Semiconductor materials prepared from rylene-(π-acceptor)copolymers

• US 9,219,233 B2
• Filed: 02/05/2009
• Issued: 12/22/2015
• Est. Priority Date: 02/05/2008
• Status: Active Grant

• Current Assignee: Flexterra, Inc.
• Original Assignee: BASF SE, Polyera Corporation
• Inventors: Facchetti, Antonio, Chen, Zhihua, Yan, He, Lu, Shaofeng, Marks, Tobin J., Zheng, Yan, Kastler, Marcel, Vaidyanathan, Subramanian, Doetz, Florian, Koehler, Silke Annika
• Primary Examiner(s): Mowla, Golam
• Application Number:
  US12/865,031
• Publication Number:
  US 20110120558A1
• Time in Patent Office: 2,511 Days
• Field of Search: 136/263, 136/252
• US Class Current: 1/1
• CPC Class Codes: C08G 61/10 only aromatic carbon atoms, e.g. polyphenylenes
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• CPC Class Codes: C09B 5/62 Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
• CPC Class Codes: C09B 69/102 containing a perylene dye
• CPC Class Codes: C09B 69/105 containing a methine or polymethine dye
• CPC Class Codes: C09B 69/106 containing an azo dye
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1458 containing sulfur as the only heteroatom
• CPC Class Codes: C09K 2211/1483 containing nitrogen and sulfur as heteroatoms
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H05B 33/14 characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source
• 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 85/113 Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
• CPC Class Codes: H10K 85/151 Copolymers
• CPC Class Codes: H10K 85/40 Organosilicon compounds, e.g. TIPS pentacene
• CPC Class Codes: H10K 85/621 Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Disclosed are new semiconductor materials prepared from rylene-(π-acceptor) copolymers. Such copolymers can exhibit high n-type carrier mobility and/or good current modulation characteristics. In addition, the polymers of the present teachings can possess certain processing advantages such as solution-processability and/or good stability at ambient conditions.

Claims

1. A polymer represented by formula:

2. The polymer of claim 1, wherein M₁ is an optionally substituted aromatic imide selected from:

3. The polymer of claim 1, wherein each of π

-1, π

-1′

, and π

-2 independently is optionally substituted with 1-6 R^a groups;

wherein;

R^a, at each occurrence, is a) halogen, b) —

CN, c) ⁻

NO₂, d) oxo, e) —

OH, f) ═

C(R^b)₂, g) a C_1-40 alkyl group, h) a C_2-40 alkenyl group, i) a C_2-40 alkynyl group, j) a C_1-40 alkoxy group, k) a C_1-40 alkylthio group, l) a C_1-40 haloalkyl group, m) a —

Y—

C_3-10 cycloalkyl group, n) a —

Y—

C_6-14 aryl group, o) a —

Y—

C_6-14 haloaryl group, p) a —

Y-3-12 membered cycloheteroalkyl group, or q) a —

Y-5-14 membered heteroaryl group, wherein each of the C_1-40 alkyl group, the C_2-40 alkenyl group, the C_2-40 alkynyl group, the C_3-10 cycloalkyl group, the C_6-14 aryl group, the C_6-14 haloaryl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group is optionally substituted with 1-4 R^b groups;

R^b, at each occurrence, is a) halogen, b) —

CN, c) —

NO₂, d) oxo, e) —

OH, f) —

NH₂, g) —

NH(C_1-20 alkyl), h) —

N(C_1-20 alkyl)₂, i) —

N(C_1-20 alkyl)-C_6-14 aryl, j) —

N(C_6-14 aryl)₂, k) —

S(O)_mH, l) —

S(O)_m—

C_1-20 alkyl, m) —

S(O)₂OH, n) —

S(O)_m—

OC_1-20 alkyl, o) —

S(O)_m—

OC_6-14 aryl, p) —

CHO, q) —

C(O)—

C_1-20 alkyl, r) —

C(O)—

C_6-14 aryl, s) —

C(O)OH, t) —

C(O)—

OC_1-20 alkyl, u) —

C(O)—

OC_6-14 aryl, v) —

C(O)NH₂, w) —

C(O)NH—

C_1-20 alkyl, x) —

C(O)N(C_1-20 alkyl)₂, y) —

C(O)NH—

C_6-14 aryl, z) —

C(O)N(C_1-20 alkyl)-C_6-14 aryl, aa) —

C(O)N(C_6-14 aryl)₂, ab) —

C(S)NH₂, ac) —

C(S)NH—

C_1-20 alkyl, ad) —

C(S)N(C_1-20 alkyl)₂, ae) —

C(S)N(C_6-14 aryl)₂, af) —

C(S)N(C_1-20 alkyl)-C_6-14 aryl, ag) —

C(S)NH—

C_6-14 aryl, ah) —

S(O)_mNH₂, ai) —

S(O)_mNH(C_1-20 alkyl), aj) —

S(O)_mN(C_1-20 alkyl)₂, ak) —

S(O)_mNH(C_6-14 aryl), al) —

S(O)_m(C_1-20 alkyl)-C_6-14 aryl, am) —

S(O)_mN(C_6-14 aryl)₂, an) —

SiH₃, ao) —

SiH(C_1-20 alkyl)₂, ap) —

SiH₂(C_1-20 alkyl), aq) —

Si(C_1-20 alkyl)₃, ar) a C_1-20 alkyl group, as) a C_2-20 alkenyl group, at) a C_2-20 alkynyl group, au) a C_1-20 alkoxy group, av) a C_1-20 alkylthio group, aw) a C_1-20 haloalkyl group, ax) a C_3-10 cycloalkyl group, ay) a C_6-14 aryl group, az) a C_6-14 haloaryl group, ba) a 3-12 membered cycloheteroalkyl group, or bb) a 5-14 membered heteroaryl group;

Y, at each occurrence, is a divalent C_1-20 alkyl group, a divalent C_1-20 haloalkyl group, or a covalent bond; and

m, at each occurrence, is 0, 1, or 2.

4. The polymer of claim 1, wherein R¹, 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, -L-Ar¹, -L-Ar¹—

Ar¹, -L-Ar¹—

R², -L-Ar¹—

Ar¹—

R², -L-Cy¹, -L-Cy¹-Cy¹, -L-Cy¹-R², and -L-Cy¹-Cy¹-R²;

wherein;

L, at each occurrence, is independently selected from —

Y—

O—

Y—

, —

Y—

[S(O)_m]—

Y—

, —

Y—

C(O)—

Y—

, —

Y—

[NR^cC(O)]—

Y—

, —

Y—

[C(O)NR^c]—

, —

Y—

[SiR^c₂]-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;

wherein;

R^c, at each occurrence, is independently H, a C_1-6 alkyl group, or a —

Y—

C_6-14 aryl group;

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, oxo, ═

C(CN)₂, a C_1-6 alkyl group, a C_1-6 alkoxy group, and a C_1-6 haloalkyl group; and

Cy¹, at each occurrence, is independently a monovalent or divalent C_3-14 cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —

CN, oxo, ═

C(CN)₂, a C_1-6 alkyl group, a C_1-6 alkoxy group, and a C_1-6 haloalkyl group;

R², at each occurrence, is independently selected from a C_1-40 alkyl group, a C_2-40 alkenyl group, a C_1-40 haloalkyl group, a C_1-40 alkoxy group, -L′

-Ar², -L′

-Ar²—

Ar², -L′

-Ar′

—

R³, -L′

-Ar²—

Ar²—

R³, -L′

-Cy², -L′

-Cy²-Cy², -L′

-Cy²-R³, -L′

-Cy²-Cy²-R³;

wherein;

L′

, at each occurrence, is independently selected from —

Y—

O—

Y—

, —

Y—

[S(O)_m]-Y—

, —

Y—

C(O)—

Y—

, —

Y—

[NR^cC(O)]—

Y—

, —

Y—

[C(O)NR^c]—

, —

Y—

NR^c—

, —

Y—

[SiR^c₂]-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;

Ar², 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 halogen, oxo, —

CN, ═

C(CN)₂, a C_1-6 alkyl group, a C_1-6 alkoxy group, and a C_1-6 haloalkyl group;

Cy², at each occurrence, is independently a monovalent or divalent C_3-14 cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, oxo, —

CN, ═

C(CN)₂, a C_1-6 alkyl group, a C_1-6 alkoxy group, and a C_1-6 haloalkyl group;

R³, at each occurrence, is a C_1-40 alkyl group, a C_2-40 alkenyl group, a C_1-40 haloalkyl group, or a C_1-40 alkoxy group;

Y, at each occurrence, is a divalent C_1-20 alkyl group, a divalent C_1-20 haloalkyl group, or a covalent bond; and

m, at each occurrence, is 0, 1, or 2.

5. The polymer of claim 1, represented by formula:

6. The polymer of claim 1, wherein R¹ is a linear or branched C_3-40 alkyl group selected from an n-hexyl group, a 1-methylpropyl group, a 1-methylbutyl group, a 1-methylpentyl group, a 1-methylhexyl group, a 1-ethylpropyl group, a 1-ethylbutyl group, a 1-3,dimethylbutyl group, and a 2-octyldodecyl group.

7. The polymer of claim 1, wherein R¹ is selected from:

8. The polymer of claim 3, wherein π

-2 is selected from;

9. The polymer of claim 3, wherein π

-2 is selected from;

10. The polymer of claim 1, wherein π

-2 is a polycyclic moiety comprising a Spiro atom or substituted with 1-4 groups selected from an oxo group and a dicyanovinylidenyl group.

11. The polymer of claim 1, wherein the polymer is

12. The polymer of claim 1, wherein the polymer is

13. The polymer of claim 1, wherein the polymer is selected from:

14. The polymer of claim 1, wherein the polymer is selected from:

18. A composition comprising the polymer of claim 1 dissolved or dispersed in a liquid medium.

19. The composition of claim 18, wherein the liquid medium comprises water or an organic solvent.

20. The composition of claim 18, the composition further comprising at least one additive.

21. The composition of claim 20, wherein the additive is independently selected from the group consisting of a detergent, a dispersant, a binding agent, a compatiblizing agent, a curing agent, an initiator, a humectant, an antifoaming agent, a wetting agent, a pH modifier, a biocide, and a bactereriostat.

22. An article of manufacture comprising the polymer of claim 1.

23. The article of manufacture of claim 22, wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device.

24. A thin film semiconductor comprising the polymer of claim 1.

25. A composite comprising a substrate and the thin film semiconductor of claim 24 deposited on the substrate.

26. A field effect transistor device comprising the thin film semiconductor of claim 24.

27. A field effect transistor device comprising the composite of claim 25.

28. The field effect transistor device of claim 26, wherein the field effect transistor has a structure selected from top-gate bottom-contact structure, bottom-gate top-contact structure, top-gate top-contact structure, and bottom-gate bottom-contact structure.

29. The field effect transistor device of claim 26 comprising a dielectric material, wherein the dielectric material comprises an organic dielectric material, an inorganic dielectric material, or a hybrid organic/inorganic dielectric material.

30. A photovoltaic device comprising the thin film semiconductor of claim 24.

31. A photovoltaic device comprising the composite of claim 25.

32. The photovoltaic device of claim 30 comprising a p-type semiconducting material adjacent to the polymer.

33. An organic light emitting device comprising the thin film semiconductor of claim 24.

34. An organic light emitting device comprising the composite of claim 25.

35. A method of making an article of manufacture comprising depositing a composition of claim 26 onto a substrate.

36. The method of claim 35, wherein depositing the composition comprises at least one of printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying.

37. The method of claim 36, wherein printing is selected from gravure printing, inkjet printing, flexographic printing, screen printing, pad printing, offset printing, and lithographic printing.

15. A polymer represented by formula I or formula I′

;

16. The polymer of claim 15, wherein 7-2 has a reduction potential greater than or equal to about −

1.2 V.

17. The polymer of claim 15, wherein π

-2 is a polycyclic moiety optionally substituted with 1-6 R^a groups.