Nanoparticles

Patent metadata

Field	Value
Publication number	US-9834640-B2
Application number	US-201415027987-A
Country	US
Kind code	B2
Filing date	Oct 10, 2014
Priority date	Oct 10, 2013
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

The present invention relates to nanoparticles of π-conjugated polymers. The present invention also relates to an aqueous composition comprising these polymeric nanoparticles, to processes for making the nanoparticles, and to the use of these nanoparticles in the fabrication of electronic devices and components.

First claim

The invention claimed is:

1. An aqueous composition comprising a plurality of nanoparticles dispersed in an aqueous medium, wherein:
(i) the nanoparticles comprise a core formed from one or more non-cross-linked organic π-conjugated polymers;
(ii) the nanoparticles have a particle size of less than 400 nm; and
(iii) the concentration of the nanoparticles in the aqueous medium is greater than or equal to 12 mM;
and wherein the non-cross-linked organic π-conjugated polymers are intrinsic semi-conductors that do not comprise any carbon-carbon triple bonds.

2. An aqueous composition according to claim 1 , wherein the core of the nanoparticles consists essentially of the one or more non-cross-linked organic π-conjugated polymers.

3. An aqueous composition according to claim 1 , wherein the polymeric backbone of the non-cross-linked organic π-conjugated polymer is uncharged.

4. An aqueous composition according to claim 1 , wherein core of the nanoparticles are coated with a stabiliser.

5. An aqueous composition according to claim 1 , wherein the monomeric units present in the non-cross-linked π-conjugated polymers are selected from the group consisting of:

wherein R, R 1 and R 2 are hydrogen or organic substituent groups (e.g. a hydrocarbyl substituent group optionally comprising 1 to 30 carbon atoms and optionally comprising one or more heteroatoms (e.g. N, O, S, Si, or P), or an aromatic or heteroaromatic group);
M is a metal (e.g. Ir, Pt, Rh, Re, Ru, Os, Cr, Cu, Pd, or Au);
L is a ligand (e.g. a halide or a hydrocarbyl substituent group optionally comprising 1 to 30 carbon atoms and optionally comprising one or more heteroatoms (e.g. N, O, S, Si, or P) or an aromatic or hetroaromatic group);
and wherein each of the above structures is optionally further substituted with one or more organic substituent groups (e.g. a hydrocarbyl substituent groups optionally comprising 1 to 30 carbon atoms and optionally comprising one or more heteroatoms (e.g. N, O, S, Si, or P) or an aromatic or heteroaromatic group).

6. An aqueous composition according to claim 1 , wherein the monomeric units present in the non-cross-linked organic π-conjugated polymers are selected from the group consisting of:

wherein R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen or a hydrocarbyl substituent group comprising 1 to 30 carbon atoms and optionally comprising one or more heteroatoms (e.g. N, O, S, Si, or P);
a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; c and d are 0, 1 or 2; e and f are 0 or 1; x is 0, 1, 2, 3 or 4; y is 0, 1, 2, 3 or 4; and z is 0, 1, 2, 3 or 4.

7. An aqueous composition according to claim 1 , wherein the aqueous medium is water.

8. An aqueous composition according to claim 1 , wherein the size of the nanoparticles is within the range of 30 to 300 nm.

9. An aqueous composition according to claim 1 , wherein the concentration of the nanoparticles in the aqueous medium is greater than or equal to 15 mM.

10. A method of forming an aqueous composition as claimed in claim 1 , said method comprising:
(i) forming the nanoparticles by emulsion polymerisation or miniemulsion polymerisation techniques to form an aqueous suspension of nanoparticles; and
(ii) optionally purifying the nanoparticle suspension.

11. A method according to claim 10 , wherein the nanoparticles are formed by a Stille or Suzuki polymerisation reaction.

12. Nanoparticles comprising one or more non-cross-linked organic π-conjugated polymers, wherein:
(i) the nanoparticles are formed from one or more non-cross-linked organic π-conjugated having a solubility in an organic solvent [e.g. chlorobenzene at room temperature] of less than 10 mg/ml; and
(ii) the nanoparticles have a particle size of less than 400 nm.

13. Nanoparticles according to claim 12 , wherein the monomeric units present in the non-cross-linked π-conjugated polymers have the formula:

wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen or a hydrocarbyl substituent group comprising 1 to 30 carbon atoms and optionally comprising one or more heteroatoms (e.g., N, O, S, Si, or P); and n is at least 1; c and d are 0, 1 or 2; and e and f are 0 or 1.

14. Nanoparticles according to claim 12 , wherein the monomeric units present in the non-cross-linked π-conjugated polymers have the formula:

wherein R 1 and R 2 are each independently selected from hydrogen or a hydrocarbyl substituent group comprising 1 to 30 carbon atoms and optionally comprising one or more heteroatoms (e.g., N, O, S, Si, or P); and n is at least 1.

15. Nanoparticles according to claim 12 , wherein the size of the nanoparticles is within the range of 30 to 300 nm.

16. A process for preparing an organic semi-conductor or photovoltaic device or component, said process comprising:
(i) depositing an aqueous composition comprising nanoparticles as defined in claim 1 onto a substrate; and
(ii) heating the substrate to a temperature above the glass transition temperature (Tg) of the nanoparticles to form a film of organic π-conjugated polymer on the substrate.

17. An organic semi-conductive film obtained by the process of claim 16 .

18. An organic semi-conductor or photovoltaic device or component obtained by a process as defined in claim 16 .

19. An organic semi-conductor or photovoltaic device or component comprising an organic semi-conductive film as claimed in claim 17 .

Assignees

• Univ Manchester
• Chromition Ltd

Inventors

• Mccairn Mark
• Turner Michael
• Muenmart Duangratchaneekorn
• Esquivel Guzman Jair Azael
• Behrendt Jonathan Maxmillian
• Foster Andrew Bryan

Classifications

• Y02E10/549

  Organic PV cells · CPC title

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title

• C08G2261/91

  Photovoltaic applications · CPC title

• C08G61/02

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title

• C08J3/12 Primary

  Powdering or granulating · CPC title