Dithienophthalimide semiconductor polymers

• US 9,006,725 B2
• Filed: 07/04/2012
• Issued: 04/14/2015
• Est. Priority Date: 07/05/2011
• Status: Expired due to Fees

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Noguchi, Hiroyoshi, Doetz, Florian, Mishra, Ashok Kumar, Vaidyanathan, Subramanian, Minh-Tien, Mai
• Primary Examiner(s): Fang, Shane
• Application Number:
  US14/129,772
• Publication Number:
  US 20140142265A1
• Time in Patent Office: 1,014 Days
• Field of Search: 528/360, 528/367, 257/40, 257/E51.005, 257/E51.024
• US Class Current: 257/40
• CPC Class Codes: C08G 2261/124 alternating
• CPC Class Codes: C08G 2261/1412 Saturated aliphatic units
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/3327 alkene-based
• CPC Class Codes: C08G 2261/344 containing heteroatoms
• CPC Class Codes: C08G 2261/364 containing hetero atoms
• CPC Class Codes: C08G 2261/92 TFT applications
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: H10K 10/484 characterised by the channel regions
• CPC Class Codes: H10K 85/113 Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
• CPC Class Codes: H10K 85/151 Copolymers
• CPC Class Codes: Y02E 10/549 Organic PV cells

Abstract

The invention concerns apolymer of the formula (I): wherein: M1 is an optionally substituted dithienophthalimide formula (II): wherein: X is N or C—R, wherein R is H or a C₁-C₄₀ alkyl group, R², at each occurrence, is independently selected from H, a C_1-40 alkyl group, a C_2-40 alkenyl group, a C_1-40 haloalkyl group, and a monocyclicor polycyclic moiety, wherein: each of the C_1-40 alkyl group, the C_2-40 alkenyl group, and the C_1-40 haloalkyl group can be optionally substituted with 1-10 substituents independently selected from a halogen, CN, —NO₂, OH, NH₂, —NH(C_1-20 alkyl), N(C_1-20 alkyl)₂, —S(O)₂OH, —CHO, —C(O)—C_1-20 alkyl, —C(O)OH, —C(O)—OC_1-20 alkyl, —C(O)NH₂, —C(O)NH—C_1-20 alkyl, —C(O)N(C_1-20 alkyl)₂, —OC_1-20 alkyl, —SiH₃, —SiH(C_1-20 alkyl)₂, —SiH₂(C_1-20 alkyl), and —Si(C_1-20 alkyl)₃; and the monocyclic or polycyclic moiety can be covalently bonded to the imide nitrogen via an optional linker, and can be optionally substituted with 1-5 substituentsindependently selected from a halogen, oxo, —CN, —NO₂, OH, ═C(CN)₂, —NH₂, —NH(C_1-20 alkyl), N(C_1-20 alkyl)₂, —S(O)₂OH, —CHO, —C(O)OH, —C(O)—C_1-20 alkyl, —C(O)—OC_1-20 alkyl, —C(O)NH₂, —C(O)NH—C_1-20 alkyl, —C(O)N(C_{1-20 alkyl)2}, —SiH₃, —SiH(C_1-20 alkyl)₂, —SiH₂(C_1-20 alkyl), —Si(C_1-20 alkyl)₃, —O—C_1-20 alkyl, —O—C_1-20 alkenyl, —O—C_1-20 haloalkyl, C_1-20 alkyl, C_1-20 alkenyl, C_1-20 haloalkyl, C_7-20 arylalkyl, C_6-20 aryloxy and C_7-20 arylcarbonyl. M₂ is a repeating unit comprising one or more cyclic moieties; and n is an integer between 2 and 5,000.

Claims

1. A polymer of the formula:

2. The polymer of claim 1, wherein:

R¹ is selected from H, a C_1-40 alkyl group, a C_2-40 alkenyl group, a C_2-40 alkynyl group, a C_1-40 haloalkyl group, -L-Ar¹—

Ar¹, -L-Cy¹, -L-Cy¹-Cy¹,

wherein;

L, at each occurrence, is independently selected from —

Y—

O—

Y—

, —

Y—

C(O)—

Y-—

, a divalent C_1-20 alkyl group, a divalent C_1-20 alkenyl group, a divalent C_1-20 haloalkyl group, and a covalent bond;

Ar¹, at each occurrence, is independently a monovalent or divalent C_6-14 aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —

CN, a C_1-6 alkyl group, a C_1-6 alkoxy group, and a C_1-6 haloalkyl group;

Cy¹, at each occurrence, is independently a monovalent or divalent C_5-14 cycloalkyl group or a 5-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —

CN, a C_1-6 alkyl group, a C_1-6 alkoxy group, and a C_1-6 haloalkyl group;

Y, at each occurrence, is independently selected from a divalent C_1-6 alkyl group, a divalent C_1-6 haloalkyl group, and a covalent bond.

3. The polymer of claim 1, wherein n is an integer between 4 and 1000.

4. An article of manufacture selected from the group consisting of an electronic de vice, an optical device, and an optoelectronic device, comprising one or more polymers of claim 1.

5. The article of manufacture of claim 4, wherein the article of manufacture is a thin film semiconductor comprising the one or more polymers.

6. The article of manufacture of claim 4, wherein the article of manufacture is a field effect transistor device comprising a thin film semiconductor comprising the one or more polymers.

7. The article of manufacture of claim 4, wherein the article of manufacture is a photovoltaic device comprising a thin film semiconductor comprising the one or more polymers.

8. The article of manufacture of claim 4, wherein the article of manufacture is an organic light emitting device comprising a thin film semiconductor comprising the one or more polymers.