U.S. patent application number 15/169119 was filed with the patent office on 2017-05-18 for electronic device including phosphine oxide functionalized triazine derivative and novel phosphine oxide functionalized triazine derivative.
The applicant listed for this patent is PUSAN NATIONAL UNIVERSITY INDUSTRY-UNIVERSITY COOPERATION FOUNDATION. Invention is credited to Sung Ho Jin.
Application Number | 20170141324 15/169119 |
Document ID | / |
Family ID | 57528989 |
Filed Date | 2017-05-18 |
United States Patent
Application |
20170141324 |
Kind Code |
A1 |
Jin; Sung Ho |
May 18, 2017 |
ELECTRONIC DEVICE INCLUDING PHOSPHINE OXIDE FUNCTIONALIZED TRIAZINE
DERIVATIVE AND NOVEL PHOSPHINE OXIDE FUNCTIONALIZED TRIAZINE
DERIVATIVE
Abstract
Provided are an electronic device including a novel structured
interface material capable of improving interface properties of the
electronic device, and the novel interface material, and more
specifically, an electronic device including the interface material
of the present disclosure to allow easy extraction and injection of
electrons, thereby exhibiting excellent interface properties, and a
phosphine oxide functionalized triazine derivative having a
structure in which an electron acceptor phosphine oxide group is
substituted in 1,3,5-triazine-based skeleton, which is the
interface material.
Inventors: |
Jin; Sung Ho; (Busan,
KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PUSAN NATIONAL UNIVERSITY INDUSTRY-UNIVERSITY COOPERATION
FOUNDATION |
Busan |
|
KR |
|
|
Family ID: |
57528989 |
Appl. No.: |
15/169119 |
Filed: |
May 31, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/0558 20130101;
H01L 51/4246 20130101; H01L 51/10 20130101; H01L 51/4253 20130101;
C07F 9/6521 20130101; H01L 51/0036 20130101; H01L 51/0037 20130101;
H01L 51/0043 20130101; Y02E 10/549 20130101; C07F 9/65586 20130101;
H01L 51/424 20130101; H01L 51/0047 20130101; H01L 51/0067 20130101;
C07D 251/30 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C07F 9/6521 20060101 C07F009/6521 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 18, 2015 |
KR |
10-2015-0161609 |
Claims
1. An electronic device comprising: a phosphine oxide
functionalized triazine represented by Chemical Formula 1 below as
an interface material: ##STR00036## in Chemical Formula 1, Ar.sup.1
and Ar.sup.2 are each independently (C6-C20)aryl unsubstituted or
substituted with fluorine; L is (C6-C20)arylene substituted with at
least one fluorine; Ar.sup.3 and Ar.sup.4 are each independently
(C1-C20)alkyl, (C6-C20)aryl, or (C3-C20)heteroaryl, wherein the
alkyl, aryl, or heteroaryl of Ar.sup.3 and Ar.sup.4 may be further
substituted with at least one selected from (C1-C20)alkyl,
halo(C1-C20)alkyl, (C1-C20)alkoxy, and halo(C1-C20)alkoxy; and the
heteroaryl includes at least one heteroatom selected from N, O, and
S, wherein the electronic device is at least one selected from an
organic solar cell, a perovskite solar cell, an organic
field-effect transistor, and an organic thin film transistor.
2. (canceled)
3. The electronic device of claim 1, wherein L is (C6-C20)arylene
substituted with at least two fluorines.
4. The electronic device of claim 1, wherein Ar.sup.1 and Ar.sup.2
are each independently phenyl, biphenyl, naphthyl, anthryl,
phenanthryl, tetracenyl, pyrenyl, or perylenyl, the phenyl,
biphenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl, or
perylenyl of Ar.sup.1 and Ar.sup.2 may be further substituted with
at least one fluorine; Ar.sup.3 and Ar.sup.4 are each independently
methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl,
biphenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl,
perylenyl, furyl, thienyl, pyridyl, thiazolyl, oxazolyl, quinolyl,
indolyl, pyrimidyl, or pyrazinyl, the methyl, ethyl, propyl, butyl,
pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, naphthyl, anthryl,
phenanthryl, tetracenyl, pyrenyl, perylenyl, furyl, thienyl,
pyridyl, thiazolyl, oxazolyl, quinolyl, indolyl, pyrimidyl, or
pyrazinyl of Ar.sup.3 and Ar.sup.4 may be further substituted with
at least one selected from methyl, ethyl, propyl, butyl,
trifluoromethyl, perfluoroethyl, methoxy, trifluoromethoxy, and
perfluoroethoxy.
5. The electronic device of claim 3, wherein L is phenylene,
biphenylene, naphthylene, anthrylene, phenanthrylene,
tetracenylene, pyrenylene, or perylenylene substituted with at
least two fluorines.
6. The electronic device of claim 5, wherein the phosphine oxide
functionalized triazine is represented by Chemical Formulas 2 to 4
below: ##STR00037## in Chemical Formulas 2 to 4, a and b are each
independently an integer from 0 to 5; n is an integer from 2 to 4;
R.sup.11 and R.sup.12 are each independently (C1-C20)alkyl,
halo(C1-C20)alkyl, (C1-C20)alkoxy, or halo(C1-C20)alkoxy; x and y
are each independently an integer from 0 to 5; X and Y are each
independently NH, O, or S; R.sup.13 and R.sup.14 are each
independently hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, or halo(C1-C20)alkoxy; R.sup.15 and R.sup.16 are
each independently (C1-C20)alkyl, the alkyl of R.sup.15 and
R.sup.16 may be further substituted with at least one selected from
(C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, and
halo(C1-C20)alkoxy.
7. The electronic device of claim 6, wherein the phosphine oxide
functionalized triazine is selected from the following compounds:
##STR00038## ##STR00039## ##STR00040## ##STR00041##
8. A phosphine oxide functionalized triazine represented by
Chemical Formula 1 below: ##STR00042## in Chemical Formula 1,
Ar.sup.1 and Ar.sup.2 are each independently (C6-C20)aryl
unsubstituted or substituted with fluorine; L is (C6-C20)arylene
substituted with at least one fluorine; and Ar.sup.3 and Ar.sup.4
are each independently (C1-C20)alkyl, (C6-C20)aryl, or
(C3-C20)heteroaryl, wherein the alkyl, aryl or heteroaryl of
Ar.sup.3 and Ar.sup.4 may be further substituted with at least one
selected from (C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, and
halo(C1-C20)alkoxy.
Description
INCORPORATION BY REFERENCE TO RELATED APPLICATIONS
[0001] Any and all priority claims identified in the Application
Data Sheet, or any correction thereto, are hereby incorporated by
reference under 37 CFR 1.57. This application claims the benefit of
Korean Patent Application No. 10-2015-0161609, filed on Nov. 18,
2015. The aforementioned application is incorporated by reference
herein in its entirety, and is hereby expressly made a part of this
specification.
TECHNICAL FIELD
[0002] The following disclosure relates to an electronic device
using a novel phosphine oxide functionalized triazine derivative,
and the novel phosphine oxide functionalized triazine
derivative.
BACKGROUND
[0003] A solar cell technology is to directly convert light, that
is, solar energy into electric energy by utilizing a photovoltaic
effect, and most commercialized solar cells are inorganic solar
cells using inorganic materials such as silicon, etc. However, the
inorganic solar cells have disadvantages in that manufacturing cost
is increased due to a complicated manufacturing process, and
high-priced materials are required, and accordingly, research into
a dye-sensitized solar cell and an organic solar cell manufactured
with low cost through a relatively simple manufacturing process and
with low-priced materials has been actively conducted.
[0004] The organic solar cell has been expected to be a low-priced
solar cell in the future since it is capable of being manufactured
with simple manufacturing processes and low installation expenses
as compared to conventional silicon or compound semiconductor solar
cells. A number of materials, structures, etc., of the organic
solar cell have currently researched to improve efficiency of solar
cells. Among them, a bulk heterojunction structure using mixture of
electron donors and electron acceptors is known to have the highest
efficiency.
[0005] However, in the bulk heterojunction structure, a diffusion
distance of excitons which are electron-hole pairs formed by
electron donors such as conductive polymers, etc., by sun light is
only about 10 nm in the polymer. Accordingly, when the excitons do
not reach interfaces of the electron donors and the electron
acceptors within this distance, they reunite again and become
extinct. In addition, after the excitons are separated into
electrons and holes at the interfaces of the electron donors and
the electron acceptors, the respective electrons and holes move
toward a metal electrode and a transparent electrode, respectively.
To this end, it is required that all of the electron donors are
linked to be in contact with an anode, and all of the electron
acceptors are linked to be in contact with a cathode while having a
co-continuous structure. However, the structures of the electron
donors and the electron acceptors may not be artificially
determined, but depend on phase separation properties after mixing
materials, and accordingly, it is not possible to obtain the ideal
structure.
[0006] To obtain facilitate electron injection in the modern
optoelectronic devices such as the organic solar cell, the
incorporation of solution processed interfacial layers on stable
metal electrodes has been widely used. The appropriate choice of
interface materials administer a platform to carefully regulate the
electrode work function (WF), protect the semiconductor layer from
the diffusion of electrodes, mitigate the charge accumulation and
recombination at the electrodes.
[0007] In order to improve the interface properties, CsF, LiF,
Cs.sub.2CO.sub.3, conjugated or non-conjugated polymer
electrolytes, fullerene derivatives, etc., are used. However, this
method has problems in that an effect for improving interface
properties is not significant, reactivity with air and water is
high, synthesis and purification methods are complicated,
reproducibility in batches is low, and only a deposition via
expensive vacuum deposition is applicable, and further, it is
difficult to apply a solution process in manufacturing a large area
device.
[0008] Documents related to solar cell technology include Korean
Patent Laid-Open Publication No. 10-2014-0112494; Adv. Funct.
Mater. 20, 4381-4387 (2010); Adv. Energy Mater. 2, 532-535 (2012);
Adv. Mater. 21, 759-763 (2009); and Adv. Energy Mater. 5, 1401692
(2015).
SUMMARY
[0009] An embodiment of the present disclosure is directed to
providing an electronic device including a novel phosphine oxide
functionalized triazine derivative.
[0010] Accordingly, in a generally applicable first aspect (i.e.,
independently combinable with any of the aspects or embodiments
identified herein), there is provided an electronic device
including a phosphine oxide functionalized triazine derivative
represented by Chemical Formula 1 below as an interface
material:
##STR00001##
[0011] in Chemical Formula 1,
[0012] Ar.sup.1 and Ar.sup.2 are each independently selected from
(C6-C20)aryl unsubstituted and (C6-C20)aryl substituted with
fluorine; L is (C6-C20)arylene substituted with at least one
fluorine; Ar.sup.3 and Ar.sup.4 are each independently selected
from (C1-C20)alkyl, (C6-C20)aryl, and (C3-C20)heteroaryl, wherein
the alkyl, aryl, or heteroaryl of Ar.sup.3 and Ar.sup.4 are
optionally substituted with one or more moieties selected from
(C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, and
halo(C1-C20)alkoxy; and wherein the heteroaryl includes at least
one heteroatom selected from N, O, and S.
[0013] In an embodiment of the first aspect (i.e., independently
combinable with any of the aspects or embodiments identified
herein), the electronic device can be selected from an organic
solar cell, a perovskite solar cell, an organic field-effect
transistor, and an organic thin film transistor.
[0014] In an embodiment of the first aspect (i.e., independently
combinable with any of the aspects or embodiments identified
herein), L can be (C6-C20)arylene substituted with at least two
fluorines.
[0015] In an embodiment of the first aspect (i.e., independently
combinable with any of the aspects or embodiments identified
herein), Ar.sup.1 and Ar.sup.2 can each be independently selected
from phenyl, biphenyl, naphthyl, anthryl, phenanthryl, tetracenyl,
pyrenyl, and perylenyl, wherein the phenyl, biphenyl, naphthyl,
anthryl, phenanthryl, tetracenyl, pyrenyl, or perylenyl of Ar.sup.1
and Ar.sup.2 can be optionally substituted with one or more
fluorines; Ar.sup.3 and Ar.sup.4 can each be independently selected
from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,
phenyl, biphenyl, naphthyl, anthryl, phenanthryl, tetracenyl,
pyrenyl, perylenyl, furyl, thienyl, pyridyl, thiazolyl, oxazolyl,
quinolyl, indolyl, pyrimidyl, and pyrazinyl, and wherein the
methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl,
biphenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl,
perylenyl, furyl, thienyl, pyridyl, thiazolyl, oxazolyl, quinolyl,
indolyl, pyrimidyl, or pyrazinyl of Ar.sup.3 and Ar.sup.4 can be
optionally substituted with one or more moieties selected from
methyl, ethyl, propyl, butyl, trifluoromethyl, perfluoroethyl,
methoxy, trifluoromethoxy, and perfluoroethoxy.
[0016] In an embodiment of the first aspect (i.e., independently
combinable with any of the aspects or embodiments identified
herein), L can be selected from phenylene, biphenylene,
naphthylene, anthrylene, phenanthrylene, tetracenylene, pyrenylene,
and perylenylene, wherein L can be substituted with at least two
fluorines.
[0017] In an embodiment of the first aspect (i.e., independently
combinable with any of the aspects or embodiments identified
herein), the phosphine oxide functionalized triazine derivative can
be represented by Chemical Formula 2, Chemical Formula 3, or
Chemical Formula 4:
##STR00002##
[0018] wherein a and b can each independently be an integer from 0
to 5; n can be an integer from 2 to 4; R.sup.11 and R.sup.12 can
each independently be (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, or halo(C1-C20)alkoxy; x and y can each
independently be an integer from 0 to 5; X and Y can each
independently be selected from NH, O, and S; R.sup.13 and R.sup.14
can each independently be selected from hydrogen, (C1-C20)alkyl,
halo(C1-C20)alkyl, (C1-C20)alkoxy, and halo(C1-C20)alkoxy; R.sup.15
and R.sup.16 can each independently be (C1-C20)alkyl, wherein the
alkyl of R.sup.15 and R.sup.16 can be optionally substituted with
one or more moieties selected from (C1-C20)alkyl,
halo(C1-C20)alkyl, (C1-C20)alkoxy, and halo(C1-C20)alkoxy.
[0019] In an embodiment of the first aspect (i.e., independently
combinable with any of the aspects or embodiments identified
herein), the phosphine oxide functionalized triazine derivative may
be selected from the following compounds, but the present
disclosure is not limited thereto:
##STR00003## ##STR00004## ##STR00005## ##STR00006##
[0020] In addition, another embodiment of the present disclosure is
directed to providing a novel phosphine oxide functionalized
triazine derivative.
[0021] In a generally applicable second aspect (i.e., independently
combinable with any of the aspects or embodiments identified
herein), there is provided a phosphine oxide functionalized
triazine derivative represented by Chemical Formula 1 below:
##STR00007##
[0022] wherein Ar.sup.1 and Ar.sup.2 can each independently be
selected from unsubstituted (C6-C20)aryl and (C6-C20)aryl
substituted with fluorine; L can be (C6-C20)arylene substituted
with at least one fluorine; and Ar.sup.3 and Ar.sup.4 can each
independently be selected from (C1-C20)alkyl, (C6-C20)aryl, and
(C3-C20)heteroaryl, wherein the alkyl, aryl or heteroaryl of
Ar.sup.3 and Ar.sup.4 can be optionally substituted with one or
more moieties selected from (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, and halo(C1-C20)alkoxy.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1 shows TGA result of PO-TAZ prepared by Example 1.
[0024] FIG. 2 shows UV-visible absorption spectrum of PO-TAZ
prepared by Example 1.
[0025] FIG. 3 shows a HOMO LUMO energy level of PO-TAZ prepared by
Example 1.
[0026] FIG. 4 shows a structure of COSC manufactured by Example
18.
[0027] FIG. 5 shows a HOMO LUMO energy level diagram of COSC
manufactured by Example 18.
[0028] FIG. 6 is a curve showing J-V property of COSC manufactured
by Example 18.
[0029] FIG. 7 shows EQE spectra of COSC manufactured by Example
18.
[0030] FIG. 8 shows a structure of IOSC manufactured by Example
19.
[0031] FIG. 9 shows a HOMO LUMO energy level diagram of IOSC
manufactured by Example 19.
[0032] FIG. 10 is a curve showing J-V property of IOSC manufactured
by Example 19.
[0033] FIG. 11 shows EQE spectra of IOSC manufactured by Example
19.
[0034] FIG. 12 shows a structure of PSC manufactured by Example
20.
[0035] FIG. 13 shows a HOMO LUMO energy level diagram of PSC
manufactured by Example 20.
[0036] FIG. 14 is a curve showing J-V property of PSC manufactured
by Example 20.
[0037] FIG. 15 shows EQE spectra of PSC manufactured by Example
20.
[0038] FIG. 16 shows a transfer curve and an out-put curve of a
device manufactured by Example 21.
[0039] FIG. 17 shows a transfer curve and an out-put curve of a
device manufactured by Example 22.
DETAILED DESCRIPTION OF EMBODIMENTS
[0040] Hereinafter, the present disclosure will be described in
detail. Meanwhile, unless technical and scientific terms used
herein are defined otherwise, they have meanings understood by
those skilled in the art to which the present disclosure pertains.
Known functions and components will be omitted so as not to obscure
the description of the present disclosure with unnecessary
detail.
[0041] The present disclosure relates to an electronic device
including a novel structured interface material capable of
improving interface properties of the electronic device, and the
novel interface material, and more specifically, to an electronic
device including the interface material of the present disclosure
to allow easy extraction and injection of electrons, thereby
exhibiting excellent interface properties, and a phosphine oxide
functionalized triazine derivative having a structure in which an
electron acceptor phosphine oxide group is substituted in
1,3,5-triazine-based skeleton.
[0042] In addition, the present disclosure provides an electronic
device including a phosphine oxide functionalized triazine
derivative represented by Chemical Formula 1 below as an interface
material:
##STR00008##
[0043] in Chemical Formula 1,
[0044] Ar.sup.1 and Ar.sup.2 are each independently (C6-C20)aryl
unsubstituted or substituted with fluorine;
[0045] L is (C6-C20)arylene substituted with at least one
fluorine;
[0046] Ar.sup.3 and Ar.sup.4 are each independently (C1-C20)alkyl,
(C6-C20)aryl, or (C3-C20)heteroaryl, wherein the alkyl, aryl, or
heteroaryl of Ar.sup.3 and Ar.sup.4 may be further substituted with
at least one selected from (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, and halo(C1-C20)alkoxy; and
[0047] the heteroaryl includes at least one heteroatom selected
from N, O, and S.
[0048] In an exemplary embodiment of the present disclosure, the
electronic device may be an organic solar cell, a perovskite solar
cell, an organic field-effect transistor, an organic thin film
transistor, etc.
[0049] In an exemplary embodiment of the present disclosure, L may
be preferably (C6-C20)arylene substituted with at least two
fluorines.
[0050] In an exemplary embodiment of the present disclosure,
specifically, Ar.sup.1 and Ar.sup.2 may be each independently
phenyl, biphenyl, naphthyl, anthryl, phenanthryl, tetracenyl,
pyrenyl, or perylenyl, the phenyl, biphenyl, naphthyl, anthryl,
phenanthryl, tetracenyl, pyrenyl, or perylenyl of Ar.sup.1 and
Ar.sup.2 may be further substituted with at least one fluorine;
Ar.sup.3 and Ar.sup.4 may be each independently methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl,
naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl, perylenyl,
furyl, thienyl, pyridyl, thiazolyl, oxazolyl, quinolyl, indolyl,
pyrimidyl, or pyrazinyl, the methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, phenyl, biphenyl, naphthyl, anthryl,
phenanthryl, tetracenyl, pyrenyl, perylenyl, furyl, thienyl,
pyridyl, thiazolyl, oxazolyl, quinolyl, indolyl, pyrimidyl, or
pyrazinyl of Ar.sup.3 and Ar.sup.4 may be further substituted with
at least one selected from methyl, ethyl, propyl, butyl,
trifluoromethyl, perfluoroethyl, methoxy, trifluoromethoxy, and
perfluoroethoxy.
[0051] In an exemplary embodiment of the present disclosure, more
preferably, L may be phenylene, biphenylene, naphthylene,
anthrylene, phenanthrylene, tetracenylene, pyrenylene, or
perylenylene substituted with at least two fluorines.
[0052] In an exemplary embodiment of the present disclosure, the
phosphine oxide functionalized triazine derivative may be more
preferably represented by Chemical Formulas 2 to 4 below:
##STR00009##
[0053] in Chemical Formulas 2 to 4, a and b are each independently
an integer from 0 to 5; n is an integer from 2 to 4; R.sup.11 and
R.sup.12 are each independently (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, or halo(C1-C20)alkoxy; x and y are each
independently an integer from 0 to 5; X and Y are each
independently NH, 0 or S; R.sup.13 and R.sup.14 are each
independently hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, or halo(C1-C20)alkoxy; R.sup.15 and R.sup.16 are
each independently (C1-C20)alkyl, wherein the alkyl of R.sup.15 and
R.sup.16 may be further substituted with at least one selected from
(C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, and
halo(C1-C20)alkoxy.
[0054] In an exemplary embodiment of the present disclosure, the
phosphine oxide functionalized triazine derivative may be selected
from the following compounds, but the present disclosure is not
limited thereto:
##STR00010## ##STR00011## ##STR00012## ##STR00013##
[0055] In an exemplary embodiment of the present disclosure, the
organic/inorganic hybrid perovskite solar cell includes a first
electrode including a conductive transparent substrate; an electron
transport layer formed on the first electrode; a light absorption
layer formed on the electron transport layer; a hole transport
layer formed on the light absorption layer; and a second electrode
formed on the hole transport layer, and further includes an
interlayer including a phosphine oxide functionalized triazine
derivative of the present disclosure between the electron transport
layer and the light absorption layer, but is not limited
thereto.
[0056] The first electrode including the conductive transparent
substrate may be a glass substrate or a plastic substrate including
a transparent electrode formed of at least one material selected
from the group consisting of indium tin oxide (ITO), fluorine tin
oxide (FTC)), ZnO--Ga.sub.2O.sub.3, ZnO--Al.sub.2O.sub.3, and
tin-based oxides.
[0057] The electron transport layer is a metal oxide layer
including metal oxide, wherein the metal oxide may be nanoparticle
oxides such as titanium dioxide (TiO.sub.2), tin dioxide
(SnO.sub.2), zinc oxide (ZnO), etc., but is not limited
thereto.
[0058] The light absorption layer is a perovskite layer including a
compound having a perovskite crystalline structure, wherein the
compounds having a perovskite structure may be one or two or more
selected from H.sub.3NH.sub.3PbI.sub.xCl.sub.y (x is a real number
satisfying 0.ltoreq.x.ltoreq.3, y is a real number satisfying
0.ltoreq.y.ltoreq.3, and x+y=3), CH.sub.3NH.sub.3PbI.sub.xBr.sub.y
(x is a real number satisfying 0.ltoreq.x.ltoreq.3, y is a real
number satisfying 0.ltoreq.y.ltoreq.3, and x+y=3),
CH.sub.3NH.sub.3PbCl.sub.xBr.sub.y (x is a real number satisfying
0.ltoreq.x.ltoreq.3, y is a real number satisfying
0.ltoreq.y.ltoreq.3, and x+y=3), and
CH.sub.3NH.sub.3PbI.sub.xF.sub.y (x is a real number satisfying
0.ltoreq.x.ltoreq.3, y is a real number satisfying
0.ltoreq.y.ltoreq.3, and x+y=3).
[0059] As the second electrode, Au, Ag, Al, etc., may be used. The
second electrode may be deposited on the hole transport layer
mainly through a thermal-deposition method.
[0060] In general, the organic solar cell has a metal/organic
semiconductor (photoactive layer)/metal structure (that is,
metal-semiconductor or insulator-metal: MSM) structure and includes
transparent electrode, indium tin oxide, having a high work
function as a cathode, and Al, Ca, or the like, having a low work
function as an anode. The hole transport layer may be inserted
between the cathode and the photoactive layer and the electron
transport layer may be inserted between the anode and the
photoactive layer.
[0061] The photoactive layer has a bulk-heterojunction structure
obtained by mixing electron donors (D) with electron acceptors (A).
Since manufacturing method of the photoactive layer is simple, and
a surface area at D/A (donor/acceptor) interface is largely
increased, possibility of charge separation is increased, and an
efficiency in charge collection as electrodes is also
increased.
[0062] The organic solar cell according to the present disclosure
preferably has a BHJ structure. Examples of the electron donors may
include P3HT (poly 3-hexylthiophene), PTB7
(Poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]
[3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b] thiophenediyl]),
PCPDTBT
(poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]dithi-
ophene)-alt-4,7(2,1,3-benzothiadiazole)), PCPTBT
(poly(N-9''-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',-
3'-benzothiadiazole)), MDMO-PPV
(poly[2-methoxy-5-(3',7'-dimethyloctyloxyl)]-1,4-phenylene
vinylene), MEH-PPV
(poly[2-methoxy-5-(2''-ethylhexyloxy)-p-phenylene vinylene]), etc.
Examples of the electron acceptors may include C60, C70, [60]PCBM
(Phenyl C.sub.61-butyric acid methyl ester), [70]PCBM (Phenyl
C.sub.71-butyric acid methyl ester), [60]ICBA (Indene-C.sub.60
Bis-Adduct), [60]PCBCR (phenyl-C.sub.61-butyric acid cholesteryl
ester), [70]PCBCR (phenyl-C.sub.71-butyric acid cholesteryl ester),
perylene, PBI (polybenzimidazole), PTCBI
(3,4,9,10-perylene-tetracarboxylic bis-benzimidazole), etc.
However, the electron donors and the electron acceptors are not
limited to the above-described examples.
[0063] In a conventional organic solar cell, the electrons are
released to the anode, and the holes are released to the cathode,
and on the contrary, in an inverted organic solar cell, the
electrons are released to the cathode, and the holes are released
to the anode. The organic solar cell of the present disclosure
includes both of the conventional organic solar cell and the
inverted organic solar cell. In general, PEDOT:PSS is mainly used
for the hole transport layer of the organic solar cell.
[0064] In addition, the present disclosure provides a phosphine
oxide functionalized triazine derivative represented by Chemical
Formula 1 below:
##STR00014##
[0065] in Chemical Formula 1,
[0066] Ar.sup.1 and Ar.sup.2 are each independently (C6-C20)aryl
unsubstituted or substituted with fluorine;
[0067] L is (C6-C20)arylene substituted with at least one
fluorine;
[0068] Ar.sup.3 and Ar.sup.4 are each independently (C1-C20)alkyl,
(C6-C20)aryl, or (C3-C20)heteroaryl, wherein the alkyl, aryl, or
heteroaryl of Ar.sup.3 and Ar.sup.4 may be further substituted with
at least one selected from (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy and halo(C1-C20)alkoxy; and
[0069] the heteroaryl includes at least one heteroatom selected
from N, O, and S.
[0070] The phosphine oxide functionalized triazine derivative
represented by Chemical Formula 1 of the present disclosure has
significantly excellent solubility in alcohols due to the presence
of a polar phosphine oxide (P.dbd.O) group in the molecular
structure, and has a 1,3,5-triazine moiety having excellent
electron transport property, such that extraction and injection of
electrons for improving interface properties may be easily
performed.
[0071] The phosphine oxide functionalized triazine derivative
according to the present disclosure is prepared by facile protocol
with extremely inexpensive 2,4,6-trichloro-1,3,5-triazine as a
starting material, which is economical, and has excellent
solubility in environmentally friendly solvents such as alcohols as
well as compatibility with a large area printing process.
[0072] The structure suggested in the present disclosure may
introduce various substituents and may control solubility in
various solvents including alcohols as well as HOMO and LUMO energy
level, by introducing the phosphine oxide, fluorine-based
substituents and 1,3,5-triazine derivatives.
[0073] Terms: "alkyl" and "alkoxy" described in the present
disclosure include both a linear chain type and a branched chain
type.
[0074] The term "aryl" described herein, which is an organic
radical derived from aromatic hydrocarbon due to removal of one
hydrogen, includes a single ring system or a fused ring system
appropriately including 4 to 7 ring atoms, preferably, 5 or 6 ring
atoms in each ring, and even includes a form in which a plurality
of aryls are connected by a single bond. Specific examples of the
aryl group include aromatic groups such as phenyl, naphthyl,
biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl,
triphenylenyl, pyrenyl, chrysenyl and naphthacenyl.
[0075] The term "arylene" described in the present disclosure is an
organic radical derived from aromatic hydrocarbon due to removal of
two hydrogens.
[0076] The term "heteroaryl" described herein, which means an aryl
group including 1 to 4 heteroatoms selected from N, O, and S as an
aromatic ring framework atom and carbon as the remaining aromatic
ring framework atom, is a 5- to 6-membered monocyclic heteroaryl
and a polycyclic heteroaryl condensed with at least one benzene
ring. In addition, the heteroaryl in the present disclosure
includes even a form in which one or more heteroaryls are connected
by a single bond. Examples of the heteroaryl include monocyclic
heteroaryls such as furyl, thiophenyl, pyrrolyl, pyranyl,
imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl,
isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl,
triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl,
pyridazinyl, etc., and polycyclic heteroaryls such as benzofuranyl,
benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl,
benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl,
indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl,
cinnolinyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl,
phenanthridinyl, benzodioxolyl, etc.
[0077] In an exemplary embodiment of the present disclosure, L may
be preferably (C6-C20)arylene substituted with at least two
fluorines.
[0078] In an exemplary embodiment of the present disclosure,
specifically, Ar.sup.1 and Ar.sup.2 may be each independently
phenyl, biphenyl, naphthyl, anthryl, phenanthryl, tetracenyl,
pyrenyl, or perylenyl, the phenyl, biphenyl, naphthyl, anthryl,
phenanthryl, tetracenyl, pyrenyl, or perylenyl of Ar.sup.1 and
Ar.sup.2 may be further substituted with at least one fluorine;
Ar.sup.a and Ar.sup.4 may be each independently methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl,
naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl, perylenyl,
furyl, thienyl, pyridyl, thiazolyl, oxazolyl, quinolyl, indolyl,
pyrimidyl, or pyrazinyl, the methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, phenyl, biphenyl, naphthyl, anthryl,
phenanthryl, tetracenyl, pyrenyl, perylenyl, furyl, thienyl,
pyridyl, thiazolyl, oxazolyl, quinolyl, indolyl, pyrimidyl, or
pyrazinyl of Ar.sup.1 and Ar.sup.4 may be further substituted with
at least one selected from methyl, ethyl, propyl, butyl,
trifluoromethyl, perfluoroethyl, methoxy, trifluoromethoxy, and
perfluoroethoxy.
[0079] In an exemplary embodiment of the present disclosure, more
preferably, L may be phenylene, biphenylene, naphthylene,
anthrylene, phenanthrylene, tetracenylene, pyrenylene, or
perylenylene substituted with at least two fluorines.
[0080] In an exemplary embodiment of the present disclosure, more
preferably, the phosphine oxide functionalized triazine derivative
may be represented by Chemical Formulas 2 to 4 below:
##STR00015##
[0081] in Chemical Formulas 2 to 4, a and b are each independently
an integer from 0 to 5; n is an integer from 2 to 4; R.sup.11 and
R.sup.12 are each independently (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, or halo(C1-C20)alkoxy; x and y are each
independently an integer from 0 to 5; X and Y are each
independently NH, O, or S; R.sup.13 and R.sup.14 are each
independently hydrogen, (C1-C20)alkyl, halo(C1-C20)alkyl,
(C1-C20)alkoxy, or halo(C1-C20)alkoxy; R.sup.15 and R.sup.16 are
each independently (C1-C20)alkyl, wherein the alkyl of R.sup.15 and
R.sup.16 may be further substituted with at least one selected from
(C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, and
halo(C1-C20)alkoxy.
[0082] In an exemplary embodiment of the present disclosure, the
phosphine oxide functionalized triazine derivative may be selected
from the following compounds, but the present disclosure is not
limited thereto:
##STR00016## ##STR00017## ##STR00018## ##STR00019##
[0083] The phosphine oxide functionalized triazine derivative of
the present disclosure may be prepared, for example, by Reaction
Scheme 1 below. The preparation thereof is described through
Examples 1 to 17 in more detail. However, the preparation method of
the phosphine oxide functionalized triazine derivative of the
present disclosure is not limited to Reaction Scheme 1 below, but
may be synthesized by various methods using known organic
reactions:
##STR00020##
[0084] in Reaction Scheme 1, Ar.sup.1 and Ar.sup.2 are each
independently (C6-C20)aryl unsubstituted or substituted with
fluorine; L is (C6-C20)arylene substituted with at least one
fluorine; and Ar.sup.3 and Ar.sup.4 are each independently
(C1-C20)alkyl, (C6-C20)aryl, or (C3-C20)heteroaryl, wherein the
alkyl, aryl, or heteroaryl of Ar.sup.3 and Ar.sup.4 may be further
substituted with at least one selected from (C1-C20)alkyl,
halo(C1-C20)alkyl, (C1-C20)alkoxy, and halo(C1-C20) alkoxy.
[0085] The Reaction Scheme 1 includes preparing
2-chloro-4,6-diaryloxy-1,3,5-triazine derivative (Compound c) by
reacting cyanuric chloride with phenol derivatives (compounds a and
b) in the presence of NaOH (Step 1); preparing a Compound e by
palladium-catalyzed cross-coupling reaction of the prepared
2-chloro-4,6-diaryloxy-1,3,5-triazine derivative (Compound c) and
an aryl boronic acid derivative substituted with at least one
fluorine (Compound d) (Step 2); preparing a phosphine oxide
functionalized triazine derivative represented by Chemical Formula
1 through regioselective lithiation of the prepared Compound e,
coupling with a chlorodiphenylphosphine derivative (Compound f),
and oxidization using hydrogen peroxide (Step 3).
[0086] Hereinafter, the present disclosure will be described in
detail with reference to Examples. These Examples are provided to
help understand the present invention, and the scope of the present
disclosure is not construed to be limited to these Examples.
EXAMPLE 1
Preparation of PO-TAZ
(2-(3-(Diphenylphosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-triazi-
ne)
##STR00021##
[0087] Preparation of 2-Chloro-4,6-diphenoxy-1,3,5-triazine (1)
[0088] 2,4,6-Trichloro-1,3,5-triazine (cyanuric chloride) (2.5 g,
14 mmol) was dissolved in acetone (200 mL) and cooled to 0.degree.
C. In a different flask, phenol (2.6 g, 28 mmol) was reacted with
NaOH (1.1 g, 20 mmol) in water (200 mL) to form a clear aqueous
solution. Then, the solution was drop-wise added to the prepared
2,4,6-Trichloro-1,3,5-triazine acetone solution. The mixture was
stirred at 0.degree. C. for 12 hours, and water (200 mL) was poured
into the mixture to form a white precipitate. The white precipitate
was filtered and washed with water and ethanol, and recrystallized
with hexane to obtain a white solid,
2-Chloro-4,6-diphenoxy-1,3,5-triazine (1).
[0089] Yield: 77%. .sup.1H NMR (300 MHz, CDCl.sub.3, .delta.): 7.43
(m, 4H), 7.28 (dd, 2H), 7.14 (m, 4H). .sup.13C NMR (300 MHz,
CDCl.sub.3, .delta.): 121.19, 121.39, 126.09, 126.52, 129.48,
129.69, 151.26, 151.52, 172.39, 173.66, 173.72.
Preparation of 2-(2,4-Difluorophenyl)-4,6-diphenoxy-1,3,5-triazine
(2)
[0090] Toluene (24 mL), ethanol (12 mL), and 2 M Na.sub.2CO.sub.3
aqueous solution (15 mL) were added to a mixture of
2-chloro-4,6-diphenoxy-1,3,5-triazine (1 g, 3 mmol),
2,4-difluorophenylboronic acid (0.53 g, 2 mmol), and
tetrakis(triphenylphosphine)palladium (0.134 g, 0.2 mmol). The
mixture was refluxed under a nitrogen atmosphere for 12 hours, and
cooled to room temperature and extracted with dichloromethane, and
dried with anhydrous Na.sub.2SO.sub.4. The solvent was removed
under reduced pressure, and residue was purified by silica gel
column chromatography (eluent: dichloromethane/hexane=4/1) to
obtain a white solid,
2-(2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-triazine (2).
[0091] Yield: 58%. .sup.1H NMR (300 MHz, CDCl.sub.3, .delta.): 8.24
(m, 1H), 7.45 (t, 4H), 7.28 (m, 6H), 6.92 (m, 2H). .sup.13C NMR
(300 MHz, CDCl.sub.3, .delta.): 105.14, 105.48, 105.81, 111.60,
111.65, 111.88, 111.94, 119.66, 119.72, 119.77, 121.33, 121.38,
121.48, 126.03, 129.10, 129.46, 133.69, 133.72, 133.86, 151.51,
151.66, 161.22, 161.39, 163.85, 164.01, 164.74, 164.90, 167.24,
173.49.
Preparation of
2-(3-(Diphenylphosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-triazin-
e (PO-TAZ)
[0092] 2-(2,4-Difluorophenyl)-4,6-diphenoxy-1,3,5-triazine (1.5 g,
4 mmol) was dissolved in THF (30 mL), and a reaction temperature
was cooled to -78.degree. C. Lithium diisopropylamide (2M, 2.5 mL)
was drop-wise added to the reaction mixture, and stirred at the
same temperature for 1 hour. Then, chlorodiphenylphosphine (1.1 g,
5 mmol) (2 mL) was added to the mixture, and stirred overnight, and
the reaction was quenched by adding water thereto. The obtained
mixture was extracted with ethyl acetate (EA) and dried with
anhydrous Na.sub.2SO.sub.4. After removing the solvent, the residue
was diluted with CH.sub.2Cl.sub.2 (30 mL) and hydrogen peroxide
(30%) (20 mL) and then stirred at room temperature for 3 hours. The
crude product was extracted with chloroform and purified by silica
gel column chromatography (eluent: EA) to obtain a white solid,
2-(3-(diphenylphosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-triazin-
e (PO-TAZ).
[0093] Yield: 72%. .sup.1H NMR (300 MHz, CDCl.sub.3, .delta.): 8.24
(m, 1H), 7.74 (m, 4H), 7.59-7.42 (m, 6H), 7.34 (m, 4H), 7.21 (m,
2H), 7.16 (d, 4H), 6.98 (m, 1H). MS (EI, m/z) : [M]+ calcd for
C.sub.33H.sub.22F.sub.2N.sub.3O.sub.3P, 577.52; found, 578.14.
.sup.13C NMR (300 MHz, CDCl.sub.3, .delta.): 111.25, 112.45,
112.95, 113.27, 120.73, 120.79, 120.87, 121.35, 126.05, 128.56,
128.73, 129.46, 131.10, 131.24, 131.88, 132.24, 132.27, 133.36,
137.71, 137.75, 127.87, 151.52, 161.16, 161.27, 164.74, 164.85,
164.96, 168.33, 168.43, 172.54, 172.98, 173.06.
EXAMPLES 2 TO 4
Preparation of F PO-TAZ Derivative Introduced with Fluorine
Substituent
##STR00022##
[0095] Ortho-F PO-TAZ (Example 2), meta-F PO-TAZ (Example 3) and
para-F PO-TAZ (Example 4) were obtained by performing the reaction
in the same manner as in Example 1 except for using 2-fluorophenol,
3-fluorophenol or 4-fluorophenol, respectively, instead of using
phenol in Example 1.
[0096] Ortho-F PO-TAZ (Example 2) .sup.1H NMR (300 MHz, CDCl.sub.3,
.delta.): 8.24 (m, 1H), 7.80-7.62 (m, 4H), 7.60-7.52 (m, 2H),
7.50-7.48 (m, 4H), 7.12-6.84 (9H).
[0097] Meta-F PO-TAZ (Example 3) .sup.1H NMR (300 MHz, CDCl.sub.3,
.delta.): 8.32-8.24 (m, 1H), 7.72-7.86 (m, 4H), 7.64-7.54 (m, 2H),
7.52-7.42 (m, 4H), 7.38-7.28 (m, 3H), 7.08-6.88 (m, 6H).
[0098] Para-F PO-TAZ (Example 4) .sup.1H NMR (300 MHz, CDCl.sub.3,
.delta.): 8.24 (m, 1H), 7.80-7.62 (m, 4H), 7.60-7.48 (m, 6H),
7.12-6.84 (9H).
EXAMPLE 5
Preparation of
2-(3-(di(o-tolyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-tria-
zine (Compound A)
##STR00023##
[0100]
2-(3-(Di(o-tolyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,-
5-triazine (Compound A) was obtained by performing the reaction in
the same manner as in Example 1 except for using chloro
di-o-tolylphosphine instead of using chlorodiphenylphosphine in
Example 1.
[0101] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (d, 1H), 7.75 (d, 1H), 7.64 (d, 2H), 7.3-6.9 (m, 16H), 2.34
(m, 6H).
EXAMPLE 6
Preparation of
2-(3-(Di(m-tolyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-tria-
zine (Compound B)
##STR00024##
[0103]
2-(3-(Di(m-tolyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,-
5-triazine (Compound B) was obtained by performing the reaction in
the same manner as in Example 1 except for using chloro
di-m-tolylphosphine instead of using chlorodiphenylphosphine in
Example 1.
[0104] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (d, 1H), 7.75 (d, 1H), 7.64 (m, 4H), 7.3-6.9 (m, 14H), 2.34
(m, 6H).
Example 7
Preparation of
2-(3-(Di(p-tolyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-tria-
zine (Compound C)
##STR00025##
[0106]
2-(3-(Di(p-tolyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,-
5-triazine (Compound C) was obtained by performing the reaction in
the same manner as in Example 1 except for using chloro
di-p-tolylphosphine instead of using chlorodiphenylphosphine in
Example 1.
[0107] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (d, 1H), 7.66 (m, 4H), 7.28-7.20 (m, 8H), 7.09-7.01 (dt, 3H),
6.98 (m, 4H), 2.34 (m, 6H).
EXAMPLE 8
Preparation of
2-(3-(Di(bis(2,4-bis(trifluoromethyl)phenyl))phosphoryl)-2,4-difluorophen-
yl)-4,6-diphenoxy-1,3,5-triazine (Compound D)
##STR00026##
[0109]
2-(3-(Di(bis(2,4-bis(trifluoromethyl)phenyl))phosphoryl)-2,4-difluo-
rophenyl)-4,6-diphenoxy-1,3,5-triazine (Compound D) was obtained by
performing the reaction in the same manner as in Example 1 except
for using (2,4-bis(trifluoromethyl)phenyl)
(2,5-bis(trifluoromethyl)phenyl)chlorophosphine instead of using
chlorodiphenylphosphine in Example 1.
[0110] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.88 (s, 2H), 7.78 (d, 1H), 7.69-7.61 (m, 4H), 7.28-7.20 (m, 4H),
7.09-7.01 (dt, 3H), 6.98 (m, 4H)
EXAMPLE 9
Preparation of
2-(3-(Di(furyl))phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-triaz-
ine (Compound E)
##STR00027##
[0112]
2-(3-(Di(furyl))phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-
-triazine (Compound E) was obtained by performing the reaction in
the same manner as in Example 1 except for using
chlorodifuran-2-ylphosphine instead of using
chlorodiphenylphosphine in Example 1.
[0113] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78-7.72 (m, 3H), 7.28-7.20 (m, 4H), 7.10 (m, 2H), 7.09-7.01 (dt,
3H), 6.98 (m, 4H), 6.63 (t, 2H).
EXAMPLE 10
Preparation of
2-(3-(Di(2,4-dimethylphenyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-
-1,3,5-triazine (Compound F)
##STR00028##
[0115]
2-(3-(Di(2,4-dimethylphenyl)phosphoryl)-2,4-difluorophenyl)-4,6-dip-
henoxy-1,3,5-triazine (Compound F) was obtained by performing the
reaction in the same manner as in Example 1 except for using
chlorobis(2,4-dimethylphenyl)phosphine instead of using
chlorodiphenylphosphine in Example 1.
[0116] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (m, 1H), 7.58 (m, 2H), 7.28-7.20 (m, 4H), 7.10 (m, 2H),
7.09-7.01 (dt, 5H), 6.98 (m, 4H), 2.34 (s, 6H).
EXAMPLE 11
Preparation of
2-(3-(Di(4-methoxyphenyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,-
3,5-triazine (Compound G)
##STR00029##
[0118] 2-(3-(Di(4-methoxyphenyl)phosphoryl)-2,4-difluorophenyl)-4,
6-diphenoxy-1,3,5-triazine (Compound G) was obtained by performing
the reaction in the same manner as in Example 1 except for using
chlorobis(4-methoxyphenyl)phosphine instead of using
chlorodiphenylphosphine in Example 1.
[0119] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (m, 1H), 7.68-7.64 (m, 4H), 7.28-7.20 (m, 4H), 7.09-7.01 (dt,
3H), 6.99 (m, 4H), 6.84 (d, 4H), 3.94 (s, 6H).
EXAMPLE 12
Preparation of
2-(3-(Di(2-methoxyphenyl)phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,-
3,5-triazine (Compound H)
##STR00030##
[0121] 2-(3-(Di(2-methoxyphenyl)phosphoryl)-2,4-difluorophenyl)-4,
6-diphenoxy-1,3,5-triazine (Compound H) was obtained by performing
the reaction in the same manner as in Example 1 except for using
chlorobis(2-methoxyphenyl)phosphine instead of using
chlorodiphenylphosphine in Example 1.
[0122] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (m, 1H), 7.70-7.64 (m, 2H), 7.39 (m, 2H), 7.28-7.20 (m, 4H),
7.09-7.01 (dt, 5H), 6.99-6.90 (m, 6H), 3.94 (s, 6H).
EXAMPLE 13
Preparation of
2-(3-(Di(4-isopropoxyphenyl))phosphoryl)-2,4-difluorophenyl)-4,6-diphenox-
y-1,3,5-triazine (Compound I)
##STR00031##
[0124]
2-(3-(Di(4-isopropoxyphenyl))phosphoryl)-2,4-difluorophenyl)-4,6-di-
phenoxy-1,3,5-triazine (Compound I) was obtained by performing the
reaction in the same manner as in Example 1 except for using
chlorobis(4-isopropoxyphenyl)phosphine instead of using
chlorodiphenylphosphine in Example 1.
[0125] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (m, 1H), 7.66 (m, 4H), 7.28-7.20 (m, 4H), 7.09-7.01 (dt, 3H),
6.99-6.92 (m, 8H), 4.82 (s, 2H), 1.38 (d, 12H).
EXAMPLE 14
Preparation of
2-(3-(Di(4-methoxy-3,5-dimethylphenyl)phosphoryl)-2,4-difluorophenyl)-4,6-
-diphenoxy-1,3,5-triazine (Compound J)
##STR00032##
[0127]
2-(3-(Di(4-methoxy-3,5-dimethylphenyl)phosphoryl)-2,4-difluoropheny-
l)-4,6-diphenoxy-1,3,5-triazine (Compound J) was obtained by
performing the reaction in the same manner as in Example 1 except
for using chlorobis(4-methoxy-3,5-dimethylphenyl)phosphine instead
of using chlorodiphenylphosphine in Example 1.
[0128] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (m, 1H), 7.28-7.20 (m, 4H), 7.09-7.01 (dt, 3H), 6.99-6.92 (m,
8H), 3.94 (s, 6H), 2.15 (d, 12H).
EXAMPLE 15
Preparation of
2-((3-(Diethyl)-phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-triaz-
ine (Compound K)
##STR00033##
[0130]
2-((3-(Diethyl)-phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-
-triazine (Compound K) was obtained by performing the reaction in
the same manner as in Example 1 except for using
chlorodiethylphosphine instead of using chlorodiphenylphosphine in
Example 1.
[0131] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.78 (m, 1H), 7.28-7.20 (m, 4H), 7.09-7.01 (dt, 3H), 6.99-6.92 (m,
4H), 1.92 (t, 4H), 1.14 (d, 6H).
EXAMPLE 16
Preparation of
2-((3-(Diisopropyl)-phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-t-
riazine (Compound L)
##STR00034##
[0133]
2-((3-(Diisopropyl)-phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1-
,3,5-triazine (Compound L) was obtained by performing the reaction
in the same manner as in Example 1 except for using
chlorodiisopropylphosphine instead of using chlorodiphenylphosphine
in Example 1.
[0134] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.76 (m, 1H), 7.28-7.20 (m, 4H), 7.09-7.01 (dt, 3H), 6.99-6.92 (m,
4H), 3.69 (m, 2H), 1.08 (d, 12H).
EXAMPLE 17
Preparation of
2-((3-(Dibutyl)-phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-triaz-
ine (Compound M)
##STR00035##
[0136]
2-((3-(Dibutyl)-phosphoryl)-2,4-difluorophenyl)-4,6-diphenoxy-1,3,5-
-triazine (Compound M) was obtained by performing the reaction in
the same manner as in Example 1 except for using
dibutylchlorophosphine instead of using chlorodiphenylphosphine in
Example 1.
[0137] Yield: 70%, .sup.1H NMR (300 MHz, CDCl.sub.3, .delta. ppm):
7.76 (m, 1H), 7.28-7.20 (m, 4H), 7.09-7.01 (dt, 3H), 6.99-6.92 (m,
4H), 1.82 (t, 4H), 1.66 (p, 4H), 1.42 (m, 4H), 0.94 (t, 6H).
EXAMPLE 18
Manufacture of COSC (Conventional Organic Solar Cell)
[0138] An indium tin oxide (ITO)-coated glass substrate was cleaned
by sonication in acetone, detergent, deionized water, and
isopropanol to remove impurities, and dried in an oven, followed by
plasma treatment.
[0139] A thin hole-collection layer (ca. 35 nm) of PEDOT:PSS
(poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)) (Clevios
P VP AI 4083, filtered at 0.45 .mu.m) was spin-coated on the
pre-cleaned ITO-coated glass substrates and baked at 140.degree. C.
for 15 min under ambient conditions.
[0140]
Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6--
diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]
(PTB7) and 1-(2-methoxycarbonly)-propyl-1-phenyl-(6,6)C71
(PC.sub.71BM) were used for the photoactive layer. PTB7 (8 mg) and
PC.sub.71BM (12 mg) were dissolved in CB (chlorobenzene, 1 mL) and
DIO (1,8-diiodooctane, 3 wt %), followed by spin-coating on the
PEDOT:PSS hole-collection layer, and drying at room temperature for
30 minutes, to form a photoactive layer having a thickness of 100
nm.
[0141] The PO-TAZ (0.05 mg) prepared by Example 1 was dissolved in
isopropanol (1 mL), followed by spin-coating on the photoactive
layer, to form a PO-TAZ layer having a thickness of 5 nm.
[0142] An aluminum electrode covered with a mask was
thermal-deposited at a thickness of 100 nm under 10.sup.-7 Torr in
a vacuum chamber.
[0143] The manufactured device was manufactured in a structure of
ITO/PEDOT:PSS(35 nm)/PTB7:PC.sub.71BM(100 nm)/PO-TAZ(5 nm)/Al(100
nm) [FIG. 4], and had a photoactive area of 0.09 cm.sup.2.
[0144] Meanwhile, FIG. 5 shows a HOMO LUMO energy level diagram of
the COSC manufactured as above, wherein the HOMO and LUMO of the
PO-TAZ were measured to be -8.44 and -4.45 eV, respectively. From
the result, an optical band gap (E.sub.g.sup.opt) of the PO-TAZ
prepared by Example 1 was calculated to be 3.99 eV. In addition, a
current density-voltage (J-V) and an external quantum efficiency
(EQE) were shown in FIGS. 6 and 7, respectively.
Example 19
Manufacture of IOSC (Inverted Organic Solar Cell)
[0145] A ZnO precursor solution was spin-coated on an ITO glass
substrate having a sheet resistance (R.sub.sheet) of 12 .OMEGA./sq,
and thermal-treated at 150.degree. C. for 10 minutes to form a ZnO
layer having a thickness of 60 nm. The PO-TAZ (0.05 mg) prepared by
Example 1 was dissolved in isopropanol (1 mL), followed by
spin-coating on the ZnO layer, to form a PO-TAZ layer having a
thickness of 5 nm.
[0146] PTB7 and PC.sub.71BM were used for the photoactive layer.
PTB7 (8 mg) and PC.sub.71BM (12 mg) were dissolved in CB (1 mL) and
stirred at 50.degree. C. for 12 hours, and DIO (3 vol %) was added
thereto, followed by spin-coating on the PO-TAZ layer, to form a
photoactive layer having a thickness of 100 nm.
[0147] PEDOT:PSS (Clevios P VP AI 4083, filtered at 0.45 .mu.m) was
diluted with isopropanol at a ratio of 1:10, followed by
spin-coating on the photoactive layer, to form a PEDOT:PSS layer
having a thickness of 10 nm.
[0148] Finally, the top-electrode Ag metal having a thickness of
150 nm was deposited through a shadow mask by thermal evaporation
in a vacuum of approximately 3.times.10.sup.-6 Torr.
[0149] The manufactured device was manufactured in a structure of
ITO/ZnO(60 nm)/PO-TAZ(5 nm)/PTB7:PC.sub.71BM(100 nm)/PEDOT:PSS(10
nm)/Ag(150 nm) [FIG. 8], and device areas defined through the
shadow mask were 0.11 and 0.38 cm.sup.2, respectively.
[0150] Meanwhile, FIG. 9 shows a HOMO LUMO energy level diagram of
the IOSC manufactured as above, wherein the HOMO and LUMO of the
PO-TAZ were measured to be -8.44 and -4.45 eV, respectively. From
the result, an optical band gap (E.sub.g.sup.opt) of the PO-TAZ
prepared by Example 1 was calculated to be 3.99 eV. In addition, a
current density-voltage (J-V) and external quantum efficiency (EQE)
were shown in FIGS. 10 and 11, respectively.
EXAMPLE 20
Manufacture of PSC (Perovskite Solar Cell)
[0151] A ZnO precursor solution was spin-coated on an ITO
substrate, and annealed at 150.degree. C. for 10 minutes to form an
ZnO layer having a thickness of 60 nm.
[0152] The PO-TAZ (0.05 mg) prepared by Example 1 was dissolved in
isopropanol (1 mL), followed by spin-coating on the ZnO layer, to
form a PO-TAZ layer having a thickness of 5 nm.
[0153] A 0.87M PbI.sub.2 DMF solution was spin-coated on the PO-TAZ
layer to form a PbI.sub.2 layer, and dried in the air, followed by
spin-coating with methyl ammonium iodide (MAI) 2-propanol solution
(40 mg/mL), to form a MAPbI.sub.3 perovskite layer having a
thickness of 250 nm.
[0154] Spiro-MeOTAD (80 mg) was dissolved in CB (1 mL), and
t-BP(t-butyl pyridine) (28.5 .mu.L) and Li-TFSI (lithium
bis(trifluoro methanesulfonyl)imide, 520 mg LI-TSFI in 1 ml
acetonitrile, Sigma-Aldrich, 99.8%) (17.5 .mu.L) were added thereto
to prepare a spiro-MeOTAD solution. The prepared spiro-MeOTAD
solution was spin-coated on the perovskite layer to form a hole
transport layer having a thickness of 200 nm.
[0155] Finally, a 150 nm thick Ag electrode was deposited by
thermal evaporation.
[0156] The manufactured device was manufactured in a structure of
ITO/ZnO(60 nm)/PO-TAZ(5 nm)/MAPbI.sub.3(250 nm)/Spiro-OMeTAD(200
nm)/Ag(150 nm) [FIG. 12].
[0157] Meanwhile, FIG. 13 shows a HOMO LUMO energy level diagram of
the PSC manufactured as above, wherein the HOMO and LUMO of the
PO-TAZ were measured to be -8.44 and -4.45 eV, respectively. From
the result, an optical bandgap (E.sub.g.sup.opt) of the PO-TAZ
prepared by Example 1 was calculated to be 3.99 eV. In addition, a
current density-voltage (J-V) and an external quantum efficiency
(EQE) were shown in FIGS. 14 and 15, respectively.
EXAMPLE 21
Manufacture of OFET (Organic Field-Effect Transistor)
[0158] An organic field-effect transistor (OFET) having a
bottom-contact and top-gate structure was manufactured on the
pre-treated glass substrate.
[0159] Au (20 nm) bottom-contact source/drain electrodes were
deposited by thermal evaporation after lithography process.
[0160]
Poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximid-
e)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2), Polyera
ActivInk.TM. N2200) which is an n-type semiconductor material was
dissolved in chlorobenzene to prepare a solution of which a
concentration is 1 wt %, and then, an organic semiconductor layer
was formed by a spin coating method.
[0161] 1 wt % of poly(methyl methacrylate) (PMMA) solution prepared
by using 1,2-dichlorobenzene as a solvent was spin-coated on the
organic semiconductor layer to form an organic insulation layer,
followed by annealing at 80.degree. C. for 20 minutes.
[0162] All spin-coating and annealing processes were carried out in
a glove box filled with nitrogen.
[0163] The aluminum (50 nm) gate electrode was deposited by thermal
evaporation through the shadow mask.
[0164] The device had a length of 20 .mu.m and a width of 1000
.mu.m. Properties of the OTFT were measured by Keithley 4800.
EXAMPLE 22
Manufacture of OTFT (Organic Thin Film Transistor)
[0165] OTFT was manufactured in a glove box filled with nitrogen
(oxygen content <0.1 ppm, moisture content <0.1 ppm).
[0166] For the bottom-gate top source/drain contact PC-.sub.71BM
TFT, an n-doped silicon was used as a gate and SiO.sub.2 was used
as an insulator.
[0167] A PC-.sub.71BM layer having a thickness of 30 nm was formed
and annealed at 120.degree. C. for 20 minutes.
[0168] The PO-TAZ (0.05 mg) prepared by Example 1 was dissolved in
isopropanol (1 mL), followed by spin-coating on the PC-.sub.71BM
layer, to form a PO-TAZ layer having a thickness of 5 nm. The
PO-TAZ layer was annealed at 120.degree. C. for 20 minutes. Lastly,
a 50 nm-thick Au electrode was deposited through a shadow mask.
[0169] The device had a length of 20 .mu.m and a width of 1000
.mu.m. Properties of the OTFT were measured by Keithley 4800.
[0170] Properties of Compounds
[0171] A decomposition temperature (T.sub.d) of the PO-TAZ prepared
by Example 1 was measured by TGA and the result was shown in FIG.
1, from which it was confirmed that T.sub.d of PO-TAZ was above
300.degree. C. Accordingly, it could be appreciated that the PO-TAZ
of the present disclosure is thermally stable.
[0172] UV-visible absorption spectra of the PO-TAZ prepared by
Example 1 were measured in a solution state and in a film state,
and the result was shown in FIG. 2, from which it was confirmed
that an optical band gap (E.sub.g.sup.opt) of the PO-TAZ prepared
by Example 1 was calculated to be 3.99 eV.
[0173] Meanwhile, the HOMO LUMO energy level of the PO-TAZ prepared
by Example 1 was measured by UPS (ultraviolet photoelectron
spectroscopy) and an optical band gap, and HOMO and LUMO of the
PO-TAZ were measured to be -8.44 and -4.45 eV, respectively [FIG.
3]. The measured values were obtained by the triazine unit and the
substitution of the electron acceptor P.dbd.O in the PO-TAZ, and
the PO-TAZ having a low LUMO level as compared to PC.sub.71BM (3.7
eV) and Perovskite (MAPbI.sub.3) (3.93 eV) could effectively
perform electron extraction from the photoactive layer to the
electrodes.
[0174] Properties of Solar Cell
[0175] An AM (air mass) 1.5 G solar simulator (Oriel Sol3A Class
AAA solar simulator, models94043A) having a light intensity of 100
mW/cm.sup.2 was used to investigate photoelectric energy properties
of the device.
[0176] Electrical properties of the solar cell devices manufactured
by Examples 18 to 20, that is, photovoltaic parameters of a maximum
power conversion efficiency (PCE), an open circuit voltage
(V.sub.oc), a short-circuit current density (J.sub.SC) and a fill
factor (FF), were shown in Table 1.
TABLE-US-00001 TABLE 1 PO- Photoactive TAZ max. layer inter- PCE
J.sub.SC FF V.sub.OC (Device type) layer [%] [mA/cm.sup.2] [%] [V]
Ex. 18 PTB7:PC.sub.71BM .largecircle. 7.72 15.04 68.81 0.74
(Conventional) Compar- PTB7:PC.sub.71BM X 4.75 14.12 51.79 0.65
ative (Conventional) Ex. 1 Ex. 19 PTB7:PC.sub.71BM .largecircle.
9.93 18.85 68.85 0.74 (Inverted).sup.a) Compar- PTB7:PC.sub.71BM X
8.72 18.11 65.70 0.72 ative (Inverted).sup.a) Ex. 2 Ex. 20
Perovskite .largecircle. 16.41 20.53 75.92 1.06
(Conventional).sup.b) Perovskite .largecircle. 16.06 20.11 75.23
1.06 (Conventional).sup.c) Compar- Perovskite X 13.92 19.19 67.26
1.06 ative (Conventional).sup.b) Ex. 3 Perovskite X 13.28 18.94
65.61 1.06 (Conventional).sup.c) .sup.a)Active layer cell area:
0.11 cm.sup.2; .sup.b)Forward direction; .sup.c)Reverse
direction
[0177] As shown in Table 1 above, the solar cells manufactured by
Examples 18 to 20 included the PO-TAZ as the interface material,
such that maximum power conversion efficiency (PCE) thereof was
more excellent than those of Comparative Examples 1 to 3 that did
not include the PO-TAZ.
[0178] Properties of Device
[0179] A transfer curve and an out-put curve of the devices
manufactured by Examples 21 and 22 were shown in FIGS. 16 and 17,
respectively, and properties of the devices manufactured by
Examples 21 and 22 were measured at V.sub.D(drain voltage) +60V,
and the result was shown in Table 2 below.
TABLE-US-00002 TABLE 2 Electron mobility Threshold On/Off
(.mu..sub.e) voltage Ratio Device Electrode (cm.sup.2/vs)
(V.sub.Th) [V] (I.sub.on/off) Ex. 21 P(NDI2OD-T2) POTAZ/Au 0.52
(.+-.0.04) 1.4 10.sup.4 (TGBC structure) Comparative P(NDI2OD-T2)
Pristine Au 0.43 (.+-.0.01) 6.5 10.sup.4 Ex. 4 (TGBC structure) Ex.
22 PC.sub.71BM POTAZ/Au 0.12 (.+-.0.007) 12.8 10.sup.3 (TGBC
structure) PC.sub.71BM POTAZ/Au 0.03 (.+-.0.05) 4.6 10.sup.3 (BGTC
structure) Comparative PC.sub.71BM Pristine Au 0.07 (.+-.0.004) 4.6
10.sup.3 Ex. 5 (TGBC structure) PC.sub.71BM Pristine Au 0.004
(.+-.0.1) 18.7 10.sup.3 (BGTC structure)
[0180] As shown in Table 2 above, the devices manufactured by
Examples 21 and 22 included the PO-TAZ as the electrode interface
layers, such that a charge mobility thereof was more excellent and
a threshold voltage thereof was lower than those of Comparative
Examples 4 and 5 that did not include the PO-TAZ.
[0181] The phosphine oxide functionalized triazine derivative
according to the present disclosure is prepared by facile protocol
with extremely inexpensive 2,4,6-trichloro-1,3,5-triazine (cyanuric
chloride) as a starting material, which is economical, and has good
solubility in environmentally friendly solvents such as alcohols as
well as compatibility with a large area printing process.
[0182] The functionalized 1,3,5-triazine moiety having the
phosphine oxide group is incorporated into an electron injection
interlayer, such that injection and extraction of the electrons
with the metal electrode having a high work function (WF) in the
electronic devices, particularly, in organic and organic-inorganic
(perovskite) solar cells and organic field-effect transistors may
be effectively achieved.
[0183] In addition, the phosphine oxide functionalized triazine
derivative according to the present disclosure is applied as an
interface material to exhibit remarkably improved electron
injection property, thereby exhibiting significantly excellent
maximum power conversion efficiency.
[0184] According to the incorporation of the phosphine oxide
functionalized triazine derivative of the present disclosure, a
low-priced printing process and tremendous improvement in device
efficiencies and ambient stability, etc., may be achieved, such
that an optoelectronic device is capable of being effectively
manufactured in large-areas roll-to-roll process.
[0185] The above description presents the best mode contemplated
for carrying out the present invention, and of the manner and
process of making and using it, in such full, clear, concise, and
exact terms as to enable any person skilled in the art to which it
pertains to make and use this invention. This invention is,
however, susceptible to modifications and alternate constructions
from that discussed above that are fully equivalent. Consequently,
this invention is not limited to the particular embodiments
disclosed. On the contrary, this invention covers all modifications
and alternate constructions coming within the spirit and scope of
the invention as generally expressed by the following claims, which
particularly point out and distinctly claim the subject matter of
the invention. While the disclosure has been illustrated and
described in detail in the drawings and foregoing description, such
illustration and description are to be considered illustrative or
exemplary and not restrictive.
[0186] All references cited herein are incorporated herein by
reference in their entirety. To the extent publications and patents
or patent applications incorporated by reference contradict the
disclosure contained in the specification, the specification is
intended to supersede and/or take precedence over any such
contradictory material.
[0187] Unless otherwise defined, all terms (including technical and
scientific terms) are to be given their ordinary and customary
meaning to a person of ordinary skill in the art, and are not to be
limited to a special or customized meaning unless expressly so
defined herein. It should be noted that the use of particular
terminology when describing certain features or aspects of the
disclosure should not be taken to imply that the terminology is
being re-defined herein to be restricted to include any specific
characteristics of the features or aspects of the disclosure with
which that terminology is associated. Terms and phrases used in
this application, and variations thereof, especially in the
appended claims, unless otherwise expressly stated, should be
construed as open ended as opposed to limiting. As examples of the
foregoing, the term `including` should be read to mean `including,
without limitation,` `including but not limited to,` or the like;
the term `comprising` as used herein is synonymous with
`including,` `containing,` or `characterized by,` and is inclusive
or open-ended and does not exclude additional, unrecited elements
or method steps; the term `having` should be interpreted as `having
at least;` the term `includes` should be interpreted as `includes
but is not limited to;` the term `example` is used to provide
exemplary instances of the item in discussion, not an exhaustive or
limiting list thereof; adjectives such as `known`, `normal`,
`standard`, and terms of similar meaning should not be construed as
limiting the item described to a given time period or to an item
available as of a given time, but instead should be read to
encompass known, normal, or standard technologies that may be
available or known now or at any time in the future; and use of
terms like `preferably,` `preferred,` `desired,` or `desirable,`
and words of similar meaning should not be understood as implying
that certain features are critical, essential, or even important to
the structure or function of the invention, but instead as merely
intended to highlight alternative or additional features that may
or may not be utilized in a particular embodiment of the invention.
Likewise, a group of items linked with the conjunction `and` should
not be read as requiring that each and every one of those items be
present in the grouping, but rather should be read as `and/or`
unless expressly stated otherwise. Similarly, a group of items
linked with the conjunction `or` should not be read as requiring
mutual exclusivity among that group, but rather should be read as
`and/or` unless expressly stated otherwise.
[0188] Where a range of values is provided, it is understood that
the upper and lower limit, and each intervening value between the
upper and lower limit of the range is encompassed within the
embodiments.
[0189] With respect to the use of substantially any plural and/or
singular terms herein, those having skill in the art can translate
from the plural to the singular and/or from the singular to the
plural as is appropriate to the context and/or application. The
various singular/plural permutations may be expressly set forth
herein for sake of clarity. The indefinite article `a` or `an` does
not exclude a plurality. A single processor or other unit may
fulfill the functions of several items recited in the claims. The
mere fact that certain measures are recited in mutually different
dependent claims does not indicate that a combination of these
measures cannot be used to advantage. Any reference signs in the
claims should not be construed as limiting the scope.
[0190] It will be further understood by those within the art that
if a specific number of an introduced claim recitation is intended,
such an intent will be explicitly recited in the claim, and in the
absence of such recitation no such intent is present. For example,
as an aid to understanding, the following appended claims may
contain usage of the introductory phrases `at least one` and `one
or more` to introduce claim recitations. However, the use of such
phrases should not be construed to imply that the introduction of a
claim recitation by the indefinite articles `a` or `an` limits any
particular claim containing such introduced claim recitation to
embodiments containing only one such recitation, even when the same
claim includes the introductory phrases `one or more` or `at least
one` and indefinite articles such as `a` or `an` (e.g., `a` and/or
`an` should typically be interpreted to mean `at least one` or `one
or more`); the same holds true for the use of definite articles
used to introduce claim recitations. In addition, even if a
specific number of an introduced claim recitation is explicitly
recited, those skilled in the art will recognize that such
recitation should typically be interpreted to mean at least the
recited number (e.g., the bare recitation of `two recitations,`
without other modifiers, typically means at least two recitations,
or two or more recitations). Furthermore, in those instances where
a convention analogous to `at least one of A, B, and C, etc.` is
used, in general such a construction is intended in the sense one
having skill in the art would understand the convention (e.g., `a
system having at least one of A, B, and C` would include but not be
limited to systems that have A alone, B alone, C alone, A and B
together, A and C together, B and C together, and/or A, B, and C
together, etc.). In those instances where a convention analogous to
`at least one of A, B, or C, etc.` is used, in general such a
construction is intended in the sense one having skill in the art
would understand the convention (e.g., `a system having at least
one of A, B, or C` would include but not be limited to systems that
have A alone, B alone, C alone, A and B together, A and C together,
B and C together, and/or A, B, and C together, etc.). It will be
further understood by those within the art that virtually any
disjunctive word and/or phrase presenting two or more alternative
terms, whether in the description, claims, or drawings, should be
understood to contemplate the possibilities of including one of the
terms, either of the terms, or both terms. For example, the phrase
`A or B` will be understood to include the possibilities of `A` or
`B` or `A and B.`
[0191] All numbers expressing quantities of ingredients, reaction
conditions, and so forth used in the specification are to be
understood as being modified in all instances by the term `about.`
Accordingly, unless indicated to the contrary, the numerical
parameters set forth herein are approximations that may vary
depending upon the desired properties sought to be obtained. At the
very least, and not as an attempt to limit the application of the
doctrine of equivalents to the scope of any claims in any
application claiming priority to the present application, each
numerical parameter should be construed in light of the number of
significant digits and ordinary rounding approaches.
[0192] Furthermore, although the foregoing has been described in
some detail by way of illustrations and examples for purposes of
clarity and understanding, it is apparent to those skilled in the
art that certain changes and modifications may be practiced.
Therefore, the description and examples should not be construed as
limiting the scope of the invention to the specific embodiments and
examples described herein, but rather to also cover all
modification and alternatives coming with the true scope and spirit
of the invention.
* * * * *