N-type thiophene semiconductors

• US 6,585,914 B2
• Filed: 07/24/2001
• Issued: 07/01/2003
• Est. Priority Date: 07/24/2000
• Status: Expired due to Term

• Current Assignee: Northwestern University
• Original Assignee: Northwestern University
• Inventors: Marks, Tobin J., Facchetti, Antonio
• Primary Examiner(s): KOPEC, MARK T
• Application Number:
  US09/915,206
• Publication Number:
  US 20030080324A1
• Time in Patent Office: 707 Days
• Field of Search: 252/500, 528/377
• US Class Current: 252/500
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• CPC Class Codes: H10K 10/46 Field-effect transistors, e.g. organic thin-film transistors [OTFT] H10K10/43 takes precedence
• CPC Class Codes: H10K 10/462 Insulated gate field-effect transistors [IGFETs]
• CPC Class Codes: H10K 10/464 Lateral top-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 10/466 Lateral bottom-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 59/00 Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
• CPC Class Codes: H10K 71/16 using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
• CPC Class Codes: H10K 71/164 using vacuum deposition
• CPC Class Codes: H10K 85/113 Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
• CPC Class Codes: H10K 85/655 comprising only sulfur as heteroatom

Abstract

The new fluorocarbon-functionalized and/or heterocycle-modified polythiophenes, in particular, α,ω-diperfluorohexylsexithiophene DFH-6T can be straightforwardly prepared in high yield and purity. Introduction of such modifications to a thiophene core affords enhanced thermal stability and volatility, and increased electron affinity versus the unmodified compositions of the prior art. Evaporated films behave as n-type semiconductors, and can be used to fabricate thin film transistors with FET mobilities ˜0.01 cm²/Vs—some of the highest reported to date for n-type organic semiconductors.

Claims

1. An n-type polythiophene composition having the structural formula

wherein R₁, R₂ and R₃ are selected from the substituent group consisting of fluoroalkyl moieties, C_nH_2n+1 and where n is about 1-12, H, F and (CH₂)_aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities;

and x, y and z are integers selected from the group of integers consisting of 1 and integers greater than 1.

2. The n-type polythiophene composition of claim 1 wherein said fluoroalkyl moiety is selected from the group consisting of linear fluoroalkyl substituents, branched fluoroalkyl substituents and cyclic fluoroalkyl substituents.

3. The n-type polythiophene composition of claim 2 wherein said fluoroalkyl moiety has a compositional formula C_nF_2n+1, where n is about 1-8.

4. The n-type polythiophene composition of claim 1 wherein x is 1 to about 4;

y is 1 to about 8, and z is 1 to about 12.

5. The n-type polythiophene composition of claim 4 wherein said fluoroalkyl moiety has the compositional formula C_nF_2n+1, where n is about 1-8.

6. An n-type polythiophene composition having the structural formula

wherein R₁, R₂ and R₃ are selected from the substituent group consisting of fluoroalkyl moieties, C_nH_2n+1 and where n is about 1-12, H, F and (CH₂)_aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities;

x and z are integers selected from the group of integers consisting of 1 and integers greater than 1; and

y is an integer selected from the group of integers consisting of 0 and integers greater than 0, said composition wherein R₂ and R₃ are not the same fluoroalkyl moieties.

7. The n-type polythiophene composition of claim 6 wherein said fluoroalkyl moiety is selected from the group consisting of linear fluoroalkyl substituents, branched fluoroalkyl substituents and cyclic fluoroalkyl substituents.

8. The n-type polyhiophene composition of claim 7 wherein said fluoroalkyl moiety has a compositional formula C_nF_2n+1, where n is about 1-8.

9. The n-type polythiophene composition of claim 6 wherein x is 1 to about 4;

y is 1 to about 8, and z is 1 to about 12.

10. The n-type polythiophene composition of claim 9 wherein said fluoroalkyl moiety has the compositional formula C_nF_2n+1, where n is about 1-8.