Organic semiconductor doping process

Patent metadata

Field	Value
Publication number	US-2016240781-A1
Application number	US-201615132413-A
Country	US
Kind code	A1
Filing date	Apr 19, 2016
Priority date	May 30, 2013
Publication date	Aug 18, 2016
Grant date	—

Abstract

The present invention relates to the doping of organic semiconductors and processes for producing layers of p-doped organic semiconductors. Disclosed is a process for p-doping organic semiconductors comprising treating the organic semiconductor with an oxidised salt of the organic semiconductor. A process for producing a layer of a p-doped organic semiconductor comprising producing a p-doped organic semiconductor by treating the organic semiconductor with an oxidised salt of the organic semiconductor; disposing a composition comprising a solvent and the p-doped organic semiconductor on a substrate; and removing the solvent is also described. Also disclosed is a process for producing a layer of a p-doped organic semiconductor comprising: disposing a composition comprising a solvent, the organic semiconductor and a protic ionic liquid on a substrate; and removing the solvent. A process for producing a semiconductor device comprising a process for doping an organic semiconductor according to the invention is also described. Finally, a high purity p-dopant composition is described.

First claim

1 . A process for producing a p-doped organic semiconductor comprising treating an organic semiconductor with a composition comprising an oxidised salt of the organic semiconductor, which oxidised salt of the organic semiconductor is a salt of formula [OS][A], wherein OS is a cation of an organic semiconductor and A is ClO 4 − , NO 3 − or an anion of formula (i), (ii), (iii) or (iv)

wherein each X is the same or different and is an electron withdrawing group, optionally wherein X is CF 3 or CF 2 CF 3 .

2 . A process according to claim 1 which comprises treating the organic semiconductor with a composition comprising from 80 to 100 wt % of the oxidised salt of the organic semiconductor.

3 . A process according to claim 1 wherein the organic semiconductor comprises:
an organic semiconductor comprising a triarylamine moiety, an organic semiconductor comprising a conjugated polymer, an organic semiconductor comprising a conjugated oligomer, or an organic semiconductor comprising a polycyclic aromatic hydrocarbon.

4 . A process according to claim 1 wherein the organic semiconductor comprises a compound of formula (V), (I), (II), (III), (IV), (VI) or (VII):

wherein:
each A 1 is the same or different and is an unsubstituted or substituted aryl ring or an unsubstituted or substituted heteroaryl ring;
L is a conjugated linker;
n is 3 or 4; and
m is an integer of 2 or more.

5 . A process according to claim 1 wherein the organic semiconductor comprises unsubstituted or substituted polythiophene or an unsubstituted or substituted oligothiophene.

6 . A process according to claim 1 wherein the organic semiconductor comprises a compound of formula (V) or (Vb):

wherein each A 1 is the same or different and is an unsubstituted or substituted aryl ring or an unsubstituted or substituted heteroaryl ring;

wherein each R 1 is the same or different and is a group selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, hydroxyl, mono-C 1-8 alkylamino, di-C 1-8 alkylamino, amino, halide, cyano, nitro, and thiol.

7 . A process according to claim 1 wherein A is bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, bis(perfluoropropanesulfonyl)imide, trifluoroacetate, or trifluoromethanesulfonate.

8 . A process according to claim 1 wherein the process further comprises producing the oxidised salt of the organic semiconductor by a process comprising:
(a) treating the organic semiconductor with an oxidant to produce an oxidation product;
(b) isolating the oxidation product;
(c) performing an anion exchange with A on the oxidation product to produce an oxidised salt of the organic semiconductor comprising A, wherein A is as defined in claim 21 and
(d) isolating the oxidised salt of the organic semiconductor.

9 . A process according to claim 8 wherein the oxidant comprises
a compound selected from percyanocarbon compounds, quinone compounds, chloroquinone compounds, halogen compounds or interhalogen compounds;
a cation selected from triarylaminium radical cations, heterocyclic radical cations, triarylcarbenium cations, tropylium cations, complex cations of metals or nitrosonium cation; or
an anion selected from a hexacyanotrimethylenecyclopropane radical anion [C 3 {C(CN) 2 } 3 ] − , or a hexachloroplatinate anion [PtCl 6 ] 2- .

10 . A process according to claim 8 wherein the oxidant comprises
a compound selected from TCNE, TCNQ, F4TCNQ, DDQ, 1,2-benzoquinone, 1,4-benzoquinone, 1,4-napthoquinone, dichlorobenzoquinone, chloranil, fluorine, chlorine, bromine, or iodine; or
a cation selected from [NAr 3 ] + , thianthrene cation, phenoxathiin cation, phenothiazine cation, N-methylphenothiazine cation, N-phenylphenothiazine cation, [CAr 3 ] + , [Ru(phen) 3 ] 3+ , [Fe(bipy) 3 ] 3+ , [Fe(η-C 5 H 4 COMe) 2 ] + , [Fe(η-C 5 H 4 COMe)Cp] + , or [FeCp 2 ] + ;
wherein Ar is an unsubstituted or substituted aryl group.

11 . A process according to claim 8 wherein the oxidant comprises a cation selected from [N(4-C 6 H 4 Br) 3 ] + , [N(2,4-C 6 H 3 Br 2 ) 3 ] + , [N(2,4,6-C 6 H 2 Br 3 ) 3 ] + , N(4-C 6 H 4 Cl) 3 ] + , [N(2,4-C 6 H 3 Cl 2 ) 3 ] + , [N(2,4,6-C 6 H 2 Cl 3 ) 3 ] + , [N(C 6 Cl 5 ) 3 ] + , [N(4C 6 H 4 —CN) 3 ] + , [N(4-C 6 H 4 CO 2 Me) 3 ] + , [N(4-C 6 H 4 Me) 3 ] + , [N(4-C 6 H 4 OMe) 3 ] + , or [N(4-C 6 H 4 NO 2 ) 3 ] + .

12 . A process according to claim 8 wherein the oxidant comprises an anion selected from [SbCl 6 ] − , [BCl 4 ] − , [AlCl 4 ] − , [PF 6 ] − , [SbF 6 ] − , [BF 4 ] − , [AlF 4 ] − , [ClO 4 ] − , or [NO 3 ] − .

13 . A process according to claim 8 wherein the oxidant comprises [N(4-C 6 H 4 Br) 3 ][SbCl 6 ] or [N(4-C 6 H 4 Br) 3 ][SbF 6 ].

14 . A process according to claim 8 wherein the amount of the oxidant is from 1 to 2 equivalents relative to the amount of the organic semiconductor.

15 . A process according to claim 8 wherein (c) comprises treating the oxidation product with a salt comprising A.

16 . A process according to claim 8 wherein (c) comprises treating the oxidation product with a salt of formula [M][A], wherein M is a cation selected from metal cations, ammonium cations or a sulfonium cation.

17 . A process according to claim 16 wherein M is selected from Li + , Na + , K + , Be 2+ , Mg 2+ , Ca 2+ , Ag + or Zn 2+ .

18 . A process according to claim 8 wherein (c) comprises treating the oxidation product with a salt selected from LiTFSI, NaTFSI, KTFSI, AgTFSI, Zn(TFSI) 2 , LiBETI, NaBETI, KBETI, AgBETI, Zn(BETI) 2 .

19 . A process according to claim 8 wherein (c) comprises treating the oxidation product with 10 to 30 equivalents of a salt comprising the anion A.

20 . A process according to claim 1 wherein the organic semiconductor is treated with from 0.1 to 50 mol % of the oxidised salt of the organic semiconductor relative to the amount of the organic semiconductor.

21 . A process for producing a layer of p-doped organic semiconductor comprising:
(a) producing a p-doped organic semiconductor by a process comprising treating an organic semiconductor with a composition comprising an oxidised salt of the organic semiconductor, which oxidised salt of the organic semiconductor is a salt of formula [OS][A], wherein OS is a cation of an organic semiconductor and A is ClO 4 − , NO 3 − or an anion of formula (i), (ii), (iii) or (iv)

wherein each X is the same or different and is an electron withdrawing group, optionally wherein X is CF 3 or CF 2 CF 3 ;
(b) disposing on a substrate a composition comprising a solvent and the p-doped organic semiconductor; and
(c) removing the solvent.

22 . A process according to claim 21 wherein the composition disposed on the substrate further comprises LiTFSI and/or tert-butyl pyridine.

23 . A process according to claim 22 wherein the composition comprises from 1 to 40 mol % LiTFSI and from 50 to 150 mol % tert-butyl py

Assignees

• Isis Innovation

Inventors

• Snaith Henry
• Leijtens Tomas
• Abate Antonio
• Sellinger Alan

Classifications

• H10K85/50

  Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3 · CPC title

• H01G9/2027

  comprising an oxide semiconductor electrode · CPC title

• H01L51/0035

  Electricity · mapped topic

• H01L51/006

  Electricity · mapped topic

• H01G9/2059

  comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution · CPC title