U.S. patent number RE47,003 [Application Number 15/254,700] was granted by the patent office on 2018-08-21 for organic thin film transistor with ion exchanged glass substrate.
This patent grant is currently assigned to Corning Incorporated. The grantee listed for this patent is Corning Incorporated. Invention is credited to Mingqian He, Jianfeng Li, James Robert Matthews, Michael S Pambianchi.
United States Patent |
RE47,003 |
He , et al. |
August 21, 2018 |
Organic thin film transistor with ion exchanged glass substrate
Abstract
Articles utilizing strengthened glass substrates, for example,
ion-exchanged glass substrates, in combination with organic
molecules or polymers are described along with methods for making
the articles. The articles are useful in electronics-based devices
that utilize organic thin film transistors.
Inventors: |
He; Mingqian (Horseheads,
NY), Li; Jianfeng (Lake St. Louis, MO), Matthews; James
Robert (Painted Post, NY), Pambianchi; Michael S
(Corning, NY) |
Applicant: |
Name |
City |
State |
Country |
Type |
Corning Incorporated |
Corning |
NY |
US |
|
|
Assignee: |
Corning Incorporated (Corning,
NY)
|
Family
ID: |
1000003211819 |
Appl.
No.: |
15/254,700 |
Filed: |
September 1, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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61567342 |
Dec 6, 2011 |
|
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Reissue of: |
13690314 |
Nov 30, 2012 |
8901544 |
Dec 2, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L
51/0001 (20130101); H01L 51/0001 (20130101); H01L
51/0508 (20130101); H01L 51/0096 (20130101); H01L
51/0508 (20130101); H01L 51/0096 (20130101); Y02E
10/549 (20130101); Y02P 70/50 (20151101); Y02P
70/50 (20151101) |
Current International
Class: |
H01L
29/08 (20060101); H01L 51/00 (20060101); H01L
35/24 (20060101); H01L 51/05 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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10 2006 061966 |
|
Jun 2008 |
|
DE |
|
102006061966 |
|
Jun 2008 |
|
DE |
|
2 169 007 |
|
Mar 2010 |
|
EP |
|
2169007 |
|
Mar 2010 |
|
EP |
|
2006031893 |
|
Mar 2006 |
|
WO |
|
2006031893 |
|
Mar 2006 |
|
WO |
|
2008106019 |
|
Sep 2008 |
|
WO |
|
2008106019 |
|
Sep 2008 |
|
WO |
|
2009123695 |
|
Oct 2009 |
|
WO |
|
2009123695 |
|
Oct 2009 |
|
WO |
|
WO 2010119243 |
|
Oct 2010 |
|
WO |
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2010136385 |
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Dec 2010 |
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WO |
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Other References
Allard et al. "Organic semiconductors for solution-processable
field-effect transistors (OFETs)" U. Angew. Chem. Int. ED. 2008,
47, pp. 4070-4098. cited by applicant .
He et al. "Alkylsubstituted thienothiophene semiconducting
materials: structure-property relationships" J. Am. Chem. Soc.
2009, 131, 11930-11938. cited by applicant .
Katz, H. E. "Recent advances in semiconductor performance and
printing processes for organic transistor-based electronics" Chem.
Mater. 2004, 16, 4748-4756. cited by applicant .
Lo et al. "Flexible glass substrates for organic TFT active matrix
electrophoretic displays" Digest of Technical Papers--Society for
Information Display International Symposium (2011), 42(Bk. 1),
387-388. cited by applicant .
Siringhaus et al. "Two-dimensional charge transport in
self-organized, high-mobility conjugated polymers" Nature 1999,
401, 685-688. cited by applicant .
He, M. et al., Synthesis and Structure of Alkyl-Substitute Fused
Thiophenes Containing up to Seven Rings; J. Org. Chem. 2007, 2,
444. cited by applicant .
Fong, H.H. et al. Tetrathienoacene Copolymers as High Mobility,
Soluble Organic Semiconductors; J. Am. Chem. Soc. 2008, 130, 13202.
cited by applicant .
Bronstein, H. et al. Thieno [3,2-b]
thiophene--Diketopryrrolopyrrole-Containing Polymers for
High-performance Organic Field-Effect Transistors and Organic
Photovoltaic Devices; J. Am. Chem. Soc. 2011, 133, 3272. cited by
applicant .
Li, Y., A High Mobility P-Type DPP-Thieno [3,2-b] thiophene
Copolymer for Organic Thn-Film Transistors; Adv. Mater. 2010, 22,
4862-4866. cited by applicant .
He et al., "Importance of C2 Symmetry for the Device Performance of
a Newly Synthesized Family of Fused-Ring Thiophenes"; Chemistry of
Materials, American Chemical Society, vol. 22, No. 9, Sep. 1, 2010,
pp. 2770-2779. cited by applicant .
PCT Search Report and Written Opinion dated Jul. 3, 2012, in
corresponding PCT Application Serial No. PCT/US2012/025856. cited
by applicant .
Toth, Z., et al., "Investigation of Indentation-Caused Cracking in
Surface-Modified Silica Glasses," Materials Science and Engineering
A; Structural Materials: Properties, Microstructure &
Processing, Lausanne, CH, vol. 387-389, Dec. 15, 2004. cited by
applicant .
Tieke, B., Conjugated Polymers Containing Diketopyrrolopyrrole
Units in the Main Chain; Beilstein J. Org. Chem. 2010, 6, 830.
cited by applicant .
Aert et al.; "Controlled Molecular Weight by the Precipitation
Polymerization of 2, 6-dimethylphenol", Journal of Macromolecular
Science, Part A--Pure and Applied Chemistry, vol. 32, No. 3, Jan.
1, 1995, pp. 515-523. cited by applicant.
|
Primary Examiner: McKane; Elizabeth
Attorney, Agent or Firm: Dinsmore & Shohl LLP
Claims
We claim:
1. An article comprising: a. a strengthened glass substrate having
a first surface and a second surface and having a Vickers crack
initiation threshold of at least .[.20.]. .Iadd.7 .Iaddend.kgf; b.
an organic semiconductor layer having a first surface and a second
surface, wherein the first surface of the organic semiconductor
layer is in direct contact with the second surface of the
strengthened glass substrate; c. a dielectric layer having a first
surface and a second surface; and d. at least one .[.additional.].
electrode; wherein the article does not contain a barrier layer
between the organic semiconductor layer and the strengthened glass
substrate; wherein the strengthened glass comprises an
ion-exchanged glass; and wherein the article comprises a top-gate
thin film transistor, photovoltaic device, diode, or display
device.
2. The article of claim 1, wherein said at least one electrode
comprises a gate electrode, drain electrode, or a source
electrode.
3. The article of claim 1, wherein the at least one electrode
comprises a metal, conducting metal oxide film, conducting metal
nanoparticulate ink, or conductive polymer.
4. The article of claim 1, wherein the organic semiconductor layer
comprises a semiconducting small molecule, semiconducting oligomer,
or semiconducting polymer.
5. The article of claim 4, wherein the semiconducting small
molecule, semiconducting oligomer, or semiconducting polymer
comprises a fused thiophene moiety.
6. The article of claim 1, wherein the dielectric layer comprises
an organic or inorganic material that may be applied as a film at a
temperature less than about 250.degree. C.
7. The article of claim 1, further comprising a functional layer on
the surface opposite of the organic semiconductor layer and
dielectric layer of the strengthened glass substrate, wherein the
functional layer is selected from an anti-glare layer, an
anti-smudge layer, a self-cleaning layer, an anti-reflection layer,
an anti-fingerprint layer, an optically scattering layer, an
anti-splintering layer, and combinations thereof.
8. The article of claim 1, wherein the article comprises a top-gate
top-contact or top-gate bottom-contact thin film transistor.
9. An article comprising: a. a strengthened glass substrate having
a first surface and a second surface and having a Vickers crack
initiation threshold of at least .[.20.]. .Iadd.7 .Iaddend.kgf; b.
an organic semiconductor layer having a first surface and a second
surface; c. a dielectric layer having a first surface and a second
surface wherein the first surface of the dielectric layer is in
direct contact with the organic semiconductor layer; d. a gate
electrode in direct contact with the strengthened glass substrate
and the second surface of the dielectric layer; and e. at least one
additional electrode; wherein the article does not contain a
barrier layer between the gate electrode and the strengthened glass
substrate wherein the strengthened glass comprises an ion-exchanged
glass; and wherein the article comprises a bottom-gate thin film
transistor, photovoltaic device, diode, or display device.
10. The article of claim 9, wherein said at least one electrode
comprises a drain electrode or a source electrode.
11. The article of claim 9, wherein the at least one electrode
comprises a metal, conducting metal oxide film, conducting metal
nanoparticulate ink, or conductive polymer.
12. The article of claim 9, wherein the organic semiconductor layer
comprises a semiconducting small molecule, semiconducting oligomer,
or semiconducting polymer.
13. The article of claim 12, wherein the semiconducting small
molecule, semiconducting oligomer, or semiconducting polymer
comprises a fused thiophene moiety.
14. The article of claim 9, wherein the dielectric layer comprises
an organic or inorganic material that may be applied as a film at a
temperature less than about 250.degree. C.
15. The article of claim 9, further comprising a functional layer
on the surface opposite of the organic semiconductor layer and
dielectric layer of the strengthened glass substrate, wherein the
functional layer is selected from an anti-glare layer, an
anti-smudge layer, a self-cleaning layer, an anti-reflection layer,
an anti-fingerprint layer, an optically scattering layer, an
anti-splintering layer, and combinations thereof.
16. The article of claim 9, wherein the article comprises a
bottom-gate top-contact or bottom-gate bottom-contact thin film
transistor.
17. A method of forming the article of claim 1, comprising: a.
providing a strengthened glass substrate having a first surface and
a second surface and having a Vickers crack initiation threshold of
at least .[.20.]. .Iadd.7 .Iaddend.kgf; b. providing an organic
semiconductor layer; c. providing a dielectric layer; and d.
providing at least one electrode; wherein the article does not
contain a barrier layer.
18. The method of claim 17, wherein the providing an organic
semiconductor layer comprises coating the strengthened glass
substrate with the organic semiconductor layer and coating the
organic semiconductor layer with the dielectric layer.
19. The method of claim 17, wherein the providing a dielectric
layer step comprises coating the strengthened glass substrate with
the dielectric layer and coating the dielectric layer with the
organic semiconductor layer.
20. The method of claim 19, wherein coating comprises sputter
coating, atomic layer deposition, ink jet printing, slot-die
printing, dip coating, spin coating, Langmuir-Blodgett deposition,
electrospray ionization, direct nanoparticle deposition, vapor
deposition, chemical deposition, vacuum filtration, flame spray,
electrospray, spray deposition, electrodeposition, screen printing,
close space sublimation, nano-imprint lithography, in situ growth,
microwave assisted chemical vapor deposition, laser ablation, arc
discharge, gravure printing, doctor blading, spray-coating, slot
die coating, or chemical etching.
21. A method of forming the article of claim 9, comprising: a.
providing a strengthened glass substrate having a first surface and
a second surface and having a Vickers crack initiation threshold of
at least .[.20.]. .Iadd.7 .Iaddend.kgf; b. providing an organic
semiconductor layer; c. providing a dielectric layer; and d.
providing a gate electrode in contact with the strengthened glass
substrate and the dielectric layer e. providing at least one
additional electrode; wherein the article does not contain a
barrier layer between the gate electrode and the strengthened glass
substrate.
22. The method of claim .[.21.]. .Iadd.17.Iaddend., wherein the
providing an organic semiconductor layer comprises coating the
strengthened glass substrate with the organic semiconductor layer
and coating the organic semiconductor layer with the dielectric
layer.
23. The method of claim 21, wherein the providing a dielectric
layer comprises coating the strengthened glass substrate with the
dielectric layer and coating the dielectric layer with the organic
semiconductor layer.
24. The method of claim 23, wherein coating comprises sputter
coating, atomic layer deposition, ink jet printing, slot-die
printing, dip coating, spin coating, Langmuir-Blodgett deposition,
electrospray ionization, direct nanoparticle deposition, vapor
deposition, chemical deposition, vacuum filtration, flame spray,
electrospray, spray deposition, electrodeposition, screen printing,
close space sublimation, nano-imprint lithography, in situ growth,
microwave assisted chemical vapor deposition, laser ablation, arc
discharge, gravure printing, doctor blading, spray-coating, slot
die coating, or chemical etching.
Description
This application claims the benefit of priority under 35 USC
.sctn.119 of U.S. Provisional Application Ser. No. 61/567,342 filed
Dec. 6, 2011 the content of which is relied upon and incorporated
herein by reference in its entirety.
FIELD
Embodiments generally relate to articles using strengthened glass
as a substrate and more particularly to using strengthened glass in
combination with organic molecules or polymers as a substrate for
electronics devices, such as thin film transistors, and methods for
making the articles.
TECHNICAL BACKGROUND
As portable electronics devices, such as e-readers, video displays,
and other gadgetry continue to gain worldwide acceptance, the
demand for improved mechanical durability in these devices grows.
Many of these devices contain thin film transistors, most often
comprising glass support substrates. For those products using glass
as the backplane substrate, an impact with the floor, harsh
environmental conditions, or similar event could cause device
failure. For example, fracturing of the glass backplane substrate
is a dominant failure mode in current e-readers.
Glass is viewed by device manufacturers as limiting the device
durability, and attempts have been made to replace it with other
materials such as metal sheets (e.g. aluminum or stainless steel)
and polymer films (polyethylene terephthalate or polyethylene
naphthalate). Although metal and polymer films are non-brittle,
these materials also have limitations. Metal films are often too
rough and require a planarization layer and polymer films are prone
to solvent incompatibility and have thermal-dimensional
limitations. Additionally, metal and polymer substrates may provide
additional compatibility issues not present with glass when used as
a support substrate.
The ideal substrate would be able to withstand increased
temperatures, provide a surface with low roughness, be unaffected
by processing solvents, and be able to withstand everyday final
product-type abuse. Current substrates fail to meet at least one of
these important factors, leading to an unmet need to find novel
substrates that have improved performance.
SUMMARY
Fabrication of active electronic structures on ion-exchanged glass
will enable strong, nearly unbreakable glass to be used as the
electronic backplane in electronic devices such as liquid crystal
displays. If the electronic backplanes were composed of
ion-exchanged glass, much of this extra hardware could be
eliminated, and new, frameless devices could be developed, with
potential for greatly improved aesthetics, lighter weight, lower
manufacturing costs, and/or improved product durability. If the
active electronics on ion-exchanged glass are also composed of
optically transparent materials, then this would enable
transparent, all-glass electronic devices.
One possibility is to use strengthened glass, such as Gorilla.RTM.
(registered Trademark of Corning Incorporated) Glass as the
backplane substrate. Ion-exchanged Gorilla.RTM. Glass, however, is
sodium and potassium rich on the surface and alkali metal is a
disadvantage in semiconductor device operation and fabrication, for
example, TFT manufacturing. Free alkali metal ions can contaminate
typical TFT devices, such as silicon (Si) TFTs, and alkali
containing glass is to be avoided in the typical high temperature
vacuum processing steps used to make inorganic TFTs may allow
transfer of alkali metal ions into the active semi-conductor, which
is detrimental to performance. Traditionally, alkali-free glass has
been used in TFTs as it will not contaminate the silicon, but
alkali-free glass does not have the mechanical reliability of
ion-exchanged glass.
Another possibility is the use of more traditional glasses that are
thermally or chemically hardened, such as soda-lime glass that has
been tempered. However, soda-lime glasses have high levels of
alkali metals as well and therefore use of these materials may also
result in contamination of TFT devices.
It has now unexpectedly been discovered that semiconductor devices,
for example, organic TFTs can be directly fabricated onto a
mechanically durable strengthened glass, for example, an
ion-exchanged substrate, with no barrier layer present. Embodiments
described herein may provide one or more of the following
advantages: provide a practical way to fabricate organic TFTs and
circuits on strengthened glass, including ion-exchanged and
tempered glass substrates; provide a means of using strengthened
glass, for example, ion-exchanged or tempered glass as suitable
substrates for display backplanes; allow the fabrication of
electronic devices on strengthened glass, for example,
ion-exchanged or tempered glasses without changing the superior
compression strength of the glass; and/or provide an improved
method with decreased cost since the removal of the barrier layer
allows for a thinner device with less production steps.
A first embodiment comprises an article comprising: a strengthened
glass substrate having a first surface and a second surface and
having a Vickers crack initiation threshold of at least 7 kgf; an
organic semiconductor layer having a first surface and a second
surface; a dielectric layer having a first surface and a second
surface; and at least one electrode; wherein the article does not
contain a barrier layer. In some embodiments, the at least one
electrode comprises a gate electrode, a drain electrode, and a
source electrode. In some embodiments, the at least one electrode
comprises a metal, conducting metal oxide film, conducting metal
nanoparticulate ink, or conductive polymer. In some embodiments,
the organic semiconductor layer comprises a semiconducting small
molecule, semiconducting oligomer, or semiconducting polymer. In
some embodiments, the dielectric layer comprises an organic or
inorganic material that may be applied as a film at a temperature
less than about 250.degree. C. In some embodiments, the
strengthened glass comprises an ion-exchanged glass. In some
embodiments, the strengthened glass comprises tempered glass. In
some embodiments, the glass is an aluminoborosilicate,
alkalialuminoborosilicate, aluminosilicate, alkalialuminosilicate,
or soda lime glass. In some embodiments, the article comprises a
thin film transistor, photovoltaic device, diode, or display
device.
In some embodiments, the article further comprises a functional
layer on the surface opposite of the organic semiconductor layer
and dielectric layer of the strengthened glass substrate, wherein
the functional layer is selected from an anti-glare layer, an
anti-smudge layer, a self-cleaning layer, an anti-reflection layer,
an anti-fingerprint layer, an optically scattering layer,
anti-splintering, and combinations thereof.
Another embodiment comprises a thin film transistor comprising: a
strengthened glass substrate having a first surface and a second
surface and having a Vickers crack initiation threshold of at least
7 kgf; an organic semiconductor layer having a first surface and a
second surface; a dielectric layer having a first surface and a
second surface; and at least one electrode; wherein the article
does not contain a barrier layer. In some embodiments, the at least
one electrode comprises a gate electrode, a drain electrode, and a
source electrode. In some embodiments, the at least on electrode
comprises a metal, conducting metal oxide film, conducting metal
nanoparticulate ink, or conductive polymer. In some embodiments,
the organic semiconductor layer comprises a semiconducting small
molecule, semiconducting oligomer, or semiconducting polymer. In
some embodiments, the dielectric layer comprises an organic or
inorganic material that may be applied as a film at a temperature
less than about 250.degree. C. In some embodiments, the
strengthened glass comprises an ion-exchanged glass.
In some embodiments, the thin film transistor further comprises a
functional layer on the surface opposite of the organic
semiconductor layer and dielectric layer of the strengthened glass
substrate, wherein the functional layer is selected from an
anti-glare layer, an anti-smudge layer, a self-cleaning layer, an
anti-reflection layer, an anti-fingerprint layer, an optically
scattering layer, an anti-splintering layer, and combinations
thereof.
In some embodiments, the thin film transistor comprises a
bottom-gate top-contact design. In some embodiments, the thin film
transistor comprises a bottom-gate bottom-contact design. In some
embodiments, the thin film transistor comprises a top-gate
top-contact design. In some embodiments, the thin film transistor
comprises a top-gate bottom-contact design.
Another embodiment comprises a method of forming an article
comprising: providing a strengthened glass substrate having a first
surface and a second surface and having a Vickers crack initiation
threshold of at least 7 kgf; providing an organic semiconductor
layer; providing a dielectric layer; and providing at least one
electrode; wherein the article does not contain a barrier layer. In
some embodiments, the providing an organic semiconductor layer
comprises coating the strengthened glass substrate with the organic
semiconductor layer and coating the organic semiconductor layer
with the dielectric layer. In some embodiments, the providing a
dielectric layer comprises coating the strengthened glass substrate
with the dielectric layer and coating the dielectric layer with the
organic semiconductor layer.
In some embodiments, coating comprises spin casting, doctor
blading, dip-coating, drop casting or various printing methods,
such as ink jet printing, slot die printing and gravure
printing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view illustration of a bottom-gate top-contact
(BG-TC) transistor based device wherein 38 is the drain electrode,
40 is the source electrode, 32 is the gate electrode, 34 is the
dielectric layer, 10 is the ion-exchanged glass substrate, and 36
is the organic semiconductor layer.
FIG. 2 is a side view illustration of a bottom-gate bottom-contact
(BG-BC) transistor based device wherein 38 is the drain electrode,
40 is the source electrode, 32 is the gate electrode, 34 is the
dielectric layer, 10 is the ion-exchanged glass substrate, and 36
is the organic semiconductor layer.
FIG. 3 is a side view illustration of a top-gate bottom-contact
(TG-BC) transistor based device wherein 38 is the drain electrode,
40 is the source electrode, 32 is the gate electrode, 34 is the
dielectric layer, 10 is the ion-exchanged glass substrate, and 36
is the organic semiconductor layer.
FIG. 4 is a side view illustration of a top-gate top-contact
(TG-TC) transistor based device wherein 38 is the drain electrode,
40 is the source electrode, 32 is the gate electrode, 34 is the
dielectric layer, 10 is the ion-exchanged glass substrate, and 36
is the organic semiconductor layer.
FIG. 5 is a transfer curve of a fabricated BG-TC organic TFT
comprising a thiophene copolymer
poly[(3,7-diheptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophen-
e-2,6-diyl)(2,2'-bithiophene-5,5'-diyl)] (P2TDC17FT4) on a polymer
dielectric layer. Based on the curve, it was determined that the
field-effect hole mobility of the device was 0.03 cm.sup.2Vs, the
on/off ration was 5.times.10.sup.3-1.times.10.sup.4, and the
threshold voltage was -2.5 V.
FIG. 6 is a transfer curve of a TG-TC organic TFT comprising
poly[(3,7-diheptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophen-
e-2,6-diyl)(2,2'-bithiophene-5,5'-diyl)] (P2TDC17FT4) organic
semiconductor in contact with the ion exchange glass substrate. The
dielectric layer is a PVP-co-PMMA polymer. The measured transfer
curve of the device reveals a field effect hole mobility of 0.02
cm.sup.2/Vs, an on/off ratio of 700, and a threshold voltage of 5
V.
FIG. 7 shows the synthesis of two possible organic semiconductor
polymers that may be used in embodiments. FIG. 7A describes the
synthesis of a fused thiophene-iosindigo polymer and FIG. 7B
describes the synthesis of a stilbene-fused thiophene polymer.
FIG. 8 shows the synthesis of two possible organic semiconductor
polymers that may be used in embodiments. FIG. 8A describes the
synthesis of a fused thiophene-diketopyrrolopyrrole polymer and
FIG. 8B describes the synthesis of a bithiophene-fused thiophene
polymer. Where R=n-heptadecyl FIG. 8B shows the synthesis of
P2TDC17FT4.
DETAILED DESCRIPTION
The present embodiments can be understood more readily by reference
to the following detailed description, drawings, examples, and
claims, and their previous and following description. However,
before the present compositions, articles, devices, and methods are
disclosed and described, it is to be understood that this
description is not limited to the specific compositions, articles,
devices, and methods disclosed unless otherwise specified, as such
can, of course, vary. It is also to be understood that the
terminology used herein is for the purpose of describing particular
aspects only and is not intended to be limiting.
The following description is provided as an enabling teaching. To
this end, those skilled in the relevant art will recognize and
appreciate that many changes can be made to the various embodiments
described herein, while still obtaining the beneficial results. It
will also be apparent that some of the desired benefits can be
obtained by selecting some of the features without utilizing other
features. Accordingly, those who work in the art will recognize
that many modifications and adaptations to the present embodiments
are possible and can even be desirable in certain circumstances and
are a part of the present description. Thus, the following
description is provided as illustrative and should not be construed
as limiting.
Disclosed are materials, compounds, compositions, and components
that can be used for, can be used in conjunction with, can be used
in preparation for, or are embodiments of the disclosed method and
compositions. These and other materials are disclosed herein, and
it is understood that when combinations, subsets, interactions,
groups, etc. of these materials are disclosed that while specific
reference of each various individual and collective combinations
and permutation of these compounds may not be explicitly disclosed,
each is specifically contemplated and described herein. Thus, if a
class of substituents A, B, and C are disclosed as well as a class
of substituents D, E, and F, and an example of a combination
embodiment, A-D is disclosed, then each is individually and
collectively contemplated. Thus, in this example, each of the
combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are
specifically contemplated and should be considered disclosed from
disclosure of A, B, and C; D, E, and F; and the example combination
A-D. Likewise, any subset or combination of these is also
specifically contemplated and disclosed. Thus, for example, the
sub-group of A-E, B-F, and C-E are specifically contemplated and
should be considered disclosed from disclosure of A, B, and C; D,
E, and F; and the example combination A-D. This concept applies to
all aspects of this disclosure including, but not limited to any
components of the compositions and steps in methods of making and
using the disclosed compositions. Thus, if there are a variety of
additional steps that can be performed it is understood that each
of these additional steps can be performed with any specific
embodiment or combination of embodiments of the disclosed methods,
and that each such combination is specifically contemplated and
should be considered disclosed.
In this specification and in the claims which follow, reference
will be made to a number of terms which shall be defined to have
the meanings detailed herein.
"Include," "includes," or like terms means encompassing but not
limited to, that is, inclusive and not exclusive.
The term "about" references all terms in the range unless otherwise
stated. For example, about 1, 2, or 3 is equivalent to about 1,
about 2, or about 3, and further comprises from about 1-3, from
about 1-2, and from about 2-3. Specific and preferred values
disclosed for compositions, components, ingredients, additives, and
like aspects, and ranges thereof, are for illustration only; they
do not exclude other defined values or other values within defined
ranges. The compositions and methods of the disclosure include
those having any value or any combination of the values, specific
values, more specific values, and preferred values described
herein.
The indefinite article "a" or "an" and its corresponding definite
article "the" as used herein means at least one, or one or more,
unless specified otherwise
As used herein, the term "substrate" can be used to describe either
a substrate or a superstrate depending on the configuration of the
device. For example, the substrate is a superstrate, if when
assembled into, for example, a photovoltaic cell, it is on the
light incident side of a photovoltaic cell. The superstrate can
provide protection for the photovoltaic materials from impact and
environmental degradation while allowing transmission of the
appropriate wavelengths of the solar spectrum. Further, multiple
photovoltaic cells can be arranged into a photovoltaic module.
Photovoltaic device can describe a cell, a module, or both.
As used herein, the term "adjacent" can be defined as being in
close proximity. Adjacent structures may or may not be in physical
contact with each other. Adjacent structures can have other layers
and/or structures disposed between them.
In a first aspect, embodiments comprise an article comprising: a
strengthened glass substrate having a first surface and a second
surface and having a Vickers crack initiation threshold of at least
7 kgf; an organic semiconductor layer having a first surface and a
second surface; a dielectric layer having a first surface and a
second surface; and at least one electrode; wherein the article
does not contain a barrier layer.
In some embodiments, the strengthened glass substrate comprises a
glass substrate that has been mechanically, thermally, or
chemically modified to increase the strength of the glass.
In one embodiment, the strengthened glass substrate is an
ion-exchanged glass substrate. Ion-exchange is widely used to
chemically strengthen glass articles for such applications. In this
process, a glass article containing a first metal ion (e.g., alkali
cations in Li.sub.2O, Na.sub.2O, etc.) is at least partially
immersed in or otherwise contacted with an ion-exchange bath or
medium containing a second metal ion that is either larger or
smaller than the first metal ion that is present in the glass. The
first metal ions diffuse from the glass surface into the
ion-exchange bath/medium while the second metal ions from the
ion-exchange bath/medium replace the first metal ions in the glass
to a depth of layer below the surface of the glass. The
substitution of larger ions for smaller ions in the glass creates a
compressive stress at the glass surface, whereas substitution of
smaller ions for larger ions in the glass typically creates a
tensile stress at the surface of the glass. In some embodiments,
the first metal ion and second metal ion are monovalent alkali
metal ions. However, other monovalent metal ions such as Ag.sup.+,
Tl.sup.+, Cu.sup.+, and the like may also be used in the
ion-exchange process.
In one embodiment, the strengthened glass substrate comprises a
strengthened glass wherein the glass is ion-exchanged to a depth of
layer of at least 20 .mu.m from a surface of the glass. In another
embodiment, the strengthened glass substrates described herein,
when chemically strengthened by ion-exchange, exhibit a Vickers
initiation cracking threshold of at least about 5 kgf (kilogram
force), in some embodiments, at least about 5, 6, 7, 8, 9, 10, 11,
12, 13, 14, 15, 16, 17, 18, 19, or 20 kgf. In some embodiments, the
strengthened glass substrates described herein, when chemically
strengthened by ion-exchange, exhibit a Vickers initiation cracking
threshold of from about 5 kgf to about 50 kgf, about 5 kgf to about
40 kgf, about 5 kgf to about 30 kgf, about 5 kgf to about 20 kgf,
about 7 kgf to about 50 kgf, about 7 kgf to about 40 kgf, about 7
kgf to about 30 kgf, about 7 kgf to about 20 kgf, about 10 kgf to
about 50 kgf, about 10 kgf to about 40 kgf, or about 10 kgf to
about 30 kgf.
In some embodiments, the strengthened glass substrate comprises an
alkali containing glass. In some embodiments, the strengthened
glass substrate comprises an aluminoborosilicate, an
alkalialuminoborosilicate, an aluminosilicate, an
alkalialuminosilicate, or a soda lime glass. In some embodiments,
the glass comprises an ion exchanged glass as described in U.S.
Prov. Appl. Nos. 61/560,434, 61/653,489, and 61/653,485, and U.S.
application Ser. Nos. 12/858,490, 12/277,573, 13/588,581,
11/888,213, 13/403,756, 12/392,577, 13/346,235, 13/495,355,
12/858,490, 13/533,298, 13/291,533, and 13/305,271, all of which
are hereby incorporated by reference in their entirety.
According to some embodiments, the strengthened glass substrate has
a thickness of 4.0 mm or less, for example, 3.5 mm or less, for
example, 3.2 mm or less, for example, 3.0 mm or less, for example,
2.5 mm or less, for example, 2.0 mm or less, for example, 1.9 mm or
less, for example, 1.8 mm or less, for example, 1.5 mm or less, for
example, 1.1 mm or less, for example, about 0.05 mm to about 2.0
mm, for example, about 0.05 mm to about 1.1 mm, for example, about
0.1 mm to about 1.1 mm. Although these are exemplary thicknesses,
the strengthened glass substrate can have a thickness of any
numerical value including decimal places in the range of from about
0.040 mm up to and including 4.0 mm.
In some embodiments, the organic semiconductor layer comprises
semiconducting small molecules, oligomers and/or polymers.
Semiconducting small molecules include the polycyclic aromatic
compounds, such as pentacene, anthracene, and rubrene and other
conjugated aromatic hydrocarbons. Polymeric organic semiconductors
include, for example, poly(3-hexylthiophene), poly(p-phenylene
vinylene), as well as polyacetylene and its derivatives. Generally
speaking, there are two major overlapping classes of organic
semiconductors--organic charge-transfer complexes and various
linear-backbone conductive polymers derived from polyacetylene and
similar compounds, such as polypyrrole, and polyaniline. However,
embodiments are not limited in scope to only these types of organic
semiconductors, and, as shown in the examples, are capable of
working with a broad range of organic semiconductors.
In some embodiments, the organic semiconductor layer comprises a
fused thiophene compound. In some embodiments, the fused thiophene
is incorporated into a polymer. Fused thiophenes and fused
thiophene polymers may comprise compounds as described in U.S. Pat.
Nos. 7,705,108, 7,838,623, 7,893,191, 7,919,634, 8,217,183,
8,278,346, U.S. application Ser. Nos. 12/905,667, 12/907,453,
12/935,426, 13/093,279, 13/036,269, 13/660,637, 13/660,529, and
U.S. Prov. Appl. Nos. 61/617,202, and 61/693,448, all herein
incorporated by reference in their entireties.
Particular examples of fused thiophene compounds that may be used
include, but are not limited to,
poly[(3,7-diheptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophen-
e-2,6-diyl)(2,2'-bithiophene)-5,5'-diyl],
poly[(3,7-diheptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophen-
e-2,6-diyl)(2,5-dihexadecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4-
(2H,5H)-dione)-5,5'-diyl], poly-3,6-dihexylthieno[3,2-b]thiophene
(PDC6FT2), poly-3,6-didecanylthieno[3,2-b]thiophene,
poly[(3,7-diheptadecylthieno[3.2-b]thieno[2',3':4,5]thieno[2,3-d]thiophen-
e-2,6-diyl)(1-hexadecyl-3-(1-hexadecyl-2-oxoindol-3-ylidene)indol-2-one-6,-
6'-diyl)], and
poly[(3,7-diheptadecylthieno[3.2-b]thieno[2',3':4,5]thieno[2,3-d]thiophen-
e-2,6-diyl)(stilbene-1,4'-diyl)]. Additional examples of fused
thiophene-based polymers are described in FIG. 7 and FIG. 8,
wherein FIG. 7A shows a fused thiophene-iosindigo polymer and FIG.
7B describes a fused thiophene-stilbene polymer. Similarly, FIG. 8A
shows a fused thiophene-diketopyrrolopyrrole polymer and FIG. 8B
shows a bithiophene-fused thiophene polymer.
In some embodiments, the organic semiconductor layer may comprise
one or more electroluminescent organic compounds. In some
embodiments, the semiconducting small molecules, oligomers and/or
polymers of the semiconductor layer may comprise electroluminescent
organic compounds.
In some embodiments, the organic semiconductor layer is formed by
such processes as dip coating, spin coating, Langmuir-Blodgett
deposition, electrospray ionization, direct nanoparticle
deposition, vapor deposition, chemical deposition, spray
deposition, screen printing, nano-imprint lithography, gravure
printing, doctor blading, spray-coating, slot die coating, ink jet
printing, laser deposition, drop casting or chemical etching.
In some embodiments, the dielectric layer comprises any organic or
inorganic material that is able to be applied as a film at or below
200.degree. C. Examples of dielectrics that may be used in
embodiments include polymers, glasses, and inorganic or organic
materials. The dielectric layer may be formed by, for example, such
processes as sputter coating, atomic layer deposition, dip coating,
spin coating, Langmuir-Blodgett deposition, electrospray
ionization, direct nanoparticle deposition, vapor deposition,
chemical deposition, vacuum filtration, flame spray, electrospray,
spray deposition, electrodeposition, screen printing, close space
sublimation, nano-imprint lithography, in situ growth, microwave
assisted chemical vapor deposition, laser ablation, arc discharge,
gravure printing, doctor blading, spray-coating, slot die coating,
or chemical etching.
In some embodiments, the electrode comprises gate, drain, and
source electrodes. Electrodes can comprise any conducting
material--including for example, metals, conducting semi-metals, or
conducting non-metals. For example, in some embodiments, an
electrode may comprise a metal or combination of metals in the form
of a coating, wire, sheet, ribbon, micro- or nanoparticle, or mesh.
Electrodes may be formed via such processes as sputter coating,
atomic layer deposition, dip coating, spin coating,
Langmuir-Blodgett deposition, electrospray ionization, direct
nanoparticle deposition, vapor deposition, chemical deposition,
vacuum filtration, flame spray, electrospray, spray deposition,
electrodeposition, screen printing, close space sublimation,
nano-imprint lithography, in situ growth, microwave assisted
chemical vapor deposition, laser ablation, arc discharge, gravure
printing, doctor blading, spray-coating, slot die coating, or
chemical etching.
Embodiments do not include a barrier layer. As used herein, a
barrier layer consists of a material positioned between the
strengthened glass substrate and the organic semiconductor layer or
the source electrode that prevents ion migration. In some
embodiments, for example BG-TC and BG-BC type transistors, there
may exist a dielectric layer between the organic semiconductor
layer and the ion exchanged glass substrate, but no barrier layer
between the gate electrode and the ion exchanged glass substrate.
In some embodiments, for example TG-TC and TG-BC type transistors,
there is no barrier layer or dielectric layer between the organic
semiconductor layer and the ion exchanged glass substrate.
Traditionally, aluminum oxide and silicon nitride have been used as
barrier layers in thin film transistors and other electronic
devices.
In some embodiments, the article further comprises an anti-glare
layer, an anti-smudge layer, a self-cleaning layer, an
anti-reflection layer, an anti-fingerprint layer, an optically
scattering layer, an anti-splintering layer, and combinations
thereof. Such layers may be incorporated through any number of
known processes, such as those disclosed in U.S. Patent Publ. Nos.
2011/0129665, 2009/0197048, 2009/0002821, 2011/0267697,
2011/0017287, or 2011/0240064, herein incorporated by
reference.
In another aspect, an embodiment of an article is an organic thin
film transistor. An organic TFT device can include: an
ion-exchanged glass substrate including the barrier layer. On the
barrier layer a gate electrode, a dielectric layer, a drain
electrode, a source electrode, and an organic semiconducting
channel layer can be formed. These layers can be stacked in
different sequences to form a laterally or vertically configured
transistor device. The organic semiconducting channel layer
includes semiconducting small molecules, oligomers and/or polymers.
The dielectric layer can be composed of any organic or inorganic
material that is able to be applied as a film at or below
200.degree. C. In this way, a mechanically durable backplane is
produced.
FIGS. 1-4 illustrate embodiments of articles comprising TFT
devices. As used herein, the term "bottom-gate top-contact
transistor" refers to a TFT device comprising an exemplary
structure as shown in FIG. 1. A gate electrode 32 is deposited on a
strengthened glass substrate, or ion-exchanged glass substrate 10
(according to any of the previously described embodiments) followed
by a dielectric layer 34 and then a semiconducting layer 36. Drain
and source electrodes 38 and 40, respectively, are further
deposited on top of the semiconducting layer 36.
The term "bottom-gate bottom-contact transistor" refers to a TFT
device comprising an exemplary structure as shown in FIG. 2. A gate
electrode 32 is deposited on a strengthened glass substrate, or
ion-exchanged glass substrate 10 followed by a dielectric layer 34
and then drain and source electrodes 38 and 40, respectively. A
semiconducting layer 36 is further deposited on top of these
underlying layers.
The term "top-gate bottom-contact transistor" refers to a TFT
device comprising an exemplary structure as shown in FIG. 3. Drain
and source electrodes 38 and 40, respectively are deposited on a
strengthened glass or ion-exchanged glass substrate 10 (according
to any of the previously described embodiments). A semiconducting
layer 36 is then deposited on top, followed by a dielectric layer
34 and then a gate electrode 32.
The term "top-gate top-contact transistor" refers to a TFT device
comprising an exemplary structure as shown in FIG. 6. A
semiconducting layer 36 is deposited on a strengthened glass
substrate, or ion-exchanged glass substrate 10 followed by drain
and source electrodes 38 and 40, respectively. A dielectric layer
34 is further deposited on top, followed by a gate electrode
32.
Another aspect comprises methods of forming embodiments,
comprising: providing a strengthened glass substrate having a first
surface and a second surface and having a Vickers crack initiation
threshold of at least 20 kgf; providing an organic semiconductor
layer; providing a dielectric layer; and providing at least one
electrode; wherein the article does not contain a barrier layer. As
noted above, it is possible via a number of processes, all
incorporated herein, to provide the various elements described. In
some embodiments, providing an organic semiconductor layer
comprises coating the strengthened glass substrate with the organic
semiconductor layer and coating the organic semiconductor layer
with the dielectric layer. In some embodiments, providing a
dielectric layer comprises coating the strengthened glass substrate
with the dielectric layer and coating the dielectric layer with the
organic semiconductor layer.
EXAMPLES
Example 1
Organic Bottom-Gate, Top-Contact Thin Film Transistors on Ion
Exchange Glass
Ion exchanged glass substrates were cleaned by using sonication in
acetone and then isopropanol. The 30 nm thick Au gate electrode was
deposited on the substrate by thermal evaporation of Au at 2
.ANG./s. The dielectric comprised a mixture of 11 wt % (film
thickness approximately 800 nm-1 .mu.m) PVP solution in PGMEA and
melamine, which was spin-cast onto the substrate at 1000 rpm for 30
seconds. This dielectric was cured via UV irradiation for
approximately 3 minutes. Then, 3 mg/mL of a semiconducting polymer
Poly[(3,7-diheptadecylthieno[3,2-b]thieno[2,3':4,5]thieno[2,3-d]thiophene-
-2,6-diyl)(2,2'-bithiophene)-5,5'-diyl] (P2TDC17FT4) dissolved in
1,2-dichlorobenzene was spin-coated onto the substrate. The device
was annealed at 100.degree. C. for 30 minutes on a hotplate.
Finally, 30 nm thick Au source and drain electrodes were deposited
by thermal evaporation of Au at 2 .ANG./s. The transfer curve (FIG.
5) of fabricated organic TFT device reveals a field-effect hole
mobility of 0.03 cm.sup.2/Vs, an on/off ratio of
5.times.10.sup.3-1.times.10.sup.4, and a threshold voltage of -2.5
V.
Example 2
Organic Top-Gate, Top-Contact Thin Film Transistors on Ion Exchange
Glass
Ion exchanged glass was cleaned by deionized water, followed by
sonication in toluene, and then acetone, and 2-propanol. Glass
substrates were then placed in a UV-Ozone cleaner for 10 mins and
subsequently exposed to a surface treatment of octyltrichlorosilane
vapor for 30 minutes. The organic semiconductor
Poly[(3,7-diheptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophen-
e-2,6-diyl)(2,5-dihexadecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4-
(2H,5H)-dione)-5,5'-diyl] (PTDC16DPPTDC17FT4) was spin cast onto
the cleaned substrates at 1000 rpm for 60 seconds, then annealed at
130.degree. C. on a hotplate for approximately 30 minutes. After
annealing, 30 nm thick Au source and drain electrodes were
deposited by thermal evaporation of Au at a rate of 2.5 .ANG./s.
Next, 2 ml of 5 wt % PVP-co-PMMA with melamine (weight ratio of
PVP-co-PMMA: melamine=10:1) solution in PGMEA solvent was spin cast
onto the substrate at 1000 rpm for 60 seconds, placed on a hotplate
at 120.degree. C. for 2 minutes to remove solvent, and cured under
UV light to cross-link the dielectric film 50 nm Au gate electrodes
were then thermally deposited at 2.5 .ANG./s. The measured transfer
curve of the device (FIG. 6) reveals a field-effect hole mobility
of 0.02 cm.sup.2/Vs, an on/off ratio of 700, and a threshold
voltage of -5 V.
* * * * *