Fluorine substitution influence on benzo[2,1,3]thiodiazole based polymers for field-effect transistor applications

Patent metadata

Field	Value
Publication number	US-10875957-B2
Application number	US-201916415832-A
Country	US
Kind code	B2
Filing date	May 17, 2019
Priority date	Nov 11, 2015
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

Four conjugated copolymers with a donor/acceptor architecture including 4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b′]dithiophene as the donor structural unit and benzo[2,1,3]thiodiazole fragments with varying degrees of fluorination have been synthesized and characterized. It has been shown that the HOMO levels were decreased after the fluorine substitution. The field-effect charge carrier mobility was similar for all polymers with less than an order of magnitude difference between different acceptor units.

First claim

What is claimed is:

1. A composition of matter, comprising:
one or more semiconducting polymers, each of the one or more semiconducting polymers having a main chain section and a repeating unit of the structure:

wherein each Ar is independently a substituted or non-substituted aromatic functional group, or each Ar is independently nothing and the valence of its respective ring is completed with hydrogen,
each R is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; and
X is C, Si, Ge, N or P.

2. The composition of matter of claim 1 , wherein each of the one or more semiconducting polymers comprise the main chain section having the repeating unit of the structure:

wherein:
each Ar 1 is independently a substituted or non-substituted aromatic functional group, or each Ar 1 is independently nothing and the valence of the ring comprising fluorine (F) is completed with hydrogen, and
each Ar 2 is independently a substituted or non-substituted aromatic functional group, or each Ar 2 is independently nothing and the valence of its respective thiophene ring is completed with hydrogen.

3. The composition of matter of claim 1 , wherein each of the one or more semiconducting polymers comprise the main chain section having the repeating unit of the structure:

wherein:
each Ar 1 is independently a substituted or non-substituted aromatic functional group, or each Ar 1 is independently nothing and the valence of the ring comprising fluorine (F) is completed with hydrogen, and
each Ar 2 is independently a substituted or non-substituted aromatic functional group, or each Ar 2 is independently nothing and the valence of its respective thiophene ring is completed with hydrogen.

4. The composition of matter of claim 1 , wherein each of the one or more semiconducting polymers have the repeating unit of the structure:

and
wherein the fluorine (F) is regioregularly arranged along each of the main chain sections.

5. The composition of matter of claim 1 , wherein carrier mobility of an OFET comprising a plurality of the semiconducting polymers is at least 0.03 cm 2 V −1 s −1 after exposure of the semiconducting polymer to the air for at least 5 days.

6. A package comprising the composition of matter of claim 1 , wherein the package exposes a plurality of the semiconducting polymers to the air for at least 5 days.

7. The composition of matter of claim 1 , further comprising an air permeable material encapsulating the composition of matter.

8. The composition of matter of claim 1 , further comprising:
the semiconducting polymers comprise a plurality of the semiconducting polymers stacked into a crystalline structure, wherein the crystalline structure is characterized by observation of a diffraction peak measured by grazing incidence wide-angle X-ray scattering (GIWAXS) of the film.

9. The composition of matter of claim 8 , wherein the semiconducting polymers comprise adjacent semiconducting polymers and a π-π distance between the adjacent semiconducting polymers is no more than 0.35 nm.

10. One or more organic field effect transistors (OFETs) comprising the composition of matter of claim 1 , each of the OFETs comprising:
a channel including a plurality of the semiconducting polymers;
a source contact to the channel;
a drain contact to the channel; and
a gate contact on or above the channel.

11. The one or more OFETs of claim 10 , wherein the semiconducting polymers are disposed on a planar, non-grooved surface, and the one or more OFETs have a hole mobility of at least 1.2 cm 2 V −1 s −1 in a saturation regime.

12. The one or more OFETs of claim 10 , wherein the hole mobility is in a range of 1.2−10 cm 2 V −1 s −1 in the saturation regime.

13. An electronic circuit comprising a plurality of the OFETs of claim 10 .

14. The composition of matter of claim 1 , comprising a plurality of the semiconducting polymers.

15. A method of making an organic field effect transistor (OFET), comprising:
forming a source contact and a drain contact to a channel comprising a plurality of semiconducting polymers;
forming a gate contact on or above the channel;
providing a dielectric between the semiconducting polymers and a gate; and
wherein:
each of the semiconducting polymers have a main chain section and a repeating unit of the structure:

each Ar is independently a substituted or non-substituted aromatic functional group, or each Ar is independently nothing and the valence of its respective ring is completed with hydrogen,
each R is independently hydrogen or a substituted or non-substituted alkyl, aryl or alkoxy chain; and
X is C, Si, Ge, N or P.

16. The method of claim 15 , further comprising fabricating the semiconducting polymers each comprising a regioregular donor-acceptor copolymer, wherein fabricating the regioregular donor-acceptor copolymer comprises:
preparing a monomer, wherein the monomer comprises a donor structure having an electron rich moiety in combination with an acceptor structure including fluorine and having electron deficient moiety;
reacting the monomer to produce the regioregular donor-acceptor copolymer that comprises a regioregular conjugated main chain section, and
performing an end-capping reaction on the regioregular donor-acceptor copolymer; wherein:
the charge carrier mobility of the regioregular donor-acceptor copolymer is greater than the charge carrier mobility of a regiorandom donor-acceptor copolymer of similar composition.

17. The method of claim 16 , wherein each of the regioregular donor-acceptor copolymers have the repeating unit of the structure:

18. The method of claim 16 , further comprising fabricating the semiconducting polymers each comprising a donor-acceptor copolymer, wherein fabricating the donor-acceptor copolymer comprises:
reacting a first compound and second compound in a solution to form a product, wherein the first compound comprises a dithiophene and the second compound has the structure:

purifying the product in a solvent mixture using chromatography to obtain a third compound having the structure:

and
polymerizing the third compound to obtain the semiconducting polymer having a repeating unit of the structure:

and
wherein the fluorine (F) is regioregularly arranged along the semiconducting polymer's conjugated main chain section; and
wherein the R are each independently an alkyl, aryl, or an alkoxy chain.

19. The method of claim 16 , wherein the preparing is such that a regioregularity of

Assignees

• Univ California

Inventors

• Wang Ming
• Bazan Guillermo C

Classifications

• C08G2261/1412

  Saturated aliphatic units · CPC title

• C08G2261/124

  alternating · CPC title

• C08G2261/344

  containing heteroatoms · CPC title

• C08G2261/414

  Stille reactions · CPC title

• C08G2261/92

  TFT applications · CPC title