U.S. patent application number 15/291508 was filed with the patent office on 2018-04-12 for degradable conjugated polymers for the selective sorting of semiconducting carbon nanotubes.
The applicant listed for this patent is Wisconsin Alumni Research Foundation. Invention is credited to Michael Scott Arnold, Gerald Joseph Brady, Padma Gopalan, Catherine Kanimozhi Kansiusarulsamy, Matthew John Shea.
Application Number | 20180099870 15/291508 |
Document ID | / |
Family ID | 61801559 |
Filed Date | 2018-04-12 |
United States Patent
Application |
20180099870 |
Kind Code |
A1 |
Gopalan; Padma ; et
al. |
April 12, 2018 |
DEGRADABLE CONJUGATED POLYMERS FOR THE SELECTIVE SORTING OF
SEMICONDUCTING CARBON NANOTUBES
Abstract
Conjugated polymers composed of bi-pyridine units linked to
9,9-dialkyl fluorenyl-2,7-diyl units via imine linkages along the
polymer backbone are provided. Also provided are semiconducting
single-walled carbon nanotubes coated with the conjugated polymers
and methods of sorting and separating s-SWCNTs from a sample
comprising a mixture of s-SWCNTs and metallic single-walled carbon
nanotubes using the conjugated polymers.
Inventors: |
Gopalan; Padma; (Madison,
WI) ; Arnold; Michael Scott; (Middleton, WI) ;
Kansiusarulsamy; Catherine Kanimozhi; (Madison, WI) ;
Brady; Gerald Joseph; (Madison, WI) ; Shea; Matthew
John; (Madison, WI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Wisconsin Alumni Research Foundation |
Madison |
WI |
US |
|
|
Family ID: |
61801559 |
Appl. No.: |
15/291508 |
Filed: |
October 12, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C01B 2202/02 20130101;
C08G 73/0627 20130101; C08G 16/0231 20130101; C01B 32/172 20170801;
C01B 2202/22 20130101; C09D 179/04 20130101; C01B 32/17 20170801;
C08G 73/00 20130101; H01L 51/0039 20130101; H01L 51/0048 20130101;
H01L 51/0558 20130101; C09D 179/04 20130101; C08K 3/041
20170501 |
International
Class: |
C01B 31/02 20060101
C01B031/02; C08G 73/06 20060101 C08G073/06 |
Goverment Interests
REFERENCE TO GOVERNMENT RIGHTS
[0001] This invention was made with government support under
MSN125061 awarded by the Department of Energy. The government has
certain rights in the invention.
Claims
1. A conjugated polymer having the structure: ##STR00004## where R
represents a functional group comprising an alkyl chain and n
represents the number of repeat units in the conjugated
polymer.
2. The conjugated polymer of claim 1, wherein R has the structure:
C.sub.xH.sub.(2x+1), where x is in the range from 6 to 30.
3. Polymer-wrapped semiconducting single-walled carbon nanotubes
comprising semiconducting single-walled carbon nanotubes coated by
a conjugated polymer having the structure: ##STR00005## where R
represents a functional group comprising an alkyl chain and n
represents the number of repeat units in the conjugated
polymer.
4. The polymer-wrapped semiconducting single-walled carbon
nanotubes of claim 3, wherein n has a value of 15 or lower.
5. The polymer-wrapped semiconducting single-walled carbon
nanotubes of claim 3, wherein R has the structure:
C.sub.xH.sub.(2x+1), where x is in the range from 6 to 20.
6. A method of separating semiconducting single-walled carbon
nanotubes from a starting carbon nanotube sample comprising a
mixture of semiconducting single-walled carbon nanotubes and
metallic single-walled carbon nanotubes, the method comprising:
forming a solution comprising the carbon nanotube sample and a
conjugated polymer having the structure: ##STR00006## where R
represents a functional group comprising an alkyl chain and n
represents the number of repeat units in the conjugated polymer,
wherein the conjugated polymer preferentially coats and disperses
the semiconducting single-walled carbon nanotubes, relative to the
metallic single-walled carbon nanotubes, in the solution; and
separating the dispersed single-walled carbon nanotubes from the
undispersed single-walled carbon nanotubes to obtain a purified
carbon nanotube sample, wherein the purified carbon nanotube sample
has a higher ratio of semiconducting single-walled carbon nanotubes
to metallic single-walled carbon nanotubes than did the starting
carbon nanotube sample.
7. The method of claim 6, wherein n has a value of 15 or lower.
8. The method of claim 6, wherein n has a value of 10 or lower.
9. The method of claim 6, wherein the purified carbon nanotube
sample comprises at least 99% semiconducting single-walled carbon
nanotubes, based on the total number of semiconducting
single-walled carbon nanotubes and metallic single-walled carbon
nanotubes.
10. The method of claim 6, further comprising removing the coating
of the conjugated polymer from the semiconducting single-walled
carbon nanotubes in the purified carbon nanotube sample.
11. The method of claim 10, wherein removing the coating of the
conjugated polymer from the semiconducting single-walled carbon
nanotubes comprises depolymerizing the conjugated polymer with
acid, heat, or a combination of acid and heat.
12. The method of claim 11, wherein removing the coating of the
conjugated polymer from the semiconducting single-walled carbon
nanotubes comprises depolymerizing the conjugated polymer with
acid.
13. The method of claim 11, wherein removing the coating of the
conjugated polymer from the semiconducting single-walled carbon
nanotubes comprises depolymerizing the conjugated polymer with
heat.
14. The method of claim 6, where R has the structure:
C.sub.xH.sub.(2x+1), where x is in the range from 6 to 20.
15. A method of separating semiconducting single-walled carbon
nanotubes from a starting carbon nanotube sample comprising a
mixture of semiconducting single-walled carbon nanotubes and
metallic single-walled carbon nanotubes, the method comprising:
forming a solution comprising the carbon nanotube sample and a
conjugated polymer having imine linkages along its polymer backbone
chain, wherein the conjugated polymer preferentially coats and
disperses the semiconducting single-walled carbon nanotubes,
relative to the metallic single-walled carbon nanotubes, in the
solution; separating the dispersed single-walled carbon nanotubes
from the undispersed single-walled carbon nanotubes to obtain a
purified carbon nanotube sample, wherein the purified carbon
nanotube sample has a higher ratio of semiconducting single-walled
carbon nanotubes to metallic single-walled carbon nanotubes than
did the starting carbon nanotube sample; and heating the conjugated
polymer-coated semiconducting single-walled carbon nanotubes to a
temperature at which the backbone of the conjugated polymer
thermally decomposes, whereby at least 60 percent, by weight, of
the coating of the conjugated polymer is removed from the
semiconducting single-walled carbon nanotubes.
16. The method of claim 15, wherein the thermal decomposition of
the conjugated polymer is carried out in the absence of acid.
17. The method of claim 15, wherein the thermal decomposition of
the conjugated polymer is carried out at a temperature in range
from 300.degree. C. to 500.degree. C.
Description
BACKGROUND
[0002] Single-walled carbon nanotubes (SWCNTs) have exceptional
electronic properties that enable a plethora of semiconducting
applications such as field-effect transistors (FETs), photovoltaics
(PVs), and gas sensors. In order to implement SWCNTs as the
semiconducting material in electronic devices, it is important to
purify and sort out the desirable semiconducting SWCNTs (s-SWCNTs)
from as-synthesized electronically heterogeneous SWCNT mixtures.
This challenge in synthetic heterogeneity has motivated researchers
to develop a number of sorting techniques, such as density gradient
ultracentrifugation, aqueous two-phase separation, and polymer
wrapping. Among these methods for sorting s-SWCNTs, polymer
wrapping is perhaps the most efficient and potentially the most
effective at selectively isolating pure s-SWCNTs. In particular,
conjugated polyfluorene polymers are useful materials that have
7E-7E interactions with a high degree of s-SWCNT selectivity based
on chirality, diameter and electronic type. However, a considerable
challenge that has yet to be fully addressed is the removal of the
remaining polymer chains attached to the sidewalls of s-SWCNTs
after sorting, which result in high inter-tube energetic barriers
and inferior s-SWCNT network connections.
SUMMARY
[0003] Conjugated polymers composed of bi-pyridine units linked to
9,9-dialkyl fluorenyl-2,7-diyl units via imine linkages along the
polymer backbone are provided. Also provided are s-SWCNTs coated
with the conjugated polymers and methods of sorting and separating
s-SWCNTs from a sample comprising a mixture of s-SWCNTs and
metallic single-walled carbon nanotubes (m-SWCNTs) using the
conjugated polymers.
[0004] One embodiment of a conjugated polymer has the
structure:
##STR00001##
where R represents a functional group comprising an alkyl chain and
n represents the number of repeat units in the conjugated
polymer.
[0005] One embodiment of a method for separating semiconducting
single-walled carbon nanotubes from a starting carbon nanotube
sample comprising a mixture of semiconducting single-walled carbon
nanotubes and metallic single-walled carbon nanotubes comprises the
steps of: (a) forming a solution comprising the carbon nanotube
sample and a conjugated polymer having the structure:
##STR00002##
where R represents a functional group comprising an alkyl chain and
n represents the number of repeat units in the conjugated polymer,
wherein the conjugated polymer preferentially coats and disperses
the semiconducting single-walled carbon nanotubes, relative to the
metallic single-walled carbon nanotubes, in the solution; and (b)
separating the dispersed single-walled carbon nanotubes from the
undispersed single-walled carbon nanotubes to obtain a purified
carbon nanotube sample, wherein the purified carbon nanotube sample
has a higher ratio of semiconducting single-walled carbon nanotubes
to metallic single-walled carbon nanotubes than did the starting
carbon nanotube sample. The conjugated polymer coating can then be
removed from the separated single-walled carbon nanotubes by
depolymerizing the conjugated polymer with acid, heat, or a
combination of acid and heat.
[0006] Another embodiment of a method for separating semiconducting
single-walled carbon nanotubes from a starting carbon nanotube
sample comprising a mixture of semiconducting single-walled carbon
nanotubes and metallic single-walled carbon nanotubes comprises the
steps of: (a) forming a solution comprising the carbon nanotube
sample and a conjugated polymer having imine linkages along its
polymer backbone chain, wherein the conjugated polymer
preferentially coats and disperses the semiconducting single-walled
carbon nanotubes, relative to the metallic single-walled carbon
nanotubes, in the solution; (b) separating the dispersed
single-walled carbon nanotubes from the undispersed single-walled
carbon nanotubes to obtain a purified carbon nanotube sample,
wherein the purified carbon nanotube sample has a higher ratio of
semiconducting single-walled carbon nanotubes to metallic
single-walled carbon nanotubes than did the starting carbon
nanotube sample; and (c) heating the conjugated polymer-coated
semiconducting single-walled carbon nanotubes to a temperature at
which the conjugated polymer thermally decomposes, whereby at least
60 percent, by weight, of the coating of the conjugated polymer is
removed from the semiconducting single-walled carbon nanotubes.
[0007] Other principal features and advantages of the invention
will become apparent to those skilled in the art upon review of the
following drawings, the detailed description, and the appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Illustrative embodiments of the invention will hereafter be
described with reference to the accompanying drawings, wherein like
numerals denote like elements.
[0009] FIG. 1 depicts a general procedure for the polymerization of
P1 and P3 (as defined in the Example).
[0010] FIG. 2 depicts a general procedure for the synthesis of
2,7-diazido-9,9-dialkyl fluorene monomers having two different R
groups.
[0011] FIG. 3 depicts the synthesis of a
2,2'-bipyridine-6,6'-dicarbaldehyde monomer.
[0012] FIG. 4 depicts the absorbance spectra for solutions of arc
discharge (Arc-D) s-SWCNTs wrapped with PFO--N--BPy in toluene and
with PFO--BPy in toluene.
[0013] FIG. 5 depicts UV-Vis-NIR spectra of PFO--N--BPy (P1)-sorted
Arc-D and HiPCo SWCNTs in toluene.
[0014] FIG. 6 depicts absorbance spectra indicating the solution
acid degradation of PFO--N--BPy (P1) with trifluoro acetic acid in
toluene.
[0015] FIG. 7 depicts absorbance spectra indicating the thin film
acid degradation of PFO--N--BPy (P1) with trifluoro acetic
acid.
[0016] FIG. 8 depicts the thin film UV-Vis spectra of PFO--N--BPy
(P1 & P3) before thermal annealing.
[0017] FIG. 9 depicts the thin film UV-Vis spectra of PFO--N--BPy
(P1 & P3) after thermal annealing at 400.degree. C. for 1 h
under vacuum.
[0018] FIG. 10 depicts the removal of the polymer PFO--N--BPy from
SWCNT surface in the presence of trifluoro acetic acid.
[0019] FIG. 11 depicts UV-Vis absorption spectra of M1 monomer, M2
monomer, and a PFO--N--BPy polymer in chloroform.
[0020] FIG. 12 depicts absorbance spectra indicating the removal of
PFO--N--BPy from the Arc-D SWCNT surface in the presence of
trifluoro acetic acid (TFA).
[0021] FIG. 13 depicts the thermal gravimetric analysis (TGA)
weight loss curves for PFO--BPy, PFO--N--BPy (P1), and PFO--N--BPy
(P3).
[0022] FIG. 14 is a schematic diagram of a thin film field effect
transistor.
[0023] FIG. 15 shows the transfer characteristics of a thin film
transistor.
[0024] FIG. 16 shows a scanning electron microscope image (SEM) of
a thin film transistor (left panel), with an enlarged view of a
portion of the channel region (right panel) showing a plurality of
aligned s-SWCNTs.
[0025] FIG. 17 depicts a graph showing effect of PFO--N--BPy
removal on the charge transport of a s-SWCNT film.
DETAILED DESCRIPTION
[0026] Conjugated polymers composed of bi-pyridine (BPy) units
linked to 9,9-dialkyl fluorenyl-2,7-diyl units via imine linkages
along the polymer backbone are provided. Also provided are s-SWCNTs
coated (also referred to as "wrapped") with the conjugated polymers
and methods of sorting and separating s-SWCNTs from a sample
comprising a mixture of s-SWCNTs and metallic single-walled carbon
nanotubes (m-SWCNTs) using the conjugated polymers.
[0027] The conjugated polymer, which is referred to as PFO--N--BPy,
has the following structure:
##STR00003##
where R represents a functional group that consists of or includes
an alkyl chain having the structure C.sub.xH.sub.(2x+1), wherein x
represents the number of carbon atoms in the alkyl chain and n
represents the number of repeat units in the polymer backbone
chain. By way of illustration, in some embodiments of the polymers
x has a value in the range from 6 to 20, inclusive. The conjugated
polymer can be synthesized in accordance with the methods presented
in the Example.
[0028] Because the conjugated polymer preferentially binds to and
disperses s-SWCNTs in solution, it can be used to selectively
separate the s-SWCNTs from a mixed carbon nanotube starting sample
to provide an ultrahigh purity s-SWCNT sample. Once the sorting is
completed, the depolymerization and removal of the conjugated
polymer can be carried out using a mild acid, a low temperature
heat treatment, or a combination of both in a procedure that does
not significantly adversely affect the electric and/or optoelectric
properties of the SWCNTs. As a result, the methods can be used to
provide s-SWCNTs that are suitable for use in electronic devices,
such as field effect transistors, and in optoelectronic devices,
such as photovoltaic cells.
[0029] The methods can be used to sort and separate s-SWCNTs having
a variety of diameters and bandgaps, including s-SWCNTs that are
suited for electronic and/or optoelectronic applications. By way of
illustration, the methods can be used to sort s-SWCNTs having
diameters in the range from about 1.3 nm to about 1.7 nm. Such
s-SWCNTs are useful as active materials in electronic devices, such
as field effect transistors, and can be made relatively
inexpensively using arc discharge techniques. Alternatively, the
methods can be used to sort s-SWCNTs having diameters in the range
from about 0.7 nm to about 1 nm. Such s-SWCNTs are useful as active
materials in optoelectronic devices, such as photovoltaic cells,
and can be made using Co--Mo catalysts (i.e., using CoMoCAT
techniques).
[0030] In one embodiment of a method of sorting and separating
s-SWCNTs from a starting sample containing a mixture of s-SWCNTs
and m-SWCNTs, a solution including the starting sample, the
conjugated polymer, and an organic solvent is formed. The organic
solvent can be a single solvent or a solvent mixture in which the
conjugated polymer is substantially soluble. Examples of suitable
solvents include toluene, chloroform, dichloromethane, and
dichlorobenzene. The conjugated polymer in the solution
preferentially binds to and wraps the s-SWCNTS, relative to the
m-SWCNTs. As a result, the s-SWCNTs are selectively dispersed in
the solution, while the m-SWCNTs selectively fall out of the
solution. Optionally, the dispersion of the s-SWCNTs can be
facilitated by agitating the solution using, for example,
ultrasonication. The undispersed m-SWCNTs can then be removed from
the solution using, for example, centrifugation followed by
filtration, leaving a purified solution that is enriched in
s-SWCNTs.
[0031] The polymer coating on the s-SWCNTs can be removed by
exposing the polymer-coated s-SWCNTs to a mild acid and/or a mild
heat treatment in order to depolymerize the conjugated polymer. As
a result, the uncoated s-SWCNTs will fall out of solution and can
be collected using, for example, centrifugation and filtration.
Organic acides, such as trifluoro acetic acid, are examples of
acids that can be added to a solution of the polymer-coated
s-SWCNTs in order to depolymerize and remove the conjugated
polymer. The acid can be added directly to the initial purified
solution of s-SWCNTs. Alternatively, the solvent from the initial
purified solution can be removed by, for example, evaporation, and
the polymer coated s-SWCNTs can be re-dispersed in a new solvent to
which the acid is added. The acids should be sufficiently weak that
they do not oxidize the sp.sup.2 carbons on the SWCNT surface to an
extent that would significantly negatively affect charge
transport.
[0032] As an alternative to, or in addition to, depolymerization
via acid degradation, thermal degradation can be used to
depolymerize the conjugated polymer coating. For example, the
polymer can be depolymerized by heating the purified solution
enriched in s-SWCNTs to an elevated temperature for a sufficient
time. By way of illustration only, this thermal treatment can be
carried out at temperatures of 500.degree. C., or lower, for time
periods of 6 hours or less. In some embodiments, the thermal
treatment is carried out at a temperature of 450.degree. C., or
lower, for a time period of 2 hours or less. For example,
temperatures in the range from about 350.degree. C. to about
450.degree. C. can be used. When both an acid treatment and a
thermal treatment are used, the polymer-coated s-SWCNTs can be
exposed to the acid and the heat simultaneously or in a sequential,
step-wise fashion.
[0033] Although the thermal depolymerization of the polymer wrapped
s-SWCNTs is described and illustrated using PFO--N--BPy coated
s-SWCNTs, the thermal treatment can also be used to remove other
conjugated polymers having imine linkages along their backbone from
s-SWCNTs. For example, the thermal depolymerization can be applied
to other conjugated polymers comprising bipyridine repeat units and
imine linkages along their backbone. In some embodiments of the
methods, exposing the polymer-coated s-SWCNTs to heat, without the
use of acid, is able to remove at least 50% of the polymer, by
weight. This includes methods in which at least 60% by weight or at
least 65% by weight of the polymer is removed using heat treatment
alone. Methods of determining the percentage of polymer weight loss
using TGA are described in the Example.
[0034] FIG. 10 is a schematic diagram of a procedure for removing
the conjugated polymer from polymer-coated s-SWCNTs in solution and
collecting the uncoated s-SWCNTs. A more detailed description of
the method is provided in the Example. Panel (a) in FIG. 10 depicts
a purified solution 1302 that is enriched in s-SWCNTs, which are
dispersed in the solution. In a first step of the process, an acid,
such as trifluoro acetic acid, is added to purified solution 1302.
As a result, the conjugated polymer is depolymerized and the
s-SWCNTs form agglomerates 1304 (panel (b)). The solvent in the
solution is then evaporated (panel (c)) and the s-SWCNTs 1304,
along with the degraded polymer, collect at the bottom of container
1306. The s-SWCNTS can then be washed in an appropriate solvent,
such as chloroform, one or more times (Step 3; panel (d)) to remove
the degraded polymer. Finally, the s-SWCNTs can be re-dispersed in
a solvent for downstream processing (Step 4). The s-SWCNT sorting
process can be repeated through multiple cycles to increase the
s-SWCNT yield. In addition, the monomers that are regenerated when
the polymer is degraded can be separated, collected, and
re-polymerized for use in subsequent cycles of the s-SWCNT sorting
process.
[0035] Notably, the conjugated polymer coatings that are composed
of even relatively short chain polymers still have a high
selectivity for the s-SWCNTs, relative to the m-SWCNTs. This
includes embodiments of the conjugated polymers having no more than
20, no more than 15, no more than 12, or no more than 10 repeat
units (i.e., conjugated polymers for which "n" is .ltoreq.20;
.ltoreq.15; .ltoreq.12; or .ltoreq.10). The use of these short
chain polymers is advantageous because short chains tend to make
the conjugated polymers more susceptible to depolymerization.
[0036] The procedures described here result in a highly pure sample
of s-SWCNTs having a ratio of s-SWCNTs to m-SWCNTs that is
substantially higher than that of the starting mixed SWCNTs sample.
In some embodiments, the methods of sorting and separating s-SWCNTs
provide a purified sample that contains at least 98% s-SWCNTs,
based on the total number of s-SWCNTs and m-SWCNTs in the sample.
This includes methods that provide a purified sample that contains
at least 99% s-SWCNTs, based on the total number of s-SWCNTs and
m-SWCNTs in the sample, and further includes methods that provide a
purified sample that contains at least 99.5% s-SWCNTs, based on the
total number of s-SWCNTs and m-SWCNTs in the sample. Methods for
quantifying s-SWCNT purity can be found in Ding, J. F., et al.
(2015). "A hybrid enrichment process combining conjugated polymer
extraction and silica gel adsorption for high purity semiconducting
single-walled carbon nanotubes (SWCNT)." Nanoscale 7(38):
15741-15747.
[0037] Once the s-SWCNTs have been purified and collected, they can
be incorporated into active or passive layers in a variety of
electronic and optoelectronic devices. For many device
applications, it is advantageous for the SWCNTs to be aligned along
their long axes. Using the method of floating evaporative assembly,
the conjugated polymer-coated s-SWCNTs can be aligned on a
substrate, prior to the removal of the conjugated polymer. Methods
for depositing a film of aligned polymer-coated CNTs onto a
substrate from a solution of the polymer-coated CNTs can be found
in Joo et al., Langmuir, 2014, 30 (12), 3460-3466; U.S. Pat. No.
9,368,723; and in PCT application publication no. WO/2015123251. In
these methods, a hydrophobic substrate is partially submerged in an
aqueous medium and a flow of a liquid solution is applied to the
surface of the aqueous medium, the liquid solution containing the
PFO--N--BPy-wrapped s-SWCNTs dispersed in an organic solvent. This
liquid solution spreads into a layer on the aqueous medium at an
air-liquid interface and the PFO--N--BPy-wrapped s-SWCNTs from the
layer are deposited as a film of aligned PFO--N--BPy-wrapped
s-SWCNTs on the hydrophobic substrate, wherein the organic solvent
in the layer, which is evaporating, is resupplied by a continuous
or discontinuous flow of the liquid solution during the formation
of the film. As the aligned PFO--N--BPy-wrapped s-SWCNTs are being
deposited on the surface of the hydrophobic substrate, that
substrate is withdrawn from the aqueous medium, such that a
continuous or discontinuous film of aligned PFO--N--BPy-wrapped
s-SWCNTs is deposited along the length of the hydrophobic substrate
as it is withdrawn from the aqueous medium. As discussed in U.S.
Pat. No. 9,425,405 and in PCT application publication no.
WO2015123251, the resulting aligned SWCNTs can have a degree of
alignment of .+-.20.degree. or better (for example, .+-.15.degree.
or better) and a SWCNT linear packing density in the film is at
least 40 single-walled carbon nanotubes/.mu.m. Once the film has
been deposited, the conjugated polymer can be removed from the
aligned SWCNTs using an acid and/or heat treatment. The films of
highly aligned, densely packed s-SWCNTs are suited for use in the
conducting channel of a thin film field effect transistor.
[0038] One embodiment of a field effect transistor (TFT)
incorporating the sorted and aligned s-SWCNTs is shown
schematically in FIG. 14. The TFT includes: a source electrode
1802; a drain electrode 1804; a gate electrode 1806; a conducting
channel 1808 in electrical contact with the source electrode and
the drain electrode; and a gate dielectric 1810 (e.g., silicon
dioxide) disposed between the gate electrode and the conducting
channel. Conducting channel 1808 comprises a film of the sorted and
aligned s-SWCNTs.
EXAMPLE
[0039] This example illustrates methods for synthesizing
PFO--N--BPy and for using PFO--N--BPy to separate s-SWCNTs for the
starting sample containing a mixture of s-SWCNTs and m-SWCNTs.
[0040] General procedure for the synthesis of
2,7-Diazido-9,9-dialkyl fluorene (M1 and M3. FIG. 2 shows the
reaction scheme for the synthesis of 2,7-diazido-9,9-dialkyl
fluorene having two different R groups (R=n-C.sub.8H.sub.17 (M1)
and R=n-C.sub.12H.sub.25 (M3)). A 100 mL round bottom flask was
charged with sodium azide (2.5 mmol) and copper (II) sulfate
pentahydrate (0.2 mmol). To this, methanol (8 mL) and
9,9-dialkyl-9H-fluorene-2,7-diyldiboronic acid (1.00 mmol) were
added. The reaction mixture was stirred at the same temperature for
48 h. After completion of the reaction, the solvent was removed
under reduced pressure and the residue was treated with petroleum
ether and filtered to remove inorganic salts. The solvent was
removed to give the 2,7-diazido-9,9-dialkyl-9H-fluorene as a pale
yellow solid.
[0041] Synthesis of 2,2'-bipyridine-6,6'-dicarbaldehyde (M2). FIG.
3 shows the reaction scheme for the synthesis of
2,2'-bipyridine-6,6'-dicarbaldehyde (M2).
6,6'-dimethyl-2,2'-bipyridine (1 mmol) was dissolved in dimethyl
sulfoxide (DMSO) (5 ml) and the mixture was warmed to 50.degree. C.
Iodine (2.5 mmol) in 25 mL of DMSO was slowly added to the
solution. The mixture was then added to a 250 mL round bottom flask
charged with 250 mL of DMSO which was preheated at 145.degree. C.
The reaction mixture was refluxed at the same temperature for 24 h,
and a vigorous exothermic reaction occurred with evolution of
dimethyl sulphide. After 24 h the excess iodine was quenched with
saturated aqueous sodium thiosulphate solution until a pale yellow
solution was obtained. Water was added to the solution to give a
total volume of 250 ml and the solution was then extracted with
dichloromethane (3.times.200 ml), washed with water (2.times.100
ml), dried over magnesium sulphate, and filtered. Finally, the
solvent was removed on the rotary evaporator to yield a beige
solid. The crude product was then crystallized by
dichloromethane/petroleum ether to yield M2 as pale yellow crystals
(71%).
[0042] General procedure for the polymerization of M2 with M1 (P1)
and of M2 with M3 (P3). FIG. 1 shows the reaction scheme for the
polymerization of M2 and M1 to form conjugated polymer P1 and the
polymerization of M2 with M3 to form conjugated polymer P3. An oven
dried 100 mL round-bottom flask was charged with M1 (200 mg, mmol),
and M2 (88 mg, mmol). This mixture was evacuated and refilled with
argon, and 15 mL of freshly distilled anhydrous toluene (50 mL)
were added under nitrogen atmosphere. This mixture was purged with
argon for 15 min to remove dissolved oxygen, after which excess
(n-Bu).sub.3P (88 mg, mmol) was added. Immediately, a dark red
color was observed with an evolution of nitrogen, indicating the
formation of the reactive phosphazene intermediate. This reaction
mixture was heated at 80.degree. C. for 48 h. After 48 h the
reaction was cooled, the solvent was reduced to half the volume,
and the product was precipitated in methanol (MeOH). Soxhlet
extraction of the crude solid with hot MeOH was carried out to
remove low molecular weight oligomers and other phosphine oxide
by-products. The polymer was collected and dried to afford a yellow
solid (200 mg, yield 65%): .sup.1H NMR (400 MHz, Chloroform-d)
.delta. 10.21 (s, 1H), 8.86 (d, J=11.0 Hz, 1H), 8.64 (d, J=7.5 Hz,
OH), 8.36 (d, J=7.0 Hz, 0H), 8.02 (s, 0H), 7.82-7.64 (m, 0H), 7.39
(s, 1H), 7.05-6.97 (m, 0H), 2.05 (s, 0H), 1.08 (s, 4H), 0.84-0.50
(m, 1H). Molecular weight GPC, Mn: 6,600 g/mol PDI: 2.01. n for P1
and P3 was 10.
[0043] Preparation of arc discharge CNT/PFO--N--BPy solutions;
HiPCo CNT/PFO--N--BPy solutions; CNT/PFO--BPy solutions; HiPCo
CNT/PFO--BPy solutions:
[0044] Large-diameter, semiconducting enriched SWCNTs were
extracted from an arc discharge carbon nanotube powder (750514,
Sigma-Aldrich) or a HiPCO carbon nanotube powder (Raw, Nanolntegris
R1-831). A 1:1 weight ratio of 1 mg/ml of the powder and 1 mg/mL
PFO--N--BPy) were dispersed in 60 ml of toluene using a horn tip
sonicator (Thermo Fisher Scientific, Sonic Dismembrator 500) at 64
W power. The sonication time of the initial dispersion was 15 min.
Following the initial dispersion, the SWCNT solution was
centrifuged (Thermo Fisher Scientific, Sorvall W X, swing bucket
rotor, TH-641) at 41 krpm for 10 min. to remove un-dispersed
materials. The upper 90% of the supernatant was collected and
centrifuged for an additional 30 min. at 41 krpm. The supernatant
was collected and, optionally, the toluene was distilled, rendering
a gel-like PFO--N--BPy SWCNT mixture. The solution was then
centrifuged and dispersed with bath sonication four times in
toluene to rinse off as much excess PFO--N--BPy as possible. For
some polymer degradation studies, the PFO--N--BPy SWCNT mixture was
then dispersed in chloroform. The final solution was prepared by
horn-tip sonication of the rinsed SWCNT pellet in chloroform for a
total of 30 seconds.
[0045] For comparison, solutions of the arc discharge carbon
nanotubes with poly(9,9-dioctylfluorene-2,7-diyl-co-bipyrine)
(PFO--BPy) (American Dye Source, Inc., Mw. 48 k), which lacks a
backbone imine linkage, were also prepared using the same procedure
described above.
[0046] Comparison of s-SWCNT Sorting: PFO--N--BPy vs. PFO--BPy.
[0047] Absorption spectra of PFO--N--BPy- and PFO--BPy-sorted arc
discharge SWCNTs in toluene (FIG. 4) were similar, indicating
selectivity for similar diameter SWCNTs. S22 and S33 peaks are the
second and third energy transitions of semiconducting SWCNTs that
were broadened due to an overlap of a wide diameter distribution
and M11 peaks were absent in the sorted spectra because of
significant removal of metallic impurities. FIG. 5 shows the
absorption spectra of PFO--N--BPy-sorted HiPCo and arc-discharge
SWCNTs in toluene.
[0048] Acid Degradation (Depolymerization) Studies of
PFO--N--BPy.
[0049] Degradation of PFO--N--BPy to remove the polymer from the
SWCNT surfaces was studied in solution and in a thin-film in the
presence of an aqueous solution of trifluoroacetic acid in toluene
(TFA, 0.1% v/v). The trifluoroacetic acid in toluene (TFA, 0.1%
v/v) and a drop of water were added to the polymer wrapped SWCNTs
in toluene. Polymer degradation was monitored by the disappearance
of the maximum absorption peak at 394 nm in solution and at 402 nm
in thin film studies. FIG. 6 and FIG. 7 show the absorbance spectra
for the PFO--N--BPy solution and PFO--N--BPy thin-film,
respectively, before the addition of the TFA and at 10 s and 40 s
after the addition of the TFA. Post TFA treatment, the solution
absorption spectra showed only the monomer absorption peaks at 320
and 280 nm, which confirmed quantitative degradation of PFO--N--BPy
in solution.
[0050] Degradation of PFO--N--BPy to remove the polymer from the
SWCNT surfaces was also studied in solution and in a thin-film in
the presence of an aqueous solution of trifluoroacetic acid in
chloroform using the process illustrated in FIG. 10. FIG. 11 shows
the absorbance spectra of the M1 monomer, the M2 monomer, the
PFO--N--BPy polymer, and the PFO--BPy polymer. FIG. 12 shows the
absorbance spectra for the PFO--N--BPy polymer, for a solution of
the PFO--N--BPy wrapped SWCNTs with TFA in chloroform, and for the
SWCNTs after polymer removal and washing the solution with
chloroform to remove the residual monomers generated after polymer
degradation. Polymer degradation was monitored by the disappearance
of absorption peak at 392 nm.
[0051] Thermal Degradation (Depolymerization) Studies of
PFO--N--BPy and PFO--BPy.
[0052] Thermal properties of PFO--N--BPy (P1 and P3) and PFO--BPy
were studied by thermogravimetric analysis (TGA) and differential
scanning calorimetry (DSC). In the TGA measurements, a single step
decomposition was typically observed in the course of ramping up
the temperature for all three polymers, as shown in the weigh loss
graph of FIG. 13. PFO--N--BPy polymers exhibited lower
decomposition temperatures (T.sub.d=360.degree. C. for P1 and
T.sub.d=345.degree. C. for P3) and .about.25% more weight loss when
compared to its non-degradable polymer analog PFO--BPy
(T.sub.d=385.degree. C.). The weight loss of .about.40% observed
for the PFO--BPy polymer is equivalent to the weight of alkyl side
chains, but for the PFO--N--BPy polymers the greater weight loss of
65% for P1 and 72% for P3 can be attributed to the simultaneous
decomposition of the side chains and the polymer conjugated
backbone. This shows that the PFO--N--BPy polymers were thermally
more labile than the PFO--BPy polymer. A higher glass transition
temperature (T.sub.g) was observed for PFO--N--BPy (145.degree.
C.-155.degree. C.) with only a few polymer repeating units
(n=10-20), which is 25-35.degree. C. greater than that of the
non-degradable polymer PFO--BPy with more than 100 repeating units.
The thermal degradation of PFO--N--BPy was also studied by
annealing the polymer thin films drop casted on glass substrates at
400.degree. C. under vacuum, followed by rinsing with chloroform.
Polymer degradation was monitored by the disappearance of the
maximum absorption peak at 402 nm. FIG. 8 shows the absorbance
spectra of the P1 and P3 thin films prior to annealing. FIG. 9
shows the absorbance spectra of the P1 and P3 thin films after
annealing. The data indicate that thermal annealing of the
thin-film can remove a majority (>95%) of the polymer. Hence
this new polymer can be degraded by mild acid as well as a thermal
process.
TABLE-US-00001 TABLE 1 Weight T.sub.d loss Solution (.degree. C.)
(%) Mn .lamda..sub.max E.sub.g (Under (Under T.sub.g Polymer
(Kg/mol) PDI DPn (nm) (eV) N.sub.2) N.sub.2) (.degree. C.) PFO-BPy
50 ~2 100 355 3.2 382 40 117 PFO-N-BPy 7 2.01 11 394 2.73 360 66
145 (P1) PFO-N-BPy 15 2.02 20 400 2.73 345 72 155 (P3) PDI =
polydispersity index; DPn = degree of polymerization.
[0053] FET device fabrication and measurement. FETs incorportating
films of aligned s-SWCNTs as channel layers were fabricated. The
aligned s-SWCNT films and the FET components were formed using the
CNT film formation methods discussed in Joo et al., Langmuir, 2014,
30 (12), 3460-3466; U.S. Pat. No. 9,368,723; and in PCT application
publication no. WO/201512325. The SWCNTs were deposited on top of a
90 nm thick, thermally-grown SiO.sub.2 dielectric on top of a
low-resistivity Si substrate, which acted as the gate dielectric
and gate electrode, respectively. In one FET, the polymer-wrapped
s-SWCNTs were used in the conducting channel without removing the
conjugated polymer wrapping. In the other FETs, prior to
fabrication of source-drain contacts, the films underwent one of
two different treatments to remove the conjugated polymer from the
SWCNT surfaces: (i) mild acid rinse using TFA in toluene solvent
(0.2% W:W) and 1 min. incubation; and (ii) a combination of (i)
followed by thermal annealing at 400.degree. C. in vacuum.
Following the formation of the s-SWCNT films, with or without a
polymer removal treatment, 30 nm thick Pd source-drain electrodes
were deposited via shadow mask lithography. FIG. 16 shows a
cross-polarized optical micrograph image of an FET made using the
mild acid rinse followed by the thermal annealing (left panel),
with an SEM image of the aligned s-SWCNT channel (right panel).
Current-voltage (I-V) measurements were taken in ambient air, and
mobility values were extracted from the linear region of the
current vs. gate voltage (swept -30 to 30 V) characteristics, which
were measured at a constant source-drain bias (-1 V). FIG. 15 shows
the I-V curves for the FET made using the mild acid rinse followed
by the thermal annealing. FIG. 17 shows that the field-effect
mobility for the three FETs increased with sequential surface
treatments.
[0054] The word "illustrative" is used herein to mean serving as an
example, instance, or illustration. Any aspect or design described
herein as "illustrative" is not necessarily to be construed as
preferred or advantageous over other aspects or designs. Further,
for the purposes of this disclosure and unless otherwise specified,
"a" or "an" means "one or more".
[0055] The foregoing description of illustrative embodiments of the
invention has been presented for purposes of illustration and of
description. It is not intended to be exhaustive or to limit the
invention to the precise form disclosed, and modifications and
variations are possible in light of the above teachings or may be
acquired from practice of the invention. The embodiments were
chosen and described in order to explain the principles of the
invention and as practical applications of the invention to enable
one skilled in the art to utilize the invention in various
embodiments and with various modifications as suited to the
particular use contemplated. It is intended that the scope of the
invention be defined by the claims appended hereto and their
equivalents.
* * * * *