(10 mL) and TFA (3 mL) and the solution was stirred at room
temperature for 2 hours. Then excess reagent and solvent were
removed under vacuum. The resulting crude product was neutralized
by NaHCO.sub.3 solution, extracted with CH.sub.2Cl.sub.2
(3.times.50 mL), dried over MgSO.sub.4 and evaporated. The crude
product was purified by silica column chromatography.
##STR00032##
[0090] Polymer 3. To the solution of compound 6 (4.1 g) in
CH.sub.2Cl.sub.2 (15 mL), was slowly added adipoyl dichloride (0.9
g) at 0.degree. C. After the addition, the solution was allowed to
warm to room temperature and stir for 2 hours. The resulting
solution was concentrated and dropwise added into isopropanol to
precipitate the polymer 3.
##STR00033##
N-decylaniline (1)
[0091] To a solution containing GuHCl (10 mg, 5 mol %) in H.sub.2O
(4 mL), was added decanal (2 mmol) and aniline (2.2 mmol) and the
mixture vigorously stirred for 15 min at room temperature. After,
NaBH.sub.4 (20 mg, 2.1 mmol) was added, the mixture was stirred for
additional 10 min. The reaction mixture was extracted with
CH.sub.2Cl.sub.2, dried over Na.sub.2SO.sub.4, concentrated under
vacuum and the crude mixture was purified by column chromatography
on silica gel to afford the pure products.
##STR00034##
2-(Decyl(phenyl)amino)ethan-1-ol (2)
[0092] To a solution of 1 (470 mg, 2.00 mmol) in toluene (5 ml) was
added triethylamine (405 mg, 4.00 mmol) and 2-bromoethanol (501 mg,
4.01 mmol), and the mixture was refluxed for 2 h. The resulting
mixture was diluted with saturated NH.sub.4Cl and extracted with
ethyl acetate. The extract was washed with brine, dried over
anhydrous MgSO4, filtered, and concentrated in vacuo. The crude
product was purified by silica gel chromatography to give 2.
##STR00035##
2-(Decyl(4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diaz-
enyl) phenyl) amino)ethan-l-ol (3)
[0093] Fast Black K Salt (25%, 30 g) was dissolved in 250 mL
acetonitrile and 250 mL NaOAc buffer solution (pH=4) and the
resulting solution was stirred for 1 hour and then sonicated for 15
min, followed by vacuum filtration. The filtrate was dropwise added
to a solution of compound 2 (6.8 g in 65 mL acetonitrile) at
0.degree. C. The resultant solution was stirred at room temperature
for 16 hours and the precipitate was filtered out and washed with
mix solvent of acetonitrile/water (1:1) and dried under vacuum. The
product was obtained as a black powder.
##STR00036##
2-(decyl(4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl)diaz-
enyl) phenyl) amino)ethyl methacrylate (4)
[0094] To the solution of compound 3 (5.0g) and triethylamine (3.5
mL) in 70 mL THF (anhydrous) at 0.degree. C., was dropwise added a
solution of methacryloyl chloride (2.5 mL) in THF (anhydrous, 10
mL). The resulting solution was warmed up to room temperature and
was stirred overnight at room temperature. The reaction solution
was filtered and THF was used to wash the insoluble; the filtrate
was concentrated under vacuum and diluted in dichloromethane. The
diluted solution was washed with water and the solvent was removed
under vacuum. The crude product was purified with column
chromatography and 3.3 g pure product 4 was isolated as a black
powder.
##STR00037##
Poly
2-(decyl(4-((E)-(2,5-dimethoxy-4-((E)-(4-nitrophenyl)diazenyl)phenyl-
)diazenyl) phenyl) amino)ethyl methacrylate (4) (Polymer 4)
[0095] Compound 4 (2.0 g) and AIBN (40 mg) were dissolved in
anhydrous toluene (6 mL) in a sealed flask and the resulting
solution was heated to 85.degree. C. for 18 hours and then cooled
to room temperature. The polymer (1.4g) was obtained by
precipitating and washing in 2-isopropanol.
[0096] While the above is a complete description of the preferred
embodiment of the present invention, it is possible to use various
alternatives, modifications and equivalents. Therefore, the scope
of the present invention should be determined not with reference to
the above description but should, instead, be determined with
reference to the appended claims, along with their full scope of
equivalents. Any feature described herein, whether preferred or
not, may be combined with any other feature described herein,
whether preferred or not. In the claims that follow, the indefinite
article "A", or "An" refers to a quantity of one or more of the
item following the article, except where expressly stated
otherwise. As used herein, in a listing of elements in the
alternative, the word "or" is used in the logical inclusive sense,
e.g., "X or Y" covers X alone, Y alone, or both X and Y together,
except where expressly stated otherwise. Two or more elements
listed as alternatives may be combined together. The appended
claims are not to be interpreted as including means-plus-function
limitations, unless such a limitation is explicitly recited in a
given claim using the phrase "means for."
* * * * *
References