# US 10,121,968 B2 · Decomposable s-tetrazine based polymers for single walled carbon nanotube applications

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- Number: US 10,121,968 B2
- Document ID: US10121968B2
- Status: Granted
- Kind: B2
- Application number: 15/401,421
- Filed: 2017-01-09
- Published: 2018-07-12
- Granted: 2018-11-06
- Earliest claimed: 2017-01-09
- Assignees: National Research Council of Canada
- Applicants: National Research Council of Canada
- Inventors: Zhao Li; Jianfu Ding; Patrick Roland Lucien Malenfant
- Web page: https://patentgrep.com/patent/US10121968B2

## CPC

- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- C08G 61/122: {derived from five- or six-membered heterocyclic compounds, other than imides}
- C08G 61/123: {derived from five-membered heterocyclic compounds}
- C08G 61/125: {with a five-membered ring containing one oxygen atom in the ring}
- H10K 10/484: {characterised by the channel regions}
- H10K 71/311: {Purifying organic semiconductor materials}
- H10K 85/151: {Copolymers}
- C08G 2261/124: alternating
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/228: Polymers, i.e. more than 10 repeat units
- C08G 2261/3221: containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
- C08G 2261/3222: containing one or more oxygen atoms as the only heteroatom, e.g. furan
- C08G 2261/3223: containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
- C08G 2261/3243: containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
- C08G 2261/92: TFT applications
- H10K 85/221: {Carbon nanotubes}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

A process for purifying semiconducting single-walled carbon nanotubes (sc-SWCNTs) extracted with a conjugated polymer, the process comprising exchanging the conjugated polymer with an s-tetrazine based polymer in a processed sc-SWCNT dispersion that comprises the conjugated polymer associated with the sc-SWCNTs. The process can be used for production of thin film transistors. In addition, disclosed herein is use of an s-tetrazine based polymer for purification of semiconducting single-walled carbon nanotubes (sc-SWCNTs).

## Claims

### Claim 1

A process for purifying semiconducting single-walled carbon nanotubes (sc-SWCNTs) extracted with a conjugated polymer, the process comprising exchanging the conjugated polymer with an s-tetrazine based polymer in a processed sc-SWCNT dispersion that comprises the conjugated polymer associated with the sc-SWCNTs.

### Claim 2 (depends on 1)

The process of claim 1, further comprising decomposing the s-tetrazine based polymer by photo irradiation or thermal treatment; followed by removal of the decomposition products.

### Claim 3 (depends on 1)

The process of claim 1, wherein the s-tetrazine based polymer has the following structure:
where A is O, S, Se or C═C; n is an integer from 1 to 4; R1 is independently H, F, CN or a C1-C20 linear or branched aliphatic group; Ar is one or more substituted or unsubstituted aromatic units; and, m is an integer 5 or greater.

### Claim 4 (depends on 1)

The process of claim 1, wherein the s-tetrazine based polymer is PBDTFTz:

### Claim 5 (depends on 1)

The process of claim 1, wherein the s-tetrazine based polymer is PDTSTTz:

### Claim 6 (depends on 1)

The process of claim 1, wherein the s-tetrazine based polymer is:
and wherein: R1 and R2=2-ethylhexyl; or R1=2-ethylhexyl and R2=hexyl; or R1=hexyl and R2=2-ethylhexyl; or R1 and R2=hexyl; or R1=methyl and R2=2-ethylhexyl.

### Claim 7 (depends on 1)

The process of claim 1, wherein the s-tetrazine based polymer is PCPDTFTz:
in which Ar=cyclopenta[2,1-b; 3.4-b′]dithiophene.

### Claim 8 (depends on 2)

The process of claim 2, wherein the decomposition products are removed by rinsing or evaporation.

### Claim 9 (depends on 1)

The process of claim 1, wherein the conjugated polymer comprises a polyfluorene.

### Claim 10 (depends on 1)

The process of claim 1, wherein the conjugated polymer comprises a polythiophene.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the conjugated polymer is poly(9,9-di-n-dodecylfluorene) (PFDD).

### Claim 12 (depends on 1)

The process according to claim 1, wherein the weight ratio of the conjugated polymer to the sc-SWCNTs has a maximum value of 2.

### Claim 13 (depends on 1)

The process according to claim 1, wherein the weight ratio of the s-tetrazine based polymer to the sc-SWCNTs has a maximum value of 4.

### Claim 14 (depends on 1)

The process according to claim 1, wherein the weight ratio of the s-tetrazine based polymer to the sc-SWCNTs is between 1 and 4.

### Claim 15

A method for producing thin film transistors, the method comprising:
a) exchanging a conjugated polymer with an s-tetrazine based polymer in a processed sc-SWCNT dispersion that comprises the conjugated polymer associated with the sc-SWCNTs, resulting in an associated complex of s-tetrazine/SWCNTs (15);
b) removing the displaced conjugated polymer;
c) applying the resulting dispersion to a substrate;
d) applying heat and/or UV light to decompose the s-tetrazine based polymer; and
e) removing the resulting decomposition products.

### Claim 16 (depends on 15)

The method according to claim 15, wherein the s-tetrazine based polymer has the following structure:
where A is O, S, Se or C═C; n is an integer from 1 to 4; R1 is independently H, F, CN or a C1-C20 linear or branched aliphatic group; Ar is one or more substituted or unsubstituted aromatic units; and, m is an integer 5 or greater.

### Claim 17 (depends on 16)

The method of claim 16, wherein the wherein the s-tetrazine based polymer is PBDTFTz:

### Claim 18 (depends on 16)

The method of claim 16 wherein the conjugated polymer is poly(9,9-di-n-dodecylfluorene) (PFDD).